Les alliages de zirconium sont utilisés notamment dans les assemblages de combustible nucléaire pour leur transparence aux neutrons ainsi que pour leur tenue mécanique et leur résistance à la corrosion. La connaissance de leur microstructure et de son évolution est nécessaire pour maîtriser les différents traitements thermomécaniques de la gamme de transformation qui comporte plusieurs trempes depuis le domaine bêta. Cette microstructure présente, à l’issue d’une trempe, des lamelles dites de Widmanstätten. Ces dernières soit se disposent parallèlement entre elles (platelets parallèles), soit se croisent en vannerie. Ces morphologies jouent sur l’étape suivante de filage ; en effet, les platelets parallèles défavorisent la fragmentation des lamelles. Une méthode a été mise en place pour quantifier ces morphologies.Lors de la transformation bêta vers alpha, un grain peut générer 12 orientations alpha (variants). Les paramètres qui influencent leur sélection sont encore peu connus. Le modèle proposé minimise la déformation moyenne lors de la transformation. D’abord analytique, il a été ensuite implémenté numériquement afin d’aborder des effets tels que la relaxation d’Eshelby, l’anisotropie élastique, une contrainte extérieure ou le voisinage. En parallèle, la sélection expérimentale a été quantifiée au moyen original de l’EBSD et des fractions des variants locales dans un ex-grain bêta. La confrontation des résultats expérimentaux avec le modèle a permis de le valider en partie et de déterminer la contrainte de trempe à la surface des éprouvettes ainsi que son effet sur la sélection de variants. / Zirconium alloys are frequently used in nuclear fuel assemblies. They are chosen for their low neutron absorption, their mechanical properties and their corrosion resistance. A better understanding of the microstructure evolution of these alloys should allow a better control of their process of fabrication. During processing, several quenches, from the beta to the alpha domain take place. The resulting microstructures are lamellar and are called Widmanstätten microstructures. These lamellae are either disposed in parallel or in crisscross and are named “parallel platelets” and “basketweaves”, respectively. These various morphologies have a significant impact on the extrusion; basketweaves facilitate grain fragmentation unlike parallel platelets. In this thesis project, a methodology was developed in order to quantify these morphologies.During the phase transformation, one beta grain can generate 12 different orientations of new alpha grains. The parameters which can influence variants selection are not yet well-known. The model proposed in the present study is based on the minimization of the mean elastic energy of the system during the phase transformation. First results were obtained analytically. Then, additional effects such as the Eshelby relaxation, the elastic anisotropy and the external strain were implemented numerically. In parallel, each alpha variant was quantified within a former beta grain by EBSD analysis. The comparison between the model and the experiments helped to partially validate the model as well as determine the quench strain on the surface of the sample. It was then possible to study the effect of quench strain on the variant selection.

No description available.

