Rozprawy doktorskie na temat „Characterization of surfaces”

Thesis (M. S.)--Chemical Engineering, Georgia Institute of Technology, 2008.<br>Committee Chair: Yulin Deng; Committee Member: Jeffery S. Hsieh; Committee Member: Sujit Banerjee; Committee Member: Zhong Lin Wang.

My research activity during the Ph. D. period has been focused on the simulation and the experimental characterization of Surface Plasmon Polaritons (SPP). Surface Plasmon Polaritons are evanescent electromagnetic waves that propagate along a metal/dielectric interface. Since their excitation momentum is higher than that of the photons inside the dielectric medium, they cannot be excited just by lighting the interface, but they need some particular coupling configurations. Among all the possible configurations the Kretschmann and the grating are those largely widespread. When the SPP coupling conditions are reached, abrupt changes of some components of the light reflected or transmitted at the metal/dielectric interface appear. Usually this resonances are characterized by a minimum of the reflectance acquired as a function of the incident angle or light wavelength. Several experimental methods are available to detect these SPP resonances, for instance by monitoring the light intensity, its polarization or its phase. Changes in the physical conditions of the metal/dielectric interface produce some changes of the SPP coupling constant, and consequently a shift in the resonance position. If these changes derive from a molecular detection process, it is possible to correlate the presence of the target molecules to the resonance variations, thus obtaining a dedicated SPP sensor. I focused the first part of my Ph.D. activity on the simulation of SPP resonances by using several numerical techniques, such as the Rigorous Coupled Wave Analysis method, the Chandezon method, and the Finite Element Method implemented through Comsol v3.5. I simulated the SPP resonance in the Kretschmann coupling configuration for plane and nano-grating structured metal/dielectric interfaces. Afterward, I calculated the SPP resonance behaviour for grating and bi-dimensional periodic structures lighted in the conical configuration. Furthermore, I analysed the correlations between the grating coupling method and the Kretschamann coupling method. Through all these simulations, I studied the sensitivity of the different SPP resonances to the refractive index variation of the dielectric in contact with the metal. In this way, I was able to find a new parameter suitable for describing the SPP resonance, i.e., the azimuthal angle. By considering this particular angle, the sensitivity of the SPP resonances could be properly set according to the experimental needs and, even more important, noticeably increased to high values. Experimentally I used two opto-electronic benches, one for the Kretschmann configuration and one for the conical mounting configuration. I have performed experimental measurements, in order to compare the experimental data with the simulations. In particular the following conditions were tested: • Plane interface, Kretschmann configuration • Nanostructured grating, Kretschmann configuration • Nanostructured grating, Conical configuration I focused my attention on the nano-structured grating in conical mounting configuration. I found an innovative way to characterize its SPP resonances, by measuring the transmitted signal as a function of the incident and azimuthal angles. The transmittance and the azimuthal sensitivities were characterized with the gratings in both air and water. In order to study the experimental azimuthal sensitivity, I changed the liquid refractive index in contact with the grating by using different water/glycerol solutions. Moreover, I functionalized the surface by using thiolated molecules that form Self Assembled Monolayer onto the metallic layer. In this way, I was able to change the SPP coupling constants and detect the corresponding azimuthal resonance shifts. I also detected the immobilization of an antibody layer onto the metallic surface of the plasmonic interface. All the devices I used in the experimental measurements were produced by the University spin off Next Step Engineering.<br>Durante il mio periodo di dottorato in Scienza e Tecnologia dell’Informazione l’attività di ricerca principale è stata focalizzata sulla caratterizzazione, simulativa e sperimentale, dei plasmoni di superficie. I plasmoni di superficie sono onde elettromagnetiche evanescenti che si propagano all’interfaccia tra un mezzo metallico ed un mezzo dielettrico. Il loro vettore d’onda è più elevato rispetto a quello della luce nel mezzo dielettrico. Per poter quindi generare l’eccitazione si devono utilizzare particolari tecniche di accoppiamento. I due metodi più diffusi sono l’accoppiamento Kretschmann e l’accoppiamento tramite reticolo. Una volta raggiunte le condizioni di accoppiamento dei plasmoni di superficie, si realizza il fenomeno della risonanza plasmonica, la quale si manifesta attraverso brusche variazioni nelle componenti della luce riflessa o trasmessa dalla superficie. Tipicamente si può registrare un minimo della riflettanza in funzione dell’angolo di incidenza della luce sulla superficie. Esistono, tuttavia, anche altre modalità per registrare e misurare queste risonanze, come ad esempio monitorando intensità, polarizzazione o fase della luce trasmessa e riflessa dalla superficie, in funzione della sua lunghezza d’onda o dei sui angoli di incidenza. Le variazioni chimico/fisiche che avvengono all’interfaccia metallo/dielettrico, modificando la costante di accoppiamento plasmonica, cambiano le condizioni di risonanza. Nel caso in cui le variazioni all’interfaccia siano dovute ad un processo di riconoscimento molecolare è possibile rilevare le molecole d’interesse valutando i cambiamenti della risonanza plasmonica, fornendo così l’opportunità per l’implementazione di sensori specifici. L’attività di dottorato è stata focalizzata innanzitutto sullo studio teorico del comportamento della risonanza plasmonica, utilizzando varie tecniche di simulazione numerica: il metodo RCWA (Rigorous Coupled Wave Analysis), Il metodo di Chandezon ed il metodo agli elementi finiti, implementato tramite Comsol v3.5. Ho poi affrontato lo studio, tramite simulazioni, delle risonanze di superficie in configurazione Kretschmann, sia per interfacce metallo/dielettrico piane sia per interfacce nano-strutturate. Considerando una configurazione conica, ho simulato le risonanze di superficie per nano-strutture reticolari e per nano-strutture bi-dimensionali periodiche. Inoltre ho analizzato il legame tra le modalità di accoppiamento grating e Kretschmann. Tramite queste simulazioni mi è stato possibile valutare e studiare la sensibilità delle varie risonanze plasmoniche alla variazione di indice di rifrazione, quando essa avviene all’interfaccia metallo/dielettrico. È stato così possibile identificare un nuovo parametro per descrivere la risonanza plasmonica e la sua sensibilità, ossia l’angolo azimutale, definito come l’angolo tra il vettore del grating ed il piano di scattering della luce. Considerando questo particolare angolo, la sensibilità del sensore può essere controllata con un’opportuna regolazione degli altri parametri coinvolti nell’eccitazione plasmonica, consentendole di raggiungere valori molto elevati. Successivamente, grazie all’utilizzo di due banchi, uno per la configurazione Kretschmann ed uno per la misura di reticoli nano-strutturati in configurazione conica, ho realizzato delle campagne di misure sperimentali. E’ stato così possibile confrontare i risultati sperimentali con le simulazioni numeriche per le seguenti condizioni: • Interfaccia piana, configurazione Kretschmann • reticolo nano-strutturato, configurazione Kretschmann • reticolo nano-strutturato, configurazione conica L’attività sperimentale si è particolarmente focalizzata sul reticolo nano-strutturato, sia per l’innovativa modalità di caratterizzazione delle sue risonanze plasmoniche (valutazione del segnale trasmesso in funzione dell’angolo di incidenza e dell’angolo azimutale), sia per l’elevata sensibilità ottenuta valutando la variazione dell’angolo azimutale. La caratterizzazione è stata effettuata sia per il reticolo esposto all’aria che per il reticolo immerso in un liquido (tipicamente acqua). Per poter verificare il comportamento della sensibilità azimutale ho variato l’indice di rifrazione del liquido in contatto con la superficie utilizzando soluzioni miste di acqua e glicerolo. Inoltre, tramite tecniche di funzionalizzazione della superficie, ovvero applicando delle molecole thiolate che vengono adsorbite sulla parte metallica dell’interfaccia, mi è stato possibile variare le costanti di accoppiamento plasmonico, in modo da verificare la capacità del dispositivo di rilevare l’avvenuta creazione di uno strato molecolare sulla superficie. Inoltre ho positivamente verificato la capacità di immobilizzare uno strato di anticorpi sulla superficie plasmonica. Tutte le misure sperimentali che ho svolto in questa tesi sono state effettuate su sensori con superfici piane o nano-strutturate prodotte dallo spin-off universitario Next Step Engineering, con il quale ho collaborato durante il percorso di ricerca.

