Les usines de l’amont du cycle du combustible nucléaire, génèrent des effluents industriels faiblement chargés en uranium. La récupération de l’uranium de ces effluents vise à les décatégoriser (diminution de la radioactivité) et à valoriser l’uranium recyclé. L’acide sulfurique est majoritairement utilisé dans l’amont du cycle du combustible. Dans ces conditions, l’uranium est sous forme de complexes de sulfates d’uranyles qu’il convient d’extraire sélectivement vis-à-vis d’ions compétiteurs comme le Mo ou le Fe. Plusieurs procédés peuvent être envisagés : précipitation, extraction liquide-liquide et extraction sur supports solides. Cette dernière technique est particulièrement attractive pour des solutions faiblement chargées en uranium : elle est éco-responsable (évite la manipulation de solvants organiques), les procédés sont compacts et nécessitent peu de manipulations (i.e. extraction sur lit fixe). Parmi les supports solides à forts potentiels, les silices mésoporeuses occupent une place de choix de par leur grande surface spécifique, leur facilité de synthèse et leur facilité de caractérisation.Cette thèse se propose d’évaluer l’extraction d’uranium en milieu sulfurique par l’utilisation de silices hybrides mésoporeuses au sein desquelles sont greffées des molécules extractantes sélectives. Dans un premier temps, différentes molécules extractantes ont été sélectionnées, synthétisées puis greffées sur une silice commerciale afin d’évaluer les propriétés extractives de ces différentes familles d’extractant. Les N,N-carbamoylalkylphosphonates ont été identifiées comme étant des molécules intéressantes en terme de propriétés extractives. De plus, cette étude souligne la nécessité d’avoir un monoacide sur le groupement phosphonate et montre l’importance des chaines alkyles aussi bien sur le phosphonate que sur le groupement amide. A la suite de ce travail, l’impact du diamètre de pore des supports de silice sur la configuration de la partie organique greffée et sur les propriétés d’extraction de l’uranium a été mis en évidence. Une gamme de porosité (entre 3 et 20 nm) pour laquelle les matériaux hybrides sont homogènes et présentent une bonne efficacité d’extraction a été identifiée. Pour parfaire la compréhension des mécanismes d’extraction via les supports hybrides, une étude paramétrique (pH, force ionique, présence d’éléments compétiteurs) a été menée en parallèle d’analyses spectrométriques (EXAFS, FT-IR, Raman, DRX). Ces techniques ont permis de proposer un mécanisme d’extraction au sein du solide impliquant deux diamido-phosphonates par uranyle. Les résultats obtenus à l’échelle moléculaire sont en accord et confortent les propriétés macroscopiques observées lors de l’analyse paramétrique. / Nuclear industries are perpetually looking for technical, economic and environmental progresses. Important volumes of acidic waste are generated by nuclear plants of the front end. The extraction of uranium from these solutions is required to decontaminate effluents (decrease of the radioactivity) and value uranium (reincorporation in the cycle). Uranium leaching is mostly achieved using sulfuric acid leading to the production of aqueous effluents that contain a large grade of sulfate complexes. In such conditions, uranyl sulfate complexes constitute the predominant uranium species in solution and its extraction represents a real scientific and technological challenge. Commonly, precipitation, solvent extraction or solid phase extraction are used. The last one is particularly adapted for low grade solutions due to it weak environmental footprint (no solvent are handling) and the facility of the process involved (i.e. fixed bed column). Among the available solid-phase extraction candidates, hybrid mesoporous silicas get a crucial part. They develop a very high specific surface areas and a driven porosity which give them a high potential of extraction capacities.In this manuscript the tailoring and the evaluation of hybrid mesoporous silicas have been investigated. Firstly, the work focus on the organic part grafted by post-synthetic pathway, the N,N-dialkylcarbamoylphosphonate based molecules have been identified to get interesting extraction properties. This study emphasizes that acid groups are required and that alkyl substituents get a real importance in the extraction efficiency. On the second hand, the role of pore size has been investigated. The results obtained disclosed that pores size diameters directly impact the grafting ratio as well as the homogeneity of the material: (1) materials with a pore size below 3 nm are heterogeneously functionalized due to steric issues, (2) a homogeneous organic monolayer grafted onto the silica skeleton occurs when the pore size ranges from 3 nm to 20 nm and (3) functionalization of material having pore size above 30 nm results in an organic multilayer covalently linked to the surface. The organic self-organization drives the extraction efficiency, only monolayers lead to promising results. At the saturation state, two molecules are required to extract one uranyl ion. To describe the molecular scale of the uranyl complex onto the solid, the local structure has been investigated by a parametric study and spectroscopic techniques (IR, EXAFS and DRX). Results reveal that two diamido-phosphonates are involved in the uranyl extraction. By this work, it is shown how the molecular scale helps to understand the macroscopic phenomena.Finally, continuous extraction in a fixed bed column confirms the extractive properties obtained in batch mode experiments and points out the potential of such material to be reused several times without any damages.