Catalytic hydrotreating (HDT) is a mature process technology practiced in the petroleum refining industries to treat oil fractions for the removal of impurities (such as sulfur, nitrogen, metals, asphaltene). Hydrotreating of whole crude oil is a new technology and is regarded as one of the more difficult tasks that have not been reported widely in the literature. In order to obtain useful models for the HDT process that can be confidently applied to reactor design, operation and control, the accurate estimation of kinetic parameters of the relevant reaction scheme are required. This thesis aims to develop a crude oil hydrotreating process (based on hydrotreating of whole crude oil followed by distillation) with high efficiency, selectivity and minimum energy consumption via pilot plant experiments, mathematical modelling and optimization. To estimate the kinetic parameters and to validate the kinetic models under different operating conditions, a set of experiments were carried out in a continuous flow isothermal trickle bed reactor using crude oil as a feedstock and commercial cobaltmolybdenum on alumina (Co-Mo/γ-Al2O3) as a catalyst. The reactor temperature was varied from 335°C to 400°C, the hydrogen pressure from 4 to10 MPa and the liquid hourly space velocity (LHSV) from 0.5 to 1.5 hr-1, keeping constant hydrogen to oil ratio (H2/Oil) at 250 L/L. The main hydrotreating reactions were hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs) and hydrodemetallization (HDM) that includes hydrodevanadization (HDV) and hydrodenickelation (HDNi). An optimization technique is used to evaluate the best kinetic models of a trickle-bed reactor (TBR) process utilized for HDS, HDAs, HDN, HDV and HDNi of crude oil based on pilot plant experiments. The minimization of the sum of the squared errors (SSE) between the experimental and estimated concentrations of sulfur (S), nitrogen (N), asphaltene (Asph), vanadium (V) and nickel (Ni) compounds in the products, is used as an objective function in the optimization problem using two approaches (linear (LN) and non-linear (NLN) regression). The growing demand for high-quality middle distillates is increasing worldwide whereas the demand for low-value oil products, such as heavy oils and residues, is decreasing. Thus, maximizing the production of more liquid distillates of very high quality is of immediate interest to refiners. At the same time, environmental legislation has led to more strict specifications of petroleum derivatives. Crude oil hydrotreatment enhances the productivity of distillate fractions due to chemical reactions. The hydrotreated crude oil was distilled into the following fractions (using distillation pilot plant unit): light naphtha (L.N), heavy naphtha (H.N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R) in order to compare the yield of these fractions produced by distillation after the HDT process with those produced by conventional methods (i.e. HDT of each fraction separately after the distillation). The yield of middle distillate showed greater yield compared to the middle distillate produced by conventional methods in addition to improve the properties of R.C.R. Kinetic models that enhance oil distillates productivity are also proposed based on the experimental data obtained in a pilot plant at different operation conditions using the discrete kinetic lumping approach. The kinetic models of crude oil hydrotreating are assumed to include five lumps: gases (G), naphtha (N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R). For all experiments, the sum of the squared errors (SSE) between the experimental product compositions and predicted values of compositions is minimized using optimization technique. The kinetic models developed are then used to describe and analyse the behaviour of an industrial trickle bed reactor (TBR) used for crude oil hydrotreating with the optimal quench system based on experiments in order to evaluate the viability of large-scale processing of crude oil hydrotreating. The optimal distribution of the catalyst bed (in terms of optimal reactor length to diameter) with the best quench position and quench rate are investigated, based upon the total annual cost. The energy consumption is very important for reducing environmental impact and maximizing the profitability of operation. Since high temperatures are employed in hydrotreating (HDT) processes, hot effluents can be used to heat other cold process streams. It is noticed that the energy consumption and recovery issues may be ignored for pilot plant experiments while these energies could not be ignored for large scale operations. Here, the heat integration of the HDT process during hydrotreating of crude oil in trickle bed reactor is addressed in order to recover most of the external energy. Experimental information obtained from a pilot scale, kinetics and reactor modelling tools, and commercial process data, are employed for the heat integration process model. The optimization problem is formulated to optimize some of the design and operating parameters of integrated process, and minimizing the overall annual cost is used as an objective function. The economic analysis of the continuous whole industrial refining process that involves the developed hydrotreating (integrated hydrotreating process) unit with the other complementary units (until the units that used to produce middle distillate fractions) is also presented. In all cases considered in this study, the gPROMS (general PROcess Modelling System) package has been used for modelling, simulation and parameter estimation via optimization process.

