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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
151

Estratégias de aquisição de nutrientes estequiometria ecológica em comunidades de campos rupestres, MG-Brasil / Strategies for the acquisition of nutrients and ecological stoichiometry in rupestrian fields communities, MG-Brazil

Candido, Hugo Galvão, 1985 20 August 2018 (has links)
Orientador: Rafael Silva Oliveira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-20T21:06:58Z (GMT). No. of bitstreams: 1 Candido_HugoGalvao_M.pdf: 2416852 bytes, checksum: e2c495e1dc8a3aa3997d789f5761655e (MD5) Previous issue date: 2012 / Resumo: A disponibilidade de nutrientes tem um papel fundamental na estruturação de comunidades vegetais. Um modelo teórico recentemente proposto por Lambers et al. 2008 postula que em regiões com solos muito antigos e pobres em fósforo e nitrogênio, as espécies dominantes teriam maior proporção de especializações radiculares e menos associações com fungos micorrízicos. Estas regiões foram classificadas como OCBILs (do inglês: old, climatically buffered, infertile landscapes). Este estudo teve como objetivo testar tal modelo e avaliar se comunidades de campos rupestres podem ser categorizadas como OCBILs, avaliar se os campos rupestres podem ser considerados OCBILs mediante uma análise comparativa de um conjunto de caracteres morfofisiológicos das plantas e características físico-químicas do solo, através do estudo de seis comunidades na Cadeia do Espinhaço, Minas Gerais. Selecionamos as dez espécies mais abundantes em cada uma áreas distribuídas ao longo de um transecto de 190 km, totalizando 60 espécies. Avaliamos os atributos foliares (concentração de N, P, análise da massa foliar por unidade de área e razão N:P) e a colonização de raízes por micorrizas. Quimicamente, os solos dos campos rupestres têm baixa disponibilidade de P e N, comparáveis aos solos de outros OCBILs (oeste da Austrália e região do Cabo na África do Sul). A proporção de colonização das raízes das plantas por fungos foi positivamente correlacionada com a [P] do solo de cada comunidade, corroborando o modelo de Lambers em uma escala regional. Espécies de campos rupestres apresentam uma alta razão N:P foliar (média de 43 para todos os campos de estudo), maior que as encontradas nos outros OCBILs, o que sugere uma forte limitação por fósforo. Foram encontradas médias de 183 g m-2 para LMA, 12,46 mg g-1 para o N foliar e de 0,36 mg g-1 para o P foliar. Pelos resultados obtidos propomos que os campos rupestres devem ser classificados também como OCBILs, status que demandaria maior atenção para esses campos ainda pouco estudados e já ameaçados ecologicamente / Abstract: The availability of nutrients plays a key role in structuring plant communities. A theoretical model recently proposed by Lambers et al. (2008) postulates that in regions with very old and poor soils in P and N, the dominant species had a higher proportion of specializations and less root associations with mycorrhizal fungi. These regions were classified as OCBILs (ols, climatically buffered, infertile landscapes). This study aims to test this model and asses whether communities of rupestrian fields might be categorized as OCBILs by analyzing the chemical composition of soil, leaf stoichiometry and % mycorrhizal root colonization by the dominant species in six communities in the Espinhaço Range, Minas Gerais. We selected the ten most abundant species in each of areas distributed along a transect of 190 km, totaling 60 species. We evaluated the leaf attributes (concentration of N, P analysis of leaf mass per unit area and N:P ratio) and colonization of roots by micorrhiza. Chemucally, the soil of the rupestrian fields shows very low availability of P and N, comparable to other soils OCBILs (Western Australia and the Cape region in South Africa). The proportion of root colonization of plants by fungi was positively correlated with [P] soil of each community, supporting the Lambers model's on a regional scale. Species of rupestrian fields have a high N:P ratio leaf (average of 43 for all fields studied), higher than those found in other OCBILs, suggesting a strong limitation by phosphorus. We found average 183 gm.m-2 for LMA, 12,46 mg.g-1 and 0,36 mg.g-1 to P leaf. The results obtained suggests that rupestrian fields should also be classified as OCBILs, status wich would require greater attention to these fields still little studied and already threatened ecologicaly / Mestrado / Ecologia / Mestre em Ecologia
152

