Dissertations / Theses on the topic 'Barium sulfide'

Разработана математическая модель, описывающая равновесный состав системы BaS–Ba(HS)₂–H₂S–H₂О, позволяющая, в частности, рассчитывать рН раствора. Модель использована для расчета движущей силы десорбции сероводорода в процессе получения карбоната бария.
A mathematical model describing the equilibrium composition of the BaS–Ba(HS)₂–H₂S–H₂О system is developed. Model allows, in particular, to calculate the pH of the solution, and was used to calculate the driving force for desorption of hydrogen sulfide in the process of obtaining barium carbonate.

This project studied the production of barium sulphate nanoparticles through inhibition of crystal growth, during precipitation, by different surfactants. Barium sulphate is the pure form of the ore baryte, which due to its high density and softness, is the most commonly used additive used to increase the density of drilling fluids. A non-agglomerating, stable nano-scale dispersion of barium sulphate particles would have significant technical and commercial impact in the drilling fluids industry. This thesis tested the possibility of precipitating barium sulphate and restricting its crystal growth with inhibitors, creating nanoparticles. Six inhibitors were tested; dodecanoic acid, palmitic acid, stearic acid, adamantane carboxylic acid, methylnonanoic acid and a mixture of phosphate esters known commercially as Fazewet. Precipitated, inhibited barium sulphate was characterised using powder XRD, DRIFT FTIR and solid-state NMR (SSNMR). All inhibitors were shown to form single-phase, orthorhombic barium sulphate crystals proving that the inhibitors affect only the surfaces of precipitated crystals and do not enter the crystal lattice. FTIR allowed the relative adsorbed concentration of each inhibitor to be assessed. The results indicate that adsorbed inhibitor increases with increasing inhibitor concentrations but that their attachment is not proportional to the concentration. In most cases concentrations of 0.1mol l-1 of inhibitor were sufficient to saturate the crystal surface. SSNMR also agreed with this although the sample size was too small, due to equipment restrictions, to make definitive conclusions. Through the use of the Debye-Scherrer equation, the crystallite size was calculated and showed that at concentrations of 0.2mol l-1 all inhibitors other than palmitic acid produced nano-scale (< 100nm) crystallites. Further analysis showed that further reductions could be achieved through precipitation in an alkaline pH environment, with the application of mechanical shear and by using adding 50% v/v of ethanol. iv Laser diffraction particle size analysis showed that the dominant factor in reducing particle size distribution was inhibitor concentration. The volume-based PSD used by the laser diffraction system was considered to distort excessively the particle sizes present and so analysis switched to dynamic light scattering. DLS showed that dodecanoic acid, palmitic acid and stearic acid, despite forming nano-scale crystallites, could not produce a nano-scale dispersion of barium sulphate and as such were unsuitable for use in drilling fluids. Stable nano-scale dispersions were found to have been formed when inhibited with adamantane carboxylic acid, methylnonanoic acid and Fazewet. DLS also confirmed that dispersed particle size rather than simply crystallite size could be reduced with an alkaline pH and high mechanical shear. Concentration was still the dominant effect, however with the smallest particles sizes (ZAvg) being observed at concentrations of 0.6mol l-1. The particle sizes for the three modifiers were approaching that of the crystallite size, suggesting that some further reduction is possible, but large reductions are unlikely. All three inhibitors produced sub 100nm ZAvgs, with the smallest produced by methylnonanoic acid of 43nm. Spherical nanoparticles were observed through the use of ESEM and TEM. Due to equipment time restrictions only 0.2mol l-1 treatment levels could be examined, but ESEM showed apparent nanoparticle clusters, later confirmed using pixel count and SFDA methods. TEM analysis showed discrete particles as small as 3nm, indicating that the lower limit for achievable particle size may be lower than PSD measurements would suggest. The results indicate that adamantane carboxylic acid, methylnonanoic acid and Fazewet sufficiently inhibit crystal growth to be potential candidates for the production of barium sulphate nanoparticles. These three inhibitors produce a barium sulphate dispersion that is stable and nano-scale even after drying and redispersion.