In general, the stability of suspension can be studied using two methods. <i>One</i> is to directly measure the forces between two interacting surfaces in media. <i>The other</i> is to study the interfacial surface free energies of the particles in suspension. Direct surface force measurements were conducted between silica surfaces in octadecyltrimetylammonium chloride (C₁₈TACl) solutions using an Atomic Force Microscope (AFM). The results showed that the hydrophobic force existed in both air-saturated and degassed C₁₈TACl solutions. The attraction decreased with NaCl addition, and was the strongest at the point of charge neutralization (p.c.n.) of silica substrate. The force measurement results obtained in C_nTACl solutions showed that the attractions decayed exponentially and became the maximum at the p.c.n.'s. The decay lengths (<i>D</i>) increased with surfactant chain length. The measured forces were fitted to a charged-patch model of Miklavic <i>et al</i>. (1994) with rather large patch sizes. It was also found that the decay length decreased linearly with the effective concentration of the CH2/CH3 groups raised to the power of -1/2. This finding is in line with the model of Eriksson <i>et al</i>. (1989). It suggested that the long-range attractions are hydrophobic forces originating from the changes in water structure across a hydrophobic surface-solution interface. For the TiO₂/water/TiO₂ system, the Hamaker constant was found to be 4±1×10^-20 J. The force curves obtained in the TiO₂/C_nTACl system showed a repulsion-attraction-repulsion transition with increasing surfactant concentration. The long-range attraction observed between TiO₂ surfaces in C_nTACl solutions reached maximum at the p.c.n., and the decay length increased with chain length. In present work, the thin-layer wicking technique was used to determine the surface free energy (γ_s) and its components of talc samples. The results showed that the basal surfaces of talc are weakly basic while the edge surfaces are acidic. The effect of chemicals on the surface free energies of talc was systemically studied. The results showed that CMC (carboxymethyl cellulose sodium salt) and EO/PO (ethylene oxide/propylene oxide) co-polymers made talc surface hydrophilic by increasing the surface free energies, especially γ^LW and γ^-. SOPA (sodium polyacrylate) increased greatly the zeta-potentials instead of the surface free energies.<br>Ph. D.

<p>The ability to create surfaces with well-defined chemical properties is a major research field. One possibility to do this is to design peptides that bind with a specific secondary structure to silica nanoparticles. The peptides discussed in this thesis are constructed to be random coil in solution, but are “forced” to become helical when adsorbed to the particles. The positively charged side-chains on the peptides strongly disfavor an ordered structure in solution due to electrostatic repulsion. When the peptides are introduced to the particles these charges will strongly favor the structure because of ion pair bonding between the peptide and the negatively charged nanoparticles. The peptide-nanoparticle system has been thoroughly investigated by systematic variations of the side-chains. In order to determine which factors that contributes to the induced structure, several peptides with different amino acid sequences have been synthesized. Factors that have been investigated include 1) the positive charge density, 2) distribution of positive charges, 3) negative charge density, 4) increasing hydrophobicity, 5) peptide length, and 6) by incorporating amino acids with different helix propensities. Moreover, pH dependence and the effect of different nanoparticle curvature have also been investigated. It will also be shown that the system can be modified to incorporate a catalytic site that is only active when the helix is formed. This research will increase our understanding of peptide-surface interactions and might be of importance for both nanotechnology and medicine.</p>

Precision surface finishes are used in a wide variety of applications. From bearing races and rolling elements to parallel slide ways, the frictional characteristics of these surfaces are critical to the performance of the products. Experimental trial and error has shown that certain surfaces outperform others in certain applications, but the specific surface characteristics that make this true have yet to be fully understood. The research goal was to develop an apparatus that can test the coefficient of rolling/sliding friction of different precision machined surfaces and to combine this data with topographic analysis of the surfaces to correlate specific 3-D parameters with the frictional performance of a surface. The sample treatments consisted of four different surface textures (hard-turned, ground, honed and isotropic finish) and four different relative surface speeds. By monitoring the torque in the sample-mounting shaft under lubricated conditions the coefficient of rolling/sliding friction of each surface was found. Utilizing white light interferometry measurement of the surfaces, a highly detailed map of each surface was obtained. Using different characteristic values of each machined surface (RMS roughness, asperity density, lay direction, etc.), the frictional behavior of the surfaces were compared to the surface characteristics yielding insight into the relationship between surface finish and friction in rolling/sliding contact. Friction coefficient was found to correlate most strongly with RMS roughness (Sq) and density of surface summits (Sds). These parameters govern mechanical interference of asperities and surface adhesion respectively. These findings suggest that friction coefficients of surfaces could be optimized through manipulation of three-dimensional surface parameters.

Industries (food, beverage, petrochemical, etc.) normally use various gravitational separation echniques in their processes. Such separation processes often suffer from the deposition of undesirable material on the active surfaces of the process equipment, e.g. a high-speed separator or decanter, causing a slew of problems with the process or product quality. To restore operational efficiencies, additional cleaning steps using both water and chemicals are required, making the process more expensive and less environmentally friendly. Other than operating time and concentration of the process fluid there are several factors such as surface nature, surface roughness, type of material, surface charge, etc which influence the fouling deposition of surfaces. Fouling on the surfaces can grow following different mechanisms. The goal of this research work is to learn more about the nature of foulant interactions with stainless steel surfaces and eventually design some antifouling methodology. It is too difficult to study foulingfor all kinds of solutions and industries, so we tried to investigate the organic deposition in dairy and brewery industries by using lab-scale synthesized milk and beer solutions, For quantitative and statistical examination of these characteristics, several experimental approaches (FTIR, percent weight change, surface roughness, surface energy) were used. It was confirmed that fouling grows on the surfaces in a non-linear fashion irrespective of the time and concentration of the solution. The fouling of surfaces can be improved by producing more hydrophilic surfaces or by reducing surface roughness. Steric hindrance, electrostatic charge, and water barrier or hydration layer theories can be used to modify the surface nature and hence the fouling deposition. For antifouling purposes, PMMA (organic) and tungsten oxide (inorganic) coatings were employed. The PMMA was deposited using a dip-coating technique using (6%,10%, and 12%) PMMA solution, and the tungsten oxide coating was carried out by using a standard two electrode electrochemical system under different voltage (3.5V and 4.5V) and time (5min, 10 min, and 20 min) conditions. The coatings were characterized by using different techniques and their antifouling effects were studied in model milk and model beer solutions<br>Vid industriella processer (livsmedel, petrokemisk etc.) används ofta olika tekniker för separation med hjälp av gravitation. Sådana separationsprocesser drabbas ofta av oönskade beläggningar och påväxt på processutrustningens aktiva ytor så som t.ex. i en separator eller en dekanter, vilket orsakar problem med processen eller produktkvaliteten. För att återställa driftseffektivitet krävs särskilda rengöringssteg med både vatten och kemikalier vilket gör processen dyrare och mindre miljövänlig. Förutom drifttid och processvätskans sammansättning finns det flera faktorer såsom ytbeskaffenhet, ytjämnhet, materialtyp, ytladdning m.m. som påverkar mängden oönskade beläggningar på ytor. Föroreningarna på ytor kan tillväxa med olika mekanismer. Målet med detta forskningsarbete är att studera interaktionen mellan olika former av påväxt och ytan på rostfritt stål och senare utforma metoder för att förhindra bildandet av sådana oönskade beläggningar. Det är en stor utmaning att studera olika typer av påväxt för alla typer av flöden och industrier. I studien undersöktes organisk påväxt inom mejeri- och bryggeriindustrin genom att använda syntetiserade mjölk- och ölprodukter i laboratorieskala, för kvantitativa och statistiska undersökningar av dessa egenskaper. Flera olika experimentella metoder användes (FTIR, viktförändring, ytjämnhet, ytenergi). Det bekräftades att tillväxten på ytorna var olinjärt oavsett tid och lösningens koncentration. Bildandet och tillväxt av oönskade beläggningar kan minskas med hjälp av mera hydrofila ytor eller genom att minska ytans ojämnhet. Steriska hinder, elektrostatisk laddning och vattenbarriär eller hydratiseringsskal kan användas för att modifiera ytan och därmed fördröja bildandet av oönskade beläggningar. För att förhindra påväxt belades ytan med PMMA (organisk) och volframoxid (oorganisk). PMMA deponerades genom en doppbeläggningsteknik med användning av (6%, 10% och 12%) PMMA-lösning och volframoxidbeläggningen utfördes med ett elektrokemiskt tvåelektrodssystem med olika spänningar (3,5V och 4,5V) och tider (5min, 10min och 20min). Ytbeläggningarna karakteriserades genom att använda olika tekniker och deras förmåga att förhindra snabb påväxt studerades i modellösningar av mjölk och öl.

