Oxide thin films and bimetallic model catalysts have been studied using metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), low energy ion scattering spectroscopy (LEISS), X – ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) under ultra high vacuum (UHV) conditions. Of particular interest in this investigation was the characterization of the surface morphology and electronic/geometric structure of the following catalysts: SiO2/Mo(112), Ag/SiO2/Mo(112), Au–Pd/Mo(110), Au–Pd/SiO2/Mo(110), and Pd– Sn/Rh(100). Specifically, different types of oxide surface defects were directly identified by MIES. The interaction of metal clusters (Ag) with defects was examined by work function measurements. On various Pd related bimetallic alloy surfaces, CO chemisorption behavior was addressed by IRAS and TPD. Observed changes in the surface chemical properties during the CO adsorption-desorption processes were explained in terms of ensemble and ligand effects. The prospects of translating this molecular-level information into fundamental understanding of ‘real world’ catalysts are discussed.

Low density surface sites are believed to play an important role in processes occurring on oxide surfaces, including catalysis and particle and film nucleation. However, our understanding of the role and chemical nature of such sites play in these processes is limited by the inability to experimentally detect minority surface sites in many oxide systems. The research performed for this dissertation is focused on developing a surface science technique utilizing fluorescent molecules to titrate specific surface sites on planar fused silica surfaces in an ultra-high vacuum (UHV) environment. High sensitivity (low detection limit) is achieved by using derivatives of perylene, a high quantum yield fluorophore. High specificity is attained by employing perylene derivatives with functional groups designed to react chemically with and titrate various sites. In addition to titrating the well-studied hydroxyl sites with perylene-3-methanol (density ~ 10¹⁴ cm⁻²), which is used to establish the technique, the detection of strained siloxane sites (~ 10¹² cm⁻²), ) with perylene-3-methanamine and oxygen vacancy sites (~ 10¹¹ cm⁻²), ) with 3-vinyl perylene is demonstrated. Particle nucleation on oxides is suspected to involve defects that trap adatoms and form critical nuclei. Using this technique, the possible role strained siloxane and oxygen vacancy sites play in trapping adatoms during the nucleation of Ge nanoparticles on silica surfaces is examined. / text

This diploma is focused on analyse existing method usable for detection surface defects of grindling surface. Also suggests and practically testing new method for detection surface defects of grindling surface

The development and control of nanoscale properties is a major goal in science and technology; for the development of such technologies it is important that there are experimental techniques which allow the monitoring of development processes in real time and in a range of environments. With this in mind much effort has been invested in the development of surface sensitive optical probes. One such technique, reflection anisotropy spectroscopy (RAS), has been applied successfully to a number of different problems since its development in the mid 1980’s. RAS as a surface specific technique is very sensitive to small changes to surface morphology, electronic structure and molecular orientation. This makes RAS a useful technique to study nanoscale changes occurring at surfaces and it is applied here to three such systems, in an attempt to develop a better understanding of both the systems and the technique. Surface defects arising from thermal processing and etching of the sample are considered and are found to have a significant effect on both the electronic structure and the morphology of the surface. The time and temperature dependences of the RAS signatures allow the monitoring of surface dynamic processes. The deposition of a monolayer of adsorbate molecules onto the surface allows a new interface to be created. Monitoring the evolution of this surface during deposition provides information about both the substrate surface and the adsorba te covered surface; a theoretical framework has been outlined to show how the sources of anisotropy from multiple thin film layers combine to give a RAS signal. Azimuth dependent RAS (ADRAS) is known to provide information on surface symmetry and can be used to determine molecular orientation. There are also a number of other angles which affect the RA spectrum from a sample. A tilted molecule causes a breakdown in surface symmetry; this work shows how such an effect can be observed.

