When a biomaterial is inserted into the body, the interaction of the surface with the surrounding biological environment is crucial. Given the importance of the surface, the ability to alter the surface properties to support a compatible environment is therefore desirable. Silicone hydrogel contact lenses (CL) allow for improved oxygen permeability through the incorporation of siloxane functional groups. These groups however are extremely surface active and upon rotation, can impart hydrophobicity to the lens surface, decreasing lens wettability and increasing protein and lipid deposition. Lens biofouling may be problematic and therefore surface modification of these materials to increase compatibility is exceedingly recognized for importance in both industry and research. The current work focuses on the creation of a novel anti-fouling polymer surface by the incorporation of 2-methacryoyloxyethyl phosphorylcholine (MPC), well known for its biomimetic and anti-fouling properties. A controlled polymerization method was used to generate a unique double-grafted architecture to explore the effect of increasing surface density of polyMPC chains on corresponding anti-fouling properties. The novel free polymer was synthesized by a 3-step atom transfer radical polymerization (ATRP). First, poly(2-hydroxyethyl methacrylate) (polyHEMA) was polymerized by ATRP, where the hydroxyl (OH) groups of the polymer then underwent an esterification to create macroinitiating sites. From these sites, a second ATRP of poly(MPC) varying in length occurred, yielding the double-grafted polymer poly(2(2-bromoisobutyryloxy-ethyl methacrylate)-graft-poly(2-methacryloyloxyethyl phosphorylcholine (pBIBEM-g-pMPC). The polymer was designed for resistance to protein adsorption through a possible synergistic effect between the surface induced hydration layer by surrounding PC groups coupled with steric repulsion of the densely grafted chains. To test its potential as a surface modifier, the polymer was grafted from model silicone hydrogel CL through a 4-step surface initiated ATRP (SI-ATRP) in a similar manner to the free polymer. First, the ATRP initiator was immobilized from the HEMA OH groups of the unmodified CL, generating Intermedate-1. A polyHEMA brush was grafted from the initiating sites yielding pHEMA-50, followed by the generation of a second initiator layer (Intermediate- 2). A sequential ATRP of poly(MPC) then generated the target pMPC-50/pMPC-100 surfaces. For the free pBIBEM-g-pMPC polymer analysis, 1H-NMR and GPC determined polymers formed with a predictable MW and low polydispersity (PDI). For surface grafting, using a sacrificial initiator, 1H-NMR and GPC indicated that the pHEMA-50 and pMPC-50/pMPC-100 polymers were well-controlled, with a MW close to the theoretical and a low PDI. For surface chemical composition, ATR-FTIR showed the presence of the ATRP initiator (Intermediate-1 and 2) by the appearance of a C-Br peak and disappearance of the OH peak. XPS confirmed the chemical composition of the 4-step synthesis by a change in the fraction of expected surface elements. Both the surface wettability and EWC of the materials increased upon pMPC modification, further improving upon increasing pMPC chain length. The contact angle was as low as 16.04 ± 2.37º for pMPC-50 surfaces and complete wetting for pMPC-100. Finally, the single protein adsorption using lysozyme and bovine serum albumin (BSA) showed significantly decreased protein levels for pMPC-50/100 lenses, as much as 83% (p 0.00036) for lysozyme and 73% (p 0.0076) for BSA, with no significant difference upon chain length variation. The aforementioned data demonstrates that the novel polymer has potential in providing an anti-fouling and extremely wettable surface, specifically regarding silicone hydrogel CL surfaces. / Thesis / Master of Applied Science (MASc)

Pb(II) removal is imperative due to its inherent toxicity at low levels and its tendency to accumulate in ecosystems. Conductive carbonaceous nanomaterials (CCNs), such as carbon nanotubes (CNTs) and carbon nanofibers (CNFs), have recently gained the interest of researchers due to their superior properties and ease of functionalization. The aim of this study is to utilize CCNs for Pb(II) removal within membrane technology and bioremediation strategies. Membranes have shown promise in their treatment abilities, producing excellent effluent quality while reducing plant footprints. The integration of CNTs within membrane technology provides an opportunity to couple its removal capacity with Pb(II) removal that exhibits regeneration capabilities. However, membrane fouling can be problematic for membrane longevity and regeneration. CNTs have also shown to be capable of mitigating fouling via electrostatic repulsion and pollutant degradation. However, little work has been conducted on its fabrication. In this work, CNTs were incorporated with poly(vinyl) alcohol (PVA) in thin film composites, where the effects of PVA chain length and degree of crosslinking were investigated. It was found that a pseudo-optimal coating can be obtained using 31-50kDa PVA with 10% crosslinking. This combination lead to a highly permeable, hydrophilic surface with good