Ziel dieser Studie war es, den Einfluss von Prophylaxemaßnahmen und künstlicher Alterung auf Veneers an menschlichen Zähnen zu untersuchen. Untersucht wurden die externen, marginalen und die internen Grenzflächen, sowie die Oberflächenstruktur der Restaurationsoberflächen. Zweiunddreißig extrahierte Prämolaren wurden mit Veneers aus polymerbasiertem Verbundwerkstoff (RBC) und polymerinfiltriertem Keramiknetzwerk (PICN) restauriert. Künstliche Alterung durch abwechselndes Thermocycling und anschließende Prophylaxemaßnahmen (Pulver-Wasserstrahl mit Glycin-Pulver oder Ultraschall-Scaling) wurde in fünf Zyklen vollzogen. Die externe, marginale Grenzfläche wurde durch Höhenprofilmessungen und die interne Grenzfläche wurde mit Hilfe der Mikro-Röntgen-Computertomographie untersucht. Darüber hinaus wurde die Oberflächenstrukturen der Veneers mit Hilfe der konfokalen Laser-Scanning-Mikroskopie analysiert. Die Anwendung beider Prophylaxeverfahren führte zu einer Vertiefung der externen, marginalen Grenzflächen (10 μm ± 8 μm) bei beiden Verbundwerkstoffen. Darüber hinaus wies die interne Grenzfläche der PICN-Restaurationen, nach beiden Behandlungen und künstlicher Alterung, marginale Lücken auf (16 μm ± 3 μm). Im Gegensatz zu den RBC-Proben wurde eine signifikante Zunahme der Oberflächenrauhigkeit bei PICN-Veneers nach der Ultraschall-Behandlung festgestellt. Es lässt sich zusammenfassen, dass die marginalen und internen Grenzflächenbereiche bei Veneers aus PICN und RBC durch Prophylaxe-Verfahren beeinflusst werden. Darüber hinaus kann es zu einer erhöhten Oberflächenrauigkeit der Veneers kommen, insbesondere bei denen aus PICN nach dem Ultraschall-Scaling, was die Bioadhäsion und Langlebigkeit beeinträchtigen könnte. Nach der zahnärztlichen Prophylaxe ermöglicht die Untersuchung externen und internen Grenzflächen, sowie der der Restauratiosnoberfläche einen präzisen Einblick in die Schädigungsmechanismen und ermöglicht eine Einschätzung der Langlebigkeit.:Abkürzungsverzeichnis III 1 Einführung 1 1.1 Nicht kariöse Zahnhartsubstanzdefekte 2 1.1.1 Abfraktion 3 1.1.2 Abrasion 3 1.1.3 Attrition 3 1.1.4 Erosion 4 1.2 Klassifizierung der Keramiken und der Verbundwerkstoffe 4 1.2.1 Glasmatrix-Keramiken 4 1.2.2 Polykristalline Keramiken 5 1.2.3 Komposit-Matrix-Keramiken 5 1.2.3.1 Grandio Blocs (RBC) 6 1.2.3.2 Enamic (PICN) 6 1.3 Professionelle Zahnreinigung und ihre Auswirkungen 7 2 Publikationsmanuskript 9 3 Zusammenfassung der Arbeit 23 4 Literaturverzeichnis 27 5 Anlagen 31 5.1 Ergänzende Informationen / Supplemental Material 31 5.2 Darstellung des eigenen Beitrags zur Publikationspromotion 33 5.4 Erklärung über die eigenständige Abfassung der Arbeit 35 5.5 Lebenslauf 37 5.6 Eigenes Publikationsverzeichnis 39 5.7 Danksagung 41 / The aim of this study was to investigate the influence of dental prophylaxis cleaning procedures and artificial aging on veneers in human teeth. The external marginal and internal tooth veneer as well as the restoration surfaces were examined. Thirty-two extracted premolars were restored with resin-based composite (RBC) and polymer-infiltrated ceramic network (PICN) veneers. Artificial aging by alternating thermocycling and subsequent prophylaxis procedure (glycine-based powder air polishing or ultrasonic scaling) was conducted for five consecutive cycles. The external marginal interface was examined by height profile measurements and the internal interface was investigated using micro X-ray computed tomography. In addition, the surface texture of the veneer surface