Objectives: While bracket debonding has been explored through shear bond-strength tests with debonding linked to the type of material used, the technique of adhesive application, and contamination, the contribution of internal voids in orthodontic adhesives is unknown. Voids may result in fracture or bond-failure, either within the adhesive or at the tooth-adhesive-bracket interfaces. The aim of this thesis is to quantify the internal volumetric voids and bonding strength of three generations of bracket adhesives. Methods: Extracted third molars were bonded with three groups of orthodontic brackets including conventionally-pasted (CP), pre-coated (PC), or pre-coated flash-free (FF) (n=5 per group). The three-dimensional internal structure of the adhesive was evaluated with Micro Computed Tomography (micro-CT) using the Skyscan micro-CT (maximum resolution of 5 microns). Data from the micro-CT were analyzed with SkyScan software to perform 3D reconstructions, image processing, and qualitative and quantitative analysis of the adhesive’s structure. The amount of void was determined by measuring the percentage of voids at the bonded interfaces (Vint) and within the adhesive (Vbulk). The total amount of void was also calculated (Vtot= Vint+ Vbulk). Differences in void between the groups were assessed using one-way ANOVA with post-hoc Tukey tests (α=0.05). The bonding strength of the three adhesives systems was evaluated via shear bond strength tests. Results: Our void quantification results showed that FF brackets had a statistically higher (p0.05) for any the analyzed locations (Vint, Vbulk). Our results indicate the majority of voids were found at bonded interfaces (Vint) compared to within the bulk (Vbulk) for all three groups, with statistically significant (p<0.05) differences for CP and FF. Our bonding strength evaluation revealed the pre-coated group (PC) to have on average the highest bond strength compared to conventionally-pasted (CP) and pre-coated flash-free (FF) groups. Conclusions: The overall amount of void in the pre-coated flash-free adhesive brackets is significantly higher compared to conventionally-pasted and pre-coated groups. The majority of the void was identified to be located at the bonded interfaces (tooth/adhesive and bracket/adhesive) rather than within the bulk of the adhesive for all groups. Our bonding strength results indicate the pre-coated brackets to have the highest bond strength compared to pre-coated flash-free and conventionally-pasted. Our preliminary set of results indicate an inverse relationship between bonding strength and amount of void of brackets adhesives, with the pre-coated exhibiting the highest bond strength and least void. However, due to a limited sample size additional data are needed to validate these conclusions and find solid relationships between adhesive voids and bonding strength. / Oral Biology

t-Butoxyl radical has been used as a chemical model for hydrogen abstractions in many enzymatic and biological systems. However, the question has arisen as to how well this reactive intermediate mimics these systems. In addressing this concern, absolute rate constants and Arrhenius parameters for hydrogen abstraction by t-butoxyl radical were measured for a broad class of substrates including amines, hydrocarbons, and alcohols using laser flash photolysis. Initially, no obvious reactivity relationship between rate constant and substrate structure was observed for these homolytic reactions. However, by closely examining the Arrhenius parameters for hydrogen abstraction, a pattern was revealed. For substrates with C-H bond dissociation energy (BDE) > 92 kcal/mole, activation energy increases with increasing BDE (as expected). However, for substrates with a lower BDE, the activation energy levels out at approximately 2 kcal/mole, essentially independent of structure. Viscosity studies with various solvents were conducted, ruling out the possibility of diffusion-controlled reactions. Entropy rather than enthalpy appears to be the dominating factor at 25°C, contributing to the free energy barrier for these reactions. Laser flash photolysis was also used to study radical anions. Using an indirect photoexcitation method, the properties of radical anions, generated from aryl ketones, were investigated. These radical anions, such as t-butyl phenyl ketone and cyclopropyl phenyl ketone, measured to have decay rate constants of 1.0 x 106 s-1, although they are known to be persistent when studied electrochemically. They also had measured activation energies around 6.0 kcal/mole and log A values close to 9.5. By extending the molecules's conjugation, the decay rate constants increased to greater than 107 s-1, decreased their activation energy by half, and lowered the log A values to 8.0. This trend was observed in aryl ketones such as trans-1-benzoyl-3-phenyl cyclopropane. It is believed that the generation of a benzyl radical during the decay that facilitates the enhancement of the unimolecular decays. These unimolecular decays were also observed with the previously studied hypersensitive SET probes, 5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one and 1,1,-dimethyl-5,7-di-tert-butylspiro[2.5]octa-4,7-dien-6-one. The decay rate constants for these radical anions were measured to be greater than 108 s-1, driven by the formation of an aromatic ring. / Ph. D.

