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Coatings play a pivotal role in everyday life and across various industries. They offer protection, corrosion resistance, insulation, optical improvements, aesthetics, etc. This study investigates the design, fabrication, characterization and evaluation of surface coatings in two areas: antimicrobial activity and fast evaporation. The COVID-19 pandemic underscored the necessity for coatings that mitigate microbial transmission through surfaces, alleviating both contagion and personal fears. The first part of this study presents the design, development, and evaluation of antimicrobial coatings that efficiently inactivate 99.9% of SARS-CoV-2 virus and kill more than 99.9% of pathogenic bacteria such as Staphylococcus aureus, methicillin-resistant Staphylococcus aureus, and Pseudomonas aeruginosa within one hour. Prioritizing rapid infectivity reduction, we designed and fabricated several coatings using silver oxide (Ag2O), cupric oxide (CuO), and zinc oxide (ZnO) particles as active ingredients. Applying small quantities of micron-sized opaque particles onto a surface yields a transparent film. Although Ag2O particles are inherently opaque, they possess potent antimicrobial properties. Consequently, incorporating small quantities of Ag2O into the coating results in the desired antimicrobial activity while maintaining transparency. Transparent antimicrobial coatings are a necessity for applications such as touchscreens, offering the benefit of reducing disease transmission while maintaining the aesthetic appeal of surfaces. We employed a variant of the Stöber process to bind Ag2O particles to the substrate using a silica matrix. To improve this coating method, we employed room-temperature spin-coating of a suspension of Ag2O/sodium silicate solution on the substrate, eliminating reactions with toxic chemicals in Stöber process and subsequent heat treatment. Two key features of the improved coating are its high robustness and its capability to kill 98.6% of Clostridioides difficile endospores in 60 minutes. On the other hand, CuO and ZnO particles exhibit mild antimicrobial properties; thus, their activity could be enhanced by a porous coating. When an infected droplet lands on such a coating, it is imbibed into the porous structure, where diffusion distances are smaller, and there is a larger active area to inactivate the virus or kill the bacteria. Furthermore, porosity facilitates faster droplet drying, leading to the concentration of cupric and zinc ions in the droplet, which are designed to be toxic to microbes. The second major topic of this thesis is the development, and evaluation of porous coatings for fast evaporation. At low Bond numbers, droplet evaporation is slow on an impermeable surface. We investigated whether application of a thin, porous coating leads to faster droplet evaporation. The droplet will imbibe quickly, but progress normal to the interface will be limited to the thickness of the coating. Therefore, the liquid will spread laterally into a broad disk to expose a large liquid–vapor interface for evaporation. As a result, the evaporation of a droplet is enhanced by a factor of 7–8 on the thin porous coatings. Factors such as coating thickness, pore size and distribution, and the contact angle of the coating, as well as ambient conditions like temperature and relative humidity, could affect the droplet evaporation rates by modifying the droplet's imbibition process and the evaporation driving force. While decreasing the coating thickness and increasing pore size and distribution promoted evaporation, the impact of contact angle is insignificant. Confocal microscopy observations of a coating composed of particles with varying sizes depicted liquid migration along the top of the coating and the edges of the interface. We developed and validated an equation to estimate the rate of evaporation. The rate correlated with the radius of the imbibition area, with higher temperatures and lower humidity further augmenting evaporation. / Doctor of Philosophy / Coatings serve as integral components in various industries and everyday settings, offering multifaceted benefits such as protection, aesthetic enhancement, and functional properties. This study investigates the design, fabrication, and evaluation of two types of surface coatings; coatings that reduce microbes transmission (antimicrobial coatings) and coatings that expedite evaporation. The COVID-19 pandemic underscored the necessity for coatings that mitigate microbial transmission through surfaces, alleviating both contagion and personal fears. The first part of this study presents the design, development, and evaluation of coatings that efficiently reduce 99.9% of COVID-19 virus and kill more than 99.9% of dangerous bacteria that can be found in hospital settings. Prioritizing rapid killing of bacteria, we designed and fabricated several coatings using metal oxides. In particular, we used silver oxide (Ag2O), cupric oxide (CuO), and zinc oxide (ZnO) particles as active ingredients. Applying small quantities of fine-sized opaque particles onto a surface yields a transparent film. Although Ag2O particles are inherently opaque, they possess potent antimicrobial properties. Consequently, incorporating small quantities of Ag2O into the coating results in the desired antimicrobial activity while maintaining transparency. Transparent antimicrobial coatings are a necessity for applications such as touchscreens, offering the benefit of reducing disease transmission while maintaining the aesthetic appeal of surfaces. A chemical reaction was used to produce a glass matrix to bind Ag2O particles to the solid, but this method required heating and toxic chemicals. So we developed a second methods that eliminated these two disadvantages. On the other hand, CuO and ZnO particles exhibit milder antimicrobial properties; thus, their activity could be enhanced by a porous coating. These coatings function as large reservoirs of antimicrobial agents for trapping and deactivating pathogens, while facilitating rapid droplet evaporation through enhanced wicking and porous structure. The second part of this study elucidates the mechanisms underlying accelerated droplet drying as a result of the application of thin, porous coatings. The speed of drying is slow for small droplets on flat surfaces. However, when a droplet is placed on a porous coating, it will be wicked quickly and spread through the porous coating to create a large area for evaporation. As a result, the speed of drying was increased by a factor of 7–8 on the thin porous coatings. Coating parameters such as thickness, pore size, and distribution, surface energy, as well as environmental factors like temperature and humidity could influence the droplet drying from porous surfaces. Decreasing the coating thickness and increasing pore size and variation in pore size promoted droplet evaporation, whereas the impact of surface energy was found to be insignificant. The rate of drying correlated with the radius of the wetted area, with higher temperatures and lower humidity further augmenting evaporation.

