Tesis sobre el tema "CaWO4"

Extensive research in recent years has failed to develop any essentially new method of large scale tungsten production. A new tungsten powder production technique from calcium tungstate (CaWO4) has recently been reported. In this thesis, this technique was further explored from the aspects of electrochemical reduction mechanism and kinetics, applicability to scheelite concentrates and industrial production. Cyclic voltammetry, constant potential and constant current electrochemical reduction tests were performed to determine the reversible cell potential. Analyses of the experimental results revealed that at least 2.2 V was required to compensate the potentials for the accompanying cell reaction and the electrode polarizations. A cell reaction was proposed by associating the experimental results and the Gibbs Energy changes of the possible reactions. An experiment (mixture) design was created to optimize the process parameters of the electrochemical reduction of CaWO4 to W in molten CaCl2-NaCl eutectic mixture. Temperature, applied voltage and the length of Kanthal wire winding of the CaWO4 pellets were selected as the process parameters and allowed to vary between the predetermined minimum and maximum values. The rates of the electrochemical reductions were interpreted from the variations of current and total charge vs. time graphs under different conditions. The analysis pointed out 640oC and 2.81 V from the created mixture design for the fastest reduction and it was seen that the effect of Kanthal wire winding on the output current was less pronounced when compared to the other two parameters. Another set of experiments was performed by full factorial design to investigate the cleaning procedure needed to remove calcium containing byproducts after electrochemical reduction experiments. Three levels were determined prior to the experiments for the selected three parameters
temperature, acid concentration and exposure time. Main effect and interaction graphs for calcium percent as a function of process parameters were plotted. Calcium contents of the samples were determined by XRF measurements. A 300 g/day capacity tungsten production line was manufactured to take the process one step closer to industrialization. Problems at larger scale were addressed as incomplete reduction, oxidation of graphite and corrosion of cathode materials. After careful research, AISI 316 Ti steel was found to impart sufficient resistance to highly corrosive environment. Oxidation of graphite anode inside the cell was lowered to acceptable levels by continuous nitrogen flow. Metallic tungsten powder was obtained from rich and flotation concentrates of Uludag Etibank Volfram Plant (closed in 1989) together with mainly iron. It was seen that tungsten and iron do not make compounds at the temperatures used for reduction (600-750oC). A basic diffusion model in the electrolyte was developed to better understand the decrease in current values and incomplete reduction encountered during large scale production. The model was used to simulate the recorded current vs. time graphs of selected experiments.

L'électronique intégrée connaît des développements importants pour des applications mettant en œuvre des capteurs en couches minces associés à une acquisition et un traitement des données appropriés. Le développement de couches minces qui peuvent être associées à des composants électroniques est un élément clé pour la mise en œuvre de nouveaux dispositifs. Un des objectifs de ma thèse est de montrer la faisabilité de couches minces de composés à base de soufre, par des techniques autres que celles mettant en jeu le vide. Ces techniques simples sont le spray et le dépôt chimique en solution aqueuse.Trois matériaux binaires et à base de soufre m'ont été proposés pour l'élaboration en couches minces par voie aqueuse, ce sont : SnS, à applications photovoltaïques, et MgS et CaS à applications dosimétriques.Le sulfure d'étain est un absorbeur utilisé dans les dispositifs photovoltaïques, connu pour ces propriétés physiques pertinentes pour cette application. Cependant, c'est un piètre conducteur et différents dopages tel que le fer, l'argent et le gallium ainsi qu'un recuit sous atmosphère contrôlé ont été réalisés dans le but d'augmenter la conductivité de ces couches minces. Il s'est avéré par la suite qu'un simple dopage des films minces de SnS n'aboutit pas à la diminution de la résistivité d'où la proposition d'un recuit sous atmosphère contrôlé dans cette étude. L'étude cristallographique révèle une amélioration cristalline avec la coexistence des deux phases pour des températures de recuit croissantes. A une certaine température, un changement de phase est noté. La transformation de phase se produit à des températures de recuit différentes pour les couches minces recuites et avec différents éléments dopants. La partie électrique étudiée par courants thermiquement stimulés montre que les pièges disparaissent pour des températures de recuit croissantes. Ce résultat a été consolidé par une augmentation progressive de l'intensité du courant d'obscurité en fonction de la température de recuit suivie d'un changement notable du processus de conduction. Ce changement observé est attribué à la transition de phase produite lors du recuit.Nous avons ensuite optimisé les paramètres de croissance des films minces de MgS et de CaSO4 à applications dans les mesures dosimétriques. Nous avons réussi par la technique de spray à élaborer des couches minces de MgS. Suivant l'analyse cristallographique et chimique, nous avons conclu à l'existence des deux matériaux : le MgSO4 en une forte proportion et le MgS en une faible proportion. La présence importante du taux d'oxygène dans les couches minces a été expliquée par le fait que la technique de croissance n'est pas sous vide d'une part et d'autre part par la présence de l'oxygène dans les réactifs. L'effet du recuit réalisé sous vide ou sous azote montre que ce matériau n'est pas stable à atmosphère ambiante et que l'élaboration de ce dernier en couches minces nécessite des techniques de fabrication plus performantes et qui mettent en jeu le vide.Par ailleurs, le CaSO4 a été élaboré par la technique de Spray. Du dopage intentionnel a été analysé afin de préciser le comportement de luminescence du matériau. Cependant, comme on a constaté que la luminescence du matériau après dopage est la même que celle du non dopé et ce quelque soit le dopage utilisé, nous pouvons conclure que la luminescence de ce composé est attribuée aux états de défauts intrinsèques.Une étude de la TL a été réalisée sur un échantillon irradié à différentes doses. Il a été noté que le signal de la TL augmente pour des doses d'irradiation croissantes.Ce travail constitue une première étape cruciale vers la maîtrise des propriétés de certaines couches minces incluses dans des dispositifs photovoltaïques et dosimétriques. Les perspectives s'ouvrent vers d'autres matériaux soufrés bien connus en dosimétrie, et pour lesquels le spray pourrait constituer une méthode de fabrication bien adaptée
This thesis reports the growth of sulfur thin films using low cost techniques other than those involving vacuum. These simple techniques are spray pyrolysis and chemical bath deposition. In this context, it is necessary to control the development of thin films. Various analyzes were performed such as: XRD, SEM, EDS, AFM, spectrophotometry and TSC. All these analyzes allowed us to improve the physical properties of thin films of SnS in photovoltaic application in a first stage and a second stage to optimize the growth parameters of dosimetric thin films.In the first part, we have elaborated tin sulphide thin films using as an absorber material in photovoltaic devices. For this, different doping such as iron, silver, and gallium as well as annealing in a controlled atmosphere have been made in order to increase the conductivity of these thin films. The doping was carried out during the growth process by adding relative concentration of the aqueous solutions containing Fe2+; Ag2+ and Ga2+ ions. It was found later that the doping of SnS thin films does not result in the decrease of resistivity. So,other physical characterizations are in progress to optimize thin films properties and particularly the resistivity by means of an appropriate heat treatment under controlled atmosphere. The XRD patterns show an increase in crystallite size with annealing temperature, correlated with an improvement in surface topography. In addition, annealing at 600°C results in the structural transition from rocksalt to orthorhombic, leading to enhanced conductivity. From TSC measurement, a gradual increase in the current intensity with increasing annealing temperature was observed. A significant change in the electrical conduction regime occurred for the film annealed at 600°C. The TSC intensity increased by 5 decades compared with that of the SnS annealed at 500°C. The SnS thin film had semiconductor electrical behavior, which can be attributed to the structural transition.During the second part of my thesis, we have optimized the growth parameters of dosimetric thin films. For this, we started with the first material the MgS using spray pyrolysis technique. Different growth parameters were varied such as the substrate temperature, the pH of the solution, the nature of the solvent and that of the carrier gas and the concentration of EDTA. Along the crystallographic analysis (XRD) and chemical (EDS), we concluded the existence of two materials: a high proportion of MgSO4 and MgS in a small proportion. The significant presence of oxygen in in thin films was explained by the fact that the growth of such compound needs a vacuum technique. Another reason may be to the presence of oxygen in the reactants. In fact, the presence of the dominant phase magnesium sulfate may be due to the little amount of the rate of the dissociation MgSO4 to release Mg2+ cation through the EDTA complexing. The effect of annealing performed under vacuum and under nitrogen atmosphere show that this material is not stable at ambient atmosphere and the development of the latter requires thin film manufacturing techniques more efficient and which involve vacuum.We then chose to prepare a second dosimeter material is CaSO4 by spray technique. Intentional doping (Sm, Mn or doubly doped such as (Cu, F), (Cu, Mn)) was analyzed to clarify the behavior of luminescence of the material. However, as it was found that the luminescence of the material after doping is the same as that in the case of undoped and whatever the doping used, we can conclude that the luminescence there is given to the states of its own defects -even and which are present in the spray solution. Hence the luminescence of the material is intrinsic. A study of the TL was performed on a sample irradiated at different doses. It was noted that the signal of the TL increases for increasing irradiation doses