Synthèse d'oxyde de zinc dopé azote sous formes de poudre et de couche mince : caractérisation du type de semiconductivité / Synthesis of nitrogen doped zinc oxide as powders ans thin films : characterization of the type of semiconductivity

Valour, Arnaud 27 January 2017 (has links)
Cette thèse fait suite à des travaux ayant permis, de manière non reproductible, la stabilisation de l’oxyde de zinc de type-p (p-ZnO:N) sur une période de plus de deux ans par décomposition de ZnO2 sous flux de NH3. L’objectif de ces travaux était de maîtriser de manière reproductible la synthèse de p-ZnO:N sous formes de poudre, puis de couche mince, dans l’optique de réaliser des homojonctions p-ZnO:N/n-ZnO ayant de potentielles applications dans le domaine de l’optoélectronique. Dans ce but, différents paramètres de la synthèse ayant permis initialement l’obtention de p-ZnO:N fortement lacunaire en zinc (20%) ont été étudiés sans aboutir de nouveau à la stabilisation du caractère-p. La formation in-situ d’impuretés NO3- mise en évidence conduit à une ambiguïté quant à l’origine du type-p dans notre matériau. Parallèlement, une nouvelle voie de synthèse a été mise en place, en utilisant l’approche colloïdale, permettant d’obtenir des nanocristaux de ZnO inférieurs à 10 nm facilement convertibles en nanoparticules de ZnO2 par simple traitement avec une solution diluée d’H2O2 à température ambiante. Le matériau final ZnO:N est obtenu après nitruration sous flux d’ammoniac à 250°C. Ces résultats ont été efficacement transposés à la réalisation de couches minces (CM) de ZnO:N par dip-coating, mais les mesures Mott-Schottky ont également révélé une conductivité de type-n pour tous les échantillons. Enfin, les résultats préliminaires des calculs théoriques menés en parallèle de cette thèse nous ont amenés à reconsidérer les conditions de synthèse pour favoriser l'insertion de NH3 / NH4+ lors de la préparation des échantillons dans la quête de p-ZnO:N. / Cette thèse fait suite à des travaux ayant permis, de manière non reproductible, la stabilisation de l'oxyde de zinc de type-p (p-ZnO:N) sur une période de plus de deux ans par décomposition de ZnO2 sous flux de NH3. L'objectif de ces travaux était de maîtriser de manière reproductible la synthèse de p-ZnO:N sous formes de poudre, puis de couche mince, dans l'optique de réaliser des homojonctions p-ZnO:N/n-ZnO ayant de potentielles applications dans le domaine de l'optoélectronique. Dans ce but, différents paramètres de la synthèse ayant permis initialement l'obtention de p-ZnO:N fortement lacunaire en zinc (20%) ont été étudiés sans aboutir de nouveau à la stabilisation du caractère-p. La formation in-situ d'impuretés NO3- mise en évidence conduit à une ambiguïté quant à l'origine du type-p dans notre matériau. Parallèlement, une nouvelle voie de synthèse a été mise en place, en utilisant l'approche colloïdale, permettant d'obtenir des nanocristaux de ZnO inférieurs à 10 nm facilement convertibles en nanoparticules de ZnO2 par simple traitement avec une solution diluée d'H2O2 à température ambiante. Le matériau final ZnO:N est obtenu après nitruration sous flux d'ammoniac à 250°C. Ces résultats ont été efficacement transposés à la réalisation de couches minces (CM) de ZnO:N par dip-coating, mais les mesures Mott-Schottky ont également révélé une conductivité de type-n pour tous les échantillons. Enfin, les résultats préliminaires des calculs théoriques menés en parallèle de cette thèse nous ont amenés à reconsidérer les conditions de synthèse pour favoriser l'insertion de NH3 / NH4+ lors de la préparation des échantillons dans la quête de p-ZnO:N.
153

An investigation into how Grade 11 Physical Science teachers mediate learning of the topic stoichiometry : a case study