Le procédé par coprécipitation est l’un des plus utilisé dans l’industrie nucléaire pour le traitement des effluents liquides radioactifs car il peut être appliqué à tous les effluents quelque soit leur composition. Ce procédé consiste à former in situ des particules solides par précipitation dans le but de capter sélectivement un ou plusieurs radioéléments. L’objectif de ce travail de thèse est de mettre en évidence les phénomènes impliqués lors de la coprécipitation d’un élément présent en faible concentration. Pour cela, cette étude propose une nouvelle modélisation des phénomènes de coprécipitation dont l’originalité tient dans la possibilité de simuler le phénomène hors équilibre thermodynamique et à l’échelle d’un réacteur chimique. Ce modèle, couplé avec la résolution du bilan de population, permet d’identifier l’influence des paramètres de procédés (débits, agitation…) sur la décontamination. Afin d’éprouver ce nouveau modèle, celui-ci est appliqué au traitement, dans les conditions industrielles, du strontium par le sulfate de baryum en réacteur continu et semi-fermé. A partir de ces simulations, des lois d’évolution de l’efficacité du traitement en fonction de différents paramètres de procédé (Temps de passage ou d’injection, agitation, concentration de BaSO4) ont été dégagées puis vérifiées expérimentalement. Cette étude permet de définir les meilleures conditions de traitement. Trois dispositifs (à recyclage, à lit fluidisé et réacteur/décanteur) permettant d’approcher ces meilleures conditions ont été testés avec succès. Ceux-ci ouvrent d’importantes perspectives pour la réduction de la quantité de boue produite. Deux brevets ont été déposés suite à ce travail
To decontaminate liquid nuclear wastes, the coprecipitation process is the most commonly used in nuclear field because it can be applied to any type of aqueous effluents whatever their composition may be. This process deals with the in situ precipitation of solid particles to selectively remove one or more radioelements. The aim of this PhD work is to investigate phenomena which take place during the coprecipitation of a trace component. To reach this objective, we have proposed a new modelling of the coprecipitation mechanism. The originality of this new approach lies in the possibility to simulate the phenomenon in non equilibrium conditions and at the reactor scale. This modelling combined with the resolution of the population balance, enable to identify the influence of process parameters (flowrates, stirring speed…) on crystal size and ultimately on decontamination. To test this new modelling, simulations of the coprecipitation of strontium ions with barium sulphate have been performed in continuous and semibatch reactors. Thanks to these simulations, laws of the treatment efficiency variation as a function of several process parameters (mean residence time, stirring speed, BaSO4 concentration) have been determined and experimentally verified. This study leads to the determination of optimal treatment conditions. Three apparatus (recycling apparatus, fluidised bed and reactor/settling tank) providing these optimal conditions have been successfully tested and offered significant outlooks for the reduction of the volume of sludge produced by the process. Two new processes are patent pending

Barium sulfate (BaSO₄)-containing polytetrafluoroethylene (PTFE) granular powder was prepared through a two-phase emulsion dispersion granulation method. Because of its large bulk density, small average particle size, narrow particle size distribution, and superior powder flowability, the granular powder is suitable for use in automatic molding machines. The effects of granulation on the tensile strength of the BaSO₄/PTFE composite were investigated, and the composite’s microstructures were characterized and analyzed using scanning electron microscopy. All these indicated that the granulation could make BaSO₄ disperse more homogeneously in PTFE and reduce many defects in molded articles. So the properties of the BaSO4/PTFE composites made by the granular powder were superior to the composite obtained from the nongranular powder. The tensile strength and elongation of the composite obtained from the granular powder could be achieved to a level of 19.4 MPa and 420%, respectively.