Yes / Despite the fact of being intensive energy consumption, MSF is a mature technology that characterised by a high production capacity of high-quality water. The multistage flash (MSF) desalination process is one of the prominent thermal desalination used in the industry of seawater desalination to produce high quantity and high quality of freshwater. However, this process consumes large amount of energy and faces thermal limitations due to its high degree of exergy destruction at several units of the process. Therefore, the research of MSF is still existed to elevate the performance indicators and to resolve the concern of high energy consumption. To rectify these limitations, it is important to determine the units responsible in dissipating energy. This study aims to model an industrial MSF process validated against real data and then investigate the exergy destruction and thermodynamic limitations of the process. As a case study, Azzour MSF seawater desalination plant, located in Al Khiran in Kuwait is under the focus. A comprehensive model is developed by analysing several published models. Specifically, the calculation of exergy destruction has embedded both physical and chemical exergies that identified as a strong point of the model developed. As expected, the highest exergy destruction (55.5%) occurs within the heat recovery section followed by the brine heater with exergy destruction of 28.26% of the total exergy destruction. This study identifies the sections of the industrial process that cause the highest energy losses.

Yes / This paper reviews and discusses the recent studies of natural flood management (NFM) and its associated microbial risks in the UK and suggests set of numerical modelling approaches for their respective investigation. This study details the importance of precise numerical representation of the NFM to flood inundations and microbial risks caused by NFM measures. Possible future numerical advancements of the numerical modelling for the NFM and microbial activities are also discussed here.

Today's large-scale, high-performance, data-intensive applications put a tremendous stress on data centers to store, index, and retrieve large amounts of data. Exemplified by technologies such as social media, photo and video sharing, and e-commerce, the rise of the real-time web demands data stores support minimal latencies, always-on availability and ever-growing capacity. These requirements have fostered the development of a large number of high-performance storage systems, arguably the most important of which are Key-Value (KV) stores. An emerging trend for achieving low latency and high throughput in this space is a solution, which utilizes both DRAM and flash by storing an efficient index for the data in memory and minimizing accesses to flash, where both keys and values are stored. Many proposals have examined how to improve KV store performance in this area. However, these systems have shortcomings, including expensive sorting and excessive read and write amplification, which is detrimental to the life of the flash. Another trend in recent years equips large scale deployments with energy-efficient, high performance co-processors, such as Graphics Processing Units (GPUs). Recent work has explored using GPUs to accelerate compute-intensive I/O workloads, including RAID parity generation, encryption, and compression. While this research has proven the viability of GPUs to accelerate these workloads, we argue that there are significant benefits to be had by developing methods and data structures for deep integration of GPUs inside the storage stack, in order to achieve better performance, scalability, and reliability. In this dissertation, we propose comprehensive frameworks that leverage emerging technologies, such as GPUs and flash-based SSDs, to accelerate modern storage systems. For our accelerator-based solution, we focus on developing a system that features deep integration of the GPU in a distributed parallel file system. We utilize a framework that builds on the resources available in the file system and coordinates the workload in such a way that minimizes data movement across the PCIe bus, while exposing data parallelism to maximize the potential for acceleration on the GPU. Our research aims to improve the overall reliability of a PFS by developing a distributed per-file parity generation that provides end-to-end data integrity and unprecedented flexibility. Finally, we design a high-performance KV store utilizing a novel data structure tailored to specific flash requirements; it arranges data on flash in such a way as to minimize write amplification, which is detrimental to the flash cells. The system delivers outstanding read amplification through the use of a trie index and false positive filter. / Ph. D.