The controlled degradation of wood surfaces with infrared light from a CO2 pulsed laser facilitated adhesion without the use of additional resins. Laser modification creates a surface phenomenon that physically and chemically alters the natural biopolymer organization of lignocellulosic materials in a way that promotes adhesion when hot pressed using typical industrial equipment. Laser optimization was determined through mechanical and microscopic observation. It was determined that a mild level of laser surface modification (scale of 30 W/mm2) resulted in the highest bond-line strength. The large spot size of the laser beam resulted in evenly modified surfaces. Surface analysis revealed that laser modification changed native wood morphology, hydrolyzed and vaporized hemicellulose, and enriched the surface with cellulose II and lignin. Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR FTIR) was used to analyze the bulk of the laser material. This experiment revealed a change in the hydroxyl region related to hydrogen bonding conformations between wood polymers, mainly cellulose. X-ray photoelectron spectroscopy (XPS) provided an elemental composition of the top 5 nanometers of the surface, which resulted in increased carbon-carbon/carbon-hydrogen linkages and decreased oxygen containing bonds due to laser ablation. Static acid-base contact angle analysis was conducted using three probe liquids to find the Lewis acid, Lewis base, and dispersion components of the top nanometer of surface chemistry. Contact angle analysis revealed laser modified samples had a surface free energy that remained similar to the control wood sample. In addition, the dispersion component of the surface free energy increased due to laser ablation while acid-base components were reduced. Atomic force microscopy (AFM) visually displays a reduction in surface roughness due to the laser technique. An additional set of experiments like thermal gravimetric analysis, thermal pre and post treatments, and heated ATR FTIR and XPS support findings which require more investigation into this adhesion phenomenon.<br>Master of Science

Today's processors commonly use caches to help overcome the disparity between processor and main memory speeds. Due to the principle of locality, most of the processor's requests for data are satisfied by the fast cache memory, resulting in a signficant performance improvement. Methods for evaluating workloads and caches in terms of locality are valuable for cache design. In this dissertation, we present a locality surface which displays both temporal and spatial locality on one three-dimensional graph. We provide a solid, mathematical description of locality data and equations for visualization. We then use the locality surface to examine the locality of a variety of workloads from the SPEC CPU 2000 benchmark suite. These surfaces contain a number of features that represent sequential runs, loops, temporal locality, striding, and other patterns from the input trace. The locality surface can also be used to evaluate methodologies that involve locality. For example, we evaluate six synthetic trace generation methods and find that none of them accurately reproduce an original trace's locality. We then combine a mathematical description of caches with our locality definition to create cache characterization surfaces. These new surfaces visually relate how references with varying degrees of locality function in a given cache. We examine how varying the cache size, line size, and associativity affect a cache's response to different types of locality. We formally prove that the locality surface can predict the miss rate in some types of caches. Our locality surface matches well with cache simulation results, particularly caches with large associativities. We can qualitatively choose prudent values for cache and line size. Further, the locality surface can predict the miss rate with 100% accuracy for some fully associative caches and with some error for set associative caches. One drawback to the locality surface is the time intensity of the stack-based algorithm. We provide a new parallel algorithm that reduces the computation time significantly. With this improvement, the locality surface becomes a viable and valuable tool for characterizing workloads and caches, predicting cache simulation results, and evaluating any procedure involving locality.

The deterministic microasperities play a vital role in reducing the coefficient of friction and wear of thrust surfaces and improve the tribological properties of the surfaces. Deterministic microasperities have a specific pattern in terms of size, shape and spacing. These specified geometries are controllable and repeatable. The microasperities are micron scaled asperities and cavities on a surface that form the surface roughness. The present thesis shows the detailed process to fabricate the deterministic microasperities on thrust surfaces, i.e. stainless substrate, using micro-fabrication processes such as lapping and ultra-violet photolithography in combination with an electroplating (nickel) process. A Novel alignment technique is used to align the photomask with the substrate to get repeatable and aligned patterns on the thrust surface. Deterministic microasperities are characterized by using precision instruments such as an Optical profilometer, Scanning Electron Microscope (SEM) and Optical microscope to study the various surface parameters such as Average roughness (Ra), Root mean square value (rms) and Peak value (PV) of the thrust surface.