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CAPES
O gesso (CaSO4) é um material utilizado em grande quantidade na construção civil brasileira como estrutura física (paredes, tetos e divisórias) para delimitar espaços entre ambientes. Placas de parede de gesso não são utilizadas como blindagem, embora a aplicação destas tem sido estudada para a área de radiodiagnóstico de baixas energias com base na NCRP (National Council on Radiation Protection and Measurement) relatório 147. O objetivo deste trabalho foi estudar a utilização do gesso brasileiro como material de blindagem e estabelecer as curvas de atenuação e camadas semi-redutoras. Foram determinadas as características do gesso, tais como composição química e granulometria. Foram confeccionadas placas quadradas com dimensões de 10x10 cm² com espessuras entre 2,5mm, 5mm e 8 mm que, quando combinadas, resultaram em 10 medidas irradiadas num estudo quantitativo. No procedimento experimental, as placas foram irradiadas em um equipamento de raios X industrial PANTAK, modelo HF320, a uma distância de 50 cm do ponto focal. As medidas de atenuação do feixe de raios X foram determinadas utilizando câmara de ionização posicionada a uma distância de 1,0 m do ponto focal. As respostas da atenuação em função da espessura de gesso resultaram na obtenção de curvas de atenuação que foram utilizadas para determinar as CSR. Os resultados obtidos possibilitaram a obtenção de curvas de atenuação e camadas semi-redutoras do gesso brasileiro que servirão como base para projetos de blindagem para a área radiológica.
The gypsum (CaSO4) is a material used in large quantities in the Brazilian civil construction as physical structure (walls, roofs and office partitions) to delimit spaces between environments. The gypsum wallboards are not used as shielding, although the application of these has been studied the area radiodiagnostic of low power according to the NCRP (National Council on Radiation Protection and Measurement) report 147. The aim of this work was to use the Brazilian gypsum as shielding material for establishes the attenuation curves and half values layers (HVL). Thus, gypsum characteristics were determined, such as chemical composition and grain measurement. Square plates were prepared with fixed dimensions 10x10 cm² and thickness varying between 2.5mm, 5mm and 8 mm which, when combined, result in the 10 irradiated measures for quantitative analysis. In the experimental procedure, the plates were irradiated in an equipment of industrial machine for X-ray Pantak, Model HF320, at a distance of 50 cm from the focal point. The potential applied to the X-ray tube was 60 kV because of N60 quality which resulted in an average of 45 keV electron energy, the current was sustained constant at 10 mA. The attenuation measurements of the Xray beam were determined using ionization chamber positioned at a distance of 1.0 m from the focal point. The responses of attenuation according to the gypsum thickness resulted in obtaining attenuation curves, used to determine the HVL. The obtained results the attenuation curves of the Brazilian gypsum will serve as a basis for shielding projects in the radiological area.

In den Untersuchungen zur Phasenbildung und -stabilität im System Na2SO4 - CaSO4 - H2O wurden die bisher existierenden Phasendiagramme für das wasserfreie System Na2SO4 - CaSO4 korrigiert. Metastabile Mischkristalle wurden bezüglich ihrer Existenzgebiete und Zusammensetzungen charakterisiert. Für den im wässrigen System stabil auftretenden Glauberit, Na2SO4 . CaSO4, wurde die Löslichkeitskonstante bis 250°C bestimmt und ist ab 100°C kleiner als bisher angenommen wurde. Zur Bestimmung der Löslichkeitskonstante wurde die Temperaturabhängigkeit der Freien Standardreaktionsenthalpie für die Zersetzung des Glauberits ermittelt. Dazu wurden die Cp-Funktionen für die an der Reaktion beteiligten Phasen Glauberit und Anhydrit, CaSO4, über Wärmekapazitätsmessungen bis 510°C bestimmt. Eine weitere Möglichkeit zur Bestimmung der Freien Standardreaktionsenthalpie durch die Ermittlung der thermodynamischen Aktivität von Na2SO4 in der Hochtemperaturmischkristallphase mit EMK-Messungen an Festkörperelektroden wurde aufgezeigt. Für das im System Na2SO4 - CaSO4 - H2O metastabile auftretende Natriumpentasalz, Na2SO4 . 5 CaSO4 . 3 H2O, wurde eine Einkristallstrukturanalyse durchgeführt und die strukturelle Verwandtschaft zum Calciumsulfat-Halbhydrtat, CaSO4 . 0,5 H2O, aufgeklärt, sowie die Bildungsbedingungen charakterisiert.

La réaction d'hydratation de l'anhydrite CaS04 orthorhombique met en jeu un mécanisme de dissolution-germination-croissance. Le tracé précis des courbes expérimentales du taux de conversion de cette réaction en fonction du temps, l'hydratation étant réalisée en milieu pur ou en présence d'activateurs (cations étrangers en solution), a conduit à deux résultats fondamentaux : l'échéance au bout de laquelle apparaît le produit de réaction (gypse CaS042H20) est d'autant plus courte que le cation activateur présente une valeur du rapport "charge électrique/rayon ionique'' (z/r) plus faible ; le cation activateur intervient essentiellement au niveau de l'étape de germination. Ces résultats ont conduit à proposer une modélisation énergétique de la germination en introduisant dans l'expression de l'enthalpie libre qui lui est associée un terme complémentaire tenant compte du potentiel électrique créé par le cation en solution au voisinage du germe. Ce modèle rend compte des résultats obtenus quand les cations activateurs sont utilisés en solution diluée. Quand les cations sont utilisés en solution plus concentrée (conditions usuelles d'emploi), l'exploitation du modèle est plus difficile mais on retrouve systématiquement le rôle efficace des cations à faible valeur de z/r dans le processus de germination, donc le rôle du potentiel électrique créé localement par ces cations. L'étude des propriétés mécaniques des produits consolidés par hydratation montre par ailleurs que les valeurs les plus élevées de la résistance en compression pure sont obtenues dans le cas de la formation de gypse dont les cristaux sont aciculaires de petites dimensions, ce qui est réalisé avec les cations activateurs les plus efficaces et confirme le rôle important du processus de germination.