was analyzed using confocal laser scanning microscopy. The application of both prophylaxis procedures resulted in a deepening of the marginal interface (10 μm ± 8 μm) for materials. Furthermore, the internal interface of PICN restorations showed marginal gaps after both treatments and artificial aging (16 μm ± 3 μm). In contrast to the RBC specimens, a significant increase in surface roughness was identified for PICN veneers after ultrasonic scaling. The marginal and internal interface regions in veneers fabricated from PICN and RBC were affected by prophylaxis procedures. Furthermore, it may result in increased veneer surface roughness, especially in PICN and after ultrasonic scaling, which might affect bioadhesion and longevity. After dental prophylaxis procedures, examination of the marginal and the internal interface as well as the veneer surface provides a precise insight into damage mechanisms and offers an assessment of longevity.:Abkürzungsverzeichnis III 1 Einführung 1 1.1 Nicht kariöse Zahnhartsubstanzdefekte 2 1.1.1 Abfraktion 3 1.1.2 Abrasion 3 1.1.3 Attrition 3 1.1.4 Erosion 4 1.2 Klassifizierung der Keramiken und der Verbundwerkstoffe 4 1.2.1 Glasmatrix-Keramiken 4 1.2.2 Polykristalline Keramiken 5 1.2.3 Komposit-Matrix-Keramiken 5 1.2.3.1 Grandio Blocs (RBC) 6 1.2.3.2 Enamic (PICN) 6 1.3 Professionelle Zahnreinigung und ihre Auswirkungen 7 2 Publikationsmanuskript 9 3 Zusammenfassung der Arbeit 23 4 Literaturverzeichnis 27 5 Anlagen 31 5.1 Ergänzende Informationen / Supplemental Material 31 5.2 Darstellung des eigenen Beitrags zur Publikationspromotion 33 5.4 Erklärung über die eigenständige Abfassung der Arbeit 35 5.5 Lebenslauf 37 5.6 Eigenes Publikationsverzeichnis 39 5.7 Danksagung 41

No / This article describes how an insight into the chemical and physical cues that affect bacterial adhesion and biofilm formation can provide ideas for creating successful antifouling or antimicrobial surfaces. To facilitate the design of new materials, the role of physical and chemical properties on bacterial adhesion is reviewed. The current approaches to reduce bacterial adhesion to various polymeric surfaces are discussed, as well as how multidisciplinary research on surface design and engineering may have an impact on both fundamental and applied microbiological science and technology.

No / This chapter describes the current approaches to reduce bacterial adhesion to various biomaterial surfaces, focusing on nonfouling surfaces through patterning and hydrophobicity plasma-assisted surface treatment and deposition; incorporation of antimicrobials, antibiotics, antibiofilms, and natural extracts that are either immobilized or released; dual function antimicrobial surfaces; incorporation of nonpathogenic bacteria, bacteriophages, and biofilm dispersal agents but also reduced bacterial adhesion through tissue integration. To facilitate the design of new materials, the role of physical, chemical, and biological surface properties on bacterial adhesion is reviewed in each case, as an insight into the chemical and physical cues that affect bacterial adhesion and biofilm formation can provide ideas for creating successful antifouling or antimicrobial surfaces. The application of these surfaces is explored based on the clinical needs and the market gaps. How multidisciplinary research on surface design and engineering may have an impact on both fundamental understanding of bacterial adhesion to biomaterials and applied biomaterial science and technology is finally discussed.