A videofluoroscopia da deglutição (VDF) é um exame considerado padrão ouro como método de avaliação da deglutição que requer que o paciente ingira o contraste de Bário em diferentes consistências para que as fases oral e faríngea sejam avaliadas com maior efetividade. Porém, existe uma disparidade entre a viscosidade dos alimentos com o contraste de Bário para a VDF e os alimentos espessados com o espessante de forma empírica, indicado subjetivamente na terapia de reabilitação. Por isso, o objetivo desse estudo foi: padronizar a quantidade de espessante a ser acrescentado à fórmula infantil nas consistências néctar (N), mel (M) e pudim (P) em 2 temperaturas: ambiente (T1) e variando de 40ºC até 44ºC (T2); comparar os valores médios das viscosidades com as sete marcas dos espessantes mais comumente utilizados e disponíveis (E1, E2, E3, E4, E5, E6, E7) nas temperaturas T1 e T2; identificar a quantidade mínima de contraste de Bário a ser acrescentado à fórmula infantil para boa resolução na videofluoroscopia (50%, 25% e 12,5%) e elaborar um manual de preparo de alimento para VFD nas diferentes consistências (N, M, P) com contraste de Bário. Para a padronização foram utilizados sete marcas de espessantes, uma fórmula infantil de partida, e a média da viscosidade avaliada por meio do viscosímetro Brookfield modelo DV-E, em duas temperaturas (ambiente e acima de 40ºC). Foram avaliadas três diluições (50%, 25% e 12,5%) do contraste de Bário (Bariogel 100%) nos leites espessados por meio de seringas no aparelho de VFD e as imagens obtidas julgadas por duas fonoaudiólogas experientes no exame. Os resultados revelaram que a padronização da quantidade de espessante a ser acrescentado à fórmula infantil para obtenção das consistências néctar, mel e pudim, nas temperaturas testadas, variou com o tipo de espessante, requerendo a orientação de um manual para correta manipulação. Os valores de viscosidade diminuíram com o aumento da temperatura, porém os valores foram mantidos dentro do intervalo proposto pela American Dietetic Association (2002) das consistências néctar, mel e pudim. Embora as três quantidades testadas de contraste de Bário tenham proporcionado imagens visíveis, avaliadas pelos juízes, os mesmos consideraram mais seguras aquelas observadas nas diluições de 25% e 50%, necessitando serem testadas outras situadas neste intervalo, uma vez que na diluição de 50% houve alteração da consistência néctar para mel. Um manual foi elaborado para orientação da padronização dos sete espessantes, nas três consistências e nas temperaturas testadas, bem como a sugestão de diluição do contraste de Bário no intervalo de 25% e 50%.
Videofluoroscopy (VDF) is considered a gold standard exam as an evaluation method for swallowing which requires that the patient ingests the Barium contrast in different consistencies so the oral and pharyngeal stages are evaluated with greater effectiveness. However, there is a difference between the viscosity of food with barium contrast for the VDF and thickened foods with the thickener, indicated subjectively in rehabilitation therapy. Therefore, the aim of this study was to standardize the amount of thickener to be added to infant formula in the following consistencies: nectar (N), honey (M) and (P) pudding in 2 environmental temperatures: (T1) and ranging from-40 degrees C to 44 C (T2); compare the average values of viscosities with seven brands of thickening agents most commonly used and available (E1, E2, E3, E4, E5, E6, E7) at temperatures T1 and T2; identify the minimal amount of barium contrast to be added to infant formula for good resolution in videofluoroscopy (50%, 25% and 12.5%), and elaborate a manual of food preparation to VFD in different consistencies (N, M, P) with Barium contrast. Seven brands of thickeners, an infant formula, and the average viscosity evaluated by Brookfield viscometer model DV-E, in two temperatures (above 40°C and environment) were used for standardization. Three dilutions (50%, 25% and 12.5%) of Barium contrast (Bariogel 100%) were used to evaluate the thickened milk by syringes into the VFD and the images obtained judged by two experienced speech language pathologists. Results revealed that the standardization of the amount of thickener to be added to infant formula to obtain the nectar, honey and pudding consistencies, in tested temperatures, varied according to the type of thickener, requiring the use of a manual for correct handling. Viscosity values decreased with increasing temperature, but the values were maintained within the range proposed by the American Dietetic Association (2002) regarding nectar, honey and pudding consistencies. Although the three tested quantities of Barium contrast have provided visible images, evaluated by the judges, those observed in dilutions of 25% and 50% were considered safer. It demanded tests in others situated in this range once in the dilution of 50% there was a change from nectar to honey consistency. A manual has been prepared for the guidance on the standardization of seven thickeners, in the three tested.