Durant cette thèse, je me suis intéressé à deux thématiques générales qui peuvent être explorées dans des systèmes d'atomes froids : d'une part, la dynamique hors-équilibre d'un système quantique isolé, et d'autre part l'influence du désordre sur un système fortement corrélé à basse température. Dans un premier temps, nous avons développé une méthode de champ moyen, qui permet de résoudre la dynamique unitaire dans un modèle à géométrie particulière, le réseau complètement connecté. Cette approche permet d'établir une correspondance entre la dynamique unitaire du système quantique et des équations du mouvement classique. Nous avons mis à profit cette méthode pour étudier le phénomène de transition dynamique qui se signale, dans des modèles de champ moyen, par une singularité des observables aux temps longs, en fonction des paramètres initiaux ou finaux de la trempe. Nous avons montré l'existence d'une transition dynamique quantique dans les modèle de Bose-Hubbard, d'Ising en champ transverse et le modèle de Jaynes-Cummings. Ces résultats confirment l'existence d'un lien fort entre la présence d'une transition de phase quantique et d'une transition dynamique.Dans un second temps, nous avons étudié un modèle de théorie des champs relativiste avec symétrie O(N) afin de comprendre l'influence des fluctuations sur ces singularités. À l'ordre dominant en grand N, nous avons montré que la transition dynamique s'apparente à un phénomène critique. En effet, à la transition dynamique, les fonctions de corrélations suivent une loi d'échelle à temps égaux et à temps arbitraires. Il existe également une longueur caractéristique qui diverge à l'approche du point de transition. D'autre part, il apparaît que le point fixe admet une interprétation en terme de particules sans masse se propageant librement. Enfin, nous avons montré que la dynamique asymptotique au niveau du point fixe s'apparente à celle d'une trempe d'un état symétrique dans la phase de symétrie brisée. Le troisième volet de cette thèse apporte des éléments nouveaux pour la compréhension du diagramme des phases du modèle de Bose-Hubbard en présence de désordre. Pour ce faire,nous avons utilisé et étendu la méthode de la cavité quantique en champ moyen de Ioffe et Mézard, qui doit être utilisée avec la méthode des répliques. De cette manière, il est possible d'obtenir des résultats analytiques pour les exposants des lois de probabilité de la susceptibilité.Nos résultats indiquent que dans les différents régimes de la transition de phase de superfluide vers isolant, les lois d'échelle conventionnelles sont tantôt applicables, tantôt remplacées par une loi d'activation. Enfin, les exposants critiques varient continûment à la transition conventionnelle.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

The United States holds the world's largest estimated reserves of coal and is also a net exporter of it. Coal gasification provides a cleaner way to utilize coal than directly burning it. Gasification is an incomplete oxidation process that converts various carbon-based feedstocks into clean synthetic gas (syngas), which can be used to produce electricity and mechanical power with significantly reduced emissions. Syngas can also be used as feedstock for making chemicals and various materials. A Computational Fluid Dynamics (CFD) scheme has been used to simulate the gasification process for many years. However, many sub-models still need to be developed and improved. The objective of this study is to use the improved CFD modeling to understand the thermal-flow behavior and the gasification process and to provide guidance in the design of more efficient and cheaper gasifiers. Fundamental research has been conducted to improve the gasification sub-models associated with the volatile thermal cracking, water-gas-shift (WGS) reaction, radiation effect, low-rank-coal gasification, coal to synthetic-natural-gas (SNG), and ash deposition mechanisms. The improved volatile thermal cracking model includes H2S and COS contents. A new empirical WGS reaction model is developed by matching the result with experimental data. A new coal demoisturization model is developed for evaporating the inherent moisture inside the coal particles during low-rank-coal gasification. An ash deposition model has also been developed. Moreover, the effect of different radiation models on the simulated result has been investigated, and the appropriate models are recommended. Some improved model tests are performed to help modify an industrial entrained-flow gasifier. A two-stage oxygen feeding scheme and a unique water quench design are investigated. For the two-stage oxygen feeding design, both experimental data and CFD predictions verify that it is feasible to reduce the peak temperature and achieve a more uniform temperature distribution in the gasifier by controlling the injection scheme without changing the composition and production rate of the syngas. Furthermore, the CFD simulation can acceptably approximate the thermal-flow and reaction behaviors in the coal gasification process, which can then be used as a preliminary screening tool for improving existing gasifiers’ performance and designing new gasifiers.