O crescimento acelerado da população mundial e o consequente aumento da produção de bens de consumo tem impulsionado uma crise na disponibilidade de recursos naturais, principalmente os hídricos. Diante da escassez de recursos hídricos, processos de tratamento de efluentes industriais e domésticos que visam o descarte zero de líquido (ZLD - Zero Liquid Discharge) vêm sendo cada vez mais estudados. Atualmente, diversos processos têm sido empregados com este propósito. No entanto, ainda há a geração, juntamente com a água recuperada, de uma corrente composta por uma solução salina concentrada, cuja composição normalmente é constituída por diferentes tipos de sais inorgânicos. Uma das formas de alcançar o descarte zero de líquidos é por meio da implementação de um processo adicional de separação, sendo a cristalização evaporativa considerada viável para essa finalidade. O emprego deste processo é limitado ao controle das características morfológicas das partículas obtidas, visto que estas influenciam diretamente na efetividade de separação dos processos subsequentes à cristalização (filtração, centrifugação). Além disso, efluentes industriais são soluções complexas, e a utilização da cristalização envolve a presença de mais de um sal em solução (co-cristalização). Este processo é pouco investigado na literatura científica, logo, a determinação de condições de processos visando controlar a características destas partículas não é trivial. Neste trabalho, foram estudados o efeito da taxa de evaporação e da presença de sementes na morfologia, composição, tamanho e hábito de partículas de cloreto de sódio e sulfato de cálcio obtidas por co-cristalização evaporativa em bateladas. Os resultados serviram para a determinação de parâmetros de operação para a co-cristalização visando a obtenção de partículas com elevado tamanho médio e baixa dispersão de tamanhos. Taxas de evaporação elevadas favoreceram a obtenção de aglomerados de partículas. A presença de sulfato de cálcio em solução resultou em partículas maiores, menos polidispersas e com menor grau de aglomeração. Tal resultado foi considerado positivo, visto que, estas características são desejáveis para a separação dos cristais da solução mãe. Foi também observado que as sementes de hemihidrato atuam inibindo a aglomeração dos cristais de NaCl. O aumento da quantidade de sementes destes sais culminou na obtenção de partículas menos aglomeradas, porém houve um alargamento das distribuições de tamanho de partículas. Nos experimentos em que foram utilizadas sementes de ambos os sais, o mesmo efeito na aglomeração foi observado. Em todos os experimentos com semeadura de hemihidrato, foi observada a aglomeração deste sal com o NaCl, que foi intensificada com o aumento da taxa de evaporação e com o aumento da concentração de sementes. Foi identificada a possibilidade de recuperação de ambos os sais e obtenção - em determinadas condições - de mais de 90% do NaCl com até 99,50% de pureza.
The accelerated growth of the world population and the consequent increase in the production of consumer goods, has driven to a crisis in the availability of natural resources, especially water. Due to the scarcity of water resources, industrial and domestic wastewater treatment processes that aim the Zero Liquid Discharge (ZLD) have been increasingly studied. Nowadays, several processes have been used for this purpose. However, in all of them, there is still the generation of a brine composed of a concentrated salt solution, concomitantly with the recovered water, whose composition is normally constituted by different types of inorganic salts. One way to achieve the ZLD is through the implementation of an additional separation process, for which the evaporative crystallization is considered technically viable for this purpose. The use of this process is limited to the control of the morphological characteristics of the particles obtained, since this influences directly the separation effectiveness of the downstream processes to crystallization (filtration, centrifugation). Besides, industrial effluents are complex solutions and its crystallization involves the presence of more than one salt in solution (cocrystallization). This process is still not well investigated on scientific literature, thus, the determination of process conditions aiming to control the characteristics of these particles is not trivial. In this work, the effect of the evaporation rate and the presence of seeds on the morphology, composition, size and habit of sodium chloride and calcium sulfate particles obtained by batch evaporative co-crystallization were studied. The results were used to determine the operating parameters for the cocrystallization in order to obtain particles with high average size and narrow dispersion of sizes. High evaporation rates favored the obtaining of agglomerated particles. The presence of calcium sulfate in solution resulted in larger particles, less polydisperse and with less degree of agglomeration. Such result was considered positive, since, these characteristics are desirable for the separation of the crystals from the solution. Seeds of hemihydrate inhibited the agglomeration of the NaCl crystals. The increase in seed load of hemihydrate culminated in obtaining less agglomerated particles, but there was an increase in particle size distributions. In the experiments in which seeds of both salts were used, the same effect in the agglomeration was observed. In all experiments with seeds of hemihydrate, agglomeration of this salt with NaCl was observed, which was intensified with increasing evaporation rate and increasing seed amount. It was identified the possibility of recovery of both salts and, for certain conditions, obtaining more than 90% of NaCl with up to 99.50% purity.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
The widespread use of ionizing radiation in medicine and industry, associated with the known risks that this type of radiation can cause, has motivated the search for new radiation detectors, seeking improvements in the dosimetric characteristics and in the cost of production in comparison with commercial dosimeters disseminated. The motivation of this work is, therefore, to produce new thermoluminescent detectors through improved routes. Unusual elements in CaSO 4 matrix doping, such as terbium (Tb) and ytterbium (Yb), were used as dopants in this matrix, as well as the europium (Eu), the thulium (Tm) and the silver (Ag), resulting in samples of CaSO 4 :Eu,Tb, CaSO 4 :Tb,Yb, CaSO 4 :Tm,Ag and CaSO 4 :Eu,Ag that were prepared by means of an adaptation of the method developed by Yamashita (1971). The route of synthesis is based on the mixture of calcium carbonate (CaCO 3 ) and dopant oxide (except for silver, incorporated in the form of metalic nanoparticles) in a solution of sulfuric acid. The mixture is heated until all the acid evaporates and only the powder of the material remains. In this route, the sulfuric acid is collected and can be reused. The phosphors produced were characterized by X-ray diffraction and radioluminescence techniques. The silver particles, produced by the polyol method, were characterized by scanning electron microscopy. Composites were obtained from the addition of Teflon to the phosphors. The thermoluminescence (TL) and the optically stimulated luminescence (OSL) of the new materials produced were investigated. Thermoluminescent characteristics such as sensitivity, linearity, reproducibility, minimum detectable dose, kinetic order and fading were evaluated and discussed. The CaSO 4 :Tb,Eu composites showed TL glow curves with peaks at temperatures of 170 °C, 270 °C and 340 °C. The CaSO 4 :Tb,Yb composites presented TL glow curves with peaks at temperatures of 90 °C, 160 °C, 240 °C and 340 °C. CaSO 4 :Tm showed peaks at temperatures of 140 °C and 225 °C and the CaSO 4 :Tm,Ag presented peaks at temperatures of 140 °C, 280 °C and 380 °C. All composites showed a linear and reproducible dose response. The TL emission spectrum of the composites was also evaluated. The samples of calcium sulfate doped with europium and silver particles (CaSO 4 :Eu,Ag) showed great potential for applicability in the OSL dosimetry.
O amplo uso das radiações ionizantes na medicina e na indústria, associado aos riscos conhecidos que esse tipo de radiação pode provocar, tem motivado o desenvolvimento de novos detectores de radiação, buscando melhorias nas características dosimétricas e no custo de produção em comparação com os dosímetros comercialmente difundidos. A motivação deste trabalho foi, portanto, produzir novos detectores termoluminescentes a partir de rotas aprimoradas. Elementos não usuais na dopagem do CaSO 4 , como o térbio (Tb) e o itérbio (Yb), foram empregados como dopantes dessa matriz, assim como o európio (Eu), o túlio (Tm) e a prata (Ag), resultando em amostras de CaSO 4 :Eu,Tb, CaSO 4 :Tb,Yb, CaSO 4 :Tm,Ag e CaSO 4 :Eu,Ag, que foram preparadas por meio de uma adaptação do método desenvolvido por Yamashita et al. (1971). A rota de síntese baseia-se na mistura do carbonato de cálcio (CaCO 3 ) e do óxido dos dopantes (exceto para a prata, incorporada na forma de nanopartículas metálicas) numa solução de ácido sulfúrico. A mistura é aquecida até que todo o ácido evapore e reste somente o pó do material. Nessa rota, o ácido sulfúrico é recoletado e pode ser reutilizado. Os fósforos produzidos foram caracterizados por técnicas de difração de raios X e de radioluminescência. As partículas de prata, produzidas pelo método poliol, foram caracterizadas por microscopia eletrônica de varredura. Compósitos foram obtidos a partir da adição de Teflon aos fósforos. A termoluminescência (TL) e a luminescência opticamente estimulada (LOE) dos novos materiais produzidos foram investigadas. Características termoluminescentes como sensibilidade, linearidade, reprodutibilidade, dose mínima detectável, ordem de cinética e desvanecimento foram avaliadas e discutidas. Os compósitos de CaSO 4 :Tb,Eu apresentaram curvas de emissão TL com picos às temperaturas de 170 °C, 270 °C e 340 °C. Os compósitos de CaSO 4 :Tb,Yb apresentaram curvas de emissão TL com picos às temperaturas de 90 °C, 160 °C, 240 °C e 340 °C. O CaSO 4 :Tm apresentou picos em temperaturas de 140 °C e 225 °C. Já o CaSO 4 :Tm,Ag apresentou picos em temperaturas de 140 ºC, 280 ºC e 380 ºC. Todos os compósitos apresentaram respostas lineares à dose e reprodutíveis. Também foi avaliado o espectro de emissão TL dos compósitos. As amostras de sulfato de cálcio dopado com európio e partículas de prata (CaSO 4 :Eu,Ag) demonstraram grande potencial para aplicabilidade na dosimetria LOE.

