Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

In the past decade there has been increasing interest in exploring the use of nanocellulose in medicine. However, the influence of the physicochemical properties of nanocellulose on the material´s biocompatibility has not been fully investigated.  In this thesis, thin films of nanocellulose from wood (NFC) and from Cladophora algae (CC) were modified by the addition of charged groups on their surfaces and the influence of these modifications on the material´s physicochemical properties and on cell responses in vitro was studied. The results indicate that the introduction of charged groups on the surface of NFC and CC results in films with decreased surface area, smaller average pore size and a more compact structure compared with the films of unmodified nanocelluloses. Furthermore, the fibres in the carboxyl-modified CC films were uniquely aggregated and aligned, a state which tended to become more prevalent with increased surface-group density. The biocompatibility studies showed that NFC films containing hydroxypropyltrime-thylammonium (HPTMA) groups presented a more cytocompatible surface than unmodified NFC and carboxymethylated NFC regarding human dermal fibroblasts. Carboxymethyl groups resulted in NFC films that promoted inflammation, while HPTMA groups had a passivating effect in terms of inflammatory response.  On the other hand, both modified CC films behaved as inert materials in terms of the inflammatory response of monocytes/macrophages and, under pro-inflammatory stimuli, they suppressed secretion of the pro-inflammatory cytokine TNF-α, with the effects of the carboxylated CC film more pronounced than those of the HPTMA CC material.  Carboxyl CC films showed good cytocompatibility with fibroblasts and osteoblastic cells. However, it was necessary to reach a threshold value in carboxyl-group density to obtain CC films with cytocompatibility comparable to that of commercial tissue culture material.  The studies presented here highlight the ability of the nanocellulose films to modulate cell behaviour and provide a foundation for the design of nanocellulose-based materials that trigger specific cell responses. The bioactivity of nanocellulose may be optimized by careful tuning of the surface properties. The outcomes of this thesis are foreseen to contribute to our fundamental understanding of the biointerface phenomena between cells and nanocellulose as well as to enable engineering of bioinert, bioactive, and bioadaptive materials.