The development and evaluation of a fuel cell test stand incorporating various methods for controlling the temperature and humidity of fuel cell reactants is described. The test stand is capable of accurately metering gas flows, controlling the temperature and humidity of the gases, and delivering the gases to the fuel cell in a safe manner. Additionally, the test stand can measure the voltage and current produced by the fuel cell during operation. Two test stands were constructed and evaluated, one using steam injection for fuel cell stacks and the other using flash evaporation for individual fuel cells. Both test stands were shown to provide adequate control at the upper end of the design range. The flash evaporation test apparatus was used to investigate the effect of inlet gas humidity on fuel cell performance. The results from this investigation showed that, for a fuel cell and reactant temperature of 75°C, the best performance was achieved with a high relative humidity (90%RH) for the hydrogen and a comparatively low relative humidity (60%) for the air. / Master of Science

My dissertation introduces the notion of "augmented authorship" and applications for prompt engineering with generative neural networks inspired by Gregory Ulmer's theories of electracy (2003) to the interdisciplinary fields that teach writing and rhetoric. With the goal of inspiring the general practice of electracy, I introduce prompt engineering as practice in flash reason (Ulmer 2008; 2012), a new collective prudence emerging from the apparatus of electracy. By situating electracy and flash reason as threshold concepts in writing studies, and by aligning principles of electracy with ACRL and NCTE digital literacy frameworks, I demonstrate how prompt engineering across modalities can help students meet digital literacy goals, before providing accessible models or "relays" in the form of AI-coauthored texts, course modules, and aesthetic models deployed in the game world Roblox.

Ce travail de thèse porte sur l'intégration de matériaux de haute constante diélectrique (High-k) en tant que diélectrique interpoly dans les mémoires non volatiles de type Flash. L'objectif est de déterminer quel matériaux High-k seraient des candidats probables au remplacement de l'empilement ONO utilisé en tant que diélectrique interpoly. Une gamme de matériaux high-k ont été étudiés via des caractérisations électriques (I-V, C-V, statistique de claquage…) et physiques (TEM, EDX, XPS…) afin d'éliminer les matériaux ne répondant pas au cahier des charges d'un diélectrique interpoly. Les difficultés et les obstacles liés a l'intégration de matériaux High-k dans une chaine de procédés de fabrication de mémoires Flash ont été pris en compte, et des solutions ont été proposées. / The work of this thesis is on integration of high dielectric constant materials (High-k) as dielectric interpoly in Flash non volatile memories. The objective is to determine which High-k materials are suitable as interpoly dielectric in place of the ONO stack currently used. A range of High-k materials have been studied by electrical characterizations (I-V, C-V, breakdown statistics…) and physical characterizations (TEM, EDX, XPS…) in order to select those with the best properties for an interpoly dielectric. The difficulties in integration of High-k materials in a Flash memory process flow have been taken in account and solutions have been proposed.

Sous l'effet d'une forte impulsion mécanique, d'une chaleur très forte ou d'une décharge électrostatique, un explosif comme le TNT ou le RDX peut accidentellement être initié. L'énergie apportée à l'explosif est convertie en chaleur, appelée point-chaud, dans des endroits spécifiques, contenant des impuretés, bulles de gaz, pores ouverts ou autres hétérogénéités. La taille d'un point-chaud de quelques micromètres peut être déjà suffisante pour initier une déflagration ou même une détonation. En réduisant la taille des particules de l'explosif, la formation des points-chauds est empêchée conduisant à un matériau moins sensible. Au sein de ce travail, un procédé continu est développé, fondé sur le principe de la cristallisation-flash, et permettant la préparation de particules énergétiques submicroniques en quantité de plusieurs grammes. Le procédé repose sur une opération de séchage par atomisation, au cours de laquelle une solution surchauffée est atomisée d'une manière continue. Afin de diminuer la taille moyenne des particules et d'obtenir une distribution de taille des particules très étroite, une étude paramétrique est réalisée. Au moyen de la cristallisation-flash, la préparation de composites énergétiques de haute qualité en grandes quantités est un succès. La qualité et quantité de ce composite énergétique sont uniques. Grâce au potentiel de ce procédé, la cristallisation-flash peut permettre la préparation de nombreuses substances et compositions énergétiques ou inertes / High explosives, such as TNT or RDX, may be accidentally initiated under the influence of a strong mechanical impulse, great heat or an electrostatic discharge. Smallest impurities, open pores, entrapped gases or other inhomogeneities within the explosive matrix may convert the delivered energy into heat, causing the formation of a so called hot-spot. A hot-spot size of a few micrometers can already be sufficient to initiate a deflagration or even a detonation of the explosive. By decreasing the particle size of the explosive, the formation of hot-spots is inhibited, resulting in a less sensitive material. In this work, a continuous operating flash-crystallization process was developed, being able to produce energetic submicron particles in a multigram scale. The process bases on a spray drying process where superheated solutions are continuously atomized. A parametric study was performed on this process in order to decrease the particle size and obtaining a narrower particle size distribution. By means of this flash-crystallization process, highly homogeneous energetic composites were prepared in a large scale. The quality and amount of the energetic composite are unique. The versatility of the flash-crystallization process allows the preparation of a large number of energetic and inert substances and compositions