The dosimetry of ionizing radiation is essential to procedures could be taken in order to maximize the beneficial effects that the use of such radiation can offer to society, as well as minimize damage from such radiation. As a result, different materials detectors have been proposed in the literature for use in personal and environmental dosimetry. Thermoluminescent detectors are widely used in these dosimetric procedures. The motivation of this work was to produce crystals of CaSO4 doped with unusual elements such as europium (Eu) and silver (Ag), including in the form of nanoparticles, prepared by an adaptation of the method developed by Yamashita (1971). The interest in the production of these materials was to investigate other methods of producing thermoluminescent materials. In the new growth route, the crystals were produced from calcium carbonate (CaCO3), by incorporating the dopants (Eu2O3 or Ag2O3) in a solution of sulfuric acid. Silver nanoparticles Ag(NP) were obtained through a synthesis route called polyol method, which is based on the reduction of Ag ions in a polyalcohol, in this case the ethylene glycol. The composites were obtained from the mixture of the base compound and glass or Teflon. The thermally stimulated exoeletronic emission of the new materials was investigated. Thermoluminescent characteristics as linearity, reproducibility, energy dependence, minimum detectable dose, fading and kinetics order were evaluated. The composites showed TL emission glow curves with a single peak centered around 200 ° C for samples containing Teflon and 230 ° C for samples with addition of glass. The new routes for the preparation of dosimeters were shown to be viable, being the dosimeter based on calcium sulfate doped with europium and silver nanoparticles (CaSO4:Eu,Ag(NP)), which provides the most intense TL emission between the preparations studied, being linear, reproducible, with low fading and low detection limit.
A dosimetria das radiações ionizantes é essencial para que procedimentos possam ser tomados com o objetivo de maximizar os efeitos benéficos que o uso dessas radiações pode oferecer à sociedade, assim como minimizar os danos decorrentes de tais radiações. Em decorrência disso, diferentes materiais detectores têm sido propostos na literatura para o emprego em dosimetria pessoal e ambiental. Detectores termoluminescentes têm larga utilização nesses procedimentos dosimétricos. A motivação deste trabalho foi produzir cristais de CaSO4 dopados com elementos não usuais como o európio (Eu) e a prata (Ag), inclusive na forma de nanopartículas, preparados por meio de uma adaptação do método desenvolvido por Yamashita (1971). O interesse na produção desses materiais foi o de investigar outras metodologias de produção de materiais termoluminescentes. Pela nova rota de crescimento, os cristais foram produzidos a partir do carbonato de cálcio (CaCO3), incorporando-se os dopantes (Eu2O3 ou Ag2O) numa solução de ácido sulfúrico. As nanopartículas de prata Ag(NP) foram obtidas através da rota de síntese chamada de método poliol, que se baseia na redução de cátions Ag em um poliálcool, neste caso o etileno glicol. Os compósitos foram obtidos a partir da mistura do composto base e da adição eletiva de vidro ou Teflon. A emissão exoeletrônica termicamente estimulada dos novos materiais produzidos foi investigada. Características termoluminescentes como linearidade, reprodutibilidade, dependência energética, dose mínima detectável, desvanecimento e ordem cinética foram avaliadas. Os compósitos apresentaram curvas de emissão TL com um único pico, centrado em torno de 200°C para as amostras contendo Teflon e 230°C para as amostras com adição de vidro. As novas rotas de preparação dos dosímetros termoluminescentes mostraram-se viáveis, sendo o dosímetro à base de sulfato de cálcio dopado com európio e nanopartículas de prata (CaSO4:Eu,Ag(NP)) o que apresenta a emissão TL mais intensa entre as preparações estudadas, sendo linear, reprodutível, com baixo desvanecimento e baixo limite inferior de detecção.

A avaliação do desempenho dos detectores termoluminescentes de CaSO4:Dy, produzidos pelo IPEN, tem como objetivo apresentar uma alternativa aos dosímetros de LiF:Mg,Ti comerciais (TLD-100), amplamente empregados em radioterapia, na dosimetria de feixes clínicos de elétrons. Os dois tipos de detectores termoluminescentes foram caracterizados, com a utilização de objetos simuladores de PMMA, água sólida do tipo RMI-457 e água, em campos de radiação de elétrons de 4, 6, 9, 12 e 16 MeV de energias nominais, nos quais as curvas de dose-resposta foram obtidas e as doses superficial e profunda foram determinadas. A dependência da resposta termoluminescente com a energia nominal dos elétrons e com o objeto simulador empregado foram estudadas. O CaSO4:Dy apresentou o mesmo comportamento do LiF:Mg,Ti; de maneira que sua aplicação como uma alternativa às pastilhas TLD-100 na dosimetria de feixes de elétrons em radioterapia é viável e apresenta a sensibilidade à radiação de elétrons significativamente mais alta como principal vantagem.
The assessment of the performance of CaSO4:Dy thermoluminescent detectors produced by IPEN in the dosimetry of clinical electron beams aims to propose an alternative to the LiF:Mg,Ti commercial dosimeters (TLD-100) largely applied in radiation therapy. The two types of thermoluminescent dosimeters were characterised with the use of PMMA, RMI-457 type solid water and water phantoms in radiation fields of 4, 6, 9, 12 and 16 MeV electrons of nominal energies in which the dose-response curves were obtained and the surface and depth doses were determined. The thermoluminescent response dependency with the electron nominal energies and the applied phantom were studied. The CaSO4:Dy presented the same behaviour than the LiF:Mg,Ti in such a way that its application as an alternative to the TLD-100 pellets in the radiation therapy dosimetry of electron beams is viable and presents the significantly higher sensitivity to the electron radiation as its main advantage.