Dans de nombreux procédés technologiques, tels que la fabrication de matériaux pour la microélectronique, l’étude des réactions chimiques à une électrode, ou encore la catalyse… L’interface entre la surface d’un solide ou d’un liquide avec un liquide ou une phase gaz joue un rôle fondamental. De façon analogue, les sciences de l’environnement ainsi que celles du vivant intègrent dans leurs modèles la réactivité aux interfaces solide/ liquide ou liquide/ gaz.L’XPS est une technique parfaitement adaptée à l’étude des interfaces et a été largement utilisée pour l’analyse des surfaces de solides. Le principal avantage de l’XPS est sa grande sensibilité aux surfaces. En effet, en raison du faible libre parcours moyen des électrons dans un solide, uniquement les photoélectrons provenant de l’extrême surface (1 – 10 nm) peuvent échapper à celle-ci. Cependant, l’XPS est traditionnellement utilisée dans des conditions d’ultravide (UHV) et cela pour deux raisons. La première est que les analyseurs d’électrons sont construits pour fonctionner en UHV. La seconde est que les électrons doivent pouvoir atteindre l’analyseur, or leur libre parcours moyen est faible dans un gaz à haute pression. Par exemple, à une pression de 1 mbar, des électrons possédant une énergie de 100 eV vont parcourir 1 mm alors qu’ en UHV ils pourront atteindre jusqu’ à 105 m.Dans le but de rendre possible l’utilisation de l’XPS à des pressions plus élevées, quelques groupes autour du monde, dont le groupe de Berkeley (sous la direction de M. Salmeron at de H. Bluhm) et celui du Fritz Haber Institute à Berlin, ont élaborés un équipement permettant d’atteindre des pressions proche de l’ambiant (5 mbar). La construction d’un analyseur d’électron capable de fonctionner à des pressions de l’ordre du mbar, c’est-à-dire à des pressions 7 ordres de grandeur supérieures à l’UHV, a été une avancée à la fois conceptuelle et technologique. Un système de pompage différentiel permet de maintenir l’échantillon dans des conditions dites environnementales tout en maximisant le libre parcours moyen des électrons de façon à ce qu’ils atteignent l’analyseur. De plus, des tensions sont appliquées à des lentilles électrostatiques dans le but d’accélérer et de focaliser ces électrons.Un système similaire (Near Ambient Pressure XPS, NAP-XPS) a été installé sur la ligne TEMPO du synchrotron Soleil en février 2013, le premier temps de faisceau ayant eu lieu au mois de mai suivant. Durant ma thèse, deux projets différents ont été développés, tous les deux liés à l’étude d’interfaces avec l’utilisation de la NAP-XPS.Le premier projet traite des procédés utilisés en micro-electronique pour déposer de fines couches d’oxydes : le dépôt chimique en phase vapeur (CVD) et la déposition de couches atomiques (ALD). En particulier, des molécules de la famille des silanes sont utilisées pour fonctionnaliser des surfaces d’oxyde de silicium ou comme précurseur, combiné à un agent oxydant comme l’eau pour le dépôt de films mince d’oxyde de silicium. Cependant, les mécanismes réactionnels des silanes sur les surfaces de silicium n’ont jamais été étudiés par des techniques telles que la microscopie a effet tunnel (STM) ou l’XPS et l’on sait peu de choses concernant leur mécanisme de dissociation et l’adsorption des divers fragments sur la surface. / In many processes or technological objects, such as coating deposition, advanced material processing for electronics, magnetic or optical devices, electrochemical processes at an electrode, sensors and catalysis, etc. the interface between a surface of a solid and a liquid or a gas phase, plays a prominent role. Analogously, environmental sciences and sciences of the Living integrate into their models chemical reactions taking place at solid/liquid or liquid/gas interfaces.XPS is a powerful technique for interface analysis and has been widely use in the case of solid surface. The main advantage of XPS is its sensitivity to the material surface. Indeed, due to the low electron mean free path of electrons in a solid, only the photoelectrons at the extreme outer surface (1-10 nm) can escape the sample. However, XPS has traditionally been conducted under ultra-high vacuum (UHV) conditions. UHV conditions are utilized for two reasons. First, the analyzers are designed to work under UHV conditions. Second, the electrons must reach the detector and their mean free path is short at high pressures. For example at a pressure of 1 mbar, 100 eV electrons will travel 1 mm while under UHV conditions, the mean free path increases to 105 m. UHV chambers (10-10 mbar) help maximize the mean free path so that a high number of electrons will reach the detector/analyzer and the signal/noise ratio will increase making it possible to analyze the spectrum produced. This constraint makes UHV the standard environment of X-ray Photoelectron Spectroscopy (XPS) experiments.In order to make possible the use of XPS on a larger pressure range, a few groups around the world have designed photoemission equipment that can be operated under ambient pressure (up to 5 mbar). The Berkeley group (M. Salmeron LBNL-Materials Sciences Division, H. Bluhm LBNL-Chemical Sciences Division), who pioneered this field, has two such setups installed at the Advanced Light Source. The Fritz Haber Institute has built a high pressure XPS based on the Berkeley prototype, installed at BESSY synchrotron (Berlin), since 2002. The building of Ambient Pressure XPS (APXPS) analyzers of the Berkeley type, able to be operated at pressures in the range of 1 mbar, about 7 orders of magnitude higher than the pressure limit of conventional UHV equipment is both a technological and conceptual breakthrough. Differential pumping stages allow the sample to remain at environmental pressures, while maximizing the mean free path of emitted electrons, so they can reach the detector. Additionally, voltages are applied to electrostatic lenses in the unit to accelerate and focus the electrons onto the focal plane of the electron energy analyzer. A similar system Near-Ambient Pressure XPS, NAP-XPS), described in details in chapter 1, was delivered in December 2012 and installed at TEMPO beamline in February 2013. The first beamtime occurred in May 2013. During my thesis that started in October 2011 two different projects were developed, both related to interface analysis using the NAP-XPS instrument.

Depuis plusieurs années, des recherches sont conduites à l'ONERA, sur les radars " transhorizon " et notamment sur le radar de surveillance côtière à onde de surface (ROS). En vue d'augmenter les performances de ce radar, il est nécessaire d'améliorer son rayonnement en onde de surface. Lors de précédents travaux réalisés à l'ONERA et à l'UPMC, il a été proposé d'utiliser un métamatériau pour lancer, vers la surface de la mer, une onde confinée, ce qui est impossible avec un matériau à permittivité positive. Le métamatériau devra être placé sur le sol, devant les antennes d'émission du radar, ce qui permettra d'augmenter leur rayonnement vers la surface, sans pour autant modifier significativement l'architecture du système. Mais l'ajout du métamatériau crée une rupture d'impédance entre le métamatériau et le sol. L'objectif de ces travaux de thèse est de répondre à deux questions principales. La rupture d'impédance existant entre le métamatériau et le sol va-t-elle diffracter l'onde de surface créée sur celui-ci ? L'augmentation du niveau de champ électrique, à la surface du métamatériau, va-t-elle se conserver lors de la propagation sur la mer ? / For many years, researches « on over the horizon radar » are investigated, especially on the High Frequency Surface Wave Radar (HFSWR), which is dedicated to the maritime surveillance. To increase the efficiency of the HFSWR we deal with the part of the electromagnetic field radiated at low elevation angle. In a previous work conducted at ONERA and UPMC, it has been suggested to use a metamaterial to launch, at the interface between air and ground a confined wave, which can not exist with a soil with positive permittivity. The metamaterial is placed on the interface in the vicinity of the transmitting antennas to allow the propagation of a strong surface wave without modifying significantly the architecture of the system. But, the inclusion of this metamaterial creates a quite high discontinuity in permittivity. The principal aim of this research work is to answer two main questions. The discontinuity of permittivity between the metamaterial and the soil, is it going to diffract the surface wave create over the metamaterial? The improvement of the electric field level at low elevation angle metamaterial, is it going to keep throughout the propagation on the sea?