Excessive CO2 emissions can negatively impact society and our planet. Reduction of CO2 is one potential avenue for its abatement. One of the most significant challenges to reducing CO2 is its extremely stable linear form. Experimentally, Cu/TiO2 has shown promise for CO2 photocatalytic reduction. Dispersed atomic catalysts can achieve high catalytic efficiency on a per atom basis. Active sites also typically having lower coordination number, and therefore may be more reactive. Using density functional theory and experimental techniques, we have investigated the role of surface oxygen vacancies (Ov) and photoexcited electrons on supported single atom catalysts and CO2 reduction. Cu atoms with Ov have shown to aid in the process of bent, anionic CO2 formation. In the first step involving CO2 dissociation (CO2* --> CO* + O*), a single Cu atom in Ov lowered the activation barrier to 0.10 - 0.19 eV, which could enable fast reduction of CO2 even at room temperature, in agreement with experimental findings. A photoexcited electron model was shown to readily promote Cu binding to the surface vacancy, and CO2 adsorption and direct dissociation. Finally, we briefly compare our results to calculations of supported single Pt atoms to determine how metals besides Cu may behave as photocatalysts for CO2 reduction, and we found a single Pt with Ov can promote CO2 dissociation. Our results show that tailoring TiO2 surfaces with defects in conjunction with atomic catalysts may lead to useful catalysts in the photoreduction of CO2.

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In this dissertation, four test approaches were developed to characterize the adhesion performance and durability of adhesive bonds for specific applications in areas spanning from structural adhesive joints to popular confectionaries such as chewing gum. In the first chapter, a double cantilever beam (DCB) specimen geometry is proposed for combinatorial fracture studies of structural adhesive bonds. This specimen geometry enabled the characterization of fracture energy vs. bondline thickness trends through fewer tests than those required during a conventional "one at a time" characterization approach, potentially offering a significant reduction in characterization times. The second chapter investigates the adhesive fracture resistance and crack path selection in adhesive joints containing patterns of discreet localized weak interfaces created using physical vapor deposition of copper. In a DCB specimen tested under mode-I conditions, fracture energy within the patterned regions scaled according to a simple rule of mixture, while reverse R-curve and R-curve type trends were observed in the regions surrounding weak interface patterns. Under mixed mode conditions such that bonding surface with patterns is subjected to axial tension, fracture energy did not show R-curve type trends while it was observed that a crack could be made to avoid exceptionally weak interfaces when loaded such that bonding surface with defects is subjected to axial compression. In the third chapter, an adaptation of the probe tack test is proposed to characterize the adhesion behavior of gum cuds. This test method allowed the introduction of substrates with well-defined surface energies and topologies to study their effects on gum cud adhesion. This approach and reported insights could potentially be useful in developing chewing gum formulations that facilitate easy removal of improperly discarded gum cuds from adhering surfaces. In the fourth chapter we highlight a procedure to obtain insights into the long-term performance of silicone sealants designed for load-bearing applications such as solar panel support sealants. Using small strain constitutive tests and time-temperature-superposition principle, thermal shift factors were obtained and successfully used to characterize the creep rupture master curves for specific joint configurations, leading to insights into delayed failures corresponding to three years through experiments carried out in one month. / Ph. D.