Thesis (MSc)--Stellenbosch University, 2015.<br>ENGLISH ABSTRACT: Biofouling is the attachment and biofilm formation that leads to negative repercussions such as persistent post-harvest infections, infections obtained from medical implants and continual surface contamination of food processing plants. Much of the problem lies with the resistance that develops against conventional treatments due to the formation of mature biofilms. Thus the focus has shifted from the removal of biofilms to the prevention of initial attachment of organisms. This entails the use of antimicrobial surfaces that either have an inherent antimicrobial activity, e.g. certain metals, or surfaces that are modified by the attachment of antimicrobial agents. The attachment of antimicrobial agents can either be through covalent bonding or adsorption, depending on the intended use of the surface as well as the mode of action of the antimicrobial agent. Antimicrobial peptides (AMPs) are ubiquitous in nature, tend to have a broad spectrum of activity, are very stable and have been shown to maintain activity when covalently bound to solid surfaces. Tyrocidines (Trcs), antimicrobial peptides produced by Bacillus aneurinolyticus, are cyclodecapeptides with a broad spectrum of activity against Grampositive bacteria, fungi, yeasts and the human malaria parasite, Plasmodium falciparum. The aim of this study was to determine the antimicrobial activity of surfaces treated with a tyrocidine extract, under which conditions the activity remained stable and to look into possible applications of these peptide-treated surfaces. The study focussed on different solid surfaces namely mixed cellulose, polyvinylidene fluoride, polycarbonate, cellulose acetate, cellulose (paper)(CL) and high density cellulose packing material (HDC), as a pilot study to assess the antimicrobial activity of Trc and gramicidin S (GS) treated solid surfaces. Peptide desorption and subsequent analysis by mass spectrometry was used to confirm the presence and integrity of the Trcs adsorbed. Scanning electron microscopy was utilised to show that the adsorbed peptides did not affect the structural integrity of the treated filters. However, it was shown that the adsorbed peptides changed the hydrophobic/hydrophilic character by means of a wettability assay. A cell viability assay and erythrocyte assay were developed from existing methodologies to determine the biological activity of the AMP-functionalised polymeric material. Seven of the AMP treated solid surfaces showed antimicrobial activity when challenged with >105 Micrococcus luteus cells/cm2. Although the polycarbonate filter lost antimicrobial activity at the high cell concentrations, it was shown to have potent antimicrobial activity at lower cell concentrations. Complete inhibition of M. luteus growth was observed for both the gramicidin S and tyrocidine extract treated high density cellulose and cellulose filters. Stability tests showed that the tyrocidines remained adsorbed to cellulose filters and biologically active when exposed multiple water washes, water washes at different temperatures (25°C - 100°C) and pH changes (pH 1-12). The antimicrobial activity was only affected after exposure to the water wash of pH 13 which is possible due to susceptibility of the CL filters to high pH solvents. A preliminary study on the effect of Trcs treated CL filters on the sterilization, germination and effect on tomato seedlings was conducted. It was found that Trcs had no effect on the germination and did not fully sterilise the seeds or environment against fungi. However, it was observed that 5 μg/mL Trcs treated filters promoted root length opposed to the toxic effect seen with filters treated with higher Trc concentrations. It is hypothesised that Trcs prefer to bind to hydrophilic surfaces exposing the hydrophobic residues and the cationic residue of the peptide to interact with the bacterial membrane to elicit its antimicrobial response. The exposed residues contain some of the hydrophobic residues and the cationic Orn9/Lys9, which are crucial to the antimicrobial activity of the peptides. Hydrophobic interaction is particularly important for the haemolytic activity which is currently the only viable method of detection of the adsorbed Trcs. Trcs also have a preference for adsorption onto cellulose and cellulose analogues which points to possible application in protective food wrapping and wood surface protection. Trcs maintains its antimicrobial activity regardless of adsorption to solid surfaces. It can therefore be concluded that Trcs treated solid surfaces hold great potential in preventing the initial bacterial colonization and subsequent biofilm formation. Antimicrobial peptide enriched solid surfaces can thus be developed and tailored to a specific application such as filters, catheters and packaging materials.<br>AFRIKAANSE OPSOMMING: Biovervuiling is die aanhegting en vorming van biofilms met negatiewe gevolge soos aanhoudende na-oes infeksies, infeksies op mediese inplantings en voortdurende oppervlak besoedeling van voedselverwerkings fabrieke. Die probleem lê grotendeels by die weerstand wat ontwikkel word teen konvensionele behandelings as gevolg van die vorming van volwasse biofilms. Die fokus het gevolglik verskuif vanaf die verwydering van biofilms na die voorkoming van aanvanklike aanhegting van organismes aan oppervlaktes. Dit behels die gebruik van antimikrobiese oppervlaktes wat of 'n inherente antimikrobiese aktiwiteit het, bv. sekere metale óf oppervlaktes wat aangepas is deur die aanhegting van antimikrobiese middels. Die aanhegting van antimikrobiese agente kan of deur kovalente binding óf adsorpsie plaasvind, afhangende van die beoogde gebruik van die oppervlak, sowel as die metode van werking van die antimikrobiese agent. Antimikrobiese peptiede (AMPe) is alomteenwoordig in die natuur, is geneig om 'n breë spektrum van aktiwiteit te hê, is baie stabiel en het getoon dat aktiwiteit in stand gehou word wanneer dit kovalent gebind word op soliede oppervlaktes. Tirosidiene (Trcs), antimikrobiese peptiede wat deur Bacillus aneurinolyticus geproduseer word, is siklodekapeptiede met 'n breë spektrum van aktiwiteit teen Gram-positiewe bakterieë, swamme, giste en die menslike malaria parasiet Plasmodium falciparum. Die doel van hierdie studie was om die antimikrobiese aktiwiteit te bepaal van oppervlaktes wat met 'n tirosidien ekstrak behandel is, te bepaal onder watter omstandighede die aktiwiteit stabiel bly en om te soek na moontlike toepassings van hierdie peptied-behandelde oppervlaktes. Die studie het gefokus op verskillende soliede oppervlaktes naamlik gemengde sellulose, polyvinylidene fluoried, polikarbonaat, sellulose asetaat, sellulose (papier)(CL) en 'n hoë digtheid sellulose verpakkings materiaal (HDC), as 'n loodsstudie om die antimikrobiese aktiwiteit van die Trcs en gramisidien S (GS) behandelde soliede oppervlaktes te ondersoek. Peptied-desorpsie en daaropvolgende ontleding deur massaspektroskopie is gebruik om die teenwoordigheid en integriteit van die geadsorbeerde Trcs te bevestig. Skandering elektronmikroskopie is gebruik om aan te toon dat die geadsorbeerde peptiede geen invloed op die strukturele integriteit van die behandelde filters het nie. Daar is egter getoon dat die geadsorbeerde peptiede die hidrofobiese / hidrofiliese karakter verander. „n Lewensvatbaarheid selgebaseerde toets en eritrosiet toets is ontwikkel uit bestaande metodes om die biologiese aktiwiteit van die AMP-gefunktionaliseerde polimeriese materiaal te bepaal. Sewe van die AMP behandel soliede oppervlaktes het antimikrobiese aktiwiteit getoon wanneer dit met > 105 Micrococcus luteus selle/cm2 gedaag is. Hoewel die polikarbonaat filter antimikrobiese aktiwiteit met hoë sel konsentrasies verloor het, is dit getoon dat dit wel uitgeproke antimikrobiese aktiwiteit het teen laer konsentrasies selle. Volledige inhibisie van M. luteus groei is waargeneem vir beide die hoë digtheid sellulose en sellulose filters wat met GS en tirosidien ekstrak behandel is. Stabiliteit toetse het getoon dat die tirosidiene geadsorbeer en biologies aktief op sellulose filters bly nadat dit blootgestel is aan verskeie water was-stappe, waterwasse by verskillende temperature (25 °C -100 °C) en pH veranderinge (pH 1-12). Die antimikrobiese aktiwiteit was net beïnvloed ná blootstelling aan die water met 'n pH 13, wat moontlik is te danke aan die vatbaarheid van die CL filters by hoë pH oplosmiddels is. 'n Voorlopige studie is gedoen om die uitwerking van Trcs behandelde CL filters op die sterilisasie, ontkieming en tamatiesaailinge te bepaal. Daar is gevind dat Trcs geen effek op die ontkieming het nie, maar dat dit nie volledig die sade en omgewing steriliseer vir fungiese groei nie. Daar is egter waargeneem dat 5 μg/mL Trcs behandelde filters wortel lengte van die saailinge bevorder teenoor die giftige uitwerking soos waargeneem vir die filters wat met hoër konsentrasies Trcs behandel is. Dit word gepostuleer dat Trcs verkies om aan hidrofiliese oppervlaktes te bind wat die van die hidrofobiese aminosure en die kationiese residu van die peptied blootstel om aan die bakteriële membraan te bind om gevolglik antimikrobiese reaksie te ontlok. Die blootgestelde deel bevat sommige van die hidrofobiese residue en positiewe Orn9/Lys9 wat noodsaaklik vir die antimikrobiese aktiwiteit van die peptiede. Die hidrofobiese interaksies is veral belangrik vir die hemolitiese aktiwiteit wat tans die enigste bruikbare metode van opsporing van die geadsorbeerde Trcs is. Trcs het ook 'n tendens vir adsorpsie op sellulose en sellulose analoë wat dui op die moontlike toepassing in beskermende voedselverpakking en die beskerming van houtoppervlaktes. Trcs handhaaf hul antimikrobiese aktiwiteit, ongeag van adsorpsie aan soliede oppervlaktes. Dit kan dus afgelei word dat Trcs-behandelde soliede oppervlaktes die potensiaal het om die aanvanklike kolonisasie van bakterië te voorkom en die daaropvolgende biofilm vorming. Antimikrobiese peptied verrykde soliede oppervlaktes kan dus ontwikkel en aangepas word vir gebruik in spesifieke toepassing soos in filters, kateters en verpakkingsmateriaal.