Detectores de sulfato de cálcio ativado com cério IV e európio III utilizando o politetrafluoretileno (PTFE, Teflon®) free-flow como aglutinante (CaSO4:Ce,Eu + Teflon®) foram produzidos pelo método da estampagem, desenvolvido em colaboração com a empresa Tecnoflon, a partir de cristais crescidos de acordo com uma nova variação da rota da evaporação lenta, também apresentada nesse trabalho, com as concentrações de 0,16 mol% de Eu3+ e de 0,15 mol% de Ce4+ na solução ácida precursora. O modelo de dosímetro pessoal desenvolvido consiste em cinco detectores aderidos a um cartão de 30 x 48 mm de cloreto de polivinila (PVC) 95% opaco à luz na faixa do espectro eletromagnético que vai do infravermelho ao ultravioleta, idêntico aos cartões de identificação utilizados no IPEN, por uma tira de 10 x 35 mm de filme adesivo do mesmo material e foi submetido aos testes de aceitação descritos no regulamento técnico IRD-RT Nº 002.01/95, Desempenho de Sistemas de Monitoração Individual Critérios e Condições, sendo aprovado em todos os testes. Para a dosimetria clínica, os próprios detectores foram considerados dosímetros termoluminescentes e submetidos aos testes de aceitação descritos no código de práticas da Agência Internacional de Energia Atômica Technical Report Series Nº 398, Absorbed Dose Determination in External Beam Radiotherapy: An International Code of Practice for Dosimetry based on Standards of Absorbed Dose to Water, [TRS-398, IAEA, 2000] adotado como protocolo de dosimetria pela maioria dos hospitais, sendo igualmente aprovados nesses testes. Os dosímetros desenvolvidos podem ser utilizados para a monitoração individual externa e para dosimetria clínica, apresentando a diferenciação do tipo e da energia da radiação com que foram irradiados e a redução de custos como as principais vantagens em relação aos dosímetros termoluminescentes atualmente utilizados nessas aplicações.
Calcium sulphate activated with cerium IV and europium III using the free-flow polytetrafluoroethylene (PTFE, Teflon®) as bonder were produced by the stamping method, developed by the collaboration of Tecnoflon industries, from crystals growth according to a new variation of the slow evaporation method, also described in this study, with Eu3+ and Ce4+ concentrations of respectively 0.15 mol% and 0.16 mol% in the precursory acid solution. The developed personal dosimeter consist of five detectors adhered to a 30 x 48 mm polyvinyl chloride (PVC) card 95% mat to light in the infrared to ultraviolet wavelengths, identical to the access cards used by IPEN staff, by a 10 x 35 mm adhesive strip of the same material and it passed the acceptance tests required by Brazilian national regulatory committee for appliance in individual monitoring of external exposure services. The own detector is considered a dosimeter as far as clinical dosimetry is concerned and it passed the acceptance tests suggested by the International Atomic Energy Agency in the Technical Report Series Nº 398, Absorbed Dose Determination in External Beam Radiotherapy: An International Code of Practice for Dosimetry based on Standards of Absorbed Dose to Water, [TRS-398, IAEA, 2000] adopted as the dosimetry protocol by most hospitals. Hence, the developed dosimeters can be applied in the individual monitoring for external exposure and in the clinical dosimetry, having the radiation type and energy differentiation and the cost reduction as the key advantages over the currently used thermoluminescent dosimeters in such applications.

Radiação gama com energias maiores que 1,25 MeV são usualmente encontradas em ambientes de reatores, aceleradores de partículas e campos de radiação de origem cósmica. Nestas energias, a resposta de um dosímetro varia fortemente com a espessura de material absorvedor, até atingir um valor máximo conhecido como espessura de equibl^rio de partículas carregadas. O objetivo principal do presente trabalho foi a determinação experimental do perfil de dose absorvida por uma amostra de alumínio, para várias energias de feixes de raios gama, de forma a obter uma relação entre a energia média do campo de radiação gama e a espessura de equilíbrio de partículas carregadas para o alumínio. Os dosímetros foram irradiados com radiação gama produzida pela captura de neutrons térmicos em 23 materiais alvos no arranjo experimental montado no canal tangencial do reator do IPEN-CNEN/SP. Na determinação da camada de equilíbrio de partículas carregadas, foi ajustada aos dados experimentais uma função semi-empirica que permitiu obter a espessura de ETPC (Equilíbrio Transitório de Partículas Carregadas) para cada espectro de radiação gama utilizado neste trabalho, com energia média variando no intervalo de 3,26 a 7,85 MeV. Os resultados experimentais do presente trabalho permitiram obter uma relação entre a energia média do campo de radiação gama e a espessura de ETPC, que apresenta uma excelente concordância com o alcance corrigido dos elétrons gerados naquela energia.
Gamma radiation with energies greater than 1.25 MeV are usually produced in reactor environments, particle accelerators and in cosmic radiation fields. For these energies, the response of a dosimeter heavily vary with the absorber material thickness, up to attain a maximum value named as charged particle equilibrium thickness. The main gol of this paper was the experimental determination of the absorbed dose profile in an aluminum sample for several energies of gamma ray beam, in order to obtain a relationship between the average energy of the gamma radiation field and the charged particle equilibrium thickness. The dosimeters were irradiated with gamma radiation produced by thermal neutron capture in 23 target materials in the experimental arrangement mounted at the tangential beam hole of the BPEN-CNEN/SP reactor. For the determination of the charged particle equilibrium thickness, it was fitted to the experimental data a semi-empirical fimction which allowed to obtain the thickness of CTPE ( Charged Particle Transient Equilibrium ) for each gamma radiation spectrum used in this work, with average energy varying in the interval from 3.26 to 7.85 MeV. The experimental results of the present paper allowed to obtain a relationship between average energy of the radiation field and the CTPE thickness, which presents an excellent agreement with the corrected range for electrons produced in that energy.

The environmental impact and sustainability of irrigation with coal-mine water was investigated from an agricultural point of view on different coal-mines in the Republic of South Africa. Field trials were carried out on a commercial and plot scale, on sites that could offer a range of soil, crop, weather conditions and water qualities such as gypsiferous, sodium sulphate and sodium bicarbonate waters. Crop production under irrigation with gypsiferous mine water is feasible on a field scale and sustainable if properly managed. No symptoms of foliar injury due to centre pivot sprinkler irrigation with gypsiferous water were observed. The presence of high Ca and Mg in the water suppressed plant uptake of K. This could be corrected by regular application of K containing fertilizers. The bigger problem experienced was waterlogging due to poor site selection, especially during the summer months. The problem is not related to the chemistry of the gypsiferous water used for irrigation. Pasture production with Na2SO4 rich mine effluent was also feasible, at least in the short term, but would need a well-drained profile and large leaching fraction to prevent salt build up. Forage quality was not affected by the Na2SO4 water used. NaHCO3 water was of very poor quality for irrigation and is not recommended for irrigation. Salt tolerant crops that are not susceptible to leaf scorching can be produced with this water, but only with very high leaching fractions and careful crop management. Regular gypsum application will be required to prevent structural collapse of the soil. Most of the salts applied will leach from the soil profile, and will probably need to be intercepted for treatment or reuse. The Soil Water Balance (SWB) model was validated successfully. The model predicted crop growth, soil water deficit to field capacity and soil chemistry reasonably well, with simulated results quite close to measured values. Soluble salts have to be leached from the soil profile, so that crop production can be sustainable, but will externalize the problem to the receiving water environment. To assess the environmental impact of irrigation with coal-mine water, it is valuable to develop a tool that can assist with prediction of offsite effects. SWB was validated for runoff quantity and quality estimations, and was found to give reasonable estimates of runoff quantity and quality. SWB also predicted the soil water and salt balance reasonably well. This gives one confidence in the ability of the model to simulate the soil water and salt balance for long-term scenarios and link the output of SWB to ground and surface water models to predict the wider impact of large scale irrigation. This will also link the findings of this work to other research oriented towards the management of mine water and salt balances on a catchment scale. It will also help authorities make informed decisions about the desirability and consequences of permitting mine water irrigation on a large scale. Irrigation with gypsiferous mine water can be part of finding the solution to surplus mine water problems. Appropriate irrigation management of mine water is essential for the long-term sustainability of irrigation.
Thesis (PhD)--University of Pretoria, 2009.
Plant Production and Soil Science
unrestricted

