This study addressed five key applications of paper spray mass spectrometry (PS-MS): (i) comparative analysis of the microporous substrate with the cellulose-based substrate in drug detection; (ii) detection of more than 190 fentanyl analogs with their fragmentation pattern can be implemented in the future reference for quicker, accurate and sensitive determination; (iii) exploring sweat in a fingerprint to be considered an alternate method to recognize non-invasive markers of metabolites, lipids, narcotics, and explosive residues that can be used in forensic testing applications; (iv) extending and improving better, cost-effective and quick real-time monitoring of the diseased stage using biofluid samples to obtain vastly different lipid information in viral infection such as COVID-19; and (v) mass spectral detection in chemical warfare agent (CWA) stimulant gas exposure with microporous structure absorbency capabilities in air quality monitoring. This novel synthetic material is known as Teslin® (PPG Industries), consisting of a microporous polyolefin single-layered silica matrix, can be used for precise, sensitive, selective, and rapid sample analysis with PS-MS. The Teslin® substrate provided longer activation time for samples and an active signal with a higher concentration of ion formation and mobility compared to cellulose-based papers. Direct analysis of multiple samples showed that, besides being more sensitive to the study and highly efficient with less sample size and spray solvent needed, Teslin® had less interaction with paper source molecules. For less than 60 seconds of processing time, PS-MS can be used as a rapid detection tool, with limited sample preparation requiring less than one microgram of the sample. Overall, the data in this analysis indicate the capacity of the PS-MS as an alternative approach for direct chemical analysis in many applications. Specifically, the waterproof and microporosity characteristics of Teslin® have proven its usefulness in detecting a variety of chemical components in liquid, solid, and gaseous phases without requiring any chemical treatment or substrate alteration.

Disertační práce se zabývá mechanickou odezvou vrstevnatých kompozitů pro stomatologické aplikace. Různé skladby vrstev a různé částicové a vláknové kompozity jsou studovány v tříbodovém ohybu za pokojové teploty. Tyto výsledky jsou korelovány s výstupy dynamické termomechanické analýzy (DMTA) a optické analýzy (vysokorychlostní video záznam, SEM). Exeprimentální data byla použita pro srovnání s výsledky analytických a numerických modelů s cílem určit nejvhodnější model pro predikci základních mechanických vlastností vrstevnatých kompozitů. Na základě těchto analýz jsou navržena základní pravidla pro klinické použití vrstevnatých kompozitů ve stomatologických aplikacích jako jsou minimálně invazivní můstky nebo stabilizační dlahy.

Ce travail de recherche a pour objectif de présenter la conception de tunnels au moyen de la méthode hyperstatique aux coefficients de réaction (HRM). Les modèles développés par la méthode HRM sont tout d'abord proposés pour étudier le comportement de tunnels en forme de fer à cheval inversée dans différentes conditions, par exemple en considérant deux cas de charge, deux géométries différentes de revêtement de tunnel, deux cas de coefficients de réaction différents, changement de la rigidité des coefficients de réaction, conditions de sol multicouches, surcharges en surface et sol saturés. Les modèles présentés permettent d’aboutir à des prévisions qualitatives avec une efficacité de calcul élevée par rapport à la modélisation numérique en différences finies. Une analyse paramétrique est ensuite réalisée pour estimer le comportement du revêtement de tunnel en forme de fer à cheval dans un grand nombre de cas couvrant les conditions généralement rencontrées dans la pratique. Ensuite, en prenant comme exemple un tunnel métropolitain à deux voies, une série de fonctions mathématiques est déduite et utilisée dans le processus d'optimisation d’un tunnel de forme complexe, ce qui offre aux concepteurs de tunnels un support théorique leur permettant de choisir la forme optimale du tunnel à mettre en oeuvre. L’effet de différents paramètres, tels que le coefficient des terres au repos, le module d’Young du sol, la profondeur du tunnel, les surcharges en surface, sur les efforts internes