Kanime, Mwene Kashiiwandapo January 2015 (has links)
Stoichiometry is proven to be one of the difficult topics for learners in the NSSC Physical Science syllabus due to its abstract nature. Over the years the Examiner’s reports reveal that learners' performance is very poor in this topic. In addition, learners fear the topic and have developed a negative attitude toward it. It is against this background that I decided to carry out a qualitative case study; investigating how teachers mediate the learning of stoichiometry. The study was conducted at two schools in the Oshikoto Region, Namibia and it involved two grade 11 Physical Science teachers. The study is located within the interpretive paradigm and made use of interviews, document analysis and lesson observations (which were video-taped and transcribed) followed by stimulated recall interviews to generate data. The generated data were analyzed using the inductive approach whereby themes were identified. The themes were later used to develop analytical statements in relation to my research questions and these were used to interpret the data. Moreover, the study adopted the notion of pedagogical content knowledge (PCK) proposed by Shulman (1986, 1987) as well as Vygotsky's (1978) mediation of learning and social constructivism as the theoretical frameworks. The data were validated by triangulation, member checking as well as using the stimulated recall interviews while watching the videos with each participant. The findings of the study show that teachers use several tools to mediate the learning process and this includes the use of language, learners' prior knowledge and analogies. In addition, it emerged in this study that teachers are faced with a number of challenges when mediating learning of this topic. Hence, the study recommends that teachers should develop their pedagogical content knowledge for them to effectively eliminate the challenges faced as well as to come up with the best teaching strategies which they can use to mediate learning and help learners make sense of the topic stoichiometry.
154

Étude de semi-conducteurs de type p nanostructurés à base de métaux de transition pour une application en DSSC-p / Study of nanostructured p-type semiconductors based on transition metals for p-DSSC applications

Polteau, Baptiste 18 October 2016 (has links)
Dans le but d'améliorer le rendement des cellules à colorant de type p (DSSC-p), ces travaux s'attachent à la synthèse et la caractérisation de matériaux semi-conducteurs de type p (SCs-p) sous forme de nanoparticules. En ce sens, des SCs-p répondant à un cahier des charges (bande de valence basse en énergie, grande surface spécifique, bon conducteur et bonne transparence) ont été étudiés. Dans ce cadre, une stratégie a été développée pour améliorer les propriétés de NiO (l'actuel matériau de référence) en optimisant sa nanostructuration, sa forte non-stœchiométrie en nickel et par son dopage à l'azote, paramètres tous favorables à la stabilisation de la valence mixte Ni3+/Ni2+, origine de la conductivité de type p. Cette longue étude a été initiée à partir d'un précurseur de nickel original nanostructuré Ni3O2(OH)4, à forte valence mixte Ni3+/Ni2+. La décomposition sous air et sous ammoniac de ce précurseur à basse température (250 °C) a permis de préparer Ni1-xO nanostructuré, fortement non-stœchiométrique (VNi = 25 %), de grande surface spécifique (240 m2.g-1) et dopé azote (NiO:N). De plus, deux matériaux non oxydes à structure delafossite, que sont les carbodiimides de nickel (NiNCN) et de manganèse (MnNCN) ont été préparés et caractérisés comme de nouveaux semi-conducteurs de type p, permettant de monter la première DSSC-p à base de NiNCN. / To improve the performances of p-Dye Sensitized Solar Cell (p-DSSC), this thesis work focuses on the synthesis and the characterization of p-type semiconductors (p-SCs) nanomaterials. These p-SCs with some specifications (low energy valence band, high specific surface area, high conductivity and transparency) were thoroughly studied. In this context, a strategy was developed to improve the NiO nanoparticles properties (commonly used as a reference) with higher nickel non-stoichiometry and nitrogen doping to promote the stabilization of the Ni3+/Ni2+ mixed valence (origin of the p-typness). This study was initiated with a nanostructured mixed valent Ni3O2(OH)4 precursor. Its thermal decomposition in air and ammonia at low temperature (250 °C) allows the formation of nanostructured Ni1-xO with a large amount of Ni vacancies (VNi = 25 %), a high specific surface area (240 m2.g-1) and a nitrogen doping (NiO:N). Moreover, two non-oxides materials with delafossite structure type, namely - nickel carbodiimide (NiNCN) and manganese carbodiimide (MnNCN) - were prepared and characterized as new p-type semiconductors. Thus, the first p-DSSC with NiNCN material was built with success.
155