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are by-products emitted from combustion sources such as municipal solid waste (MSW) incineration plants. These organic compounds are recognized as toxic, bioaccumulative and persistent in the environment. PCDD/Fs are removed from flue gases before released from MSW incineration. However, the PCDD/Fs are not destroyed but retained in the residues, thus in the environment. Understanding the pathways that lead to their formation is important in order to develop ways to suppress their formation and prevent their release into the environment. Suppressing the formation can also allow less expensive air pollution control system to be used, and/or the costs of thermally treating the residues to be reduced. The main objective of the studies underlying this thesis was to elucidate process, combustion and fuel parameters that substantially affect the emission levels and formation of PCDD/Fs in flue gases from MSW incineration. The experiments were conducted under controllable, realistic combustion conditions using a laboratory-scale reactor combusting artificial MSW. The parameter found to most strongly reduce the PCDD/F emissions, was prolonging the flue gas residence time at a relatively high temperature (460°C). Increasing the sulfur dioxide (SO2) to hydrogen chloride (HCl) ratio to 1.6 in the flue gas was also found to reduce the PCDF levels, but not the PCDD levels. Fluctuations in the combustion process (carbon monoxide peaks), high chlorine levels in the waste (1.7%) and low temperatures in the secondary combustion zone (660°C) all tended to increase the emission levels. The PCDD/PCDF ratio in the flue gas was found to depend on the chlorine level in the waste, fluctuations in the combustion process and the SO2:HCl ratio in the flue gas. The formation pathways were found to be affected by the quench time profiles in the post-combustion zone, fluctuations in the combustion process and addition of sulfur. In addition, increased levels of chlorine in the waste increased the chlorination degrees of both PCDDs and PCDFs. A tendency for increased SO2 levels in the flue gas to increase levels of polychlorinated dibenzothiophenes (sulfur analogues of PCDFs) was also detected, however the increases were much less significant than the reduction in PCDF levels.

This thesis contributes to an increased understanding of the formation of dioxins and dioxin-like compounds in combustion processes. Although emissions to air from waste incineration facilities have been greatly reduced by the use of efficient air pollution control measures, the resulting residues (ashes and filters) are highly toxic and are classified as hazardous waste. The main objective of the work underlying this thesis was to elucidate the formation and chlorination pathways of dioxins and dioxin-like compounds in waste combustion flue gases in the temperature range 640-200°C in a representative, well-controlled laboratory-scale reactor using artificial municipal solid waste. This could contribute to the reduction of harmful emissions to air and also reduce the toxicity of waste incineration residues, thus reducing or even eliminating the need for costly and potentially hazardous after-treatment. A comparison of four different quenching profiles showed that the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) was rapid and mainly occurred in the 640-400°C temperature region, with high dependency on sufficient residence time within a specific temperature region. Prolonged residence time at high temperatures (450/460°C) reduced the PCDD yields, even at lower temperatures along the post-combustion zone. PCDD, PCDF and PCN (polychlorinated naphthalene) isomer distribution patterns indicated contributions from chlorophenol condensation as well as chlorination reactions for all three classes of compounds. The formation of PCDDs was largely influenced by chlorophenol condensation and to some extent by chlorination reactions. For the PCDFs, chlorine substitution adjacent to the oxygen bridges was unfavoured, as demonstrated by the notably lower abundance of 1,9-substituted congeners. This was supported by bidirectional orthogonal partial least squares (O2PLS) modelling. The variable with the greatest influence on the distribution of PCDD congeners was the relative free energy (RΔGf). The O2PLS models displayed distinct clusters, dividing most of the homologues into two or three sub-groups of congeners which seemed to correspond to the probability of origination from chlorophenol condensation. The effects of injection of aromatic structures into the flue gas differed for each class of compounds. Injection of naphthalene increased the formation of