et la forme du tunnel. Dans la dernière partie du manuscrit, l’influence d’un changement de température sur les efforts dans le revêtement d’un tunnel circulaire au moyen de la méthode HRM est étudiée en tenant compte de différents facteurs, tels que l’épaisseur du revêtement de tunnel, le module d’élasticité du revêtement et le coefficient de dilatation thermique du sol. / This research work aims to present the design of tunnel by means of the Hyperstatic Reaction Method (HRM). The models developed by the HRM method are firstly proposed for investigating the behaviour of U-shaped tunnels under different conditions, considering two load cases, two different geometries of U-shaped tunnel lining, two different cases of springs, change of the spring stiffness, multi-layered soil conditions, surcharge loading, and saturated soil masses. The presented models permit to obtain good predictions with a high computational efficiency in comparison to finite difference numerical modelling. Then a parametric analysis has permitted to estimate the U-shaped tunnel lining behaviour in a large number of cases which cover the conditions that are generally encountered in practice. Thereafter, taking a twin-lane metro tunnel as an example, a series of mathematical functions used in the optimization progress of sub-rectangular tunnel shape is deduced, which gives to tunnel designers a theoretical support to choose the optimal sub-rectangular tunnel shape. The effect of different parameters, like the lateral earth pressure factor, soil Young’s modulus, tunnel depth, surface loads, on the internal forces and shape of sub-rectangular tunnel is then given. In the last part of the manuscript, the influence of a temperature change on the lining forces of circular tunnel by means of the HRM method is investigated, considering different factors, such as the tunnel lining thickness, lining elastic modulus and ground coefficient of thermal expansion.

Ce travail a pour objectifs de comprendre et de prédire les gauchissements de plaquettes en silicium durant le procédé de fabrication des composants électroniques de type PTIC. Ces gauchissements sont en partie responsables de plusieurs problèmes de productivité. Cette étude repose sur un couplage entre les calculs analytiques, la modélisation par élément finis et l’expérimentation. La caractérisation mécanique des films minces constituant l’empilement a été effectuée par des techniques spécifiques comme la nanoindentation complétée par des modélisations numériques. Les contraintes intrinsèques dans les films minces ont été déterminées en couplant des mesures de gauchissements des plaquettes et des calculs par éléments finis. Les valeurs du module d’Young et des contraintes intrinsèques obtenues constituent des variables d’entrée pour calculer les gauchissements de la plaquette par des approches analytiques et numériques. La complexité des structures (plaquettes avec des milliers de puces) a nécessité l’utilisation des modèles d’homogénéisation pour estimer numériquement les gauchissements. Les résultats obtenus ont permis de prédire les gauchissements à l’échelle des plaquettes dans le but d’optimiser les conditions de fabrication afin de minimiser les risques d’apparition des problèmes mécaniques. / The aim of this work is to understand and predict the warpage of silicon wafers during the fabrication process of PTIC microelectronic components. The warpages are partially responsible for several productivity problems. This study is done by coupling analytical calculation, finite element modeling and experimentation. The mechanical characterization of thin films constituting the multi-layered stack has been carried out by an experimental method nanoindentation with the help of a finite element model. The intrinsic stress in the thin films has been determined by coupling measurements of the wafer warpage and a finite element model. The obtained Young’s modulus and intrinsic stress are used to feed the database for calculating the wafer warpage by analytical and numerical approaches. The complexity of the structures (thousands of components in the wafer) required the use of homogenized models to calculate the wafer warpage. These results obtained allow the prediction of the wafer-level warpage in order to optimize the fabrication process flow and therefore reduce the risk of the mechanical problem.

