<p dir="ltr">Zeolites are microporous crystalline aluminosilicates that are widely used as catalysts for upgrading hydrocarbons and oxygenates to higher value chemicals and fuels. The substitution of tetrahedral Si⁴⁺ with Al³⁺ in a charge-neutral silica framework ([SiO_4/2]) generates anionic centers ([AlO_4/2]^-), which charge-compensate Brønsted acid protons (H⁺) that serve as active sites for catalysis. Brønsted acid sites in aluminosilicates of diverse topologies have similar acid strength, but can be located within varying intracrystalline (or internal) microporous environments (0.4‒2 nm diameter) or at extracrystalline (or external) surfaces and mesoporous environments (>2 nm diameter); yet, catalytic diversity exists, <i>even</i> for a fixed zeolite framework topology, because micropores impose constraints on molecular access to and from intracrystalline active sites and provide van der Waals contacts that influence the stabilities of reactive intermediates and transition states. Tailoring the material properties of a given zeolite framework for targeted catalytic applications requires strategies to design both the bulk crystallite properties (e.g., morphology, active site density) that influence intracrystalline diffusion and the secondary environments that surround active sites and influence intrinsic kinetics, and further necessitates molecular-level insights to elucidate the influences of bulk and active site properties on catalysis. In this work, we provide synthetic and post-synthetic strategies to respectively tune active site environments within varying micropore voids and at external surfaces of zeolites, and develop gas-phase toluene methylation and liquid-phase mesitylene benzylation as probe reactions to quantify the catalytic consequences of active site environments on aromatic alkylation catalysis.</p><p dir="ltr">The MFI framework (orthorhombic phase) consists of 12 crystallographic distinct tetrahedral-sites and 26 unique framework oxygen atoms located around channels (~0.55 nm diameter) or channel intersections (~0.70 nm diameter). The synthesis of MFI zeolites using the conventional tetra-<i>n</i>-propylammonium (TPA⁺) organic structure directing agent (OSDA) is known to place framework Al and their attendant H⁺ sites within the larger intersection environments, because electrostatic interactions are favorable between such locations of [AlO_4/2]^- and the quaternary N⁺ center in TPA⁺ that becomes positioned rigidly within channel intersections during crystallization. The methylation of toluene by dimethyl ether (DME; 403 K) on MFI-TPA zeolites of fixed active site densities (~2 Al per unit cell) result in <i>ortho</i>-xylene (<i>o</i>-X; ~65%) as the major product over <i>para</i>-xylene (<i>p</i>-X; ~27%) and <i>meta</i>-xylene (<i>m</i>-X; ~8%). In contrast, toluene methylation on MFI zeolites (~2 Al per unit cell) synthesized using non-conventional OSDAs, such as ethylenediamine (EDA) or 1,4-diazabicyclo[2.2.2]octane (DABCO), predominantly forms <i>p</i>-X (~75%) over <i>o</i>-X (~23%) and <i>m</i>-X (~2%). Within the subsets of MFI-TPA and MFI-EDA/DABCO zeolites, measured xylene formation rates and isomer selectivities are independent of crystallite sizes (0.1‒13 µm), toluene conversions (0.02‒2.0%) and external H⁺ content (up to 9% external H⁺ per total Al), indicating negligible effects of diffusion-enhanced secondary xylene isomerization reactions at intracrystalline or extracrystalline domains. The invariance of xylene isomer selectivity with reactant pressures (0.2‒9 kPa toluene, 25‒66 kPa DME) or methylating agent (1‒4 kPa methanol) indicate that differences in reactivity of toluene to form each xylene isomer reflects differences in the stabilities of their respective kinetically relevant transition states that share the same reactive intermediate. Measured xylene isomer formation rate constants and rate constant ratios, obtained from mechanism-derived rate expressions and interpreted using transition state theory formalisms, are used alongside density functional theory (DFT) calculations to reveal that intersection void environments (~0.70 nm diameter) similarly stabilize all three xylene transition states over unconfined surfaces (>2 nm diameter) without altering the established aromatic substitution patterns, while channel void environments (~0.55 nm diameter) preferentially destabilize bulkier <i>o</i>-X and <i>m</i>-X transition states thereby resulting in high intrinsic <i>p</i>-X selectivity. DFT calculations reveal that the ability of protonated DABCO complexes to reorient within MFI intersections and participate in additional hydrogen-bonding interactions with anionic Al centers during synthesis, facilitates the placement of Al in smaller channel environments that are less favored by TPA⁺. These molecular-level details, enabled by combining synthesis, characterization, kinetics and DFT, establish a mechanistic link between OSDA structure, active site placement and transition state stability, and provide active site design strategies orthogonal to crystallite design approaches that rely on complex reaction-diffusion phenomena.</p><p dir="ltr">For various reactions including toluene methylation at higher reaction temperatures (573‒773 K) and toluene conversions (>10%), extracrystalline H⁺ sites in MFI zeolites are reported to influence reactivity, selectivity, and deactivation behavior during catalysis in undesired ways. Post-synthetic chemical treatments to passivate external H⁺ sites on MFI zeolites result in unintended (but not always undesirable) changes to bulk structural properties and Al and H⁺ contents. The number of extracrystalline H⁺ sites is difficult to quantify using conventional spectroscopic or titrimetric methods, especially when present in dilute amounts on samples whose surfaces have been passivated. The systematic treatment of MFI zeolites (2.4, 5.7 and 7.1 Al per unit cell) using ammonium hexafluorosilicate (AHFS) at varying treatment duration times, AHFS concentrations and number of successive treatments resulted in MFI zeolites that retain their bulk structural properties and total Al and H⁺ contents, except for one parent MFI sample containing a significant amount of non-framework Al species. The benzylation of mesitylene by dibenzyl ether (363 K) occurs exclusively at external H⁺ sites because the bulky 1,3,5-trimethyl-2-benzylbenzene product is sterically prevented from forming at intracrystalline H⁺ sites. The intrinsic zero-order rate constant (per external H⁺) for mesitylene benzylation is extracted from rate measurements (per total Al) on a suite of untreated MFI samples with known amounts of external H⁺ sites (1‒15% external H⁺ per total Al) quantified using bulky 2,6-di-<i>tert</i>-butylpyridine base titrants. Measured zero-order rate constants on AHFS-treated MFI zeolites are used to quantify the extent to which AHFS treatments passivate external H⁺ sites, revealing efficacies that depend on the specific treatment conditions and the parent sample used. The developed kinetic methods demonstrate the utility of catalytic probes, when compared to stoichiometric probes based on spectroscopic or titration methods, in amplifying and quantifying dilute concentrations of external H⁺ sites on zeolites. The methods enable comparisons of the efficacy of various post-synthetic passivation strategies and permit rigorous assessments of the influence of external H⁺ during acid catalysis.</p><p dir="ltr">Overall, this work provides (post-)synthetic strategies to tune active site environments within intracrystalline micropores or at extracrystalline surfaces and develops quantitative kinetic probes that enable a molecular-level understanding of catalytic consequences of active site environments on aromatic alkylation reactions. Taken together, the methodology and findings of this study have broader implications in zeolite catalyst design for selectively upgrading traditional fossil feedstocks (crude oil and shale gas) and emerging feedstocks (biomass and waste plastics).</p>