Les phenomenes physico-chimiques mis en jeu lors d'une precipitation sont particulierement complexes ; de plus, le phenomene est en soi tres rapide, et donc difficile a controler. Il est desormais connu que, lors d'une precipitation, la facon dont les reactifs sont melanges influe fortement sur la distribution de tailles des cristaux. De nouveaux moyens de mise en contact ont ete proposes recemment, et donc de nouvelles geometries, mais aussi l'utilisation de nouvelles technologies. Pour ameliorer la mise en contact des reactifs, une voie possible est d'utiliser les ultrasons de puissance qui ameliorent le transfert de matiere en provoquant, par le biais de la cavitation, une intense agitation microscopique. Apres avoir etudie en parallele l'effet des ultrasons sur le micromelange et sur la precipitation du sulfate de baryum, nous avons pu constater que l'effet sur le micromelange restait somme toute limite, alors que les ultrasons modifiaient considerablement la nucleation. Les ultrasons permettent en effet d'obtenir des cristaux plus fins, de tailles et de formes moins dispersees, et ce, quelles que soient les conditions de melange. Afin d'etudier plus precisement la nucleation sous ultrasons, et dans le but de comprendre comment les ultrasons pouvaient agir sur ce processus, nous avons dissocie experimentalement la nucleation et la croissance dans deux reacteurs continus en serie pouvant etre soniques separement. Cette etude a montre que les ultrasons provoquent de la nucleation secondaire, simultanee a la nucleation primaire, dont le mecanisme se rapprocherait de la nucleation secondaire de contact. Ce phenomene peut etre du a l'arrachement de germes en croissance a la surface des cristaux par les phenomenes accompagnant l'implosion de bulles de cavitation (onde de choc, jet de liquide). Une modelisation simple des cinetiques de nucleation et de croissance par bilan de population sur chacun des deux reacteurs nous a permis d'appuyer ces hypotheses.

Cette étude avait été lancée en vue de modéliser les effets de mélange sur le processus de précipitation. La précipitation de sulfate de baryum a été choisie pour ce faire. Une nouvelle méthode basée sur des mesures en continu de la composition de la solution et de la D. T. C. A été développée pour déterminer les vitesses de nucléation et de croissance cristalline. Une première série d'expériences de précipitation spontanée stœchiométrique en réacteur fermé dans une unité pilote de 20 litres a été effectuée et les vitesses de nucléation et de croissance cristalline ont été déterminées. Une deuxième étude expérimentale a été menée pour déterminer les effets de la présence des contre-ions sur les lois cinétiques en variant le couple de réactifs. La vitesse de nucléation est sensible à ce choix alors que la vitesse de croissance est peu sensible. Enfin, l'effet de la non-stœchiométrie a été aussi étudié et s'est avéré très interessant: la cinétique de précipitation du sulfate de baryum est très sensible à la stœchiométrie. À la suite de cette étude, le choix de la précipitation de sulfate de baryum est déconseillé pour étudier des effets de mélange sur la précipitation

Dans les champs petroliers en depletion on utilise frequemment en recuperation assistee l'injection d'eau. Il se pose alors le probleme de compatibilite chimique entre l'eau d'injection et l'eau de gisement. Malheureusement on assiste dans bien des cas apres leur melange a la formation de depots dans les puits producteurs et/ou dans les installations de surface. Ils sont constitues dans la plupart des cas de sulfate de baryum. Il est donc indispensable d'inhiber ces precipitations en reagissant au niveau de la germination et de la croissance des cristaux par utilisation de produits appropries de type polyacrylate de poids moleculaire voisin de 2000. Pour optimiser ce type de traitement il est indispensable de maitriser les differents mecanismes mis en jeu. Compte tenu du nombre important de parametres intervenants, nous avons utilise dans notre etude la methodologie des plans factoriels fractionnaires permettant de hierarchiser ces parametres et d'en connaitre leurs interactions. Apres une etude en laboratoire, nous sommes passes a l'essai pilote sur le site de tin fouye tabankort en algerie. Les resultats sont tres satisfaisants et corroborent parfaitement les etudes en laboratoire