Métodos de produção eficientes que economizam tempo e energia são sempre exigidos e novos processos de sinterização de baixo custo têm sido desenvolvidos para materiais cerâmicos e implementados por empresas e pesquisadores em todo o mundo. Com este objetivo, uma nova abordagem conhecida como Flash Sintering está atraindo grande interesse. Esta nova técnica de sinterização envolve a aplicação de campo elétrico através de uma amostra durante o aquecimento, gerando assim aceleração abrupta da cinética de densificação, diminuindo o tempo de sinterização de horas para segundos e diminuindo o aquecimento do forno em até centenas de graus Celsius. Frequentemente descritas para cerâmicas policristalinas e compósitos de cerâmica e vidro, a sinterização auxiliada por campo elétrico com apenas vidro não foi encontrado na literatura. A sinterização assistida por campo elétrico foi controlada com sucesso, sem que ocorresse o escoamento da amostra, obtendo uma elevada densidade relativa do vidro comercial. Um vidro de janela soda-cal-sílica não estequiométrica foi usado na pesquisa devido à sua importância comercial, por ser um material de partida de baixo custo, por apresentar condução iônica e haver na literatura dados de propriedades físicas e de cinética de sinterização convencional. O campo elétrico também influencia fortemente a cinética de sinterização do vidro soda-cal-sílica. Os resultados experimentais foram comparados com cálculos analíticos realizados a partir do modelo de Clusters não-isotérmico de sinterização de vidro por fluxo viscoso com cristalização concorrente. O aumento de temperatura nos compactos de pó de vidro durante o aquecimento do forno e aplicação de campo elétrico foi estimado usando um modelo de radiação de corpo negro. Preliminarmente, o aumento da temperatura devido ao efeito Joule pode explicar a diminuição da temperatura de amolecimento em comparação com a temperatura do forno e a sinterização rápida do vidro estudado. / Efficient production methods saving time and energy are always demanded and novel reduced-cost sintering processes have being developed for ceramic materials and implemented by companies and researchers of all over the world. With this aim, a new sintering approach generally known as flash sintering is attracting great interest. This new sintering technique involves the application of electric field through a sample while heating, thereby generating abrupt acceleration of the densification kinetics, decreasing the sintering time from hours to seconds and decreasing the oven heating in up to hundreds of degrees Celsius. Well described for polycrystalline ceramics and ceramic-and-glass composites, the sintering of pure glass aided by electric field is still lacking in the literature. The sintering assisted by electric field, was successfully controlled, without sample flow, achieved a high relative density of a commercial glass. A non-stoichiometric soda-lime-silica window glass was used due to its commercial importance, low cost starting material, ionic conduction, and literature on physical properties and conventional sintering kinetics. Electric field was observed to also strongly influence window glass sintering kinetics. The experimental results were compared with analytical calculations obtained from the non-isothermal Clusters model of glass sintering by viscous flow with concurrent crystallization. The temperature increase in the glass powder compacts during oven heating and electric field application was estimated by using a black-body radiation model. Preliminary, the temperature increase due to Joule effect can explain the softening temperature decrease compared with the oven temperature, and the fast sintering of the studied glass.