No description available.

No description available.

Commercial fuels are mixtures with large numbers of components. Continuous thermodynamics is a technique for modelling fuel mixtures using a probability density function rather than dealing with each discreet component. The mean and standard deviation of the distribution are then used to model the chemical reactions of the mixture. This thesis develops the necessary theory to apply the technique of continuous thermodynamics to the oxidation reactions of hydrocarbon fuels. The theory is applied to three simplified models of hydrocarbon oxidation: a global one-step reaction, a two-step reaction with CO as the intermediate product, and the four-step reaction of Müller et al. (1992), which contains a high- and a low-temperature branch. These are all greatly simplified models of the complex reaction kinetics of hydrocarbons, and in this thesis they are applied specifically to n-paraffin hydrocarbons in the range from n-heptane to n-hexadecane. The model is tested numerically using a simple constant pressure homogeneous ignition problem using Cantera and compared to simplified and detailed mechanisms for n-heptane. The continuous thermodynamics models are able not only to predict ignition delay times and the development of temperature and species concentrations with time, but also changes in the mixture composition as reaction proceeds as represented by the mean and standard deviation of the distribution function. Continuous thermodynamics is therefore shown to be a useful tool for reactions of multicomponent mixtures, and an alternative to the "surrogate fuel" approach often used at present.