Les boues ste constituent un dechet radioactif principalement compose de sulfate de baryum. Pour elaborer un materiau ceramique a partir de ce dechet, la synthese solide-solide du titanate de baryum a partir de sulfate de baryum et d'anatase a ete etudiee. Une application des resultats au dechet simule est presentee. Trois proprietes physico-chimiques importantes pour le conditionnement ceramique de dechets radioactifs sont etudiees: le frittage, la lixiviation et l'irradiation du titanate de baryum elabore a partir du sulfate de baryum a haute temperature

Portland clinker is thanks to its large-scale production a continuously studied topic. Clinker, or Portland cement, is used for construction purposes, or for insulation and special applications. One of these special applications could be shielding of different types of radiation by making use of the content of barium ions. The present master’s thesis examines the influence of barium oxide on the formation and properties of Portland clinker, which could be, by incorporation of barium ions into the system, used as a binder for buildings resistant to various types of radiation. Barium sulfate and barium carbonate were added to the raw meal in order to prepare clinkers with different content of barium oxide. The effect of barium on the formation of clinker phases was studied (by XRD – Rietveld analysis and by the microscopic point integration), as well as the effects on the variations of temperature of the phase formation (TG-DTA) and the rate of alite formation under isothermal conditions. Furthermore, the ability of barium to become a part of clinker minerals was studied by SEM with EDS, and the solubility of barium phases by ICP-OES. The hydration of clinker minerals containing barium was studied by isothermal calorimetry.

La synthese des apatites a ete realisee dans un milieu liquide d'eau douce ou marine, par transformation de carbonate et par precipitation directe. La cristallogenese de ces mineraux necessite une activite bacterienne indispensable a la biodegradation de la matiere organique (arn) et a la mineralisation du phosphore sous forme d'acide phosphorique. En plus de leur activite biodegradante, les bacteries servent de site a la nucleation et a la cristallisation purement chimique de l'apatite hors de leur membrane. Cette nucleation est favorisee par une forte saturation en phosphore, calcium et fluor dans un micro-milieu cree a proximite de ces micro-organismes. Les apatites synthetisees se presentent sous forme de micro-grains, constitues de cristallites enchevetres, possedant une grande surface et determinant des micropores fermes dans lesquels se piegent l'eau connee et la matiere organique. Les elements traces trouvent donc plusieurs sites possibles : insertion dans le reseau cristallin, adsorption sur la grande surface offerte par les cristallites, piegeage dans les micropores.