In this bachelor thesis we report on our numerical investigations into the optimal design of protective multi-layer coatings subject to an external force of Hertzian form. In view of mechanical reliablity and durability of the substrate and the coating we aim to find the best composition of given materials with the least computational effort. Numerical studies are carried out using the simulation software ELASTICA being the first non-FEM approach for the computation of stress fields within multi-layer coated, elastic materials. We thereby made use of the massive parallel computer CLiC (Chemnitzer Linux Cluster) where we ran our Windows based application in a Wine Environment. The outcome of the optimization is in general very sensitive towards the input parameters(i.e., material properties) which are not always available in the desired accuracy. However, the scheme outlined in this work is shown to produce very good results and could contribute a great deal to find optimal solutions for real applications. / Diese Bachelorarbeit befasst sich mit numerischen Untersuchungen zum optimalen Design von schützenden Mehrschichtbeschichtungen, die einer externen, Hertzschen Last ausgesetzt sind. Hinsichtlich der mechanischen Zuverlässigkeit und Haltbarkeit von Substrat und Beschichtung, versuchen wir die beste Zusammensetzung von gegebenen Materialien mit möglichst geringem Rechenaufwand zu finden. Die numerischen Berechungen wurden mit der Simulationssoftware ELASTICA durchgeführt, welches das erste kommerzielle, nicht-FEM-basierte Programm zur Berechnung von Stressfeldern innerhalb mehrfach beschichteter, elastischer Materialien darstellt. Dafür benutzten wir auf dem massiven Parrallelrechner CLiC (Chemnitzer Linux Cluster) unsere Windows basierte Anwendung unter der Emulationssoftware Wine. Das Ergebnis der Optimierung hängt im allgemeinen sehr stark von der Qualität der Eingangsparameter (z.B. Materialeigenschaften) ab, welche nicht immer in der erwünschten Genauigkeit vorliegen. Es wird gezeigt, dass die in dieser Arbeit vorgestellte Vorgehensweise sehr gute Resultate liefert und für reale Anwendungen einen äusserst ressourcenschonenden Lösungsweg darstellt.

In recent developments of mixed potential gas sensors based on Yttrium Stabilized Zirconia (YSZ), the combination of Au/AuPt-admixtures and oxides was found to be promising electrode materials. With this material combination, satisfactory sensing characteristics were achieved, but the role of Au addition, especially its effect on the processes contributing to the mixed potential formation, has not yet been well understood. Deeper insights of the influence of Au on the electrochemical behaviors of this kind of electrodes are necessary for better understanding of the sensing behaviors and for achieving further technological improvements, as for instance, enhancement of the long-term stability. This situation motivated studies of a layered Au,Pt-YSZ mixed potential gas sensing electrode and its dependence on the thickness of the Au-layer and the sintering conditions. In this work, for the first time three variations of this kind of electrode, which generally comprises a thick-film Pt-YSZ electrode and a thin-film Au layer deposited on top, were studied by different kinds of material analytical approaches and electrochemical methods. These studies elucidated the correlation among the electrochemical behaviors of the electrodes, the amount of gold deposition and its non-uniform distribution over the electrode. Based on these structural and electrochemical data, a qualitative model for the first time is proposed to interpret the sensing mechanism of the layered Au,Pt-YSZ electrodes. In the past such a theory was only available for the electrodes at which the Au was homogeneously admixed with the Pt-YSZ composite. From the structural studies including the ESEM, the XRD and the Glow Discharge-Optical Emission Spectroscopy analysis (GD-OES), it was shown that the thin film Au layer at the layered Au,Pt-YSZ electrodes is not uniformly admixed with the Pt-YSZ bulk after firing, but results in a non-uniform lateral distribution on the electrode surface and a concentration gradient of Au from top over the thickness of the electrode. This Au distribution is strongly affected by the sintering temperature. The higher sintering temperature (1050 °C) results in not only a more uniform morphology of the electrode surface without a separate crystalline phase of gold , but also a better alloying of Au and Pt in the inner parts of the electrode during the sintering process, compared to the electrodes sintered at a lower temperature (850 °C). These clear structural differences of the electrodes fired at different temperatures are related to different