Silicon photonics is emerging as a potential field to achieve optical interconnects towards the realization of ultra high bandwidth. The indirect band-gap property of silicon still remains as a big challenge to incorporate silicon photonic active device, for example, silicon-based laser. In the Laboratory of Semiconductor Materials at KTH, a monolithic integration platform based on nano-epitaxial lateral overgrowth (nano-ELOG) technique has been proposed to integrate III-V semiconductor materials with silicon for light source application. The integration process involves uneven surface morphology at different stages. The surfaces of the indium phosphide seed layer on silicon used for ELOG, the mask deposited on it (the silicon/silicon dioxide waveguide) and the ELOG indium phosphide layer grown on it prior to laser growth are often rough. In this thesis work, we have optimized chemical mechanical polishing (CMP) technique in order to achieve an even surface. The same procedure is also necessary to reach the optimal thickness of different layers to enable effective coupling of light from the laser source into the waveguide. CMP of indium phosphide to obtain an average surface roughness of < 1 nm has been optimized by a two-step polishing using different slurries; it results in a step height of ca 3 nm. Similarly the surface of silicon/silicon dioxide “waveguide” has also been optimized with the roughness of ~ 0.5 nm. In the latter case, a step height of 40 nm is retained and this increase with respect to InP is identified to be mainly due to limitations of the polishing machine which is different from that used for indium phosphide. The reduction in step heights with polishing time is analyzed and compared with an existing theoretical model. Our results are in good qualitative agreement with the model. The optimized surface morphology obtained in this work was tested for its suitability for integration. For this evaluation, InP was grown by ELOG in a hydride vapour phase epitaxy reactor with and without CMP of the involved surfaces. The surface after CMP yields layers of better surface morphology with fewer defects as revealed by atomic force microscopy, surface profilometer and cathodoluminescence analysis. The results indicate that the CMP process is useful for monolithic integration for silicon photonics.

For elucidating catalytic processes and enhancing process efficiency, the characterisation of porous catalysts is crucial. While the chemical characterisation of the catalyst surface, e.g. by infrared and X-ray photoelectron spectroscopy, is standard practice, the energetic characterisation of surface sites is often neglected, although all heterogeneously catalyzed reactions take place at the surface. Inverse gas chromatography is a gas phase method to investigate a large number of physico-chemical, morphological and energetical surface properties of particles, granulates or fibers. In this dissertation, silica materials with well-defined surface properties and a large specific surface area (porous glass beads, pyrogenic silica) were investigated. For potential catalytic and sensoric applications, the silica material was additionally grafted with organofunctional silanes. The overall aim of this Thesis was to apply IGC-theories to different silicas before and after surface modification, to examine the potential of this characterisation method. The validity of the results was set against its limitations, to verify the IGC as sensitive method even for small changes of physico-chemical surface properties. It was observed that the physicochemical properties of the surface are predominatly determined by silanol and siloxane groups. In particular the LEWIS-acid silanol groups strongly interact with LEWIS-basic polar probe molecules. This results in high values for free surface energy with a dominant polar component and an overall LEWIS-acidity of the silica. Measurements indicated specific surface areas respectively to the applied probe molecule. In particular 2-propanol showed strong interactions, a very high surface area, but also a heterogenous adsorption behaviour. According to PAPIRERs Patchwork model of condensation approximation, two different states of adsorption were found. With DFT-simulation these were identified as low energetic hydrogen bonds between 2-propanol and siloxan and as high energetic hydrogen bonds between 2-propanol and silanol groups. Nevertheless, all of the IGC findings point to a reduction of the acidity of silica and an increase in hydrophobicity by surface modification due to the loss of silanol groups with the silane grafting. Finally, the IGC can be presented as a many-faceted useful tool for surface characterisation. Its variability and sensitivity expands most other classical methods. Complex surface properties like free surface energies, acid-base functionality, kinetic parameters, specific surface area and surface heterogenity can be determined from single chromatographic peaks with the respective theories. Throughout the investigation, a new non-linear parameter estimation approach was introduced in contrast to the common linear computation models. Therefore, an increasing number of involved probe molecules and also the use of bipolar probes yields in statistical more reliable results.

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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 / 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.

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