Eye Movement Desensitization and Reprocessing, EMDR, is a new clinical treatment shown to be effective for victims of trauma. EMDR is a time efficient, comprehensive methodology backed by positive, controlled research, for the treatment of disturbing experiences that underlie many pathologies. An eight phase treatment approach that includes using eye movements or other left-right stimulation, EMDR helps victims of trauma reprocess disturbing thoughts and memories. The purpose of this research project was to describe and explore the utilization of EMDR by licensed clinical social workers who were registered as members of the National Association of Social Workers.

Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. The assessment of the quality properties of recycled polymers is therefore crucial to guarantee the performance of recyclates in further applications. Three key quality properties have been defined for this quality analysis: degree of mixing (composition), degree of degradation, and presence of low molecular weight compounds (degradation products, contaminants, additives). Furthermore, detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS used in packaging applications, and electrical and electronic equipment (E&E). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applicat / Vilaplana Domingo, FJ. (2008). Analytical strategies for the quality assessment of recycled high-impact polystyrene (HIPS) [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/2186 / Palancia

Des recherches sur de nouvelles sources énergétiques ont été initiées pour faire face à la hausse de la demande mondiale. Dans le domaine nucléaire, la filière Th-U est envisagée pour compléter ou remplacer la filière U-Pu. Toutefois, des améliorations technologiques sont nécessaires avant l’aboutissement industriel de ce projet, notamment sur l’adaptation du procédé de retraitement du combustible U-Pu à celui du cycle Th-U, qui consiste à dissoudre le combustible en milieu acide nitrique, suivi d’une extraction liquide-liquide. Or, contrairement à l’uranium, l’oxyde de thorium n’est pas soluble dans HNO₃ concentré. Un ajout de petites quantités de fluorures est nécessaire à l’obtention d’une dissolution totale. Cependant, la dissolution reste lente et le milieu HNO₃-HF est très corrosif. L’objectif de cette étude est de comprendre les réactions mises en jeu afin d’optimiser la composition de la solution pour diminuer la corrosion et améliorer la cinétique de dissolution. La poudre d’oxyde de thorium synthétisée en laboratoire est solubilisée dans des conditions expérimentales et selon un protocole prédéfinis. L’effet des caractéristiques du solide, de la méthode de dissolution et du milieu de dissolution ont été étudiés. La morphologie de l’oxyde a une forte influence sur la vitesse de dissolution. L’impact majeur des ultrasons de puissance est l’augmentation de la température, qui améliore considérablement la vitesse de dissolution. Le remplacement des fluorures par d’autres complexants du thorium n’a pas permis d’atteindre une dissolution quantitative de l’oxyde. L’augmentation des concentrations de HF et de HNO₃ accélère la dissolution, mais une concentration trop importante de fluorure mène à la formation d’un précipité blanc qui passive la surface. Sur la base de cette étude, un mécanisme réactionnel a été proposé. L’étape limitante est la formation d’un complexe activé. L’écriture et la résolution des équations cinétiques et des équilibres thermodynamiques a permis d’établir une relation analytique exprimant le taux de dissolution de ThO₂ en fonction des paramètres expérimentaux. La simulation des résultats expérimentaux à l’aide de cette relation a ensuite permis de déterminer les constantes thermodynamiques et cinétiques rendant compte de tous les phénomènes observés, validant ainsi le mécanisme proposé. / Studies of new energy sources are necessary to meet the rising global demand. In the nuclear area, Th-U cycle has been reinvestigated to supplement or replace the currently used U-Pu cycle. This project though needs further improvement to be operated in an industrial plant, especially on the reprocessing process, which consists in fuel dissolution in nitric acid medium, followed by liquid-liquid extraction. Still, unlike uranium, thorium oxide does not dissolve in concentrated nitric acid. Small amounts of fluoride are required to achieve the dissolution. The dissolution is rather slow and HNO₃-HF mixture is very corrosive. The aim of this project is thus to find an efficient dissolution method which both decreases corrosion and improves dissolution rate. The synthetized thorium oxide powder has been dissolved in chosen conditions. Effects of solid parameters, dissolution method and dissolution medium have been studied. Results show a strong dependence on oxide crystallinity. No improvement on dissolution rate was observed with power ultrasounds, except for the temperature increase, which greatly enhances dissolution rate. No other complexing agents than fluoride allows total dissolution. Rising HNO₃ and HF concentrations increases dissolution rate until the amount of fluorides is so high that a precipitate forms at the surface. This study led to the proposal of a dissolution mechanism whose limiting step is the formation of an activated complex. Based on kinetics and equilibrium equations, initial dissolution rate was then written as a function of the different studied parameters. Experimental results were finally fitted by this relation to find kinetics and thermodynamics constants, proving the accuracy of the proposed mechanism.

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.