catalytic activities over the electrode layer, and accordingly affect their open circuit potential (OCP) sensing behaviors and other electrochemical properties. With respect to selectivity and stability of the sensors, the highest sensing response was observed in the H2 containing gases compared to the other gas species like CO, CH4, and C3H6 for both the type II (low temperature sintered) and the type III (high temperature sintered) sensors. However, clear response and potential stability losses were observed at exposure to C3H6. Formation of coking layers on the electrode seems to be correlated with this response decrease. Surprisingly, the response degradation was even observed by aging the sensors at 600 °C in ambient air. Combined OCP, CV and EIS studies revealed that, the aging process results in some minor irreversible but mainly reversible changes at the electrode/electrolyte interface. Both induce the response degradation which is well correlated with an impedance increase and a CV current decrease. The reversible changes are assumed to be attributed to the formation of an oxidation phase of the metallic parts at the TPB, which is well described in literature. Now, for the first time in this work it could be demonstrated that this reversible response degradation can be nearly fully recovered by the application of cathodic polarization sequences. Consequently, due to the strong correlation between the OCP response to CO and the dynamic electrochemical behaviors ((EIS and CV)) at ambient air, both the EIS and the CV method can be used as efficient tools to check the sensitivity of the sensor at ambient air conditions. In case of OCP response degradation, the sensitivity can be almost fully regenerated by application of cathodic polarization at enhanced temperatures (T700°C). This combination of OCP measurements with dynamic electrochemical methods and the application of cathodic polarization procedures is of enormous practical relevance and was filed for a patent. It excited high interest of the sensor chip producer (Lamtec Meß- und Regeltechnik für Feuerungen GmbH, Walldorf) because it allows sensitivity estimation and regeneration of layered Au,Pt-YSZ gas sensing electrodes whenever ambient air conditions are given. For instance, in case of long-term CO/HC-monitoring for improvement of automated combustion process control of firing appliances, this procedure could be carried out in breaks between firing batches without the need of de-installation of the sensor and, indeed, without any exposure to model gases.

This doctoral research work focuses on the simulation of progressive collapse of reinforced concrete structures. It aims at contributing to the ‘alternate load path’ design approach suggested by the General Services Administration (GSA) and the Department of Defense (DoD) of the United States, by providing a detailed yet flexible numerical modelling tool. <p><p>The finite element formulation adopted here is based on a multilevel approach where the response at the structural level is naturally deduced from the behaviour of the constituents (concrete and steel) at the material level. One-dimensional nonlinear constitutive laws are used to model the material response of concrete and steel. These constitutive equations are introduced in a layered beam approach, where the cross-sections of the structural members are discretised through a finite number of layers. This modelling strategy allows deriving physically motivated relationships between generalised stresses and strains at the sectional level. Additionally, a gradual sectional strength degradation can be obtained as a consequence of the progressive failure of the constitutive layers. This means that complex nonlinear sectional responses exhibiting softening can be obtained even for simplified one dimensional constitutive laws for the constituents.<p><p>This numerical formulation is used in dynamic progressive collapse simulations to study the structural response of a multi-storey planar frame subject to a sudden column loss. The versatility of the proposed methodology allows assessing the influence of the main material and design parameters in the structural failure. Furthermore, the effect of particular modelling options of the progressive collapse simulation technique, such as the column removal time or the strategy adopted for the structural verification, can be evaluated.<p><p>The potential strain rate effects on the structural response of reinforced concrete frames are also investigated. To this end, a strain rate dependent material formulation is developed, where the rate effects are introduced in both the concrete and steel constitutive response. These effects are incorporated at the structural level through the multilayered beam approach. In order to assess the degree of rate dependence in progressive collapse, the results of rate dependent simulations are presented and compared to those obtained via the rate independent approach. The influence of certain parameters on the rate dependent structural failure is also studied.