Investigations were performed on the stability, mechanism of formation and an application of alkyl monolayers chemomechanically prepared on silicon surfaces. A new method of surface modification, laser-activation modification of surfaces (LAMS), and multivariate analyses of time-of-flight secondary ion mass spectrometry (ToF-SIMS) images of LAMS spots were also reported. X-ray photoelectron spectroscopy (XPS) and other data show that alkyl monolayers prepared by scribing silicon under 1-iodoalkanes and 1-alkenes were stable over extended periods of time to air, water, a boiling acid and Al Ka X-rays. The stability is attributed to direct Si-C bonding in the monolayers. The observation that the oxygen signals gradually increased and the iodine signals gradually decreased, with both finally reaching plateaus is attributed to the oxidation of exposed silicon by scribing, and the hydrolysis of Si-I bonds, respectively. In alkyl monolayers prepared with 1-alcohols, the carbon signals decreased about 50% after two 1-h immersions in a boiling acid, suggesting unstable Si-O bonding. In the analogous experiment of grinding silicon with alkyl halides, the expected free-radical combination and disproportionation byproducts were observed. This observation provides evidence for the mechanism previously proposed for alkyl monolayer formation on silicon by chemomechanically scribing. Miniaturized sample supports for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were made on hydrophobic silicon or glass surfaces by scribing. With these sample supports, improved MALDI-MS signal intensities and reproducibilities were achieved for a test peptide, as expected. A new and promising method for surface modification, LAMS, was developed. XPS and ToF-SIMS analyses show that both silicon and germanium were effectively modified by LAMS with even quite inert compounds. This technique was also used to make miniaturized MALDI-MS sample supports. Compared to scribing, LAMS is faster and can be more precisely controlled. Multivariate analyses, automated expert spectral image analysis (AXSIA) and principal component analysis (PCA), were used in interpreting ToF-SIMS images of silicon surfaces modified with 1-alkenes by LAMS. Both analyses show that modified and unmodified areas are chemically different.

Vibrational spectroscopy is used to elucidate the adsorption mechanisms of model volatile organic pollutants with a variety of mineral oxides. Vapor phase adsorption processes are particularly important in the vadose zone of an aquifer, where void spaces are filled with air and vapor transport is significant. Gaining a better understanding of the interactions occurring at the oxide-air interface is critical in developing or improving remediation strategies. In this work, Raman and infrared spectroscopy are used to obtain molecularly specific information concerning model pollutant-oxide adsorption processes. The choices of pollutants are varied to include several classes of compounds. The interactions of azaarenes, aromatics, chlorinated aromatics, trichloroethylene, and tributyl phosphate are investigated with several mineral types. Pure mineral phases such as silica, alumina, hydrated iron oxide, and montmorillonite clay are used to provide a basis set of interactions, which can be extended to more complex systems in the future. Pollutantoxide interactions, including weak physisorption, hydrogen bonding, Bronsted acid-base, and Lewis acid-base, were identified in this work and varied depending on the specific pollutant-oxide system. This research provides surface adsorption information on environmentally relevant contaminants and the techniques may be utilized to verify the accuracy of pollutant fate and transport models and to improve remediation strategies for such pollutants.

Thesis: S.B., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2016.<br>Cataloged from PDF version of thesis.<br>Includes bibliographical references (page 30).<br>Condensation is a process utilized by about 85% of power plants in their power generation cycles. Superhydrophobic surfaces can potentially improve the heat transfer due to condensation when compared to the untreated surfaces typically used in condensers. This can improve the efficiency of power plants by up to 3%. These surfaces are made by combining nanoscale roughness with chemical hydrophobicity, and can promote the mode of condensation that has the least resistance to heat transfer. However, it is unclear how long these surfaces will last under industrial conditions. This thesis is focused on testing the robustness of the surfaces in multiple experiments and analyzing the data gathered from these experiments, along with theorizing the mechanism behind any surface functionality deterioration that may be seen. Hydrophobic and superhydrophobic surface samples that have been prepared previously were subjected to water immersion and continuous condensation tests. For the water immersion tests, samples were submerged in water under neutral (pH = 7) and basic (pH = 10) conditions at room (~25°C) and elevated (~50°C) temperatures. The continuous condensations tests were run at a steam temperature of 27°C as well as 100°C. To understand the change in surface properties over the duration of the tests, the surface contact angle was chosen as the metric to be measured. The contact angles of water droplets on the samples were taken beforehand and throughout the tests using a micro-goniometer in order to quantify the change in surface functionality. The data gathered from these experiments were processed in Matlab to produce plots of the change in contact angle over the duration of each test. These plots showed significant contact angle decreases for the hydrophobic surfaces but little change in the contact angle for the superhydrophobic surfaces. This suggests that the addition of nanostructures on the surface, and thus the promotion of super- hydrophobicity, inhibits the surface functionality deterioration mechanism that is seen with the hydrophobic surfaces.<br>by Emmanuel E. Simpri.<br>S.B.

The research projects described in this Dissertation were designed to investigate the interfacial chemistry of alkylsilanes on metal and oxide surfaces, specifically Ag and silica, respectively. A variety of surface analysis tools, including FTIR and Raman spectroscopies, electrochemistry, ellipsometry, and x-ray photoelectron spectroscopy, have been applied to study important aspects of bonded alkylsilane structures. Two model silica surfaces were designed and fabricated as substrates for the attachment of alkylsilanes. The first model silica surface employs self-assembled monolayers of hydrolyzed and condensed (3-mercaptopropyl)trimethoxysilane (3MPT) on Ag surfaces. The Ag substrate is used to provide a small enhancement to the Raman scattering at the interface. Octadecyltrichlorosilane (OTS) and dimethylchlorooctadecylsilane (DOS) are covalently bonded to these surfaces. Monolayers of OTS on 3MPT-modified Ag surfaces are ordered, while submonolayers of DOS, the maximum coverage achievable, are disordered. Results obtained from this study demonstrate the importance of van der Waals interactions and siloxane cross-linking in promoting an ordered alkylsilane structure. The second model silica surface studied is based on thin silica films prepared through sol-gel technology. These are prepared by spin-coating prehydrolyzed solutions of tetratmethoxysilane (TMOS) onto 3MPT-modified Ag surfaces. These surfaces are designed to contribute to an understanding of the partitioning process associated with alkylsilane stationary phases in reversed-phase liquid chromatography (RPLC). OTS layers covalently attached to such surfaces were studied previously in this laboratory. In this Dissertation, the sol-gel methodology used is improved to enable silica films in the ultrathin (< 100 Å) regime to be fabricated. These substrates allow study of model stationary phases of DOS. Both FTIR and Raman spectroscopies indicate that the DOS alkyl chains on silica are disordered, consistent with previous notions about monomeric alkylsilane stationary phases in RPLC. Further characterization of these thin silica films reveals them to be non-porous, dielectric, and homogeneous. Their dielectric strengths are found to be equivalent to or better than those from device-quality thermally grown silica. This research expands application of the well-defined sol-gel technology to the fabrication of ultrathin silica films that may be useful as insulating layers in the microelectronics and semiconductor industries.