Evaluating problem solving proficiency of grade 12 physical science learners in Highveld Ridge East and West circuits when solving stoichiometry problems / Evaluating problem solving proficiency of grade twelve physical science learners in Highveld Ridge East and West circuits when solving stoichiometry problems

Tigere, Edwin 11 1900 (has links)
The aim of this study was to evaluate the problem solving proficiency of Physical Science learners in Highveld Ridge East circuits in Mpumalanga Province of South Africa. The objectives of this study were to determine the relationship between proficiency in conceptual and algorithmic problem solving, to compare the percentage of algorithmic and conceptual problems that were correctly and incorrectly answered, problems not attempted at all and finally to categorize Physical Science learners according to their stoichiometry problem solving proficiencies. The target population for this study was Grade 12 Physical Science learners in Highveld Ridge East and West circuit in Mpumalanga Province of South Africa. To achieve the aim of this study and its subsequent objectives random sampling was used to select the three schools and the sample after a stoichiometry achievement test was administered by Physical Science teachers, who were teaching the participants at their respective schools. The researcher scored the tests using a memorandum. The results of this study indicated that learners’ proficiency in both algorithmic and conceptual problem solving was low, there was a weak positive correlation between algorithmic and conceptual problem solving proficiency, the percentage of solutions that were correctly solved was the lowest compared to the percentage of incorrect solutions and problems not attempted. The other result of this study was that there were no grade 12 Physical Science learners with high algorithmic and high conceptual abilities, a few learners had high algorithmic and low conceptual abilities and the majority of the learners had low algorithmic and low conceptual problem solving abilities. This implies that Physical Science teachers in these circuits should focus on developing both algorithmic and conceptual problem solving strategies when teaching stoichiometry. / Science and Technology Education / M. Sc. (Mathematics, Science and Technology Education)
156

Odsíření práškového granulačního kotle K3 na Teplárně Olomouc / Desulphurization of pulverized coal bouler (dry bottom ash) in Teplarna Olomouc

Haluza, Jakub January 2012 (has links)
This master thesis deals with the feasibility studies desulphurization of powder granulation K3 boiler at Olomouc heating station. K3 boiler burns black energetic coal and after January 1st, 2016 will not meet new more strict emission limits. The theoretical part of the thesis charts usable desulphurization methods from which the semi-dry NID appears as the most appropriate one. In the practical part there is performed a stoichiometric calculation of the flue gas and the balance of raw materials and output products. The possibility of NID method usage is confirmed here. Next the annual operating cost of the desulfurization process is calculated and some NID systems already installed references are presented.
157

System design for production of biopreservatives from yeasts for reduction of fruit and beverage spoilage organisms