I det här arbetet har tätningsmetoder för aluminiumhus undersökts. Arbetet avgränsades mot fordonsindustrin och statiska packningar. Examensarbetet tar upp flänskonstruktionens inver-kan på tätheten och packningen, packningstyper, ytjämnhetens inverkan på packningsmateri-al, porositet, relativ materialkostnad och fästelement.Arbetet grundar sig på en litteraturstudie och intervjuer med berörda personer på företaget. Även praktiska prover genomfördes på ett urval av material från leverantörer där material exponerades för olika kemikalier och därefter dragprovades.Materialet som insamlats genom intervjuer och litteraturstudien vittnar om att många paramet-rar påverkar vilka tätningsmetoder som är möjliga att använda. Det är inte bara materialval som det behövs tas hänsyn till. Faktorer som flänskonstruktioner, materialkostnader, ytdefek-ter, fästelement samt porositet har en stor påverkan. De praktiska proverna vittnar om att olika kemikalier har olika stor inverkan på materialens mekaniska egenskaper och svullnad.Slutligen föreslås ett par packningsmaterial som är lämpliga för företaget att använda i deras produkter. / In this work sealing methods for aluminum housing have been investigated. The work was delimited to the automotive industry and static gaskets. The thesis brings up how the flange impacts on the sealing capability and the gasket, sealing types, the surface impact on gasket materials, porosity, relative material cost and fasteners.The work is based on a literature study and interviews with concerned people at the company. Practical samples were carried out on a number of materials from suppliers and the materials where exposed to different chemicals and then tensile tested.The materials that were collected through interviews and the literature study testify that many parameters influence the possible sealing methods. It’s not just the material itself that needs to be taken into account. Factors like flange design, material cost, surface defects, fasteners and porosity have a great impact. The practical sample testifies that different chemicals have dif-ferent impact on the mechanical properties and swelling of the material.Finally, a couple of sealing materials are suggested that are suitable for the company to use in their products.

Les câbles d’acier sont utilisés comme renforts au sein des pneumatiques poids lourds, et servent notamment à supporter les efforts dus à la pression de gonflage et au poids du véhicule. Un câble est un ensemble de fils d’acier perlitique assemblés en hélices sur différentes couches. Il existe donc de nombreuses possibilités d’assemblage pour définir l’architecture d’un câble. Lors de leur sollicitation en service, les câbles sont soumis à des chargements cycliques à l’origine d’un endommagement en fatigue. Dans un contexte de réduction de la consommation et d’allègement des véhicules, la compréhension des mécanismes impliqués représente donc un enjeu majeur pour les manufacturiers de pneumatiques, en vue d’optimiser l’architecture des câbles vis-à-vis de la tenue en fatigue. Un essai de flexion cyclique représentatif de la sollicitation en service a été mis au point. Les éprouvettes testées sont des nappes composites constituées de câbles alignés au sein d’une matrice de gomme. Des essais interrompus à différents stades de l’endommagement suivis d’observations ex-situ (tomographie à rayon X, MEB) ont été réalisés. Un modèle de simulation par éléments finis de la nappe composite a été développé en vue d’étudier les interactions filgomme. La comparaison des observations aux simulations a permis de comprendre la cinétique de l’endommagement des renforts lors d’une sollicitation de flexion cyclique.L’étude de chacun des mécanismes susceptibles de contribuer à l’endommagement d’un câble a permis d’expliquer la meilleure tenue en fatigue des architectures pénétrées par la gomme. Un outil probabiliste de prédiction de la durée de vie des câbles basé sur la propagation des défauts en surface des fils a été développé. / Steel cables are used as reinforcements in heavy truck tires, in particular to support the forces resulting from the tire pressure and the vehicle's weight. A cable is a set of pearlitic steel wires assembled in helical form on different layers. There are therefore many assembly possibilities to define the cable architecture. The cables are subjected to cyclic loadings during service, resulting in fatigue damage. In a context of reduced fuel consumption and lighter vehicles, understanding the mechanisms involved is thus a major challenge for tire manufacturers, in order to optimize the architecture of cables with respect to fatigue resistance. A cyclic bending test representative of mechanical in-service loading has been developed. The tested specimens are composite layers made of cables aligned within an elastomer matrix. Interrupted tests at different stages of damage followed by ex-situ observations (X-ray tomography, SEM) were performed. A finite element model of the composite layer has been developed in order to understand wire-rubber interactions. The comparison of the observations with the simulations made it possible to understand the kinetics of cable damage during cyclic bending loading.The study of each of the mechanisms likely to contribute to the cable damage has made it possible to explain the better fatigue resistance of the architectures penetrated by the rubber. A stochastic cable fatigue life model based on wire surface defect propagation has been developed.