Denitrification is a microbially-catalyzed reaction which reduces nitrate to N2 through a series of intermediate nitrogen compounds. Nitrate is a nutrient and its release into the environment may lead to eutrophication, depending on the amount that is released and the state of the recipient. The release of nitrate from the mining industry in Kiruna (Sweden) has been identified as an eutrophication risk, and a denitrifying bioreactor is to be constructed at the site to reduce the nitrate release.Since the denitrification rate decreases with temperature and the temperature in Kiruna during large parts of the year drops below 0˚C, the denitrifying bioreactor therefore has to be designed for the site-specific environment in terms of flow rate and hydraulic residence time. Laboratory column studies are used to study and determine the nitrate removal rate in a low temperature environment (5˚C) with pine wood chips as reactive matrix/ electron donor; the input solution had an average concentration of 35 mg NO3-N/L and a high sulfate concentration. Nitrate removal was studied as a function of hydraulic residence time and temperature. Parameters that were monitored include pH, alkalinity and concentrations of ammonium, nitrite and sulfate in the effluent from the columns. On three occasions, samples were gathered along the flow path in the columns (concentration profiles) such that changes in nitrate, nitrite, and occasionally ammonium concentration could be studied in relation to each other. The study concluded that a denitrifying bioreactor utilizing pine wood chips as the reactive matrix is a suitable option for nitrate treatment in a low temperature (5˚C) environment. Under the conditions of the study, effluent nitrate, nitrite, and ammonium concentrations are below limits established in legislation. Nitrate removal rates are given for zero-order nitrate reduction and overall first-order nitrate reduction, as the concentration profiles revealed a decrease in nitrate removal rate as nitrate concentration dropped below 3 mg NO3-N/L. / Nitrat är ett näringsämne som kan orsaka övergödning vid utsläpp, beroende på halterna och recipienten. Växterna som tar upp kväve kommer så småningom att dö och sjunka mot botten där de förmultnar. Förmultningen kräver syre, och vid ökad växtlighet så ökar även konsumtionen av syre då det finns mer organiskt material att bryta ned. Detta leder i slutändan till syrefria områden, där djurliv och växtlighet är mer begränsade. Nitratutsläpp från gruvindustrin i Kiruna har blivit identifierad som en potentiell övergödningsrisk och en denitrifierande bioreaktor ska därmed installeras för att minska utsläppen. Denitrifikation är en mikrobiell reaktion som reducerar nitrat till kvävgas genom en serie av intermediära kväveföreningar. En denitrifierande bioreaktor använder sig utav denitrifikation för att minska nitratkoncentrationer i vatten som passerar genom bioreaktorn som består av huvudsakligen; (1) bakterierna som sköter denitrifikationen, och (2) en kolkälla som fungerar som ”mat” till de denitrifierande bakterierna, Hastigheten varvid nitrat omvandlas till kvävgas genom denitrifikation, minskar med temperatur och den denitrifierande bioreaktorn måste därmed anpassas till omgivningen där den ska placeras med avseende på uppehållstid i reaktorn. Uppehållstiden måste vara tillräcklig för att minska nitratkoncentrationen till önskad nivå, men samtidigt så får uppehållstiden inte vara för lång då andra ämnen kan reagera och bilda ofördelaktiga produkter vid låga nitratkoncentrationer. Kolonnstudier i en låg-tempererad miljö (5˚C) är ett första steg för att studera hastigheten av nitratförbrukning i en sådan omgivning, och används i detta arbete med träflis av tall som kolkälla. Parametrar som påverkar, och varierar som ett resultat av, denitrifikation (exempelvis pH och sekundära föroreningar) övervakas. Hastigheten av nitratförbrukning som fås från kolonnstudierna kan sedan används som riktlinjer för konstruktionen av en denitrifierande bioreaktor i fältskala i Kiruna. Studiens slutsats är att en denitrifierande bioreaktor med träflis av tall som reaktivt medium är ett fungerande alternativ för nitrat reducering i en lågtempererad miljö (5˚C) då nitrat effektivt reduceras till under gränsvärden fastslagna i lag. Även andra potentiella biprodukter (exempelvis nitrit och ammonium) som kan resultera från den miljö som den denitrifierande bioreaktorn ger upphov till är under de gränsvärden som finns fastslagna i lag.

Die Temperaturverhältnisse beim Ziehen und Wärmebehandeln von Draht werden mit mathematisch-analytischen Methoden auf der Grundlage der FOURIERschen Wärmeleitungsgleichung eingehend untersucht. Insbesondere wird unter den spezifischen Wärmeübergangsbedingungen zwischen Draht und Ziehdüse sowie zwischen Draht und Ziehtrommel deren thermische Wechselwirkung analysiert. Ein Näherungsverfahren zur Berechnung der Drahttemperaturen in Zugfolgen unter Berücksichtigung des Ziehdüseneinflusses wird angegeben und mit einem Beispiel zum Nassziehen stark verzinkten Stahldrahts illustriert. Aus geschwindigkeitsabhängig gemessenen Änderungen des Drahtdurchmessers werden unter thermoelastischer Ziehringdurchmesserkorrektur Schmierfilmdicken bestimmt. Diffusionsgleichungen werden analysiert und ein Zusammenhang zur Reaktionskinetik wird hergestellt. Ein neues reaktionskinetisches Werkstoffmodell, das insbesondere auch im Falle stärker anisothermer Verhältnisse, also bei Kurzzeitwärmebehandlung anwendbar ist, wird vorgestellt.