monochlorinated naphthalene but the remaining homologues appeared to be unaffected. This was probably due to insufficient residence time at temperatures necessary for further chlorination. Injected dibenzo-p-dioxin was decomposed, chlorinated and re-condensated into PCDDs and PCDFs, whereas injection of dibenzofuran and fluorene reduced the PCDD levels in the flue gas. / Denna avhandling fokuserar på olika aspekter som kan bidra till en ökad förståelse av bildning av dioxiner och dioxin-lika föreningar i förbränningsprocesser. Även om utsläppen till luft från sopförbränningsanläggningar har minskat kraftigt tack vare effektiva rökgasreningsmetoder, så återstår problemet med mycket giftiga rökgasreningsprodukter (askor och filter), vilka klassificeras som farligt avfall. Det huvudsakliga syftet med arbetet bakom denna avhandling var att klarlägga bildnings- och kloreringsvägarna för dioxiner och dioxin-lika föreningar i temperaturintervallet 640-200°C i rökgaser från sopförbränning. Detta kan möjliggöra lösningar för ytterligare emissionsminskningar och en avgiftning av biprodukterna från avfallsförbränning, vilket minskar eller till och med eliminerar behovet av kostsam och riskfylld efterbehandling. Realistiska och välkontrollerade försök har utförts i en lab-skalereaktor där en artificiell hushållssopa har förbränts. En jämförelse av fyra olika temperatur- och uppehållstidsprofiler visade att bildning av polyklorerade dibenso-p-dioxiner (PCDD) och dibensofuraner (PCDF) sker snabbt och huvudsakligen inom temperaturintervallet 640-400°C. Bildningen var starkt beroende av en tillräckligt lång uppehållstid inom ett visst temperaturområde. En förlängd uppehållstid vid höga temperaturer (>450°C) resulterade i minskade halter av PCDD, vilka förhöll sig låga även senare i efterförbränningszonen. Isomermönstren av PCDD, PCDF och PCN (polyklorerade naftalener) visade alla tecken på att härröra från både klorfenolkondensation och kloreringsreaktioner. PCDD-mönstret visade tydliga indikationer på bildning från klorfenoler, och till mindre grad bildning via klorering. För PCDF var klorsubstitution i positioner angränsande till syrebryggan missgynnad, vilket bekräftades av multivariat modellering (O2PLS). Den variabel som starkast påverkade bildningen av PCDD var relativa fria energin (RΔGf). Modellerna visade på en distinkt gruppering av PCDD- och PCDF-kongenerna i två eller tre grupper för varje kloreringsgrad, och föreslås vara relaterad till sannolikheten för respektive kongen att bildas via klorfenolkondensation. Injektion av aromatiska kolstrukturer i rökgaskanalen gav upphov till skilda effekter. Injektion av naftalen ökade bildningen av monoklorerad naftalen medan resterande homologer inte verkade påverkas, sannolikt på grund av för kort uppehållstid för ytterligare klorering. Dibenso-p-dioxin spjälkades sannolikt till fenoliska fragment som klorerades och sedan återkondenserades till PCDD och PCDF, medan dibensofuran och fluoren kraftigt reducerade PCDD-koncentrationerna.

Proton-coupled electron transfer (PCET) is one of the elementary reactions occurring in many chemical and biological systems, such as photosystem II where the oxidation of tyrosine (TyrZ) is coupled to deprotonation of the phenolic proton. This reaction is here modelled by the oxidation of a phenol covalently linked to a Ru(bpy)32+-moitey, which is photo-oxidized by a laser flash-quench method. This model system is unusual as mechanism of PCET is studied in a unimolecular system in water solution. Here we address the question how the nature of the proton accepting base and its hydrogen bond to phenol influence the PCET reaction. In the first part we investigate the effect of an internal hydrogen bond PCET from. Two similar phenols are compared. For both these the proton accepting base is a carboxylate group linked to the phenol on the ortho-position directly or via a methylene group. On the basis of kinetic and thermodynamic arguments it is suggested that the PCET from these occurs via a concerted electron proton transfer (CEP). Moreover, numerical modelling of the kinetic data provides an in-depth analysis of this CEP reaction, including promoting  vibrations  along the O–H–O coordinate that are required to explain the data. The second part describes the study on oxidation of phenol where either water or an external base the proton acceptor. The pH-dependence of the kinetics reveals four mechanistic regions for PCET within the same molecule when water is the base. It is shown that the competition between the mechanisms can be tuned by the strength of the oxidant. Moreover, these studies reveal the conditions that may favour a buffer-assisted PCET over that with deprotonation to water solution.