I fordonsindustrin är kemisk renlighet ett grundläggande kriterium för att säkerställa kvaliteten och hållbarheten hos den slutliga produkten. Kemisk renlighet kan defineras som den maximala nivån av kemiska föroreningar (t.ex. olja, fett, ytaktiva ämnen, kemikalier, etc.) som är tillåten på ytan av en produkt, men som tillåter produkten att fortfarande fungera som normalt. En ren yta fri från kemiska föreningar kommer således att säkerställa en robust binding mellan olika substrat. Syftet med den här rapporten är att undersöka och fastställa en kvantiativ method för att utvärdera kemisk renlighet för Formed in Place Gaskets (FIGP). De instrument som kommer att användas för att analysera nivån av kemisk kontaminering (rengöringsmedel) är: F-Scanner, SITA CleanoSpector och Krüss MSA One-Click SFE Mobile Analyzer. För att anvgöra hur nivån av kontaminering (rengöringsmedel) påverkar silikonens tätningsförmåga kommer dolly pull-off adhesionsprov och dragprov att användas. Resultatet visar att F-Scanner och SITA CleanoSpector kan skilja mellan olika nivåer av kontaminering (rengöringsmedel). Dock kan det från dolly pull-off adhesionsprov och dragprov inte dras någon slutsats om att en högre koncentration av kontaminering (rengöringsmedel) leder till en lägreadhesionsstyrka. / In the automotive industry chemical cleanliness is a fundamental criterion for ensuring the quality and durability of the final product. Chemical cleanliness can be defined as the maximum level of chemical contaminants (e.g. oil, grease, surfactants, chemical residues, etc.) permitted on the surface of a part, that still allows the part to function as normal. Hence, a clean surface that is free of chemical contaminants will ensure a robust adhesive bond between different substrates. The following thesis aims to investigate and establish a quantitative method to evaluate chemical cleanliness applicable to Formed in Place Gaskets (FIGP). Different instruments: F-Scanner, SITA CleanoSpector, and Krüss MSA One- Click SFE Mobile Analyzer, for surface analysis will be investigated and used to determine the level of chemical contamination (detergent) on the surface. To determine how the level of contamination (detergent) affects the adhesion properties of sealant, the dolly pull-off adhesion test and tensile test will be used. The results show that the F-Scanner and SITA CleanoSpector can distinguish between different levels of contamination (detergent). However, from the dolly pull-off adhesion test and tensile test, it cannot be concluded that a higher concentration of contamination (detergent) leads to a decrease in the adhesion strength of the sealant.

One of the most challenging goals in nanoparticle research is to develop successful protocols for the large-scale, simple and possibly low-cost preparation of morphologically pure nanoparticles with enhanced properties. The work presented in this thesis was focused on the synthesis, characterisation and testing of magnetic nanoparticles and their potential applications. There are a number of magnetic nano-materials prepared for specific applications such as metal oxide nanoparticles encapsulated with various porous materials including Fe₃O₄/Fe₂O₃ coated with soft bio-organic materials such as glycol chitosan and bovine serum albumin and hard materials such as silica (SiO₂) and zinc sulphide (ZnS). The preparation of these materials was achieved principally by bottom-up methods with different approaches including micro-emulsion, precipitation, electrostatic and thermolysis processes. The thesis also presents the uses of various analytical techniques for characterising different types of nano-materials including Attenuated Total Reflection Fourier Transformer Infrared Vibrational Spectroscopy (ATR-FTIR), Ultraviolet Visible- Near Infrared (UV-Vis-NIR) Spectroscopy, Zeta Potentiometric Surface Charge Analysis, Superconducting Quantum Interference Device (SQUID) and Vibration Sample Magnetometry (VSM) for magnetic analysis and powder X-Ray Diffraction (XRD) for crystallographic pattern analysis. There are many applications of magnetic nanoparticles, including nano-carriers for biological and catalytic reagents. The magnetic nanoparticles can facilitate separation in order to isolate the carriers from solution mixtures as compared to many inefficient and expensive classic methods, which include dialysis membrane, electrophoresis, ultracentrifugation, precipitation and column separation methods. There are six key chapters in this thesis: the first chapter introduces the up-to-date literature regarding magnetic nano-materials. The uses of magnetic nano-materials in drug binding and for protein separation are discussed in the second and third chapters. The fourth chapter presents the use of magnetic nanoparticle in conjunction with a photo-catalytic porous overlayer for the photo-catalytic reduction of organic molecules. The fifth chapter describes different analytical techniques used for the characterisation of nanoparticles and the underlying principles and the experimental details are also given. The sixth chapter summarises the results and provides an overview of the work in a wider context of future applications of magnetic nanoparticles.