Zur Bestimmung der toxizitätsrelevanten Thiolreaktivität wurde ein Chemoassay mit dem Modellnukleophil 4-Nitrothiophenol (NBT) entwickelt. Es wurden die Reaktionsgeschwindigkeitskonstanten kNBT für insgesamt 145 Verbindungen aus verschiedenen Stoffklassen bestimmt. Ein Modell zur Berücksichtigung der Flüchtigkeit der Elektrophile bei der Berechnung von kNBT wurde entwickelt. Außerdem wurde der Einfluss des pH-Werts auf die Thiolreaktivität unter reaktionsmechanistischen Gesichtspunkten diskutiert. Die NBT-Reaktivität wurde mit der Reaktivität gegenüber anderen toxizitätsrelevanten Nukleophilen verglichen. Zur Einordnung der Thiolreaktivität in den toxikologischen Zusammenhang wurden die Korrelationen zwischen kNBT und ausgewählten toxikologischen Endpunkten betrachtet. Am Beispiel der aquatischen Toxizität im Bioassay mit Tetrahymena pyriformis konnten stoffklassenspezifische Modelle zur Beschreibung der absoluten Toxizität log EC50 und der Toxizitätserhöhung log Te mit guter bis sehr guter Vorhersagekraft abgeleitet werden.

Kunststoffgebundene Dauermagnete kommen bereits seit einem dreiviertel Jahrhundert in diversen Anwendungen zum Einsatz. Dabei werden die gängigen Kunststoffverarbeitungsverfahren wie beispielsweise Spritzgießen, Extrudieren, Pressen und Kalandrieren angewandt. Ähnlich zu der Aufteilung in der Verarbeitung von herkömmlichen Kunststoffen, werden auch für die kunststoffgebundenen Dauermagnete nur selten duroplastische Matrixmaterialien im Spritzgießverfahren eingesetzt. Dabei bringt gerade diese Werkstoffklasse hervorragende Eigenschaften mit sich, die eine Verbesserung der Eigenschaften von kunststoffgebundenen Dauermagneten zur Folge haben können. Neben der Medien- und Temperaturbeständigkeit dieser Werkstoffklasse spielt dabei auch deren Viskosität eine bedeutende Rolle für diese Anwendung. Im Rahmen der vorliegenden Arbeit soll geprüft werden, ob der Einsatz duroplastischer Matrixmaterialien zu einer Verbesserung der Eigenschaften kunststoffgebundener Dauermagnete führen kann. Hierfür werden anisotrope Magnetpartikel in den Kunststoff eincompoundiert und während der Verarbeitung im Spritzgießverfahren orientiert. Dies geschieht durch ein integriertes Magnetfeld im Spritzgießwerkzeug. Insbesondere sollen der Einfluss des Matrixmaterials, der Partikelgeometrie, der Fließrichtung sowie des Richtfeldes auf die Partikelorientierung untersucht werden. Zusammen mit grundlegenden analytischen Untersuchungen der Ausgangsmaterialien sollen abschließend Richtlinien für eine Bauteilauslegung definiert und erste Ansätze für eine Simulation der magnetischen Bauteileigenschaften erarbeitet werden. / Polymer bonded magnets are used for different applications for over 70 years yet. These materials are produced within known polymer processing procedures as injection molding, extruding, compression molding and calendaring. However, as for standard plastics thermoset materials are seldom used in injection molding even though they show great potential regarding temperature and media resistance as well as in terms of a low viscosity. These properties could be of use in case of polymer bonded magnets. Within this work the use of thermoset matrix materials for polymer bonded magnets should be evaluated and thus their properties shall be improved. Therefore anistotropic magnetic particles will be incorporated in the thermoset matrix and they will be oriented during the injection molding process which requires a magnetic field in the cavity during processing. Especially the influences of the matrix material, the particle geometry, the flow direction and the aligning field on the particle orientation should be investigated and together with fundamental analytical procedures guidelines for engineering of parts should be generated as well as first approaches for a simulation of the part properties shall be given.