Thesis (MEng) -- Stellenbosch University, 2014.
ENGLISH ABSTRACT: When desalinating brackish water by reverse osmosis (RO) or other techniques, high overall water recoveries are essential to minimize brine production and the associated disposal costs thereof. As the overall water recovery increases, concentrations of sparingly soluble salts (e.g. barium sulphate, calcium sulphate) reach levels above saturation, especially near the membrane surface, drastically increasing the scaling propensity. Antiscalants are typically dosed into the feed water to prevent such scaling during RO desalination. However, the carry-over of antiscalant into the concentrate stream can complicate subsequent salt precipitation processes that may be used to increase overall water recovery. These precipitation techniques are sometimes used to reduce the levels of super-saturation in the RO concentrate prior to a subsequent RO desalination step. The purpose of this study was to assess the feasibility of reducing calcium sulphate scaling on RO membranes, by using periodic permeate flushing when feeding a lab-scale RO unit with a supersaturated calcium sulphate solution in the absence of anti-scalant. The overall water recovery was increased by recycling the concentrate, after an intermediate de-supersaturation step. This simulated a multiple-stage RO system, typical of processes used in high-recovery acid mine drainage (AMD) treatment plants. De-supersaturation of the concentrate intermediate was achieved with direct seeded gypsum precipitation, in the absence of any antiscalant. On the membrane surface inside the membrane unit, calcium sulphate concentrations greatly exceeded saturation levels – a combined consequence of the normal concentration process and the well-known surface-based concentration polarisation phenomenon. Therefore, periodic forward-flushing of the supersaturated solution from the membrane unit was performed with permeate. In theory, the periodic flushing removes the highly concentrated layer at the membrane surface during every flush, before scaling can occur. Various flushing regimes were evaluated to assess the effectiveness of the process. A lab-scale desalination unit with a 0.106 m2 flat sheet polyamide RO membrane was designed and constructed. The unit could operate at a feed rate of 12-14 L/h and at permeate fluxes of 12-24 LMH. Super-saturated feed solutions were prepared by mixing sodium sulphate and calcium chloride dihydrate salts with demineralised water, with an initial salinity of ± 5300 mg/L TDS, corresponding to a gypsum saturation index (SIg) of 1.2 for most experiments. The total production time, net permeate production and flux decline were used to compare the flushing efficiency in different experimental runs. Initial tests showed that scaling could be prevented (when operating the unit in full recycle mode, i.e. where both concentrate and permeate were recycled to feed), at flushing frequencies between 12 and 2.4 h-1, when the membrane feed and concentrate were slightly under-saturated (SIg = 0.9) and slightly super-saturated (SIg = 1.1) respectively. However, when switching the same system to non-flushing mode after 24 hours of operation, membrane scaling occurred within 2-3 hours, as indicated by a strong decline in flux. However, when operating the system in concentrate recycle mode (i.e. permeate is withdrawn) with super-saturated feed solutions (e.g. SIg = 1.2), and thus a notably more super-saturated solution in the membrane concentrate, scaling could not be prevented (albeit delayed for some time) with intermittent permeate flushing. A fractional 25-1 factorial design was used to determine which factors had the most significant effect on total production time and permeate production rate, testing five factors: 1) flushing frequency, 2) flushing volume, 3) permeate soak time, 4) permeate flux and 5) instantaneous recovery. The ANOVA analysis showed that total production times were, not surprisingly, primarily affected by the permeate flux, where operation at 24 LMH resulted in a lower net permeate production between 3.0 - 4.2 L, compared to 7.6 - 9.7 L at 12 LMH. Higher permeate fluxes clearly resulted in higher levels of concentration polarisation at the membrane surface, thus increasing the propensity for membrane scaling. Flushing frequency and instantaneous recovery also affected the net permeate production, where 6 h-1 and 10 % were the optimal values respectively within the range of test conditions. The lowest permeate production rate resulted in the highest net permeate volume production (i.e. also longest total production time), confirmed by a least squares regression. In summary: This study showed that periodic permeate flushing could delay the membrane scaling process. However, it failed to prevent membrane scaling completely when operating the system with supersaturated calcium sulphate solutions in the absence of antiscalants. The flushing technique effectively delayed the onset of precipitation, but scaling eventually occurred if the lab-scale RO system was operated in concentrate recycle mode with oversaturated feed solutions (SIg = 1.2). Additional experiments at different cross-flow velocities during permeate flushing, while using an optimised RO test cell flow channel design, are recommended for future studies.
AFRIKAANSE OPSOMMING: Gedurende die ontsouting van brakwater deur tegnieke soos tru-osmose (TO), is ʼn maksimum herwinning van water noodsaaklik om die produksie, en die gepaardgaande kostes van verwydering, van die sout/brak neweproduk te minimeer. Soos die herwinning van water verhoog, so ook verhoog die konsentrasie van moeilik-oplosbare soute (soos bariumsulfaat, kalsiumsulfaat) in die sout konsentraat stroom, totdat die soute uiteindelik superversadiging bereik. Hierdie superversadiging gebeur veral naby die membraanoppervlak, waar dit lei tot ʼn verhoogde kans van presipitasie en skaalvorming. Om dit te voorkom word die voerwater na ʼn TO stelsel tipies gedoseer met antiskaalmiddels. Hierdie antiskaalmiddels verlaat die stelsel saam met die konsentraat, waar hulle gevolglike die presipitasie van soute bemoeilik. Presipitasie van soute uit die konsentraat kan tipies gebruik word om die vlak van superversadiging in die konsentraat te verlaag, waarna verdere TO behandeling gebruik word om selfs ʼn hoër algehele waterherwinning te bewerkstellig. Die doel van hierdie studie was om die vatbaarheid van die vermindering van kalsiumsulfaat (gips) skaalvorming in die afwesigheid van antiskaalmiddels op TO membrane te toets. Dit is bewerkstellig deur ʼn laboratoriumskaal TO eenheid te voer met ʼn superversadigde kalsiumsulfaat oplossing en die membraan periodies met skoon produkwater (permeaat) te was. Die algehele waterherwinning is verhoog deur met ʼn tussenstap die versadigingsvlak van gips in die konsentraat te verlaag, waarna dit hersirkuleer is na die voertenk. Sodoende is ʼn multi-stadium TO stelsel nageboots, soos dit tipies in hoë herwinningsaanlegte, soos met die herwinning van suur mynwater (E: acid mine drainage, AMD), gebruik word. ʼn Verlaging in superversadiging van die konsentraat in die tussenstap is behaal deur die konsentraat direk aan gipskristalle bloot te stel om presipitasie te bewerkstellig in die afwesigheid van enige antiskaalmiddels. Gedurende eksperimente het die soutkonsentrasie op die membraanoppervlak in die TO eenheid superversadigingsvlakke vêr oorskry, as gevolg van die natuurlike konsentrasie proses en die bekende konsentrasie polarisasie oppervlaksverskynsel. Om hierdie superversadiging teen te werk is periodiese saamstroom spoeling van die membraan met skoon produkwater uitgevoer. In teorie het die periodiese spoeling die hoogs gekonsentreerde oplossing van die membraan oppervlak verwyder voor skaalvorming kan plaasvind. Verskillende spoelpatrone is ondersoek om die doeltreffendheid van die spoeling te bepaal. Om die eksperimente uit te voer is ʼn laboratoriumskaal ontsoutingsaanleg met ʼn maklik verwyderbare 0.106 m2 plat-vel poli-amied TO membraan ontwerp en gebou. Die aanleg kan vloeistof voertempo’s tussen 12-24 L/h hanteer en skoon produkwater teen 12-24 LHM lewer. Die superversadigde voer oplossings, soos gebruik in die meerderheid van die eksperimentes is voorberei deur natriumsulfaat en kalsiumchloried-dihidraat soute te meng in gedemineraliseerde water, tot ʼn soutgehalte van ± 5300 mg/L TDS bereik is. Hierdie soutgehalte stem ooreen met ʼn gips versadigingsindeks (E: gypsum saturation index, SIg) van 1.2. Die skoon produkwater totale produksietyd en netto produksie, asook die membraan vloed afname, is gebruik as veranderlikes om die spoel doeltreffendheid tussen eksperimentele lopies te vergelyk. Aanvanklike toetse het getoon dat skalering voorkom is by effens onderversadigde (SIg = 0.9) en effens superversadigde (SIg = 1.1) voer oplossings met die onderskeie spoel frekwensies van 12 en 2.4 h-1, (terwyl die aanleg in algehele hersirkulasie bedryf is, m.a.w. wanneer beide die konsentraat en produkwater gedurig na die voertenk hersirkuleer word). ʼn Effens-superversadigde eksperiment is ook sonder spoeling uitgevoer vir 24 uur. In hierdie geval het skaalvorming binne twee tot drie uur gebeur, soos bevestig deur ʼn skerp afname in die membraan vloed. Skaalvorming kon nie verhoed word terwyl die aanleg bedryf word met superversadigde (SIg = 1.2) voeroplossings en slegs konsentraat hersirkulasie nie (m.a.w. skoon produkwater word opgevang), alhoewel skaalvorming vertraag kon word. Hierdie operasie het tot beduidend meer gekonsentreerde oplossings in die membraan gelei. Om te bepaal watter faktore die grootste invloed op totale produksietyd en netto produksie van skoon produkwater het, is ʼn fraksionele faktoriaalontwerp van 25-1 uitgelê wat vyf faktore toets, naamlik: 1) spoel frekwensie, 2) spoel volume, 3) skoon produkwater weektyd, 4) membraanvloed en 5) oombliklike herwinning. ʼn AVOVA analise het getoon dat totale produksietyd hoofsaaklik deur membraanvloed beïnvloed is, soos verwag kan word. Dit word gestaaf deurdat die aanleg, bedryf teen 24 LMH, slegs 3 - 4.2 L netto produkwater gelewer het, teenoor 7.6 - 9.7 L by 12 LMH. Hoër membraan vloedtempo’s het tot hoër vlakke van konsentrasie polarisasie op die membraanoppervlak gelei, wat ʼn groter neiging tot skaalvorming tot gevolg gehad het. Spoelfrekwensie en oombliklike herwinning het ʼn invloed op die netto produksie van skoon produkwater gehad, met 6 h-1 en 10 % as die onderskeie optimale waardes. ʼn Kleinstekwadraat regressie het aangedui dat die laagste produksietempo van skoon produkwater die hoogste netto produksie van skoon produkwater gelewer het, (asook die langste produksietyd). In opsomming: Hierdie studie het getoon dat gereelde spoeling met skoon produkwater die membraan skaalproses kan vertraag. Gedurende bedryf met superversadigde kalsiumsulfaat oplossings sonder enige antiskaalmiddels is daar gevind dat skaalvorming nie geheel en al vermy kon word nie. Die spoeltegniek, soos gebruik in hierdie studie, het die aanvang van skaalvorming in die laboratorium skaal TO eenheid vertraag, maar bedryf met konsentraat hersirkulasie en superversadigde oplossings (SIg = 1.2) het steeds skaal gevorm. Bykomende eksperimente teen verskeie kruisvloei snelhede gedurende die spoel stap word aanbeveel vir toekomstige studies.