This thesis describes investigations into the role of non-stoichiometry in the surface and bulk properties of SrTiO₃ single crystals. A family of (n×n) reconstructions, where n = 2, 3, 4, 5, 6 are produced by argon ion sputtering of the SrTiO₃ (111) single crystals and subsequent annealing in UHV or in an oxygen rich environment. The sputtering process introduces defects or oxygen vacancies in the surface region of the sample, whilst the annealing gives rise to surface reconstructions. The surface preparation conditions such as sputtering time, annealing temperature and environment are optimized to obtain various reconstructions in a controlled and reproducible manner. High resolution STM images of these reconstructions are also obtained and utilized in the investigation of the surface reactivity. Fullerene molecules are deposited on the reconstructed surfaces to elucidate the surface reactivity through template assisted growth. Fullerene molecules are first deposited with substrate surfaces held at room temperature. Being the most highly reduced among the (n×n) family, the 5×5 reconstruction significantly influenced the growth of fullerenes. Both C₆₀ and C₇₀ adsorb as individual molecules and produce clusters with magic numbers. The 4×4 and 6×6 reconstructed surfaces encourage the formation of close-packed structures upon the deposition at room temperature. When the surface covered with fullerenes is heated to a temperature of around 200 °C, epitaxial islands are observed. The 6×6 reconstructed surface appeared to be less reactive than the 4×4. Electrical transport, cathodoluminescence (CL) and electron spin resonance (ESR) experiments are also carried out to investigate the effect of oxygen vacancies on the bulk properties of UHV annealed SrTiO₃ single crystals. Thermal reduction leads to carrier doping of the material, which not only gives rise to electrical conduction but also induces room temperature luminescence. Both the electrical conductivity and CL intensity increases with annealing time. The work presented in this thesis provides insight into the defect driven properties in both the surface and bulk of SrTiO₃ single crystals, which could play an important role in the development of oxide-based electronic devices.

The initiation and high resolution control of surface confined chemical reactions would be both beneficial for nanofabrication and fundamentally interesting. In this work, spatially controlled scanning probe directed organometallic coupling, patterned functional protein immobilisation and highly localised reversible redox reactions on SAMs were investigated. Catalytically active palladium nanoparticles were mounted on a scanning probe and an appropriate reagent SAM was scanned in a reagent solution. This instigated a spatially resolved organometallic coupling reaction between the solution and SAM-phase reagents. Within this catalytic nanolithography a spatial resolution of ~10nm is possible, equating to zeptomole-scale reaction. The methodology was applied to reactions such as Sonogashira coupling and local oligo(phenylene vinylene) synthesis. By altering the experimental protocols, relating probe scan velocity to reaction yield and characterising the nanopattern, a PVP matrix model describing a proposed mechanism of catalytic nanolithography, was presented. Though ultimately limited by probe deactivation, calculations indicated that activity per immobilised nanoparticle is very high in this configuration. For biopatterning, surface nanopatterns defined by carboxylic functionality were generated from methyl-terminated SAMs by local anodic oxidation (LAO) initiated by a conductive AFM probe. By employing suitable linker compounds, avidin and Stefin-A quadruple Mutant (SQM) receptive peptide aptamers were patterned at sub-100nm resolution. The multiplexed sensing capability of an SQM array was demonstrated by reacting generated patterns with single or a mixture of multiple antibodies. The reversible redox conversion and switching of reactivity of hydroquinone-terminated SAMs was electrochemically demonstrated prior to an application in redox nanolithography. In this methodology, spatially controlled probe-induced in situ "writing" and "erasing" based on reversible redox conversion were conducted on hydroquinone terminated SAM. In combination with dip-pen nanolithography, a novel method of redox electro-pen nanolithography was designed and the method’s application for lithography was examined.