electrical conductivity that exhibited a molecular weight cut off of 2000kDa. Biosorption has shown promise in Pb(II) removal in the lab scale but its large-scale use is hindered from rapid saturation of binding sites and low regeneration abilities. Exoelectrogens were proposed as reactive biosorbents to couple biosorption with bioreduction in an attached growth configuration. CCNs were investigated as bacterial scaffolds, where their efficacy and Pb(II) dosage concentration was studied. It was found that CNFs were superior in removing Pb(II), exhibiting Pb(II) concentrations ≤0.10 ppm where removal increased when Pb(II) dosage increased from 0.5 to 5ppm. SEM-EDX analysis provided evidence that bioreduction dominated Pb(II) removal. A long-term study was further conducted using CNFs, revealing its robustness in long term removal over suspended growth reactors with a sustained removal of ≈ 80%. A numerical model was further proposed which exhibited a goodness of fit with an R-squared of 0.92. This model confirmed that bioreduction dominated Pb(II) removal and revealed biofilm thickness and Monod kinetics to be the main influential parameters on Pb(II) removal. / Thesis / Master of Applied Science (MASc)

Non-wetting surfaces mainly categorized into superhydrophobic (SHS), lubricant-infused (LIS) and solid-infused surfaces (SIS), by virtue of their superior water repellant properties have wide applications in several energy and environmental systems. In this dissertation, the role of non-wetting surfaces toward the enhancement of condensation effectiveness is analyzed by taking into consideration the tube side and shell side individual interfacial energy transport processes namely, drag reduction, convection heat transfer enhancement, fouling mitigation and dropwise condensation heat transfer. First, an analytical solution is developed for effective slip length and, in turn, drag reduction and friction factor on structured non-wetting surfaces. Secondly, by combining the solution for effective slip length on structured non-wetting surfaces and the fractal characterization of generic multiscale rough surfaces, a theoretical analysis of drag reduction, friction factor, and convection heat transfer enhancement is conducted for scalable non-wetting surfaces. Next, fractal representation of rough surfaces is used to theoretical derive the dropwise condensation heat transfer performance on SHS and novel SIS surfaces. The aspect of dynamic fouling mitigation properties of non-wetting surfaces is explored by conducting systematic experiments. Using Taguchi design of experiments, this work for the first time presents a closed formed relationship of fouling mitigation quantified in terms of asymptotic fouling resistance with Reynolds number, foulant concentration and viscosity of the infusion material that represents the different surface types in a unified manner. Furthermore, it was observed that LIS and SIS offer excellent fouling mitigation compared to SHS and conventional smooth surfaces, however only SIS owing to the presence of solid-like infusion materials is observed to be robust for practical applications. / Doctor of Philosophy / Inspired by the naturally occurring water repellant lotus leaf and pitcher plant, metallic surfaces have undergone engineering modifications to their native wetting properties. By generating roughness features ranging from nanometer to micrometer length scales, subjecting them to low surface energy treatments and by choosing an appropriate water repellant infusion material, the water repellant properties seen on lotus leaf and pitcher plant can be engineered. Such water repellant (non-wetting) surface fabrication methods are widely available in the literature however very few are scalable to surface types (e.g. copper, aluminum etc.), surface size (millimeters to meters) and shape (plain, curved, inside of tubes etc.). In this work, considering scalable fabrication methods such as electrodeposition and chemical etching, a systematic analysis is conducted on enhancement of four interfacial processes that are a part of many industrial applications. First, the extent of water repellency by structured non-wetting surfaces for the flow of fluid (water) quantified in terms of effective slip length of flow is analytically derived. Using this theory and a self-similar (fractal) nature of the more generic rough surface designs, a theoretical analysis into the drag reduction, convection heat transfer enhancement on non-wetting surfaces is conducted. Next, using the fractal nature of the rough superhydrophobic surfaces (SHS) a theoretical investigation into dropwise condensation performance is used to derive bounds on condensation heat transfer enhancement. Through systematic experimental investigations, it is shown that a solid-infused surface (SIS) and lubricant-infused surfaces (LIS) which, respectively, incorporate a polymer and a slippery lubricant in the interstitial region of metallic asperities, exhibit superior dynamic mineral fouling mitigation performance compared to SHS and conventional smooth surfaces. In addition, it is demonstrated that SIS is a far robust and durable choice when compared to LIS for use in the long run.