In U.S. schools, Black and Hispanic youth receive discipline in the form of office discipline referrals and out-of-school suspensions at a rate greater than their White peers. Contributing factors to this “discipline gap” may be found across a number of ecological variables. Therefore, multifaceted and systemic interventions such as school-wide positive behavior interventions and supports (SWPBIS) should be evaluated for their effectiveness in producing more equitable school discipline rates. In light of mixed evidence for the relationship of SWPBIS with discipline equity, the purpose of this study was to examine the merits of five critical elements of SWPBIS for reducing discipline rates for Black and Hispanic students and for closing the discipline gap. Among a sample of 322 Florida SWPBIS-implementing schools serving a total of 292,490 students, SWPBIS fidelity’s relationships with discipline rates and with disparities were investigated. The Benchmarks of Quality, a psychometrically sound measure of SWPBIS fidelity completed by a school-based team and an external coach, was completed at each school. Results of multiple linear regression analyses indicated that higher fidelity to SWPBIS Classroom Systems was related to decreased discipline risk for all students, including Black and Hispanic students, but not more equitable discipline practices. Higher fidelity to SWPBIS Expectations was related to higher suspension risk among Black students while higher levels of Recognition were related to more equitable suspension practices. No significant relationships were observed between Lessons and Data Analysis and disciplinary rates or equity. Implications for the research and practice of SWPBIS are discussed, along with connections to other lines of research addressing educational equity.

Underground excavations break the balance of the initial stress field and cause stress redistributions in the surrounding rock masses. Problems normally arise as the stress exceeds the rock mass strength. In addition, the rock mass contains preexisting defects, such as the fissures, fractures, joints, faults, shear zones, dikes, etc., which could significantly weaken the rock mass strength and make the rock mass behavior complicated. The stability of underground excavations is of great importance to an operating mine project since it ensures the safety of the working environment and the successful ore exploration. Due to the complex geological conditions and engineering disturbances, the assessment of rock mass stability for a practical engineering problem is extremely challenging and difficult, which needs to be solved by the modern numerical methods. In this dissertation, the rock mass stability around tunnels in an underground mine in the USA was investigated by performing three-dimensional modeling using the 3DEC 3-Dimensional Distinct Element Code. Comprehensive stress analyses were respectively carried out on a preliminary model and a more advanced model. In the preliminary study, the built model contains the inclined lithologies, a non-persistent fault, and a convoluted tunnel system. The geomechanical property values used for the rock masses and discontinuities in the numerical model were estimated using the available geotechnical information and the experience of the research group. The Mohr-Coulomb and strain softening constitutive relations were prescribed for the rock masses; the coulomb slip joint model was assigned for the discontinuities. The influence of the boundary conditions, block constitutive models, horizontal in situ stress and rock support system on the tunnel stability was investigated. The rock mass behavior was quantified using the results of stress, displacement, and yielded zones around the tunnels. It showed that the roller boundary conditions resulted in slightly different but comparable results with the combined boundary conditions (roller and stress combined) where K0 equals to 0.4 or 0.5. Whereas the in-situ stress field for a complex geological system can only be obtained by applying proper boundary stresses and then by performing stress analysis. The softening behavior of the rock masses caused more deformations and yielded zones around the tunnels; the rock masses around the tunnels were observed to reach the residual strength values, which can be treated as failed areas. In addition, the M-C and s-s rock masses reacted differently as the K0 value changed. At K0=1.0, the tunnels seemed to be the most stable; K0=1.5, however, provided the worst scenario with roof and floor problems. With respect to the effectiveness of the support system, a large amount of the bonds of the supports was failing, thus, the deformations and yielded zones around the tunnels were slightly improved. Finally, comparisons between the numerical modeling results and the field measurements implied the applicability of strain softening behavior and a K0 value between 0.5 and 1.0 for the mine. Based on the specific geological, geotechnical, and construction information, a numerical model incorporating accurate features was developed. It includes a non-planar, weak interlayer, the persistent and non-persistent faults, and the open and backfilled excavations. The mechanical property values used for the rock masses and faults were estimated based on the laboratory test results of the intact rock and smooth joints. The strain softening behavior was specified for the rock masses belonging to the average quality, and the rock masses that reached residual strengths were assumed to be failing. The linear relations between the fault stiffnesses and normal stress were described using the continuously yielding joint model. To simulate the mine construction process in the field, the sequential excavation, backfilling, and supporting procedures were numerically implemented; additionally, a novel routine was applied to account for the delayed installation of the supports. Results showed that the tunnels close to the fault and the backfilled area were less stable. Most of the displacements around the tunnels occurred within a distance of zero to 2 or 3 m from the tunnel surface. The varying K0 value caused great changes in the rock mass behavior and the shear behavior of the major fault; significant instability of the tunnels was triggered by the high horizontal in situ stress. Parametric studies on the rock mass condition, rock mass residual strengths, and fault property values showed that the tunnel stability was more sensitive to the former two factors than the last one. A systematic investigation was conducted to evaluate the current rock supports installed at the mine where the increasing stress relaxation was incorporated. The deformations and of the failure zone thicknesses around the tunnels were reduced up to 8% and 20% after applying the supports instantaneously, and the reductions were improved by the delayed installation of supports. Additionally, the safety of supports was evaluated by the bond shear and bolt tensile failures, which was also improved with incorporation of delayed supporting. It was found that the current rock supports are insufficient in length, bond and tensile strengths. Therefore, a stronger support system was suggested. The stronger supports worked better in stabilizing the tunnels. Based on the deformations and failures of the rock masses, the length of the bolts on walls was suggested to be 4-5 m. At the end, the horizontal convergence strain predicted by the numerical simulations were calculated at two locations where the tape extensometers were installed. Good agreements with the field measurements were obtained for the cases that have the average rock mass properties and K0 values in the range 0.5-1.25.