This thesis reports on the elemental growth of oxide thin films including TiO_x, BaO_x and Ba_xTi_yO_z by Ti/Ba deposition and oxidation. The films were grown on two different substrates, Au(111) and SrTiO₃(001), and studied using a variety of surface characterisation techniques. On the reconstructed Au(111) surface, three different TiO_x structures were obtained with increasing Ti amounts deposited: a (2 × 2) Ti₂O₃ honeycomb structure, a pinwheel structure that is the result of a Moiré pattern, and a triangular island TiO_1.30 structure. The structures arise from raised Ti coverages and have increased Ti densities. Although Ba deposited on the reconstructed Au(111) has a weak interaction with the substrate, the BaO_x thin films can grow epitaxially and lift the Au(111) reconstruction. Two well-ordered phases, a (6 × 6) and a (2√3 × 2√3) BaO_x structure, were obtained which may have octopolar-based surface structures. For Ba & Ti deposition on Au(111), a locally ordered (5 × 5) BaxTiyOz structure was observed in the sub-monolayer regime. What is more interesting is the possible formation of a BaO-TiO surface alloy with short-range ordering achieved by Ba deposition on the (2 × 2) Ti₂O₃-templated Au(111) surface. This is the first time that surface-alloying has been observed for oxides. When Ti is deposited onto the SrTiO₃(001) surface, it is incorporated into the substrate by forming a variety of Ti-rich SrTiO₃ surface reconstructions, such as c(4 × 2), (6 × 2), (9 × 2) and (√5 ×√5)-R26.6°. Ti deposition provides a completely different route to obtaining these reconstructions at much lower anneal temperatures than the previously reported preparation procedures involving sputtering and annealing the SrTiO₃ sample. Anatase islands with (1 × 3) and (1 × 5) periodicities were also formed by increasing the Ti deposition amount and post-annealing. Reconstructed SrTiO₃ substrate surface has a lattice that differs from the bulk crystal and affects the epitaxial growth of BaO, however, a locally ordered BaO_x structure was observed on the sputtered substrate with a growth temperature of 300 °C. Depositing Ba & Ti on SrTiO₃(001) results in the formation of BaO_x clusters and the Ti incorporation into the substrate, forming the familiar Ti-rich SrTiO₃ surface reconstructions.

Grâce à ses propriétés d’antioxydant, d’anti-usure et éventuellement d’extrême pression le dithiophosphate de zinc (ZDDP) fait partie des additifs les plus utilisés dans les lubrifiants pour moteurs thermiques. De nos jours, dans un souci de respect de l’environnement, de nouveaux lubrifiants possédant de bonnes performances en lubrification (frottement faible et usure limitée) sont développés en prenant compte des limitations d’utilisations actuelles du ZDDP. L’idée étant de réduire dans ceux-ci les teneurs en phosphore et soufre (Normes euros VI), éléments essentiels du ZDDP qui endommagent les pots catalytiques. L’objectif de cette thèse est l’étude du comportement tribologique du phosphate de zinc di alkyl (ZP) en comparaison avec le ZDDP. La méthodologie expérimentale étudiée pour comprendre le mécanisme d’action de ces additifs, associe des essais de frottement à descaractérisations physico-chimiques des surfaces frottantes après essais.Cette comparaison a été effectuée en fonction de la température (25°C et 100°C), la vitesse de glissement (25, 50 et 100 mm/s) et la concentration en additif (200 et 600 ppm dephosphore). Les meilleures actions anti-usure sont obtenues avec le ZDDP pour une température de 100°C et une vitesse de glissement de 100 mm/s et le ZP pour une température de 25°C et une vitesse de glissement de 25 mm/s. Les analyses de surface XPS, AES, XANES et MET-EDX ont permis de mettre en évidence la présence d’un film protecteur constitué principalement de phosphate de zinc, ceci pour les deux additifs.Une synergie de comportement tribologique a été mise en évidence avec un lubrifiantconstitué de ZP (usure faible) et d’oléate d’urée (frottement faible). Des essais complémentaires sur un tribomètre dynamique ont permis d’étudier le niveau de frottement du tribofilm formé à partir du ZDDP. Le caractère visqueux du tribofilm de ZDDP a été mis en évidence. / Thanks to its antioxidant, anti-wear and extreme pressure properties, zinc dialkyldithiophosphate (ZDDP) is nowadays the most used anti-wear additives in engine oil. Due to environmental protection concerns, new lubricants with good tribological performances (low friction and low wear) are developed. This research aims to evaluate the current limitations of ZDDP and to find alternative environmentally friendly solutions. Thus, the target is to reduce the quantity of phosphorus and sulphur in lubricants, two essential elements of ZDDP molecule that damage catalytic. The objective of this thesis is to study tribological behavior of zinc phosphate di alkyl (ZP) in comparison to ZDDP. The experimental method performed is the coupling of friction test with surface physico-chemical characterisation of rubbing surface after tests.This comparison carried out according to the temperature (25°C and 100°C), the sliding speed (25, 50, 100 mm/s) and additives concentrations (200 and 600 ppm). The best anti-wear efficiency is obtained with the ZDDP additive at 100°C - 100 mm/s and with the ZP at 25°C - 25 mm/s. For both additives and under these conditions, tribofilms are mainly made of zinc phosphate.A tribological synergy are obtained with a lubricant contained ZP (low wear) and oleyl urea (low friction). Complementary tests were made on a original dynamic tribometer for a better understanding of ZDDP tribofilm friction behavior. The viscous character of ZDDP tribofilm was obtained.