Ngongang, Maxwell Mewa January 2019 (has links)
Thesis (PhD (Chemical Engineering))--Cape Peninsula University of Technology, 2019 / The agro-processing industry is currently facing losses due to microbial spoilage of agricultural produce and associated value-added products such as beverages. Decay and undesired fermentation of fruit and beverages by fungal, yeast and bacterial spoilage organisms are among the major contributors of product losses in the food industry. When looking at the different level of food spoilage, it is common to find different spoilage organisms occurring in the same food item; which usually requires food producers to utilise a mixture of synthetic preservatives for spoilage organism control. Some of the synthetic chemical compounds with growth inhibition properties that have been used in food preservation are sulphur dioxide, benzoic, lactic, sorbic and acetic acid. These compounds act against a variety of spoilage microorganisms. In post-harvest control of fungi, triazoles, hydroanilide fenhexamid, dicarboximides and succinate dehydrogenase are also being used. Some spoilage organisms have been found to be resistant to the use of synthetic chemical preservatives which usually favour the use of higher dosage of preservatives in food. The use of synthetic chemicals as preservative and as postharvest control agents has been found to present serious health risks such as cardiovascular diseases, muscles and stomach pains, eyesight and skin damages and impairment of brain functions. The problem posed by the current use of synthetic chemicals in food put pressure on food producers and exporters to seek alternatives that will allow for the eradication of the use of synthetic chemicals as preservative in beverages and as postharvest control agents on fruits. Yeasts have been found to have the ability to grow at a faster rate on cheap media and to colonise dried surfaces rapidly. It has also been found that yeasts produce extracellular compounds of proteinaceous and volatile organic nature with growth inhibition properties against spoilage organisms. The current findings lack some engineering concept that could assist in the design of a production system for high scale production of biopreservation compounds from yeasts. The availability of a cost effective production media, the growth and production kinetics data using a cheaply available nutrient sources as well as the biological thermodynamic data are some of the gaps in biopreservation bioprospecting. Although several yeasts have already been studied to have great inhibition properties against fruit fungal pathogens, it was still unclear what was the minimum inoculum dose to be able to have a fungistatic and fungicidal effect on the growth of fruit spoilage organisms. The concept of combination of biopreservatives and the interaction effect of their biopreservation activity against consortia of spoilage organisms has also been lacking. As an attempt to seek alternatives to the use of synthetic chemicals as preservatives or postharvest control agents, Candida pyralidae Y1117, Pichia kluyveri Y1125 and Pichia kluyveri Y1164 strains were assessed for antimicrobial activity against spoilage yeasts (Dekkera bruxellensis, Dekkera anomala, Zygosaccharomyces bailii) and spoilage fungi (Botrytis cinerea, Colletotrichum acutatum and Rhizopus stolonifer). As alternative to refined media, a cost effective approach was explored whereby the use of agro-waste, i.e. grape pomace extracts (GPE), as production medium for biopreservation compounds, was studied. Production kinetics using modified existing models, subsequent to optimization using response surface methodology (RSM) for biopreservation compounds production was studied for the three biocontrol yeasts using GPE broth as the fermentation medium. The evaluation of the interaction study between mixtures of crude biopreservatives against consortia of common spoilage organisms present in beverages was also conducted by producing the crude biopreservation compounds separately from yeasts and then formulating growth inhibition combinations (GICs); GIC 1 (Candida pyralidae Y1117 and Pichia kluyveri Y1125); GIC 2 (C. pyralidae Y1117 and P. kluyveri Y1164), GIC 3 (P. kluyveri Y1125 and Pichia kluyveri Y1164); GIC 4 (C. pyralidae, P. kluyveri Y1125 and P. kluyveri Y1164). The spoilage organism consortia combinations, i.e. SC1, D. anomala and D. bruxellensis; SC2 (D. anomala and Z. bailii); SC3 (D. bruxellensis and Z. bailii) and SC4 (D. anomala, D. bruxellensis and Z. bailii) were also prepared. This study also investigated the effect of varying inoculum dose (ID) of Candida pyralidae strain Y1117, Pichia kluyveri Y1125 and Pichia kluyveri Y1164 on the biocontrol of Botrytis cinerea by contaminating the headspace of the growth medium with a fungal plug subsequent to biotreatment with different initial inoculum dose of the respective biocontrol yeasts. Finally, grape pomace extracts was used as fermentation medium to study the biological thermodynamics of biopreservation compound production from the three biocontrol yeasts. The results obtained demonstrated some interesting results. The antagonistic properties of C. pyralidae and P. kluyveri were observed on cheap solidified medium (grape pomace extracts) as well as on fruits (grapes and apples). These yeasts produced extracellular volatile organic compounds (VOCs) that could be responsible for yeast and fungal growth inhibition. Twenty-five VOCs in the category of alcohols, organic acids and esters were identified by GC-MS. The results of the kinetic study showed that the highest volumetric zone of inhibition (VZI) was 1.24 L contaminated solidified media (CSM) per mL biopreservation compounds used (BCU) when Candida pyralidae Y1117 was inoculated in a pH 3-diluted GPE broth (150 g L−1) incubated at 25 °C for 24 h. Similar conditions were applied for Pichia kluyveri Y1125 and P. kluyveri Y1164, albeit under slightly elongated fermentation periods (up to 28 h), prior to the attainment of a maximum VZI of only 0.72 and 0.76 L CSM mL−1 ACU, respectively. The potential biopreservation compounds produced were identified to be isoamyl acetate, isoamyl alcohol, 2-phenyl ethylacetate and 2-phenyl ethanol. The growth inhibition interaction study showed a variation in growth inhibition proficiency depending on the spoilage organisms or the consortia of spoilage organisms being deactivated. It was then suggested that, a food environment contaminated with a consortium of spoilage organisms can be controlled by employing either the crude biopreservation compounds from individual yeast or those of the following yeast combinations, GIC1-4, which showed a better growth inhibition proficiency against SC1-3. The fungistatic and fungicidal effects on the fungal pathogen were dose dependent. The fungistatic characteristics against Botrytis cinerea were displayed after 7 days when 102-105 cells mL-1 of Candida pyralidae Y1117, Pichia kluyveri Y1125 and Pichia kluyveri Y1164 were independently used in-vitro and in-vivo. However, 106-108 cells mL-1 inoculum doses displayed fungicidal characteristics. Additionally, the fungicidal property of yeasts studied was also confirmed on table grape (in vivo studies) using closed jar method. The biological thermodynamic study showed that, dried biomass molecular weight of 28.9 g/C-mol, 29.163 g/C-mol, and 27.176 g/C-mol were obtained for Candida pyralidae strain Y1117, Pichia kluyveri Y1125 and Pichia kluyveri Y1164 respectively. The results obtained successfully established useful biological thermodynamic data applicable to the design of adequate biopreservatives production system from yeasts using cheaply available nutrients source.
158