The research presented in this dissertation is focused on the construction of complex molecular structures on planar gold and silicon dioxide surfaces using a variety of surface modification techniques, along with thorough surface characterization at each modification step. The dissertation is structured into six separate chapters. In Chapter 1, an introduction to the importance and implications of molecular level surface modification, commonly employed surface modification methods, and available surface characterization techniques is presented. Chapter 2 shows applications of novel methodologies for the functionalization of gold surfaces using alkane dithiol self-assembled monolayers and thiol-ene click chemistry. The resulting functionalized gold substrates demonstrate higher chemical stability than alkanethiol self-assembled monolayers alone and allow spatially controlled functionalization of gold surfaces with light. In Chapter 3, work on tunable hydrophobic surfaces is presented. These surfaces are prepared using a combination of organosilane chemistry, layer-by-layer polyelectrolyte deposition, and thiol-ene chemistry. These hydrophobic surfaces demonstrate high mechanical and chemical stability, even at low pH (1.68). The pinning of water droplets could be tuned on them by the extent of their thermal treatment. Comprehensive surface characterization using X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), spectroscopic ellipsometry, atomic force microscopy, and water contact angles was carried out on the molecular assemblies prepared on gold and silicon dioxide surfaces. Chapters 4 and 5 are focused on the application, data interpretation, and enhancement in sensitivity of different surface characterization methods. In Chapter 4, XPS, ToF-SIMS, and principal components analysis are used to probe a real world corrosion-type problem. This systemic study showed the destruction of a protective coating composed of a nitrilotris(methylene)triphosphonic acid by a low-intensity fluorine plasma. In Chapter 5, enhancement in ToF-SIMS signals is shown via bismuth metal deposition. These surfaces are also probed by spectroscopic ellipsometry using the interference enhancement method. Finally, Chapter 6 concludes this dissertation by describing possible future work.

The synthesis of a variety of novel functionalized polymers using living polymerization techniques to achieve functional and stimuli responsive coatings on silica surfaces are described. Since microscopic features on a surface influence the overall wetting properties of the surface, a systematic investigation of the influence of polymer architecture on the microscopic characteristics of the modified surfaces was studied using silane-functionalized linear and novel star-branched polystyrene (PS). Star-branched modifiers provide functional and relatively well-defined model systems for probing surface properties compared to ill-defined highly branched systems and synthetically challenging dendrimers. Using these simple star-shaped macromolecules it was shown that the topographies of the polymer-modified surfaces were indeed influenced by the polymer architecture. A model explaining the observed surface features was proposed. A living polymerization strategy was also used to synthesize centrally functionalized amphiphilic triblock copolymers. The amphiphilic copolymers exhibited stimuli responsive changes in surface hydrophobicity. In spite of multiple solvent exposures, the copolymer films remained stable on the surface indicating that the observed changes in surface properties were due to selective solvent induced reversible rearrangement of the copolymer blocks. The chemical composition of the copolymers was tailored in order to tune the response time of the surface anchored polymer chains. Thus, the polymer coatings were used to reversibly change the surface polarities in an on-demand fashion and could find possible applications as smart adhesives, sensors and reusable membrane devices. In contrast to the afore-mentioned covalent modification approach, which often leads to permanent modification of surfaces, renewable surfaces exhibiting â universalâ adhesion properties were also obtained through non-covalent modification. By employing hydrogen bonding interactions between DNA bases, surfaces functionalized with adenine groups were found to reversibly associate with thymine-functionalized polymers. This study describing the solvato-reversible polymer coating was the first demonstration on silica surfaces. A systematic investigation of the influence of surface concentration of the multiple hydrogen bonding groups and their structure on the extent of polymer recognition by the modified surfaces is also discussed.<br>Ph. D.

Many smooth, highly specular coatings such as automotive paints are subjected to considerable performance demands as the customer expectations for appearance of coatings are continually increasing. Therefore it is vital to develop robust methods to monitor surface quality online. An automated visual assessment of specular coated surface that would not only provide a cost effective and reliable solution to the industries but also facilitate the implementation of a real-time feedback loop. The scope of this thesis is a subset of the inspection technology that facilitates real-time close loop control of the surface quality and concentrates on one common surface defect the seed defect. This machine vision system design utilizes surface reflectance models as a rational basis. Using a single high-contrast image the height of the seed defect is computed; the result is obtained rapidly and is reasonably accurate approximation of the actual height.

Accurate terrain models provide the chassis designer with a powerful tool to make informed design decisions early in the design process. During this stage, engineers are challenged with predicting vehicle loads through modeling and simulation. The accuracy of these simulation results depends not only on the fidelity of the model, but also on the excitation to the model. It is clear that the terrain is the main excitation to the vehicle [1]. The inputs to these models are often based directly on physical measurements (terrain profiles); therefore, the terrain measurements must be as accurate as possible. A collection of novel methods can be developed to aid in the study and application of 3D terrain measurements, which are dense and non-uniform, including efficient gridding, stochastic modeling, and compact characterization.<br />Terrain measurements are not collected with uniform spacing, which is necessary for efficient data storage and simulation. Many techniques are developed to help effectively grid dense terrain point clouds in a curved regular grid (CRG) format, including center and random vehicle paths, sorted gridding methods, and software implementation. In addition, it is beneficial to characterize the terrain as a realization of an underlying stochastic process and to develop a mathematical model of that process. A method is developed to represent a continuous-state Markov chain as a collection of univariate distributions, to be applied to terrain road profiles. The resulting form is extremely customizable and significantly more compact than a discrete-state Markov chain, yet it still provides a viable alternative for stochastically modeling terrain. Many new simulation techniques take advantage of 3D gridded roads along with traditional 2D terrain profiles. A technique is developed to model and synthesize 3D terrain surfaces by applying a variety of 2D stochastic models to the topological components of terrain, which are also decomposed into frequency bandwidths and down-sampled. The quality of the synthetic surface is determined using many statistical tests, and the entire work is implemented into a powerful software suite. Engineers from many disciplines who work with terrain surfaces need to describe the overall physical characteristics compactly and consistently. A method is developed to characterize terrain surfaces with a few coefficients by performing a principal component analysis, via singular value decomposition (SVD), to the parameter sets that define a collection of surface models.<br>Master of Science