Transparent conducting oxides (TCOs) combine optical transparency in the visible region with a high electrical conductivity. In2O3 doped with Sn (widely, but somewhat misleadingly, known as indium tin oxide or ITO) is at present the most important TCO, with applications in liquid crystal displays, touch screen displays, organic photovoltaics and other optoelectronic devices. Surprisingly, many of its fundamental properties have been the subject of controversy or have until recently remained unknown, including even the nature and magnitude of the bandgap. The technological importance of the material and the renewed interest in its basic physics prompted the research described in this thesis. This thesis aims (i) to establish conditions for the growth of high-quality In2O3 nanostructures and thin films by oxygen plasma assisted molecular beam epitaxy and (ii) to conduct comprehensive investigations on both the surface physics of this material and its structural and electronic properties. It was demonstrated that highly ordered In2O3 nanoislands, nanorods and thin films can be grown epitaxially on (100), (110) and (111) oriented Y-stabilized ZrO2 substrates respectively. The mismatch with this substrate is -1.7%, with the epilayer under tensile strain. On the basis of ab initio density functional theory calculations, it was concluded that the striking influence of substrate orientation on the distinctive growth modes was linked to the fact that the surface energy for the (111) surface is much lower than for either polar (100) or non-polar (110) surfaces. The growth of In2O3(111) thin films was further explored on Y-ZrO2(111) substrates by optimizing the growth temperature and film thickness. Very thin In2O3 epilayers (35 nm) grew pseudomorphically under high tensile strain, caused by the 1.7% lattice mismatch with the substrate. The strain was gradually relaxed with increasing film thickness. High-quality films with a low carrier concentration (5.0  1017 cm-3) and high mobility (73 cm2V-1s-1) were obtained in the thickest films (420 nm) after strain relaxation. The bandgap of the thinnest In2O3 films was around 0.1 eV smaller than that of the bulk material, due to reduction of bonding-antibonding interactions associated with lattice expansion. The high-quality surfaces of the (111) films allowed us to investigate various aspects of the surface structural and electronic properties. The atomic structure of In2O3 (111) surface was determined using a combination of scanning tunnelling microscopy, analysis of intensity/voltage curves in low energy electron diffraction and first-principles ab initio calculations. The (111) termination has an essentially bulk terminated (1 × 1) surface structure, with minor relaxations normal to the surface. Good agreement was found between the experimental surface structure and that derived from ab initio density functional theory calculations. This work emphasises the benefits of a multi-technique approach to determination of surface structure. The electronic properties of In2O3(111) surfaces were probed by synchrotron-based photoemission spectroscopy using photons with energies ranging from the ultraviolet (6 eV) to the hard X-ray regime (6000 eV) to excite the spectra. It has been shown that In2O3 is a highly covalent material, with significant hybridization between O and In orbitals in both the valence and the conduction bands. A pronounced electron accumulation layer presents itself at the surfaces of undoped In2O3 films with very low carrier concentrations, which results from the fact the charge neutrality level of In2O3 lies well above the conduction band minimum. The pronounced electron accumulation associated with a downward band bending in the near surface region creates a confining potential well, which causes the electrons in the conduction band become quantized into two subband states, as observed by angle resolved photoemission spectra (ARPES) Fermi surface mapping. The accumulation of high density of electrons near to the surface region was found to shrink the surface band gap through many body interactions. Finally epitaxial growth of In2O3 thin films on α-Al2O3(0001) substrates was investigated. Both the stable body centred cubic phase and the metastable hexagonal corundum In2O3 phase can be stabilized as epitaxial thin films, despite large mismatches with the substrate. The growth mode involves matching small but different integral multiples of lattice planes of the In2O3 and the substrate in a domain matching epitaxial growth mode.