Les outils lithiques sont nombreux aux âges des métaux, mais encore peu étudiés. Dans les activités de mise en forme des métaux, ils sont représentés essentiellement par les supports de frappe, les abrasifs, les brunissoirs, les outils d’aiguisage et les outils de broyage. Certains sont également fabriqués en métal (supports de frappe) ou en céramique (abrasifs, outils d’aiguisage). Les formes contemporaines de ces outils sont trop différentes pour permettre une comparaison directe. Il est donc nécessaire de travailler à partir de la fonction des outils, déduite de l’analyse de leur structure. Les supports de frappe liés à la mise en forme du métal sont facilement identifiables. Ils permettent de restituer de façon plus ou moins précise les objets qu’ils ont servis à fabriquer. Les abrasifs sont difficiles à relier à un matériau, mais leurs traces d’utilisation sont caractéristiques des profils des objets. Les brunissoirs sont caractéristiques du travail du métal, surtout la tôle. Les outils d’aiguisage sont essentiellement conçus pour l’entretien des lames, mais il est possible d’identifier certains outils utilisés pour le travail de taillanderie. Les outils de broyage sont également utilisés pour la cuisine. Mais on peut distinguer les exemplaires utilisés pour le broyage des matériaux (terre, dégraissant). L’étude de la pierre permet également de reconstituer les sources d’approvisionnement en matériaux et de reconstituer les axes d’échanges et d’exploitation du territoire. / Lots of lithic tools are present in Metal Ages, but few are studied. In metal production, they are especially constitued by strike supports, abrasives, burnishers, sharpening tools and crushing tools. A part of them are in metal ( strike supports) or in ceramic (abrasives, sharpening tools). Contemporary forms of these tools are too different to permit a dierct comparison. It is necessary to work on the function of the tools, deduced from the analysis of these structure. Strike supports used for metal working are easily identifiable. They allow to reproduce more or less precisely the objects that they were fabricated with. Abrasives are difficult to relate to a material, but the traces of use are characteristic of the profile of the objects. Burnishers are characteristic of metal working, especially sheet metal. The sharpening tools are mainly designed for the maintenance of the blades, but it is possible to indentify some of the tools used for edging.Ê The crushing tools are also used for cooking. But we can distinguish the models used for grinding materials (earth, degreaser). The study of the stone also helps reconstitute the sources of axes of trade and exploitation of the territory.