Afin d'expliquer le role propre des ions phosphate syncristallises dans la reactivite, vis-a-vis de l'eau, des produits de deshydratation des phosphogypses industriels, des solutions solides gypse-brushite de formule (1-x) caso#4. 2h#2o-xcahpo#4. 2h#2o (x<0,2) ont ete preparees par coprecipitation en phase aqueuse. La cinetique du phenomene a ete suivie par methode conductimetrique. L'analyse des solides obtenus et leur caracterisation par differentes methodes physico-chimiques (analyse thermique differentielle, diffraction des rayons x, spectroscopie i. R. , meb) ont montre que des solutions solides etaient effectivement obtenues mais pratiquement toujours accompagnees de monetite (cahpo#4 anhydre). Les hemihydrates prepares par deshydratation a 130c et 150c des solutions solides gypse-brushite sont egalement des solutions solides et le suivi, par calorimetrie et conductimetrie, de leur cinetique de rehydratation a permis de mettre en evidence le role fortement inhibiteur de l'ion hydrogenophosphate hpo#4#2# dans le reseau cristallin du dihydrate au cours de formation de celui-ci a partir de la phase aqueuse. Ce travail montre clairement que les ions hydrogenophosphate syncristallises dans le reseau du gypse ont un role predominant par rapport a celui des autres impuretes contenues dans les phosphogypses industriels

Ce travail est une contribution a une meilleure comprehension des mecanismes a l'origine de la thermoluminescence des solides inorganiques a l'etat cristallin, en particulier le sulfate de calcium dope aux ions lanthanides ou au manganese, puissant dosimetre utilise notamment en datation par thermoluminescence et l'oxyde mixte de bismuth et de germanium, dont les applications industrielles sont nombreuses, notamment en holographie. Un dispositif de luminescence a tres basses temperatures, a partir de 10k (263#oc) a ete realise. Il permet une analyse spectrale fine des emissions. En ce qui concerne le sulfate de calcium, la nature des centres pieges associes aux pics dans le domaine des basses temperatures a ete proposee. Apres avoir montre l'insuffisance des relations habituelles reliant l'energie d'activation a la seule mesure de la temperature du maximum d'un pic, la mise en evidence d'une composante basse temperature dans le domaine de l'initial rise a permis de proposer un autre mode de traitement des courbes et de caracteriser la profondeur d'un piege par une seule valeur de l'energie d'activation. Nous avons montre que les ions lanthanides et manganese sont excites par un transfert d'energie non radiatif non resonnant. Grace a la resonance paramagnetique electronique, la presence systematique de deux impuretes presentes a l'etat de traces, a ete decelee dans tous les cristaux et la concentration relative impurete/dopant a permis de prevoir l'influence des constituants sur les mecanismes de luminescence. En ce qui concerne l'oxyde mixte de bismuth et de germanium, ce travail a permis d'identifier les niveaux electroniques responsables de ses proprietes opto-electroniques. Nous avons montre que le processus de thermoluminescence est caracterise par un ordre evoluant avec le degre de vidage d'un centre piege. Nous avons egalement montre que la thermoluminescence obeit a une loi expone

In den Untersuchungen zur Phasenbildung und -stabilität im System Na2SO4 - CaSO4 - H2O wurden die bisher existierenden Phasendiagramme für das wasserfreie System Na2SO4 - CaSO4 korrigiert. Metastabile Mischkristalle wurden bezüglich ihrer Existenzgebiete und Zusammensetzungen charakterisiert. Für den im wässrigen System stabil auftretenden Glauberit, Na2SO4 . CaSO4, wurde die Löslichkeitskonstante bis 250°C bestimmt und ist ab 100°C kleiner als bisher angenommen wurde. Zur Bestimmung der Löslichkeitskonstante wurde die Temperaturabhängigkeit der Freien Standardreaktionsenthalpie für die Zersetzung des Glauberits ermittelt. Dazu wurden die Cp-Funktionen für die an der Reaktion beteiligten Phasen Glauberit und Anhydrit, CaSO4, über Wärmekapazitätsmessungen bis 510°C bestimmt. Eine weitere Möglichkeit zur Bestimmung der Freien Standardreaktionsenthalpie durch die Ermittlung der thermodynamischen Aktivität von Na2SO4 in der Hochtemperaturmischkristallphase mit EMK-Messungen an Festkörperelektroden wurde aufgezeigt. Für das im System Na2SO4 - CaSO4 - H2O metastabile auftretende Natriumpentasalz, Na2SO4 . 5 CaSO4 . 3 H2O, wurde eine Einkristallstrukturanalyse durchgeführt und die strukturelle Verwandtschaft zum Calciumsulfat-Halbhydrtat, CaSO4 . 0,5 H2O, aufgeklärt, sowie die Bildungsbedingungen charakterisiert.