The primary cause of corrosion in transportation structures is due to chlorides which are applied to bridge decks as deicing salts. The direct cost of corrosion damage to the country's infrastructure is approximately $8.3 billion per year. One of the most common corrosion abatement methods in the United States is the barrier protection implemented through the application of fusion bonded epoxy coatings. The purpose of this study was to investigate various coating and exposure parameters to determine their effects on the corrosion of reinforcing steel. The parameters investigated were: chloride content at the bar depth, coated bar corroded area, corrosion product color under the coating, epoxy coating adhesion, coating color, coating damage (holidays and holes), coating thickness, TGA, DSC and EDS analysis and SEM coating cracking investigation. This was accomplished by testing new coated bar specimens as well as specimens extracted from 27 bridge decks located in Virginia. This study demonstrated the following: The extracted ECR coating samples presented extensive cracking compared to the new ECR samples in which the coating cracking was limited to only one sample. The DSC results showed that both the extracted samples as well as new samples are not fully cured during the manufacturing process. The coating degree of curing data also showed that the bars are insufficiently and unevenly heated prior to the application of the powder coating. Additionally, the samples investigated presented significant permanent adhesion loss with little or no epoxy coating residue present on the bar surface, while the EDS analysis showed that once adhesion is lost, corrosion will proceed unimpeded under the coating even in the absence of chlorides. The parameters that presented a direct correlation with the observed corrosion activity were the number of holidays and the number of damaged areas per unit length of bar. This indicates that the passivation of the bare steel exposed to the concrete pore solution at the breaches in the epoxy coating is not the same as a bare bar under similar exposure conditions allowing it instead to corrode at lower concrete chloride concentration levels than bare bars. The results also show a distinct loss of quality control in the handling and possibly storage of new coated bars. The new ECR samples had significantly higher damage density than the samples extracted from concrete even though the coating is damaged during the placement of the concrete, while there was no change in the number of holidays and cure condition. Finally, the data presented further evidence that while limited, the non-destructive corrosion assessment methods available for bare steel reinforced structures may also be used on ECR reinforced structures. In particular, the corrosion rate measurements correlated reasonably well with the chloride concentrations at bar level. This indicates that while the chlorides may not influence the corrosion activity under the coating, they do influence the corrosion activity at breaches in the coating. / Ph. D.

Novel coatings have been designed to solve problems associated with biofouling of marine structures, particularly ship hulls. The best candidates to date are multilayered coatings incorporating silicone rubber technology. These materials are efficient because they exhibit excellent release properties. However, they are very soft and tend to be more susceptible to various forms of mechanical damage. Fundamental analysis of the durability of these coatings has been done using standard laboratory tests. Simulative studies are essential to screen candidates as well as to predict the true life of the systems. The goal of this project was to develop a testing protocol for the evaluation of the durability of elastomeric easy release coatings and to implement it on selected candidate coatings. A brushing apparatus was designed and built to simulate the cleaning processes of ship hulls. Wear was measured with profilometry. The proposed methodology is valuable to study the processes of wear of the coatings, to screen various materials and to identify parameters, either functional or material, which would directly affect their durability. Two groups of candidate coatings were tested: the EXS series and the NRL series. The EXS samples showed better wear resistance than the NRL samples and showed no dependence on the rotational speed of the brushes. The NRL samples showed that increasing the sliding speed resulted in a decrease in wear. An increase in the applied load resulted in increased wear for both sample series. The effect of coating thickness was also investigated and discrimination between the proposed coatings could not be established because the tips of the bristles were sharp and irregular. Scratches matching the path of the brush bristles were observed in the wear scars of both sample types under all load and speed conditions. The NRL samples also exhibited ridges perpendicular to the sliding direction similar to the abrasion pattern. / Ph. D.