Biohybrid structures consisting of biotinylated glycodendrimers and proteins: influence of the biotin ligand’s number and chemical nature on the biotin–avidin conjugation

Ennen, Franka, Boye, Susanne, Lederer, Albena, Cernescu, Mihaela, Komber, Hartmut, Brutschy, Bernhard, Voit, Brigitte, Appelhans, Dietmar 06 December 2019 (has links)
We present the bioconjugation of avidin as a central and/or bridging building block with mono-, bi- and tetravalent biotinylated glycodendrimers to fabricate defined supramolecular nanostructures for future (bio)medical applications. For this purpose mono-, bi- and tetravalent biotinylated glycodendrimers, decorated with short alkyl-linked or long PEG-linked biotin ligands, were synthesized and characterized by NMR, IR and mass spectrometry and HABA displacement assay. Various techniques (UV/Vis, DLS, TEM, LILBID-MS and AF4) were used in order to obtain information about the structural properties of different conjugates of avidin and mono-, bi- and tetravalent biotinylated glycodendrimers. The biotin ligand’s spacer length, its chemical structure and the degree of biotin functionalization are essential parameters in the formation of nanostructures with avidin having a controlled composition and size dimension up to 100 nm. Biohybrid structures with avidin as a central unit require monovalent glycodendrimers with PEG-linked biotin, while bi- and tetravalent glycodendrimers with short alkyl-linked biotin ligands are more efficient than their counterparts with longer PEG–biotin ligands in the fabrication of defined biohybrid structures (∅ up to 100 nm) with avidin as a bridging unit. The most dominating key issue, combined with other conjugation issues, is the optimal ligand–receptor stoichiometry to fabricate biohybrid structures with diameter of <20, <30 or up to 100 nm.
159

Experiences Teaching Stoichiometry to Students in Grades 10 and 11

Bridges, Cynthia Denise 01 January 2015 (has links)
Many students have problems learning stoichiometry, a complex mathematical chemistry concept used to determine how much product will be produced or formed from a given quantity of reactants. The problem addressed in this study was teachers' lack of understanding of how to teach stoichiometry in a Midwestern urban school district. The conceptual framework of the study was based upon constructivist theory. A qualitative narrative approach was used to obtain the perceptions of 5 high school chemistry instructors related to their experiences, successful or unsuccessful, in teaching stoichiometry to students in Grades 10 and 11. Data were gathered through face-to-face interviews, which were analyzed via an inductive approach to reveal 6 themes: a difficult subject to teach, presentation of stoichiometry, relevancy, students' reactions, barriers, and gender differences. Findings suggested the need for teachers to be knowledgeable, creative, and resourceful in their subject areas to help their students to learn stoichiometry. Findings also revealed the need for teachers to adapt their instructional strategies and modes of delivery to reflect their students' individual learning styles. Understanding how the participating teachers explained stoichiometry to their students might help other chemistry teachers to examine and adapt their own instructional styles and delivery methods of the concept. This understanding might, in term, help to improve student achievement in stoichiometry in particular and chemistry in general.
160