De la peau de l’être humain aux écrans d'ordinateur et d'eBook en passant parl'argile, les papyrus, la peau des animaux et le papier, les supports de l'écrit ont varié etévolué tout au long de ces siècles. Le lecteur a dû s'adapter à cette évolution des supports et,par là, de l'écriture et il a changé sa manière de lire.Avec la diffusion des nouvelles technologies, leur présence incontournable dansnotre quotidien et l'apparition de nouveaux outils comme l'eBook et l'iPad, cette rechercheexploratoire s'est intéressée aux changements de stratégies utilisées par des étudiantsuniversitaires qui lisent en situation d'apprentissage du Français Langue Etrangère surdifférents supports : l'écran d'ordinateur, le livre électronique et le support papier.Les types de discours sont également pris en compte. La nouvelle, qui relève dudiscours du raconter, et l'article d'opinion journalistique, qui relève du discours de l'exposer,ont également influencé les stratégies de reconstruction du sens des textes lus. Pour le recueildes données, les principaux outils d'investigation ont été le questionnaire et l'entretien.L'analyse du corpus a débouché sur l'établissement de figures de lecteurs et la miseen évidence de la manière de lire. Sur le plan didactique, ce travail met l'accent surl'importance de l'enseignement des stratégies en fonction des supports et des types dediscours dans le cadre de l'apprentissage d'une langue étrangère ou non. / From human skin to computer screens and eBooks, with clay, papyrus, animal skinsand paper in between writing materials have varied and evolved throughout the centuries.Readres have had to adapt to this evolution in the materials and the wrinting and they havechanged the way they read.With the wide spread use of new technologies and their omnipresence in our dailylives, the arrival of new tools, such as the eBook or the iPad. This study has sought to explorethe changes in the strategies used by university students learning French as a foreignlanguage. When reading with different reading materials : the computer screen, the eBook orpaper.The types of discourse have also been taken into consideration. The short story andthe newspaper editorial influence the strategies of the reconstruction of the meaning of thetexts that were read. To gather the data, the main tolls of investigation were questionnairesand interviews.The analysis of this data has permitted us to establish readers' types and to showhow they read. This study insists on the importance of teaching strategies that take intoconsideration the materials being used as well as the types of discouse being read, whetherin language learning or not.

La symbiose à Rhizobia ainsi que la symbiose endomycorhizienne à arbuscules, présentes dans la rhizosphère, possèdent un intérêt agrobiologique et écologique majeur ; elles permettent aux plantes de croître naturellement sur un sol aride et peu fertile. Il a été démontré récemment que les signaux (facteurs « Myc ») impliqués dans la mise en place de la symbiose endomycorhizienne à arbuscules appartiennent à la famille des lipo-chitooligosaccharides. Une nouvelle synthèse du facteur de mycorhization [Myc-IV (C16:0, S)], le plus abondant et bioactif, a été effectuée en utilisant une stratégie de synthèse par blocs utilisant des méthodes robustes de glycosylation, le diméthyldioxirane pour l’ouverture oxydante régiosélective des acétals de benzylidène et l’emploi d’un thiol peu toxique et peu odorant pour former les donneurs thioglycosides. Étant donné la purification laborieuse par chromatographie sur gel de silice des oligosaccharides après les étapes de glycosylation, une nouvelle méthode utilisant des liquides ioniques supportés a été appliquée permettant de modifier les propriétés physico-chimiques des saccharides. Les produits sont purifiés par de simples lavages grâce à ce motif ionique présent en position anomérique. Le chitooligosaccharide (CO-IV), intermédiaire clef pour la synthèse de lipo-chiooligosaccharides non sulfatés d’intérêts ou de la TMG-chitotriomycin, a ainsi été obtenu. / Rhizobia symbiosis and arbuscular mycorrhiza symbiosis have an agrobiological and ecological interest because they allow plants to grow on aride and infertile soil. Recently, the symbiotic signals (« Myc factors ») were identified as a mixture of lipo-chitooligosaccharides (LCOs). The preparation of Myc factor [Myc-IV (C16:0, S)], the most abundant and bioactive, was carried out using a blockwise synthesis. Dimethyldioxirane for a regioselective oxidative cleavage of benzylidene acetals and an odorless and few toxic thiol to form thioglycoside donors were employed. To eliminate the laborious purifications of oligosaccharides by chromatography on silica gel after each glycosylation step, we developped an ionic liquid supported strategy. The ionic liquid part changes the physico-chimical properties of the expected product and we isolated the glycostructures by simple phase-extractions. The chitooligosaccharide (CO-IV), key intermediate for the synthesis of non-sulfated lipo-chitooligosaccharides or TMG-chitotriomycin, was obtained by this strategy.