<p><p>The differences obtained in terms of progressive failure degree for the considered parametric variations and modelling options are analysed and discussed. The parameters observed to have a major influence on the structural response in a progressive collapse scenario are the ductility of the steel bars, the degree of symmetry and/or continuity of the reinforcement and the column removal time. The results also depend on the strategy considered (GSA vs DoD). The strain rate effects are confirmed to play a significant role in the failure pattern. Based on these observations, general recommendations for the design of progressive collapse resisting structures are finally derived.<p><p><p><p><p>L’effondrement progressif est un sujet de recherche qui a connu un grand développement suite aux événements désastreux qui se sont produits au cours des dernières décennies. Ce phénomène est déclenché par la défaillance soudaine d’un nombre réduit d’éléments porteurs de la structure, qui provoque une propagation en cascade de l’endommagement d’élément en élément jusqu’à affecter une partie importante, voire la totalité de l’ouvrage. Le résultat est donc disproportionné par rapport à la cause. La plupart des codes de construction ont inclus des prescriptions pour le dimensionnement des structures face aux actions accidentelles. Malheureusement, ces procédures se limitent à fournir des ‘règles de bonne pratique’, ou proposent des calculs simplifiés se caractérisant par un manque de détail pour permettre leur mise en oeuvre.<p><p>Cette thèse de doctorat intitulée Simulation de l’Effondrement Progressif des Structures en Béton Armé: Influence des Paramètres Materiaux et de Dimensionnement et Investigation des Effets de Vitesse a pour but de contribuer à la simulation numérique de l’effondrement progressif des structures en béton armé. Une formulation aux éléments finis basée sur une approche multi-échelles a été développée, où la réponse à l’échelle structurale est déduite à partir de la réponse au niveau matériel des constituants (le béton et l’acier). Les sections des éléments structuraux sont divisées en un nombre fini de couches pour lesquelles des lois constitutives unidimensionnelles sont postulées. Cet outil permet une dégradation graduelle de la résistance des sections en béton armé suite à la rupture progressive des couches. Des comportements complexes au niveau des points de Gauss peuvent être ainsi obtenus, et cela même à partir de lois unidimensionnelles pour les constituants.<p><p>Cette formulation est utilisée pour la simulation de l’effondrement progressif d’ossatures 2D, avec prise en compte des effets dynamiques. La versatilité de la présente stratégie numérique permet d’analyser l’influence de différents paramètres matériaux et de dimensionnement, ainsi que d’autres paramètres de modélisation, sur la réponse structurale face à la disparition soudaine d’une colonne.<p><p>Les effets de la vitesse de déformation sur le comportement des matériaux constituants est aussi un sujet d’attention dans ce travail de recherche. Des lois constitutives prenant en compte ces effets sont postulées et incorporées au niveau structural grâce à l’approche multi-couches. Le but est d’étudier l’influence des effets de la vitesse de chargement sur la réponse structurale face à la disparition d’un élément porteur. Les resultats obtenus à l’aide de cette approche avec effets de vitesse sont comparés à ceux obtenus avec des lois indépendantes de la vitesse.<p><p>Les différences dans la réponse à la disparition d’une colonne sont analysées pour les variations paramétriques étudiées. Les paramètres ayant une influence importante sont notamment: la ductilité des matériaux constituants et la disposition et/ou la symétrie des armatures. Les effets de vitesse sont également significatifs. Sur base de ces résultats, des recommandations sont proposées pour le dimensionnement et/ou l’analyse des structures face à l’effondrement progressif.