Nonwetting surfaces including superhydrophobic (SHS) and liquid infused surfaces (SLIPS) exhibit diverse exceptional characteristics promoting numerous application opportunities. Engineered textured surfaces demonstrate multiple features including drag reduction, fouling reduction, corrosion resistance, anti-fogging, anti-icing, and condensation enhancement. Integrating these properties, nonwetting surfaces have shown significant potential in improving the efficiency of energy applications. The first part of the thesis work aims at developing a fundamental mathematical understanding of the wetting process on the solid surface followed by presenting fabrication methodologies specifically focused on metallic substrates. The second part of this thesis presents an exhaustive survey on recent advancements and researches about features of nonwetting surfaces that could be implemented in major industrial applications. To establish how realistically these features could enhance the real-life applications, the third part of this work investigates the dynamic performance and economic benefits of using textured surfaces fabricated using an electrodeposition process for condenser tubes in thermoelectric power plants. The textured surfaces are expected to provide enhanced performance by deterring fouling and promoting dropwise condensation of the steam on the shell side. Using a thermal resistance network of a shell and tube condenser, detailed parametric studies are carried out to investigate the effect of various design parameters on the annual condenser performance measured in terms of its electric energy output of a representative 550 MW coal-fired power plant. A cost modeling tool and a new Levelized cost of condenser (LCOC) metric have been developed to evaluate the economic and performance benefits of enhanced condenser designs. The LCOC is defined as the ratio of the lifetime cost of the condenser (and associated costs such as coating, operation and maintenance) to the total electric energy produced by the thermoelectric power plant. The physical model is coupled with a numerical optimization method to identify the optimal design and operating parameters of the textured tubes that minimizes LCOC. Altogether, the study presents the first effort to construct and analyze enhanced condenser design with textured tube surfaces on annual thermoelectric power plant performance and compares it against the baseline condenser design with plain tubes. / Master of Science / Liquid repellant surfaces have attracted lots of attention due to their numerous promising characteristics including promoting condensation, drag reduction, prohibiting fouling/deposition, corrosion, and fog/dew harvesting. These attributes have the potential to inspire a variety of applications for these surfaces in power plants, automotive and aviation industries, oils/organic solvents clean-up, fuel cells, solar panels, membrane distillation, stone/concrete protection, surgical fabrics, and biological applications, to name a few. Some of these applications have reached their potential for real-life implementation and more are still at the research phase needing more experimental and fundamental studies to get them ready. The first part of this study presents the fundamentals of the wetting process. Next, fabrication methods for metallic surfaces have been explored to identify the most scalable and cost-effective approaches which could be administered in large scale industrial applications. A comprehensive review of recent publications on features of nonwetting surfaces has been carried out and presented in the second part of this thesis. To establish how realistically these features could enhance the real-life applications of a thermo-economic a performance model is developed for a powerplant condenser in the third section. Through a simple and cost-effective electrodeposition process, the common condenser tubes are modified to achieve textured tubes with superhydrophobic properties. The influence of using textured tubes on the plant's performance and its economic benefits are investigated to predict the potential promises of nonwetting surfaces.