<p>Additive manufacturing of gun propellants is an emerging and promising field which addresses the limitations of conventional manufacturing techniques. Gun propellants are manufactured using wetted extrusion, which uses volatile solvents and dies of limited and constant geometries. On the other hand, additive techniques are faced with the challenges of maintaining the gun propellant’s energetic content as well as its structural integrity during high pressure combustion. The work presented in this thesis demonstrates the feasibility of producing functioning gun propellant grains using vibration-assisted 3D printing, a novel method which has been shown to extrude extremely viscous materials such as clays and propellant pastes. At first, the technique is compared to screw-driven additive methods which have been used in printing gun propellant pastes with slightly lower energetic content. In chapter two, diethylene glycol dinitrate (DEGDN), a highly energetic plasticizer, was investigated due to its potential to replace nitroglycerin in double base propellants with high nitroglycerin content. A novel isoconversional method was applied to analyze its decomposition kinetics. The ignition and lifetime values of diethylene glycol dinitrate were obtained using the new isoconversional method, in order to assess the safety of using the plasticizer in a modified double base propellant. In chapter three, a modified double base propellant (M8D) containing DEGDN was additively manufactured using VAP. The printed strands had little to no porosity, and their density was nearly equal to the theoretical maximum density of the mixture. The strands were burned at high pressures in a Crawford bomb and the burning was visualized using high speed cameras. The burning rate equation as a function of the M8D propellant as a function of pressure was obtained. Overall, this work shows that VAP is capable of printing highly energetic gun propellants with low solvent content, low porosity, with high printing speeds, and which have consistent burning characteristics at high pressures. </p>

Au cours des dernières années, le développement des batteries Li-ion a révolutionné nos modes de vie. Compte tenu de la croissance exponentielle en batteries, le besoin se répercute sur les matériaux de base, qui sont entre autres, synthétisés à partir de sels de lithium de haute pureté. Nemaska Lithium, une entreprise partenaire du projet, est reconnue en tant que nouveau producteur d’hydroxyde de lithium, par l’entremise d’un procédé électromembranaire breveté. Comparativement au procédé conventionnel, la solution mise en place est l’une des méthodes la plus économique et écologique à l’échelle mondiale. Dans le but de diminuer encore plus les coûts énergétiques du procédé, l’usage d’une anode dépolarisée à l’hydrogène ((ADH); H2(g) ⇄ 2H+(aq) +2é; E=0,00 V) est considérée. Cette approche demande une certaine compréhension et optimisation de l’électrode à des fins d’adaptation pour l’électrolyse. Ainsi, ce travail tant fondamental qu’appliqué a été réalisé afin d’étudier les phénomènes se produisant à l’ADH. Dans un premier temps, une étude portée sur la cinétique de réaction de l’oxydation de l’hydrogène à l’aide d’une électrode à disque tournant est réalisée. L’influence d’ions lithium et d’une couche catalytique composite sur l’efficacité de la réaction a ainsi pu être démontrée. L’identification des limitations du système a ensuite permis l’optimisation de l’ADH à l’aide d’un plan d’expérience. L’ADH est composée d’un ionomère, d’un catalyseur et d’un support à catalyseur, qui ont des propriétés intrinsèques ayant un impact direct sur l’efficacité et la durabilité de celle-ci. Conséquemment, pour une étude de performance et d’optimisation, plusieurs configurations d’assemblage d’électrode à membrane (MEA) ont été considérées visant à faire varier les proportions des différentes composantes avec un plan d’expérience. Ce projet a ainsi permis l’étude menant à une meilleure compréhension d’une nouvelle technologie d’électrolyse membranaire. / In recent years, the development of Li-ion batteries has revolutionized our lifestyles. Given the exponential demand for batteries, the requirement is for base materials, which are synthesized from high-purity lithium salts. Nemaska Lithium, a partner in the project, is recognized as a new producer of lithium hydroxide, using a patented electromembrane process. Compared to the conventional process, this solution is one of the most economical and environmentally friendly methods worldwide. In order to further reduce the energy costs of the process, the use of a hydrogen depolarized anode ((HDA); H2(g) ⇄ 2H+(aq) +2é; E0=0,00 V) is considered. This approach requires some understanding and optimization of the electrode for electrolysis adaptations. Thus, this fundamental and applied work was conducted to study the phenomena occurring at the HDA. First, a study on the kinetics of the hydrogen oxidation reaction using a rotating disk electrode is performed. The influence of lithium ions and a composite catalytic layer on the efficiency of the reaction was demonstrated. The identification of system limitations allowed the optimization of the DHA using a design of experiment. The components of a HDA have intrinsic properties which have a direct impact on its efficiency and durability. They consist of an ionomer, a catalyst, and a catalyst support. Consequently, for a performance and optimization study, several membrane electrode assembly (MEA) configurations were considered in order to vary the proportions of the different components with a design of experiment. This study provided a better understanding and development of this new membrane electrolysis technology.