No description available.

Title: Palladium catalysts deposited over novel siliceous supports Author: Pavlína Křečková Department: Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Supervisor's e-mail address: stepnic@natur.cuni.cz Advisor: prof. Ing. Jiří Čejka, DrSc. Advisor's e-mail address: jiri.cejka@jh-inst.cas.cz Abstract Keywords: palladium; deposited catalysts; siliceous supports; C-C coupling reaction. The aim of this work was to prepare a deposited palladium catalyst from Pd2+ and twodimensional zeolite ITQ-2 bearing ≡SiCH2CH2CH2NHCH2CH2NEt2 groups at the surface. This catalys has been evaluated in the Heck reaction between n-butyl-acrylate and brombenzene to give n-butyl-cinnamate. Influence of the reaction temperature, the solvent, base and hydrate water on the progress of the Heck reaction was investigated. This work also deals with the possibility of recycling the catalyst and, due to its nature, with the quantity of leached palladium into the reaction mixture. Furthermore, the work describes differences in morphology between the fresh and a recycled catalyst.

A nonlinear finite element analysis was performed for an existing road bridge in order to see if that could show a higher load bearing capacity, as an alternative to repairing or replacing. The regular linear analysis had shown that the bridge could not take any traffic load due to the effects from large and uneven support settlements. It is a five-span reinforced concrete bridge with a continuous slab on supports made out of rows of columns. The width-to-span ratio was around 1 and the supports were angled up to about 30°, giving rise to a complex three-dimensional behaviour, which was seen and studied in the nonlinear results. Since the bending moment was the limiting factor, the nonlinear analysis focused on that. The direct result was that the load bearing capacity was 730 kN for the traffic vehicle boogie load, B, in the ultimate limit state. This was however only for the load case tested, and several more disadvantageous vehicle positions may exist. Other aspects also became limiting, as the maximum allowed vertical deflection in the serviceability limit state was reached at 457 kN. The most restraining though, was the shear capacity from the linear analysis; 78 kN, since it was not possible to simulate that type of failure with the shell elements used in the nonlinear finite element analysis. The main aim of the thesis was nonetheless reached, since the nonlinear analysis was able to show a significant increase in load bearing capacity.  A comparison was made with the settlements for the nonlinear case, to see how much influence they had on the load bearing capacity for traffic load. This was performed for both the bridge and a simple two-span beam. Both showed that there was no effect on the load bearing capacity in the ultimate limit. One thing to note was that the full settlements were applied, and with no relaxation due to creep.  Another aim of the thesis was to make comments on the practical usability of the nonlinear finite element method in load bearing capacity assessments. A linear analysis was performed before the nonlinear in order to be able to determine the load case to be used in the latter. This worked well, as the strengths of the two methods could then be utilized. Convergence problems were however encountered for the nonlinear when using the regular static solver. Due to this, the dynamic explicit calculation scheme was used instead, treating the case as quasi-static. This managed to produce enough usable results. It was concluded that the nonlinear finite element method is useable for assessment calculations, but that its strengths and weaknesses must be known in order to make it an efficient method.

Positive Behavior Support (PBS) programs are being implemented in schools in the United States to support faculty, staff, and students. The purpose of this study was to evaluate a PBS system at a rural west Texas middle school to discover what improvements are necessary for district-wide implementation and sustainability. The study drew on Bandura's social learning theory, which posits that people learn from each other through observation, imitation, and modeling. PBS systems provide the framework for exhibiting specific behavior expectations so students and teachers can get the most from their educational experiences. A program evaluation was completed using discipline data from 2008-2012 from the middle school, observations at the middle school, and archival campus improvement plan results from the campus needs assessment from 2012. The research instrument used to assess the information was a pre-established PBS evaluation system called the School-Wide Evaluation Tool (SET) designed for programmatic assessment. The SET assessment tool guided the evaluation of information gathered from 100 students, 15 teachers, and an administrative team survey to highlight the strengths and weaknesses of the PBS program in the school and district, identify necessary changes to improve its effectiveness, and determine how to best implement the system district-wide. These findings were used to inform a white paper outlining how to implement a successful program and how to maintain the program over time. This evaluation provided specific steps to strengthen each component of a PBS program to ensure school-wide application and sustainability. A positive social change is experienced by students, teachers, and parents by the enhancement of a PBS system that improves student behavior in the school and district.