This dissertation introduces assembly of spherical particles as a novel topography-based anti-biofouling coating. It also provides new insights on the effects of surface topography, especially local curvature, on cell–surface and cell–cell interactions during the evolution of biofilms. I investigated the adhesion, colonization, and biofilm formation of the opportunistic human pathogen Pseudomonas aeruginosa on a solid coated in close-packed spheres of polystyrene, using flat polystyrene sheets as a control. The results show that, whereas flat sheets are covered in large clusters after one day, a close-packed layer of 630–1550 nm monodisperse spheres prevents cluster formation. Moreover, the film of spheres reduces the density of P. aeruginosa adhered to the solid by 80%. Our data show that when P. aeruginosa adheres to the spheres, the distribution is not random. For 630 nm and larger particles, P. aeruginosa tends to position its body in the confined spaces between particles. After two days, 3D biofilm structures cover much of the flat polystyrene, whereas 3D biofilms rarely occur on a solid with a colloidal crystal coating of 1550 nm spheres. On 450 nm colloidal crystals, the bacterial growth was intermediate between the flat and 1550 nm spheres. The initial preference for P. aeruginosa to adhere to confined spaces is maintained on the second day, even when the cells form clusters: the cells remain in the confined spaces to form non-touching clusters. When the cells do touch, the contact is usually the pole, not the sides of the bacteria. The observations are rationalized based on the potential gains and costs associated with cell-sphere and cell-cell contacts. I concluded that the anti-biofilm property of the colloidal crystals is correlated with the ability to arrange the individual cells. I showed that a colloidal crystal coating delays P. aeruginosa cluster formation on a medical-grade stainless-steel needle. This suggests that a colloidal crystal approach to biofilm inhibition might be applicable to other materials and geometries. The results presented in appendix 1 suggest that colloidal crystals can also delay adhesion of Methicillin resistant staphylococcus aureus (MRSA) while it supports selective adhesion of this bacterium to the confined spaces. / Ph. D.

Achieving energy neutrality has shifted focus towards aeration systems optimization, due to the high energy consumption of aeration processes in modern advanced wastewater treatment plants. The activated sludge wastewater treatment process is dependent on aeration efficiency which supplies the oxygen needed in the treatment process. The process is a complex heterogeneous mixture of microorganisms, bacteria, particles, colloids, natural organic matter, polymers and cations with varying densities, shapes and sizes. These activated sludge parameters have different impacts on aeration efficiency defined by the OTE, % and alpha. Oxygen transfer efficiency (OTE) is the mass of oxygen transferred into the liquid from the mass of air or oxygen supplied, and is expressed as a percentage (%). OTE is the actual operating efficiency of an aeration system. The alpha Factor (α) is the ratio of standard oxygen transfer efficiency at process conditions (αSOTE) to standard oxygen transfer efficiency of clean water (SOTE). It is also referred to as the ratio of process water volumetric mass transfer coefficient to clean water volumetric mass transfer coefficient. The alpha factor accounts for wastewater contaminants (i.e. soap and detergent) which have an adverse effect on oxygen transfer efficiency. Understanding their different impacts and how different treatment technologies affect aeration efficiency will help to optimize and improve aeration efficiency so as to reduce plant operating costs. A pilot scale study of fine pore diffuser fouling and mitigation, quantified by dynamic wet pressure (DWP), oxygen transfer efficiency and alpha measurement were performed at Blue Plains, Washington DC. In the study a mechanical cleaning method, reverse flexing (RF), was used to treat two diffusers (RF1, RF2) to mitigate fouling, while two diffusers were kept as a control with no reverse flexing. A 45 % increase in DWP of the control diffuser after 17 month of operation was observed, an indication of fouling. RF treated diffusers (RF1 and RF2) did not show any significant increase in DWP, and in comparison to the control diffuser prevented a 35 % increase in DWP. Hence, the RF fouling mitigation technique potentially saved blower energy consumption by reducing the pressure burden on the air