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Das bei der Sanierung von großen segmentalen Knochendefekten bestehende Risiko einer fremdkörperassoziierten Infektion soll durch die Integration eines Wirkstofffreisetzungssystems in ein bestehendes textiles Knochenimplantat gemindert werden. Durch Immobilisierung des Wirkstoffs in eine degradierbare Polymermatrix wird eine zeitlich verzögerte Freisetzung bewirkt. Als Wirkstofffreisetzungssystem wird die Kombination von Polylactid (PLA) bzw. Poly(Lactid-co-Glycolid) (PLGA) als Matrixpolymer mit dem Antibiotikum Gentamicin als Wirkstoff untersucht, welches durch Beschichtung der textilen Scaffolds mittels Dip-Coating eingebracht werden soll. Es stehen die drei Beschichtungsmethoden „Suspension“, „Emulsion“ und „Schichtaufbau“ zur Auswahl, die jeweils über eigene Parameter zur Beeinflussung des Freisetzungsprofils verfügen. Die Methode „Suspension“ und die damit verbundenen Einflussfaktoren Korngröße, Korngrößenverteilung sowie Masseanteil des Antibiotikums und Schichtdicke der aufgetragenen Polymerschicht wurde als die günstigste herausgearbeitet. Im Teil II dieser Arbeit wird diese soweit optimiert, dass nahezu über den gesamten geforderten Zeitraum die festgelegte notwendige Dosierung aufrechterhalten werden kann. Erste in vitro Versuche weisen auf eine gute Zellverträglichkeit sowie eine ausreichende mikrobielle Wirksamkeit hin. / To reduce the risk of infection in the treatment of long bone defects, a novel embroidered bone implant is to be provided with an antibiotic drug delivery system. Prolonged and controlled drug release can be achieved by coating the thread material with antibiotics incorporated in a degradable polymer matrix. The chosen drug delivery system is composed of polylactide acid (PLA) or poly(lactide-co-glycolide) acid (PLGA) as matrix polymer and the antibiotic gentamicin. It is integrated into the textile structure by dip-coating providing the three different methods suspension, emulsion and layered. Each method bears its appropriate parameters to influence the releasing profile. The suspension-method and its parameters grain size and grain size distribution as well as mass fraction of the antibiotic and the coating thickness could be proved as the most feasible. In part II of this essay the chosen coating set-up gets optimized so that a drug release nearly along the whole required term can be achieved. Preliminary in vitro studies show a good cell tolerance besides a sufficient microbial efficacy.

This thesis was inspired by the discovery of Bi14Rh3I9, the first so-called weak three-dimensional topological insulator (3D-TI) and has been concerned with the topic of TIs in general. Two aspects were tackled to gain a deeper understanding of this new state of matter. On one hand, the expansion of the material’s basis and on the other hand developing a simple model of the structure and analysing it via density-functional theory (DFT) based methods. To discover new materials, a systematic investigation of the metal-rich parts of the bismuth–platinum-metal–iodine phase systems was conducted. It led to six new phases among the bismuth subiodides. Some of which, e.g. Bi14Rh3I9, share a honeycomb network of platinum-metal-centred bismuth-cubes and are the seed of a family of materials with this structural motive. The others show strand-like structures or layered structures with platinum-platinum bonds. The latter were so far unknown amongst bismuth subiodides. The honeycomb network was separately analysed and shown to host the TI properties. Structurally and electronically it can be seen as a “heavy graphene analogue”, which refers to the fact that graphene with hypothetical strong spin-orbit coupling (“heavy graphene”) was the first TI put forward by theoreticians. Apart from DFT-calculations, physical experiments confirmed the TI properties. Angle-resolved photoelectron spectroscopy (ARPES) was used to verify the electronic structure and scanning tunnelling microscopy and spectroscopy (STM and STS) to reveal the protected 1D edge states present at the cleaving surface of this material. As the arrangement of the honeycomb layer varies between the different known and newly discovered materials within this family of structures, this influence was also investigated. All further materials were also characterised by DFT-calculations and physical experiments, e.g. magnetisation and transport measurements. This thesis might give an experimental and theoretical basis for a deeper understanding of the TI state of matter. The 1D edge states on the surface of Bi14Rh3I9 could be a chance to handle spins and therefore propel spintronic research, or they could host Majorana fermions, which could be used as qubits in quantum computing.

In der Dissertation wurden Nanokomposite mit unterschiedlichen Kautschuken (HNBR, EPDM, MAH-g-EPDM) als Basismaterial sowie diversen modifizierten Schichtsilikaten als Füllstoff hergestellt und charakterisiert. Untersucht wurden die sich ausbildenden Strukturen bzw. die Morphologie (Aggregation, mögliche Orientierungen), die mechanischen Eigenschafte (Verstärkungswirkung) sowie die Füllstoff-Füllstoff-Wechselwirkungen und die Polymer-Füllstoff-Wechselwirkungen.