Nanoscience and Nanotechnology have become research areas that promote the design and fabrication of novel devices with a number of different applications with the aim of satisfying the growing demand of the society regarding technological advances. The breakthrough in some of these subjects directly associates with the development of specific molecular systems with new and advanced features, applicable toward the development, at the nanoscale, of efficient materials that could act as molecular switches or active components in memory devices, transistors or sensors, among others. In this regard, promising molecular-based systems, to be applicable in these fields, are the so-called Curcuminoids (CCMoids). These molecules can present versatile structures, displaying always (i) a conjugated chain of seven carbon atoms, which confers the molecules with reasonable conductive properties; (ii) a β-diketone group located in the middle of the chain, that opens the possibility of coordinating with metallic centers, and (iii) two aromatic groups, located on both sides of the molecules that add fluorescent, redox active and optical properties, among others. The main goal of this thesis rest on the design and synthesis of new CCMoids that can be applied in different areas of nanoscience. Thus, different modifications on their structure were carried out in order to achieve interesting properties. The results obtained in this work have been grouped in five different sections; corresponding each one to a different area. This way: (1) Molecular Magnetism: the first section is focused on the search of systems which display interesting magnetic properties, especially systems with single molecule magnet behavior. Thus, magneto-structural studies were performed by the synthesis of several coordination compounds using magnetic metallic centers (CoII and NiII) coordinate with a CCMoid ligand called 9Accm. In addition, a study of the influence of the paramagnetic centers on the fluorescent properties derived from the CCMoid ligand was also performed together with deposition studies on HOPG (highly oriented pyrolytic graphite). (2) Molecular Electronic: the second section focuses on the study of the electronic transport of a new CCMoid system within a three terminal nanodevice containing few layer graphene (FLG) electrodes. This study centers in the improvement of the conductive properties of a previously measured CCMoid system, in which 9Accm was used as a nanowire in a molecular transistor by π-π stacking interactions with the graphene electrodes. The new CCMoid contains an elongated conjugated skeleton that improves the anchoring properties of the final system with the FLG electrodes. (3) Molecular Sensors: the third section is based on the immobilization of fluorescent CCMoids on surfaces and their used as chemical sensors for boron ions. The immobilization was carried out on functionalized SiO2 surfaces by the use of the Microcontact printing technique (μ-CP) that allowed the creation of fluorescent micropatterns on the surfaces. In addition, studies regarding the coordination of boron to the CCMoids attached on the surfaces and the effect in their fluorescent properties was performed to explore they as chemical sensors. (4) Molecular Host-Guest Chemistry: the fourth section is focused on the fabrication of supramolecular host-guest systems based on CCMoids. In the first part, a study of the CCMoid acting as a guest was performed. In this case, a novel CCMoid molecule that contain a ferrocene group is inserted in different host cavities (cyclodextrin and cucurbituril). This study was performed in solution and on Au surfaces. On the other hand, the synthesis of another CCMoid was carried out to be used as a host, being the main ligand in the formation of molecular cages. (5) Molecular Donor/Acceptor Chemistry: the fifth section is based on the study of the donor/acceptor properties of additional CCMoids with the idea of using them as components of organic photovoltaics cells (OPVs). For this study, the synthesis of two families of CCMoids with acceptor and donor moieties on the sides of the molecules was performed, and additional variations on their structure were achieved to assess their influence on the optical and electronic properties of the systems.<br>La nanociencia y la nanotecnología se han erigido como las áreas encargadas en diseñar y fabricar nuevos dispositivos cada vez más potentes y rápidos con el fin de satisfacer la creciente demanda tecnológica de nuestra sociedad. Una familia de moléculas muy prometedoras para ser aplicable en estos campos es la conocida como Curcuminoides (CCMoides) debido a su gran versatilidad. Esta tesis se centra en el diseño y síntesis de nuevos CCMoides para su posterior aplicación en diferentes campos de la nanociencia. Para ello, se han llevado a cabo distintas modificaciones en sus estructuras con el fin de conseguir propiedades interesantes. Los resultados obtenidos han sido agrupados en 5 secciones, cada uno de los cuales corresponde a un área de investigación diferente: (1) Magnetismo Molecular: La primera sección se centra en la búsqueda de sistemas que presenten propiedades de imán molecular. Para ello, se llevó a cabo un estudio magneto- estructural mediante la síntesis de varios compuestos de coordinación utilizando centros metálicos magnéticos (CoII y NiII) coordinados con el ligando CCMoide llamado 9Accm. (2) Electrónica Molecular: La segunda sección se centra en el estudio del transporte electrónico de un nuevo sistema CCMoide como parte activa de un sistema de tres terminales que actúa como transistor molecular de efecto campo. (3) Sensor Molecular: La tercera sección se centra en la inmovilización de CCMoides fluorescentes en superficies funcionalizadas que puedan actuar como sensores químicos de boro. Esta inmovilización se llevara a cabo en superficies de SiO2 mediante el uso de la técnica Microcontact printing. (4) Huésped-Anfitrión Molecular: La cuarta sección se centra en la fabricación de sistemas supramoleculares huésped-anfitrión. El primer estudio se centra en la utilización de ligandos CCMoide (huésped), que interaccionan con dos sistemas (ciclodextrina y cucurbiturilo) (anfitriones). Por otro lado, se realizó la síntesis de un nuevo CCMoide con el objetivo de que pudiese actuar como anfitrión mediante la formación de cajas moleculares. (5) Dador-Aceptor Molecular: La quinta sección se centra en el estudio de las propiedades aceptoras/dadoras de CCMoides para que puedan ser utilizados en la fabricación de celdas fotovoltaicas orgánicas (OPVs), llevándose a cabo la síntesis de dos familias de CCMoides con grupos aceptores y dadores.

Im Mittelpunkt dieser Arbeit steht die selektive Funktionalisierung von Siliziumoxidnanostrukturen auf alkyl-passivierten Siliziumoberflächen welche durch rasterkraftmikroskopisch induzierte lokale anodische Oxidation (LAO) erzeugt werden. Bei der gezielten Immobilisierung von funktionalen Molekülen auf den Strukturen werden zwei verschiedene Routen verfolgt – Anbindung von ionischen Farbstoffen über elektrostatische Wechselwirkungen sowie stufenweise kovalente chemische Anbindung von bi-funktionalen Verbindermolekülen und Farbstoffen. Eine Untersuchung der hergestellten funktionalen Strukturen erfolgt mittels Rasterkraftmikroskopie, Raster-Kelvin-Mikroskopie sowie zeitaufgelöster Fluoreszenzmikroskopie und-spektroskopie. Durch zwei unabhängige Methoden kann gezeigt werden dass die Ladungen im lokalen Oxide vergleichsweise stabil sind und die elektrostatische Anbindung somit auch noch nach Tagen möglich sein sollte. Das Verhalten der elektrostatisch angebundenen Farbstoffe hängt stark von deren Art ab. Während es bei Rhodamin 6G nur zu einer minimalen spektralen Änderung im Vergleich zur Lösung kommt so zeigen spermin-funktionalisierte Perylenbisimidfarbstoffe eine deutliche H-Aggregation und Ausbildung von Excimerzuständen. Diese Zustände sind eindeutig thermisch aktiviert und zeigen eine wesentlich höhere Aktivierungsenergie als bei allen anderen bisher untersuchten Perylenaggregaten sowie eine Hysterese bei Temperaturveränderung. Die physikalische Ursache für dieses Phänomen liegt allem Anschein nach in der elektrostatischen Anbindung selbst welche ein instabiles Gleichgewicht mit der Wechselwirkung der Moleküle untereinander bildet. Eine geordnete kovalente Anbindung von funktionalen Silanmolekülen an die mittels LAO erzeugten Strukturen erfordert sehr definierte Prozessparameter. Die spektroskopische Untersuchung von an die funktionalen Silane chemisch angebundenen Fluoresceinfarbstoffen lässt indirekte Schlüsse auf deren Belegungsdichte und damit die Qualität der Silanmonolage zu.

The soil-structure interface is fundamental to the performance of many geotechnical engineering systems; including penetration test devices, deep foundations, and retaining structures. In geotechnical engineering structures, the counterface may range from a polymer in the case of a geosynthetically reinforced earth retaining structure to steel for cone penetration testing or pile foundations. Interface strength is affected by many factors, among which surface roughness is the most dominant. To date common practice has been to characterize counterface surface roughness by a roughness parameter based on only its spatial properties and soil roughness separately by various incompatible means resulting in two roughness values unrelated to each other. The vast number of analyzing methods and developed parameters reveal the general confusion regarding this concept. Rather than analyzing the particulate and continuum media separately, it is compulsory to coalesce the analysis and quantify the relative nature of interface behavior. This can be accomplished by examining the particulate and continuum media through the same powerful tools. The motive of this study is to develop a unified approach to determining the index properties of particles and surfaces in a particle-surface interface. This is accomplished by examining several particle shape and surface roughness parameters in terms of their ability to uniquely describe and distinguish particulate medium and continuum roughness, respectively. In this study, surfaces are analyzed as derived particles by wrapping surface profiles and particles are evaluated as derived surfaces via unrolling particle outlines. In addition, particle shape parameters are modified to allow surface roughness analysis and surface roughness parameters are modified to characterize particle shape. A unified approach for particulate shape and continuum roughness would ultimately lead to a better understanding of micro-scale interaction mechanism and better quantification of macro-scale mobilized resistance for soil and engineering surface interaction.