blower and the blower energy requirement. However, no significant impact of the RF fouling mitigation treatment technique in preventing a decrease in alpha-fouling (𝝰F) of the fine pore diffusers over time of operation was observed. This was because either the RF treatment method maintained wide pore openings after cleaning over time, or a dominant effect of other wastewater characteristics such as the surfactant concentration or particulate COD could have interfered with OTE. Further studies on the impact of wastewater characteristics (i.e., surfactants and particulate COD) and operating conditions on OTE and alpha were carried out in another series of pilot and batch scale tests. In this study, the influence of different wastewater matrices (treatment phases) on oxygen transfer efficiency (OTE) and alpha using full-scale studies at the Blue Plains Treatment Plant was investigated. A strong relationship between the wastewater matrices with oxygen transfer characteristics was established, and as expected increased alphas were observed for the cleanest wastewater matrices (i.e., with highest effluent quality). There was a 46 % increase in alpha as the total COD and surfactant concentrations decreased from 303 to 24 mgCOD/L and 12 to 0.3 mg/L measured as sodium dodecyl sulphate (SDS) in the nitrification/denitrification effluent with respect to the raw influent. The alpha improvement with respect to the decrease in COD and surfactant concentration suggested the impact of one or more of the wastewater characteristics on OTE and alpha. Batch testing conducted to characterize the mechanistic impact of the wastewater contaminants present in the different wastewater matrices found that the major contaminants influencing OTE and alpha were surfactants and particulate/colloidal material. The volumetric mass transfer coefficient (kLa) measurements from the test also identified surfactant and colloidal COD as the major wastewater contaminants present in the influent and chemically enhanced primary treatment (CEPT) effluent wastewaters impacting OTE and alpha. Soluble COD was observed to potentially improve OTE and alpha due to its contribution in enhancing the oxygen uptake rate (OUR). Although the indirect positive impact of OUR on alpha observed in this study contradicts some other studies, it shows the need for further investigation of OUR impacts on oxygen transfer. Importantly, the mechanistic characterization and quantitative correlation between wastewater contaminants and aeration efficiency found in this study will help to minimize overdesign with respect to aeration system specification, energy wastage, and hence the cost of operation. This study therefore shows new tools as well as the identification of critical factors impacting OTE and alpha in addition to diffuser fouling. Gas transfer depression caused by surfactants when they accumulate at the gas-liquid interface during the activated sludge wastewater treatment process reduces oxygen mass transfer rates, OTE and alpha which increases energy cost. In order to address the adverse effect of surfactants on OTE and alpha, another study was designed to evaluate 4 different wastewater secondary treatment strategies/technologies that enhances surfactant removal through enhanced biosorption and biodegradation, and to also determine their effect on oxygen transfer and alpha. A series of pilot and batch scale tests were conducted to compare and correlate surfactant removal efficiency and alpha for a) conventional high-rate activated sludge (HRAS), b) optimized HRAS with contactor-stabilization technology (HRAS-CS), c) optimized HRAS bioaugmented (Bioaug) with nitrification sludge (Nit S) and d) optimized bioaugmented HRAS with an anaerobic selector phase technology (An-S) reactor system configuration. The treatment technologies showed surfactant percentage removals of 37, 45, 61 and 87 %, and alphas of 0.37 ±0.01, 0.42 ±0.02, 0.44 ±0.01 and 0.60 ±0.02 for conventional HRAS, HRAS-CS, Bioaug and the An-S reactor system configuration, respectively. The optimized bioaugmented anaerobic selector phase technology showed the highest increased surfactant removal (135 %) through enhanced surfactant biosorption and biodegradation under anaerobic conditions, which also complemented the highest increased alpha (62 %) achieved when compared to the conventional HRAS. This study showed that the optimized bioaugmented anaerobic selector phase reactor system configuration is a promising technology or strategy to minimize the surfactant effects on alpha during the secondary aeration treatment stage / Ph. D.