碩士
國立臺北科技大學
材料科學與工程研究所
98
Two kinds of calcium sulfate and calcium phosphate bio-ceramics, because of excellent biocoMPatibility, non-toxic cell, and for major components of the human skeleton, has been extensively studied and used in orthopedics and dental surgery such as bone defect repair materials. Calcium sulfate is a bone induction, but the absorption rate of fast. Calcium phosphate has osteoconduction, but take a long time to be absorbed, so guided bone growth is extremely slow. This study investigated the hydrated calcium sulfate and calcium phosphate are made of composite materials, research Physical properties, Mechanical Properties, degradation rate and biocoMPatibility of the effect, and the use of SEM, EDS, XRD analysis of the materials. The establishment a group of TiO2 added to the effects in cell culture. And for material degradation results of the experiment, the establishment kinetics of reaction equation. The results show that the calcium sulfate and calcium phosphate compound into, When the calcium sulfate content of 70 ~ 90wt%, the mechanical strength of the best, shows that have a strengthening effect of calcium phosphate additions. Aspects of cell activity, when the calcium phosphate concentration increases, the cell activity promotion, Which contain TiO2, this group of specimens, but also get a better cell activity value, showing a high biocoMPatibility of TiO2.

碩士
國立中山大學
機械與機電工程學系研究所
94
This study develops and demonstrates a microfluidic module for investigating the mechanism of inorganic fouling caused by the precipitation of calcium sulfate (CaSO4) on nanofiltration membranes. The developed microfluidic module enables sensitive system responses, rapid detection and real time observation of inorganic fouling commonly encountered in water treatment industries. For this development, CaSO4 is selected as the model salt due to its unique fouling characteristics. The effect of the operating conditions, such as pressure and permeate flux, was on the fouling behavior is investigated. A plate-frame type microfluidic chip was fabricated and employed in a dead-end filtration mode for constant-flux fouling experiments. The nanofiltration chip module has a dimension of 50 mm × 25 mm × 12 mm. It is consisted of a polymeric nanofilter, a pressure acquisition unit, a C.C.D., and micro electrodes on the nanofilter for investigating the relationships among trans-membrane pressure, conductivity on membrane surface and permeate fluxes. With the microfluidic system, real-time concentration polarization, bulk nucleation of CaSO4 and surface crystal accumulation were observed in terms of the variations of pressure and conductivity on membrane surface, which were verified with scanning electron micrographs to confirm the corresponding fouling stage. It is found that membrane surface conductivity increases with trans-membrane pressure before bulk crystallization of CaSO4, then slightly decreases after the formation of bulk nuclei due to the removal of solute in the aqueous phase. The conductivity remains relatively constant during cake formation stage while trans-membrane pressure steadily increases. This study successfully integrates microfluidic technology with pressure and electrical measurements for detecting the dynamic transition during CaSO4 fouling, and reports for the first time the experimental measurement of the initiation of inorganic cake formation.

碩士
義守大學
生物醫學工程學系碩士班
95
Periodontal disease and bone cancer might cause severe alveolus bone loss. One common used therapy to treat this disease is so-called debridement. After that, a bone conductive material is put into defect of alveolus bone to improve the regeneration of bony tissues. Thus, the purpose of the thesis is to prepare chitosan/CaSO4 microspheres, by using a high voltage electrostatic system, to act as dental implant (filling) materials. Besides, platelet gel that enriched growth factors are also used an ingredient to prepare chitosan/CaSO4/PRP microspheres which probably can serve as growth factors slow release carrier (after activated with thrombin). The preliminary results revealed that the chitosan/CaSO4/PRP microspheres are in the range of 322.2 ± 40.8μm ~ 471.6 ± 57.9μm in diameter. The in-trapped growth factors are able to sustained release at 24-hour period test. Three groups of microspheres, chitosan/CaSO4 microspheres (Group A) , chitosan/CaSO4 microspheres mixed with thrombin (Group B), chitosan/CaSO4/PRP microspheres mixed with thrombin (Group C) are prepared and the efficacy of these microspheres in bone regeneration are evaluated in pig oral model. The animal implantation study will be observed by HE stain and Trichrome stain.

碩士
國立臺灣大學
食品科技研究所
90
Soy is an excellent source of protein with low cost and high quality. Recently many reports have pointed out that soy protein reduces cholesterol in human blood. US Food and Drug Administration (FDA) approved the health claims of “it may reduce the risk of coronary heart disease” for soy protein- containing foods. The act has induced more consumption of soy foods. Defatted soy flour has been used in this study for investigating the gelation behavior during heating. The additives, CaSO4 and glucono-δ-lactone (GDL), were used to understand their effects on soy-protein gelation. The gelation of soy protein/starch composites was also studied for developing new food materials for various products. The results showed that the main endothermic peak (82.9 oC) accompanying gelatinization of the starch in the composite was higher than that (68.54oC) for starch only with 60％ moisture content. The raise of gelatinization of starch might be resulted from the competition for water between soy protein and starch. From the dynamic rheological measurements, the addition of CaSO4 or GDL enhanced the strength of the composite gel. Some partially denatured protein interacted with GDL resulted in the initial gelation at temperatures lower than 68℃ (the denaturation temperature of 7s protein). From the microscopic observation, the protein denatured and starch gelatinized independently in the composite during heating. The composite appeared to be a filled gel. It is different from the mixed gel formed by starch and pork muscle protein (Lee, 2002).

Deposition of dispersed phase from flowing dispersions onto a substrate surface is of utmost relevance for various industrial processes like fouling of sparingly soluble salts, such as CaCO3 and CaSO4 in heat exchangers and desalination evaporators which tend to form deposits on flow surfaces of tubes or pipelines conveying hard water and in water filtration and purification processes since concentration of CaCO3 in many natural water resources is equal to or greater than the saturation level. The study of deposition is also of intrinsic interest for biophysics and colloid science where vascular calcification i.e. precipitation and deposition of calcium phosphates (hydroxyapatites) in the muscular layer of the blood reduces arterial compliance and promotes congestive heart failure. Experiments were conducted on straight, circular cross section silica tubing of inner di-ameter (ranging from 0.88 mm to3.40 mm) to study the effect of electrostatic interaction and hydrodynamics on the deposition behavior of CaCO3 on silica surface when streams of aqueous solutions of Ca(NO3)2 and Na2CO3 with a concentration of 40.0 g l−1 and 25.9gl−1 respectively flowing at a volumetric flow rate of 1 l h−1 each is mixed to form CaCO3 dispersion which was then transported through silica tubing at a steady volumetric flow rate of 2lh−1. The in situ phenomenology of CaCO3 particles transport, deposition, and evolution of spatial and temporal patterns of the CaCO3 deposition on the silica surface along with the dendritic growth of CaCO3 during the flow was visually documented with the aid of a 100X optical microscope. The study discussed the deposition behavior of dispersed phase of CaCO3 from its aqueous dispersion on the silica tubing during flow and attributed charge inversion from negative to positive of silica surface, due to the adsorption of Na+ formed during precipitation reaction of CaCO3, as a plausible reason for the reversal of electrostatic interaction from attraction between initially negatively charged silica surface and positively charged CaCO3 particles which promoted deposition and subsequent evolution of patterns of CaCO3 deposition on the silica surface during the early stage of experiments to repulsion between finally net positively charged silica surface and positively charged CaCO3 particles which resulted in retarded deposition and subsequent emergence of sparsely adhered CaCO3 agglomerates as localized, limited patches of CaCO3 deposits on the silica surface during the later stage of the experiments