Bakgrunden till detta examensarbete var att Qumex Materialteknik vid ett flertal tillfällen konstaterat att material av typen SS 0725 har uppvisat bristfälliga härdresultat. Materialet, som är relativt nytt på marknaden, är ett gjutjärn av typen segjärn och utmärker sig gentemot andra segjärn på grund av sitt höga innehåll av kisel. Då segjärn enligt den nu gällande EN-standarden klassificeras efter sina mekaniska egenskaper uppstår ett problem gällande SS 0725. Materialet uppfyller de krav som är ställda för EN-GJS-500-7 och hamnar därmed under samma materialbeteckning som ett segjärn med betydligt lägre kiselhalt. Att två material med olika kemisk sammansättning hamnar under samma beteckning kan innebära problem. Syftet med denna rapport är att fastslå vilken påverkan den höga kiselhalten har på materialet vid värmebehandling av typen släckhärdning med efterföljande anlöpning. I försöken ingick fyra material. Det som skiljde materialen åt var halterna av koppar och kisel. De härdades vid tre olika temperaturer och under tre olika tider för att sedan släckas i olja. Målet med släckhärdningen var att materialen skulle få en helt martensitisk struktur vilket då klassades som ett bra härdresultat. Resultatet utvärderades sedan genom optisk mikroskopi och hårdhetsmätningar. En undersökning av materialens fasomvandlingstemperaturer genomfördes med hjälp av Differential Scanning Calorimetry. Resultatet visar att kiselhalten har stor påverkan på den temperatur som krävs för att erhålla ett bra härdresultat. För material med låg kiselhalt uppnåddes fullständig martensitbildning efter släckhärdning från 840°C. För material med hög kiselhalt uppnåddes liknande strukturella och hårdhetsmässiga resultat först vid en så hög temperatur som 900°C och behandlingstider längre än 1 h. Den relativa skillnad som uppmättes i fasomvandlingstemperatur med hjälp av Differential Scanning Calorimetry mellan högkiselmaterial och lågkiselmaterial var 45°C. Detta resultat kombinerat med analyserna av härdprocesserna visar att det krävs kraftigt ökad temperatur vid värmebehandling av högkiselmaterialet SS 0725. / The background to this thesis was that Qumex Materialteknik at several occasions had received material of type SS 0725 that had shown deficient heat treatment results. The material, which is relatively new, is a cast iron of type ductile iron and differ against other ductile irons because of its high silicon content. According to EN standard ductile irons are classified by their mechanical properties. A problem then occurs with the new material SS 0725 because of this. The material fulfils the requirements for EN-GJS-500-7 and is therefore in the same classification as a ductile iron with much lower silicon content. Two materials having major differences in chemical composition ending up in the same classification can be problematic. The purpose of this report is to determine impact of high silicon content in ductile iron when heat treated and quench hardened. The experiment included four materials, and the major difference between the materials were their content of copper and silicon. The heat treatment process was performed at three different temperatures and three different treatment times. Afterwards the samples were quenched in oil. The ambition of the quench hardening was to obtain a material structure of 100% martensite. By optical microscopy and hardness measurements the results then were evaluated. An investigation of the phase transformation temperature in the materials was made by using Differential Scanning Calorimetry. The results show that the amount of silicon content has great influence on the temperature for receiving good hardening results. To achieve 100% martensite after quench hardening in materials with low silicon content the temperature needs to be over 840°C. For material with high level of silicon content the temperature for achieving 100% martensite needs to be 900°C and the treatment time should be over 1 h. The relative difference in phase transformation temperature was measured using Differential Scanning Calorimetry. The results of the measurements between the materials with high silicon content and materials with low silicon content was 45°C. This result combined with the analysis of the heat treatment process shows that a major increase of the temperature is needed to heat treat SS 0725.