Study of the U-Am-O ternary phase diagram / Etude du diagramme de phases ternaire U-Am-O

Epifano, Enrica 17 November 2017 (has links)
Les isotopes de l’Américium sont les principaux contributeurs à la radioactivité des déchets nucléaires. Parmi les scénarios pour diminuer la toxicité des déchets, la transmutation dans les réacteurs à neutrons rapides utilisant des pastilles d’oxyde mixte (U,Am)O2 est une voie prometteuse. Dans ce cadre, la connaissance des propriétés thermodynamiques du système U-Am-O est essentielle pour prédire le comportement des pastilles (U,Am)O2 en conditions nominale et accidentelle. Cette thèse est dédiée à l’étude expérimentale d’oxydes mixtes (U,Am)O2 dans une large gamme de composition (7,5 % at. ≤ Am/(Am+U) ≤ 70 % at.). L’objectif est d’acquérir des données pour développer un modèle thermodynamique avec la méthode semi-empirique CALPHAD. Les résultats peuvent être classés en trois catégories : données structurales, données de diagramme de phase et données thermodynamiques. Pour la modélisation thermodynamique d’un système ternaire, l’optimisation des sous-systèmes binaires est nécessaire. Comme des questions restaient en suspens sur le système Am-O, le diagramme de phase Am-O a tout d’abord été étudié par diffraction des rayons X à haute température. L’existence d’un domaine de composition de la phase bcc AmO1.61 a été mis en évidence et la lacune de miscibilité dans la phase fluorite, proposée dans la littérature, n’a pas été confirmée. Grâce à ces nouveaux résultats, le modèle CALPHAD de Gotcu et al a été modifié. Dans une deuxième étape, des analyses structurales des dioxydes (U,Am)O2±x ont été effectuées par DRX, XAS et spectroscopie RAMAN. La DRX a permis de confirmer que tous les échantillons sont constitués d’une seule phase de structure fluorite. Le rapport O/M (avec M=U+Am) mesuré à température ambiante est inférieur à 2 ; la stabilité de l’Américium trivalent Am3+ a été mise en évidence. Celle-ci induit l’oxydation partielle de l’U4+ en U5+. Cette distribution de charge s’accompagne par la formation de défauts de l’oxygène complexes dans la structure fluorite. Lors de l’étude par DRX HT des oxydes mixtes sous air, il a été montré que la présence d’Am3+ stabilise la phase fluorite par rapport aux oxydes plus riches en oxygène (U4O9, U3O8). De nouvelles données de diagramme de phase ont été obtenues : des conodes dans les domaines biphasés M4O9-M3O8 and MO2+x-M3O8 et la solubilité de l’Américium dans les oxydes M4O9 et M3O8. L’étude du diagramme de phase U-Am-O a été poursuivie par la détermination des températures de solidus/liquidus des oxydes mixtes par une technique de chauffage laser, sous argon et sous air, et par la caractérisation des échantillons après fusion par SEM et XAS. La température de fusion des oxydes mixtes diminue avec une teneur croissante d’Américium (Am/(Am+U)) et d’oxygène (O/(Am+U)). Finalement, les propriétés thermodynamiques des oxydes (U,Am)O2±x ont été mesurées : les incréments enthalpiques par calorimétrie de chute et les pressions partielles des espèces gazeuses par Spectrométrie de Masse couplée à une cellule de Knudsen (KEMS). Une contribution d’excès de la capacité calorifique a été observée à haute température, attribuée à la réduction des oxydes (avec formation de lacunes d’oxygène). Les résultats de KEMS ont permis de déterminer une composition congruente de vaporisation à 2300 K, pour un rapport Am/(Am+U) de 0,6 et un rapport O/(U+Am) inférieur à 1,9. Finalement, la modélisation thermodynamique du système U-Am-O par la méthode CALPHAD a été abordée par la description de la phase fluorite. Un bon accord est obtenu entre le modèle et les données de potentiel d’oxygène pour l’oxyde (U0.5Am0.5)O2±x et de distribution des cations. De plus, le modèle permet de reproduire de façon satisfaisante les données de KEMS. En perspective de ce travail, la modélisation thermodynamique du ternaire sera étendue à la description des équilibres de phase mettant en jeu les oxydes M4O9, M3O8 et la phase liquide. / Americium