Surface chemistry of wood is based on the exposed cut surface that is the combination of intact (lumen wall) and cut cell wall material. It is inherently complex and changes with history of processing. Modification of wood surface through noncovalent attachment of amine containing water soluble polyelectrolytes provides a path to create functional surfaces in a controlled manner. Furthermore, modification of the surface can be performed using layer-by-layer (LbL) assembly, where the adsorption of polyelectrolytes or nanoparticles in sequential steps yields a multilayer film with a defined layer sequence on a given substrate. The objective of this study was to quantify adsorption of polyelectrolytes onto wood surface and use these polyelectrolytes as adhesives. In this study, optimal pH conditions for modifying wood surfaces, by anchoring adsorbing polyelectrolytes, were detected using zeta- ( )-potential measurements. Positively charged wood surfaces were also detected by the same technique after a layer of poly(diallyldimethylammonium chloride) (PDDA) or poly (ethylenimine) (PEI) was adsorbed. Both X-ray photoelectron spectroscopy (XPS) and Carbon-Nitrogen-Sulfur analyzer (CNS) were used to quantify the amount of charged polymer on wood surfaces to elucidate optimal pH and ionic strength for polyelectrolyte adsorption. Confocal laser scanning microscopy (CLSM) and Environmental Scanning Electron Microscope (ESEM) were used to characterize adsorbed LbL multilayers of poly(acrylic) acid (PAA) and poly(allylamine hydrochloride) (PAH). Cross-linking between PAA and PAH at various temperatures was studied by Fourier Transform Infrared Spectroscopy (FTIR) and the evaluation of multilayer as bonding agents was carried out by compression shear test following ASTM D905 standard. / Master of Science

Water treatment facilities commonly reduce soluble contaminants, such as soluble manganese (Mn2+), in water by oxidation and subsequent filtration. Previous studies have shown that conventional porous filter system removes Mn2+ from drinking water by developing Mn-oxides (MnOx(s)) bearing coating layers on the surface of filter media. Multiple models have been developed to explain this Mn2+ removal process and the formation mechanism of MnOx(s) coatings. Both, experimental and theoretical studies to date have been largely focused on the micrometer to millimeter scale range; whereas, coating layers are composed of nanoscale particles and films. Hence, understanding the nanoscale particle and film formation mechanisms is essential to comprehend the complexity of soluble contaminant removal processes. The primary objective of this study was to understand the initial MnOx(s) coating formation mechanisms and evaluate the influence of filter media characteristics on these processes. We pursued this objective by characterizing at the micro and nanoscale MnOx(s) coatings developed on different filter media by bench-scale column tests with simulating inorganic aqueous chemistry of a typical coagulation fresh water treatment plant, where free chlorine is present across filter bed. Analytical SEM and TEM, powder and synchrotron-based XRD, XPS, and ICPMS were used for characterization of coatings, filter media and water solution elemental chemistry. A secondary objective was to model how surface coating formation occurred and its correlation with experimentally observed physical characteristics. This modeling exercise indicates that surface roughness and morphology of filtering media are the major contributing factors in surface coating formation process. Contrary to previous models that assumed a uniform distribution and growth of surface coating, the experimental results showed that greater amounts of coating were developed in rougher areas. At the very early stage of coating formation, unevenly distributed thin films and/or particle aggregates were observed, which provided active sites for further surface coating growth. The predominant MnOx(s) phase in the surface coatings was identified to be poorly crystalline birnessite having scavenging activity by intercalation and/or sorption. This would explain the enhancement of efficiency in removing soluble manganese and other contaminants during water filtration. Moreover, the increased Mn2+ removal effect of having aluminum (Al) in pre-treated water is explained. These results indicate that the surface roughness and morphology need to be incorporated into particle capture models to more precisely describe the soluble manganese removal process. / Ph. D.