The aims of this study were to, 1) investigate the surface characteristics of polished titanium plates/discs treated with acid-etching and ultraviolet irradiation (UV); and 2) investigate the change in surface characteristics of polished titanium plates/discs treated with acid-etching and UV irradiation after aging in air, saline and citric acid for six weeks. A total of one hundred and ninety-eight commercially pure grade two titanium plates and 50 titanium discs were prepared. Titanium samples were divided into four groups: 1) polished group, 2) polished and UV group, 3) acid-etched group and 4) acid-etched and UV group. Polishing was performed by abrasive silicon carbide paper grinding. UV treatment was performed by 15W germicidal UVC, 254 nm, for 48 h. Acid-etching was performed with 67% H2SO4 at 120 ºC for 75 s. The four groups were then subjected to an aging process for six weeks in sealed containers with three different media: air, physiologic saline and citric acid. They were analyzed immediately after treatment and after aging for surface characterization: topography, roughness, wettability, crystallinity, and chemistry. The polished surface showed relatively smooth surface with typical grooves from the grinding process. Acid-etching produced micro-roughened surface with sharp pits and ridges. The average surface roughness of polished, polished-UV was lower than that of the acid-etched and acid-etched-UV surfaces (p < 0.05). Storage of titanium in saline and citric acid did not provoke any morphological or roughness changes at micron scale level when compared to the samples stored in air. Immediately after preparation and treatment, the polished and acid-etched titanium surfaces appeared to be hydrophilic with similar contact angle values (p > 0.05). After UV treatment, there was a significant reduction in contact angles (superhydrophilic) in both surfaces (p < 0.05). After storage in air for six weeks, the contact angles of the four groups significantly increased (p < 0.05) and the surfaces converted to a hydrophobic state. In contrast to samples stored in air, samples stored in saline and citric acid revealed superhydrophilic surfaces regardless of the surface type. Titanium hydride crystals were present in the acid-etched and acid-etched-UV surfaces but not in the polished and polished-UV surfaces. Titanium tetrachloride crystals were present in saline-stored surfaces. The polished surface acquired significantly higher titanium and oxygen concentrations and lower carbon contaminants compared to acid-etched surface. UV treatment substantially decreased carbon contamination and increased the titanium and oxygen concentrations in the acid-etched groups (p < 0.05). After storage for six weeks in air, the four studied surfaces had no significant changes in the surface chemistry. Storage of the titanium samples in saline and citric acid relatively increased the carbon contamination and decreased titanium and oxygen concentrations. UV treatment may be an effective way to produce clean titanium surfaces with less carbon especially after roughening the titanium surface by acid-etching. Storage of the freshly prepared titanium surface in media such as saline or citric acid could preserve the hydrophilic property of these surfaces, however, it may also negatively influence the surface chemistry due to increased carbon contaminants.<br>published_or_final_version<br>Dentistry<br>Master<br>Master of Philosophy

This work investigates the technique of mass fabrication of nanowires on semiconductor InP (100) surfaces by low energy Ar+ ion beam bombardment. Systematic investigation shows that under some crucial experimental parameters, nanowire arrays of regular periodicity can be produced. An ambient Atomic Force Microscope was used in contact mode to examine the morphology of the irradiated InP surfaces. The chemical composition of the irradiated samples was characterized by X-ray Photoelectron Spectroscopy (XPS). The electronic structure of the fabricated nanowire arrays was jointly explored by Scanning Tunnelling Spectroscopy and XPS. The research shows that In enriched ripples and nanowires form under prolonged irradiation by Ar+ ions due to preferential sputtering of P from InP under grazing ion incident angle above some crucial irradiation ion dose. A model of mergence from tailed cones is proposed to account for the formation of these ripples and nanowires. The drive to the formation of periodic ripples and nanowires is believed to be stress-field induced self-organisation of strained cones. The cone-mergence model is a combination of the model of stress-field induced self-organization and the model of ripple topography by Bradley and Harper (BH). The research proposes that the mobility of atoms on the corresponding solid surfaces under ion bombardment decides whether the surface morphology is generated by the stress-field, the BH, or a combination of the two models. Monte-Carlo simulation was used to evaluate the effect of surface damage and preferential sputtering of P from InP and N from Si3N4. The calculations predict that P and N can be preferentially sputtered from InP and Si3N4 surfaces.

Providing antireflection in the visible spectrum is useful for a number of applications. Solar cells, LCD screens, optical lenses and stealth surfaces are a few examples of applications that can benefit from antireflection. In this work, maximizing the performance of a biomimetic motheye metamaterial antireflection layer via optimization of its design parameters was investigated. Additionally, case studies of designing optimized antireflection solutions were carried out for some of the most demanding applications such in solar cells and stealth coatings. More specifically, simulations of the moth-eye design parameters for feature period, height, density factor, shape and topology were carried out. For feature height, it was found that for a height larger than 400nm, the gains in providing antireflection for the visible spectrum are low, so it is not necessary to create features taller than this to achieve a good antireflection performance. For feature density factor an almost linear monotonic relationship was observed, so for this design parameter, maximization is necessary. For the feature period parameter, it was found that a simple rule could not be extracted and thus to optimize performance, a tailoring of the period for each application has to be done whilst taking into account the incident spectrum. An optimization of the feature period was carried out for monocrystalline silicon solar cells and the AM 1.5 solar spectrum and it was found that for this spectrum, the optimum period is 397nm. Feature topology was not found to provide a significant advantage to the antireflection behaviour of the metamaterial layer in terms of power, however it does provide a more diffuse scattering of the backscattering diffraction order which emanates from the structure at high angles of incidence, an attribute which is very useful for stealth applications. To verify simulation results, fabrication of moth-eye antireflection structures were carried out via nano-imprint, electron-beam and nanosphere lithography. The nanosphere lithography technique presented was optimized specifically for the samples required in this thesis. Complete monolayer coverage of large areas (2x2cm2) was accomplished and thus complex biomimetic feature topologies could be readily investigated. Optical experiments measuring specular reflectance and the backscattered diffraction orders were carried out both with readily available and custom built optical setups. The simulation trends were all verified successfully and a summary of suggested design parameters for a range of different applications has been suggested.

Thesis (M.A.)--Boston University<br>This study is a part of an environmental impact assessment of the Gulf War on the desert and the coastal zones of Kuwait. Due to the appearance of many new surface features, a study was necessary to characterize their spectral signatures as detected by Landsat Thematic Mapper (TM) data. A sophisticated image analysis was applied to the Landsat TM scene. An unsupervised classification technique produced a thematic map of the area. Data was collected on the ground at eighty sites in southeastern Kuwait. A radiometer (SE-590) was used to identify the spectral reflectance of desert surface features. A Global Positioning System (GPS) reading on each site was also recorded to register accurately the field observations on a specific pixel from over 72 million pixels in the lower right scene of Kuwait. Field data were collected on surface feature color, soil grain stze, vegetation types and density, and the amount of oil or soot contamination. Statistical correlation's and companson of Landsat and the SE-590 measurements in the visible and near-infrared bands describe the interaction between radiation and different desert surfaces. The oil lakes class was identified to have the lowest reflectance of all the classes. Brightness values gradually increase as less oil, soot or desert vegetation is found. The highest brightness value belongs to the class which represents active sand.

Thesis (Ph. D.)--Mechanical Engineering, Georgia Institute of Technology, 2006.<br>Dr. David W. Rosen, Committee Chair ; Dr. Farrokh Mistree, Committee Member ; Dr. W. Jack Lackey, Committee Member ; Dr. Cliff Henderson, Committee Member ; Dr. Ali Adibi, Committee Member.