<p>In industrial use of paint systems a swift processing is crucial. Another very important issue is to improve the quality of the final coating. This report investigates the film formation process of powder coatings, specially the spreading of individual powder particles. The obtained results can be used to understand and control the film formation process. In this way the desired levelling can be achieved and thus the desired gloss or other surface characteristics that may be required. This means that the method could be used when evaluating different polymer and additive combinations that could be used to change film formation behaviour or curing time for powder coating systems to suit various substrates. It makes it possible to avoid and minimize different surface defects as orange peel or cratering in the powder coated film.</p><p>We used a reflection optical microscope to better understand the film formation process and especially the spreading of a powder melt on surfaces with various surface energies. The obtained data were: the particle diameter, the area, area ratio and the contact angle of the powder particle as a function of time and temperature. This information can be used to derive the surface tension of any powder melt.</p><p>In this report we evaluate the dependencies of temperature, heat rate and surface energy for powder coatings on different substrates. The method provides information that can be used to optimize the film formation of a specific powder coating/substrate combination. This method can be used to evaluate the powder spreading and levelling on different substrates from a surface tension point of view.</p><p>We found, as expected, that the powder flows out on a hydrophilic surface and is inhibited by a hydrophobic. The increase of the area ratio on a hydrophilic surface was about five times as the initial area coverage and on a hydrophobic surface only two times the initial area coverage. The contact angle between the melted powder particle on the different surface types could be calculated. The melt surface tension could be calculated since three substrates surfaces with various surface energies were used. The melt surface tension was found to be about 18.5 mN/m.</p> / <p>Sammanfattning</p><p>Vid industriell användning av ett färgsystem är det viktigt med en snabb och smidig målningsprocess. En viktig del är att förbättra kvaliteten på den färdiga ytan. Denna rapport undersöker filmbildningsprocessen för pulverfärg, närmare bestämt spridningen av individuella pulverpartiklar. Resultaten från utvärderingen av denna metod kan användas för att bättre förstå och få kontroll över filmbildningsprocessen. Med denna undersökningsmetod kan den önskade utslätningen uppnås och därmed den önskade glansen eller annan yteffekt som kan vara önskvärd.</p><p>Metoden kan användas för att utvärdera olika polymer- och additivkombinationer som kan användas för att ändra filmbildningens uppförande eller bestämma härdningstiden för en pulverfärg att passa ett visst substrat. Metoden gör det möjligt att förhindra och minska olika ytdefekter såsom apelsinskals- eller kratereffekter i pulverfärgens yta.</p><p>Ett optiskt reflectionsmikroskop användes för att bättre kunna förstå filmbildningsprocessen och särskilt spridningen av smält pulver på substrat med olika ytenergier. De mätdata vi fick var partikeldiameter, area, areaförändring och kontaktvinkeln för pulverpartiklar som funktion av tid och temperatur. Ur denna information kunde pulversmältans ytenergier härledas.</p><p>I denna rapport utvärderas pulvrets beroende av temperatur, uppvärmning och ytenergi på olika substrat. Denna metod ger information som kan användas för att optimera filmbildningen av en specifik kombination av pulverfärg och substrat. Denna metod kan också användas för att utvärdera pulverspridning och utjämning av färgfilmen på olika substrat med avseende på ytenergierna.</p><p>Som förväntat flyter pulvret ut på hydrofila ytor och utflytningen ändras på en hydrofob yta. På en hydrofil yta sprider sig partikeln till fem gånger den ursprungliga arean över substratet och motsvarande två gånger för en hydrofob yta. Kontaktvinkeln mellan en smält pulverpartikel på olika sorters substrat från utförda mätningar beräknas utifrån utförda mätningar. Kontaktvinklar mellan pulver och olika substrat kan användas för att beräkna smältans ytspänning. Smältans ytspänning kan beräknas då experiment gjorts på tre sorters ytor med olika kända ytenergier. Smältans ytspänning var 18,5 mN/m.</p><p>Slutsatsen är att det går att observera och utvärdera resultaten av utsmältningsförloppet för pulverfärg med denna metod.</p>