Reinforced cylindrical shells are used in numerous industries; common examples include undersea vehicles and industrial piping. Current models typically incorporate approximate theories to determine shell behavior, which have limitations in terms of both thickness and frequency. In addition, many applications feature coatings on the shell surface that normally have thicknesses which must also be considered. To increase the fidelity of such systems, this work develops an analytical model of an elastic cylindrical shell featuring periodically spaced ring stiffeners with an acoustic coating applied to the outer surface. There is an external fluid environment. Beginning with the equations of elasticity for a solid, spatial-domain displacement field solutions are produced incorporating unknown wave propagation coefficients. These fields are used to determine stresses at the boundaries of the shell and coating, which are then coupled with stresses from the stiffeners and fluid. The stress boundary conditions contain double-index infinite summations, which are decoupled, truncated, and recombined into a global matrix equation. The solution to this global equation results in the displacement responses of the system as well as the scattered pressure field. Two distinct loadings are considered: a ring loading and an incident acoustic wave. Thin-shell reference models are used for validation, and the acoustic response of the system is examined. It is shown that the reinforcing ribs and acoustic coating have a considerable effect on system behavior. / Master of Science / Reinforced cylindrical shells are used in numerous industries; common examples include undersea vehicles and industrial piping. Current models typically incorporate approximate theories to determine shell behavior, which have limitations in terms of both thickness and frequency. In addition, many applications feature coatings on the shell surface that normally have thicknesses which must also be considered. To increase the fidelity of such systems, this work develops an analytical model of an elastic cylindrical shell featuring periodically spaced ring stiffeners with an acoustic coating applied to the outer surface. There is an external fluid environment. Beginning with elastic equations of motion for a solid, the displacements of the system can be found. These displacements are used to determine stresses at the boundaries of the shell and coating, which are then coupled with stresses from the stiffeners and fluid. Techniques are used to transform the stress boundary conditions into a large matrix equation, and the solution to this global equation results in the displacement responses of the system as well as the scattered pressure field. Two distinct loadings are considered: a ring loading and an incident acoustic wave. Thin-shell reference models are used for validation, and the acoustic response of the system is examined. It is shown that the reinforcing ribs and acoustic coating have a considerable effect on system behavior.

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No / Reverse roll coating is probably the most widely used coating operation, much less investigated than its counterpart and inherently unstable forward roll coating. A new data to complement earlier work which was limited to large gaps and thus “thick” films is presented. The intention is to assess the feasibility of reverse roll coating to yield very thin films (<10 μm) at high speeds (>1 m/s) for application in the newer technologies, such as the production of solar cells and plastic electronics. The data obtained demonstrate this is possible but at the lowest permissible gap (25–50 μm) with low-viscosity fluids (∼7 mPa s). The study also developed a new understanding of how instabilities are controlled. It was seen that the size of the inertia forces generated by the applicator roller in relation to surface tension, as expressed by the Weber number and not the applicator Capillary number (viscous forces/surface tension) which is the critical parameter.

This research focused on the surface modification and interfacial profile studies of a siloxane modified polyimide, BDS [BTDA (3,3\4.4'~ benzophenonetetracarboxylic dianhydride) ~ DDS (3.3'~diaminodiphenyl sulfone) - PSX (polydimethylsiloxane) copolymer], used as a coating material. The BDS coating surface can be modified by pretreatment in an alkaline solution. This surface pretreatment etched away the top siloxane surface layer, activated the surface by exposing and creating polar functional groups, particularly carboxylic acid groups, and roughened the surface. These changes on the coating surface significantly improved the wettability and the strength of the bond between the coating surface and a polar adhesive. Interfacial composition profiles were obtained from angular dependent X-ray photoelectron spectroscopy and Auger electron spectroscopy. Two kinds of interphases were found near the bond line of the coating/metal substrate. One was a component gradient interphase which was formed by component segregation of the BDS copolymer. The component gradient was different on different metal oxide surfaces with the siloxane interfacial excess in the order of AI > Ti > Zn. The relative acidities of the metal oxide surfaces were characterized by poly(vinyl chloride) adsorption tests which were quantified by XPS measurements. The relative acidities were found in the order of AI > Ti > Zn. Therefore, the cause for the BDS component segregation was suggested to be the influence of acid·base interactions between components of the BDS copolymer and the metal surface oxides. The other kind of interphase was a polymer-metal oxide mixture interphase which formed on penetration of the BDS copolymer solution into porous aluminum surfaces. / Master of Science