isotopes are the main contributors to the long-term radiotoxicity of the nuclear wastes, after the plutonium extraction. Among the reprocessing scenarios, the transmutation in fast neutron reactors using uranium-americium mixed oxide (U,Am)O2±x pellets seems promising. In this frame, the knowledge of the thermodynamics of the U-Am-O ternary system is of essential for the prediction of the behavior of (U,Am)O2 pellets and their possible interaction with the cladding, under normal and accidental conditions. This thesis is dedicated to the experimental investigation of U-Am mixed oxides on a wide range of Am contents (7.5 at.% ≤ Am/(Am+U) ≤ 70 at.%), with the aim to collect data for developing a thermodynamic model based on the semi-empirical CALPHAD method. The obtained results can be classified in three categories: structural, phase diagram and thermodynamic data. For the thermodynamic modeling of the ternary system, the assessment of the binary sub-systems is first required. As open questions still existed on the Am-O system, a first part of the work was dedicated to the study of the Am-O phase diagram by high-temperature (HT) XRD. The existence of a composition range of the bcc AmO1.61 phase was highlighted and the miscibility gap in the fluorite phase, proposed in the literature, was not found. Thanks to the new experimental data, the existing CALPHAD model of Gotcu et al. was modified. In a second step, structural investigations were performed on synthesized (U,Am)O2±x dioxides by coupling XRD, XAS and Raman spectroscopy. For all the compositions, the XRD confirmed the formation of a single fluorite structure. The O/M ratio (with M=U+Am) at room temperature was determined to be lower than 2; the stability of trivalent americium Am3+ in the dioxide solid solution was highlighted, which induces a partial oxidation of uranium from U4+ to U5+. This charge distribution, peculiar for a dioxide, is accompanied by the formation of complex oxygen defects in the fluorite structure. By a HT-XRD investigation of the mixed oxides under air combined with XAS characterization of the oxidized samples, it was shown that the presence of Am3+ leads to a stabilization of the dioxide fluorite phase toward the formation of oxides richer in oxygen, in comparison to the U-O system. New phase diagram data were obtained in the oxygen rich region at 1470 K: tie-lines in the M4O9-M3O8 and MO2+x-M3O8 domains were determined and the solubility of americium in the M4O9 and M3O8 oxides was estimated. The investigation of the U-Am-O phase diagram continued at higher temperature with the study of the solidus/liquidus transitions using a laser-heating technique, under argon and air, and post-melting characterizations conducted by SEM and XAS. The melting temperature of Am-U dioxides decreases with the increase of both the Am/(Am+U) and O/M ratios. Finally, thermodynamic properties of the U1-yAmyO2±x oxides were measured: enthalpy increments using drop calorimetry, partial vapor pressures by Knudsen cell effusion mass spectrometry (KEMS). An excess contribution to the heat capacity at high temperature was observed and this was attributed to the reduction of the dioxides at high temperature (formation of oxygen vacancies). The KEMS results lead to determine the congruent vaporization composition at 2300 K, for a Am/(Am+U) ratio of 0.6 and an O/M ratio lower than 1.9. Finally, the CALPHAD thermodynamic assessment of the U-Am-O system was started, by focusing the attention on the modelling of the fluorite phase. A good agreement between the model and the oxygen potential data for (U0.5Am0.5O2±x) and the cation distribution was achieved. Furthermore, the model is able to satisfactorily reproduce the KEMS data and hence the equilibrium between the dioxide and gas phase. For the perspectives of this work, the optimization of the thermodynamic model should be extended to describe the phase equilibria involving the M4O9, M3O8 oxides and the liquid phase.

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