This dissertation presents a detailed account of the study undertaken on the subject of fouling of Exhaust Gas Recirculator (EGR) coolers. The fouling process in EGR coolers is identified to be due to two primary reasons — deposition of fine soot particles and condensation of hydrocarbons known as dry soot and wet soot fouling, respectively. Several numerical simulations are performed to study the fouling process. Preliminary analysis of the particle forces for representative conditions reveal that drag, thermophoresis and Brownian forces are the significant transport mechanisms and among them, the deposition process is dominated by thermophoresis. Soot deposition in a representative turbulent plain channel shows a direct relationship of the amount of deposition with the near-wall temperature gradient. Subsequently, periodic and developing flow simulations are performed on a wavy channel geometry, a common EGR design for various Reynolds numbers and thermal boundary conditions. Constant heat flux boundary condition is used in the periodic fully-developed calculations, which assist in establishing various deposition trends. The wavy nature of the walls is noted to affect the fouling process, resulting in specific deposition patterns. For the lower Reynolds number flows, significantly higher deposition is observed due to the higher particle residence times. On the other hand, the developing flow calculations facilitate the use of wall temperature distributions that typically exist in EGR coolers. The linear dependence of the amount of deposition on the near-wall temperature gradient or in other words, the heat flux, is ascertained. It is also observed in all the calculations, that for the sub-micron soot particles considered, the deposition process is almost independent of the particle size. In addition, the nature of the flow and heat transfer characteristics and the transition to turbulence in a developing wavy channel are studied in considerable detail. Finally, a study on the condensation of heavy hydrocarbons is undertaken as a post-processing step, which facilitates the prediction of the spatial distribution and time-growth of the combined fouling layer. From the calculations, the maximum thickness of the dry soot layer is observed to be near the entrance, whereas for the wet soot layer, the peak is found to be towards the exit of the EGR cooler. Further, parametric studies are carried out to investigate the effect of various physical properties and inlet conditions on the process of fouling. / Master of Science

The purpose of this work is to develop and evaluate electroding methods for a reverse osmosis (RO) membrane that results in an in situ sensor able to detect RO membrane protein fouling. Four electroding techniques were explored: i) gold exchange-reduction, ii) encapsulated carbon grease, iii) "direct assembly process" (DAP), and iv) platinized polymer graft. The novel platinized polymer graft method involves chemically modifying the RO membrane surface to facilitate platinization based on the hypothesis that deposition of foulant on the platinized surface will affect platinum/foulant/solution interfacial regions, thus sensor impedance. Platinized polymer graft sensors were shown to be sensitive to protein fouling. Electrodes were characterized by their electrical properties, SEM and XPS. Assembled sensors were evaluated for sensitivity to electrolyte concentration and protein fouling. Micrographs showed coating layers and pre-soak solution influence gold exchange-reduction electrode formation. High surface resistance makes gold exchange-reduction an unsuitable method. Concentration sensitivity experiments showed carbon grease and DAP electroding methods produce unusable sensors. Carbon grease sensors have time-dependent impedance response due to electrolyte diffusion within the micro-porous polysulfone support. DAP electroded sensors proved quite fragile upon hydration; their impedance response is transient and lacks predictable trends with changes in concentration. A parametric study of the platinized polymer graft method shows amount of grafted monomer correlates to grafting time, and deposited platinum is a function of exchange-reduction repetitions and amount of grafted monomer. Platinized polymer graft sensors were fouled in both dead-end and cross-flow RO systems, and their impedance trends, while varying between sensors, indicate protein-fouling sensitivity. / Master of Science

Yes / A new class of material resistant to bacterial attachment has been discovered that is formed from polyacrylates with hydrocarbon pendant groups. In this study, the relationship between the nature of the hydrocarbon moiety and resistance to bacteria is explored, comparing cyclic, aromatic, and linear chemical groups. A correlation is shown between bacterial attachment and a parameter derived from the partition coefficient and the number of rotatable bonds of the materials' pendant groups. This correlation is applicable to 86% of the hydrocarbon pendant moieties surveyed, quantitatively supporting the previous qualitative observation that bacteria are repelled from poly(meth)acrylates containing a hydrophilic ester group when the pendant group is both rigid and hydrophobic. This insight will help inform and predict the further development of polymers resistant to bacterial attachment. / Wellcome Trust (grant number 085245) and EMRP (IND56)

科学研究費補助金 研究種目:基盤研究(C)(2)14550735 課題番号: 研究代表者:森 英利 研究期間:2002-2003年度