京都大学 / 0048 / 新制・課程博士 / 博士(人間健康科学) / 甲第20294号 / 人健博第42号 / 新制||人健||4(附属図書館) / 京都大学大学院医学研究科人間健康科学系専攻 / (主査)教授 二木 淑子, 教授 精山 明敏, 教授 村井 俊哉 / 学位規則第4条第1項該当 / Doctor of Human Health Sciences / Kyoto University / DFAM

Tungsten (W) is listed among the European Union (EU) critical raw materials (CRMs) for its supply risk and economic importance. Primarily, tungsten is produced from scheelite and wolframite mineral ores with 0.08-1.5% tungsten trioxide (WO3) grade. However, as primary deposits for these resources are becoming less or lower in grade, alternative sources need to be explored. These alternative tungsten sources include scrap from end-of-life products, mine waste and rejects from the ore beneficiation processes (tailings). The latter alternative source is the focus within this thesis. Historical tailings repositories often pose environmental risks but may also become secondary sources of CRMs. This is because of relatively high minerals and metals content due to less efficient extraction methods and/or relatively low metal prices at the time of active mining. Therefore, reprocessing of such tailings is not only a supply risk-reducing measure but also an approach to remediation that contributes to the mining industry’s aim of moving towards a circular economy. The aim of this thesis has been to develop efficient methods for separating valuable minerals from the tailings in order to leave behind a stable and environmentally safe residue. Geometallurgical studies were conducted by collecting drill core samples from the Smaltjärnen tailings repository in Yxsjöberg, Sweden, for evaluating the potential of this repository for further processing. The tailings were originally produced from the ore that was mined by Yxsjö Mines while it was in operation from 1935 to 1963, with average ore grades of 0.3-0.4 wt.% WO3, 0.2 wt.% Cu and 5-6 wt.% fluorspar. The exploited minerals were scheelite for W, chalcopyrite for Cu and fluorspar. The tailings repository is estimated to have about 2.2 million tons of tailings covering an area of 26 hectares, with elemental concentrations of 1-2 wt.% S, 0.02-0.2 wt.% Cu, 0.02-0.3 wt.% W, 0.02-0.04 wt.% Sn and 0.02-0.03 wt.% Be. Sampling and characterization of the historical tailings were conducted based on geometallurgical units (i.e. a distinction between different layers and locations in the repository), followed by metallurgical test work. The tailings were characterized with regard to color and granulometry, particle size distribution, chemical composition, scheelite mineral occurrence, texture and mineral liberation, as well as mineralogical composition. Based on a comprehensive literature survey, tailings characteristics, and assessment of the earlier processes from which the Yxsjöberg tailings were produced, feasible separation methods were pre-selected involving dry low-intensity magnetic separation (LIMS) and high intensity magnetic separation (HIMS), enhanced gravity separation (EGS) using a Knelson concentrator, and batch froth flotation. The average WO3 and Cu concentration in these tailings based on the sampled locations was 0.15 % and 0.11 % respectively. Applying them to the estimated 2.2 million tons of tailings in this repository gives approximately 3300 tons of WO3 and 2512 tons of Cu. From the metallurgical test work, several feasible processing routes have been identified that need to be further assessed based on the economic and environmental criteria. / REMinE (Improve Resource Efficiency and Minimize Environmental Footprint)

Funktionella neurologiska symtom är vanliga och funktionsnedsättande symtom som ofta anses svårbehandlade. En vanlig förklaringsmodell har varit att den drabbade varit med om något stressande och traumatiskt som lett till kroppsliga symtom. Denna förklaringsmodell leder till frågan om psykologisk behandling med fokus på trauma kan påverka funktionella neurologiska symtom. En systematisk litteraturöversikt, i enlighet med riktlinjer från Statens beredning för medicinsk och social utvärdering, har genomförts för att undersöka om psykologisk traumabehandling med kognitiv beteendeterapi och Eye Movement Desensitization and Reprocessing Therapy kan minska funktionella neurologiska symtom vid symtom på komorbid posttraumatiskt stressyndrom. Resultaten av litteraturöversikten består av totalt 10 artiklar, merparten fallstudier. Slutsatsen av litteraturöversikten tyder på att den forskning som gjorts visar på minskning av funktionella neurologiska symtom efter behandling av symtom på posttraumatiskt stressyndrom. Detta forskningsområde är dock väldigt litet och består främst av fallstudier med något bristande kvalitet. Trots detta anser vi att det finns underlag för att rekommendera att det bör finnas ett fokus på erfarenheter av trauma vid bedömning av funktionella neurologiska symtom.

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Polymers are subjected to physical and chemical changes during their processing, service life, and further recovery, and they may also interact with impurities that can alter their composition. These changes substantially modify the stabilisation mechanisms and mechanical properties of recycled polymers. Detailed knowledge about how the different stages of their life cycle affect the degree of degradation of polymeric materials is important when discussing their further waste recovery possibilities and the performance of recycled plastics. A dual-pronged experimental approach employing multiple processing and thermo-oxidation has been proposed to model the life cycle of recycled high-impact polystyrene (HIPS). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applications. The results from the life cycle degradation simulation were compared with those obtained from real samples from a large-scale mechanical recycling plant. A combination of different analytical strategies (thermal analysis, vibrational spectroscopy, and chromatographic analysis) is necessary to obtain a detailed understanding of the quality of recycled HIPS as defined by three key properties: degree of mixing, degree of degradation, and presence of low molecular weight compounds. / QC 20101119