Cette thèse s’inscrit dans le domaine de la décontamination des effluents aqueux radioactifs, fortement salins et contenant plus spécifiquement du 90Sr.Deux échangeurs ioniques contenant des ions Ba2+, un titanate de baryum et une zéolithe LTA au baryum, ont été étudiés pour extraire le Sr de ce type d’effluents. L’originalité de ces extractants tient dans leur double mécanisme d’extraction du strontium : d’une part, le strontium en solution est extrait principalement par échange d’ions avec les ions Ba2+ du matériau ; et d’autre part, les ions Ba2+ libérés en solution précipitent à la surface de l’échangeur ionique avec les sulfates présents dans l’effluent et entraînent le Sr par un second mécanisme de coprécipitation. La coprécipitation du strontium avec le sulfate de baryum est cruciale au sens où elle conduit à une sélectivité élevée pour le strontium vis-à-vis du calcium. Cette étude mécanistique et comparative ouvre la voie au développement de nouveaux sorbants sélectifs du strontium.La zéolithe au baryum, qui s’avère plus performante (meilleures capacité et sélectivité) que le titanate de baryum pour le traitement d’effluents salins, a été évaluée pour une utilisation dans des procédés de types industriels (réacteur agité et colonne). Des expériences menées à sursaturation ou proportion des réactifs de précipitation [SO4]/[Ba] variables permettent d’identifier les conditions optimales d’utilisation des poudres de zéolithe au baryum en réacteur agité de type batch. Ces résultats montrent tout le potentiel de ce matériau en remplacement du procédé actuel de coprécipitation en réacteur agité mis en œuvre dans les STEL. Des billes de zéolithe au baryum ont également été évaluées pour le traitement des effluents en procédé continu de type colonne. La cinétique de diffusion des ions dans le matériau s’avère limitante pour ce procédé continu et la mise en forme du matériau reste à optimiser.Mots-clés : décontamination, strontium, sélectivité, échange d’ions, titanate, zéolithe LTA, coprécipitation, sulfate de baryum
This thesis concerns the treatment of radioactive wastewaters, specifically 90Sr containing highly saline effluents.Two types of Ba2+ containing ion exchange materials were examined as possible Sr sorbents: a barium titanate and a barium zeolite LTA. The extractants originality lies in its double extraction mechanism. Firstly, the majority of the Sr present in the solution is removed via ion exchange with the Ba present in the sorbent. A secondary process then sees the now free Ba precipitate onto the sorbents surface as BaSO4. The effluent itself is the sulfate source. This precipitation reaction initiates a second coprecipitation reaction with the remaining Sr. Strontium coprecipitation with barium sulfate is crucial to leading to a high strontium selectivity in the presence of calcium. This thesis outlines a mechanistic and comparative study which will hopefully open the way to the development of new strontium selective sorbents.The barium zeolite, which is more efficient (higher capacity and selectivity) than the barium titanate for treatment of saline effluents, was evaluated for use in industrial type processes (stirred reactor and column). Experiments conducted with variable supersaturation or molar ratio [SO4]/[Ba] allowed us to identify optimal conditions for the use of barium zeolite powders in batch type stirred reactor. These results demonstrate the potential of this material to replace the current coprecipitation process in stirred reactors, which is carried out in effluent treatment plants. Barium zeolite beads were also evaluated for effluent treatment in a column type continuous process. Ion diffusion kinetics in the material were shown to be limiting for this continuous process. The material shaping has still to be optimized.Keywords: decontamination, strontium, selectivity, ion exchange, titanate, zeolite LTA, coprecipitation, barium sulfate

Ce travail a pour but d'etudier les proprietes de luminescence par stimulation optique (osl) du sulfure de magnesium dope cerium samarium, afin d'evaluer ses potentialites en dosimetrie du personnel. Les travaux menes au laboratoire ont en effet mis en evidence les avantages de la stimulation optique sur la stimulation thermique en dosimetrie. Parmi tous les materiaux osl testes, le sulfure de magnesium dope cerium samarium a ete selectionne du fait qu'il possede un numero atomique effectif acceptable pour la dosimetrie du personnel et qu'il emet un signal osl tests, le sulfure de magnesium dope cerium samarium a ete selectionne du fait qu'il possede un numero atomique effectif acceptable pour la dosimetrie du personnel et qu'il emet un signal osl relativement intense. On a ete conduits a fabriquer ce materiau et a etudier l'influence des concentrations en dopants afin d'optimiser l'intensite du signal osl. En ce qui concerne l'etude du potentiel dosimetrique de ce materiau, on a procede a l'etalonage et a la mise en place d'un dispositif de protection d'une source de rayons x, basse energie. L'etude spectroscopique effectuee a montre que le signal osl donne par ce sulfure devrait etre facilement detectable puisque ces spectres de stimulation et d'emission etaient respectivement situes dans l'infrarouge et le visible. L'etude des spectres d'emission a permis de preciser le role des dopants. La determination experimentale des variations du signal osl en fonction de la dose, pour des irradiations aux rayons x et au co#6#0, a montre que le sulfure de magnesium dope cerium samarium permet la detection de doses cumulees de l'ordre de 100 micro-gray. Il ressort de l'etude du fading qu'a la temperature ambiante, la perte de signal etait de l'ordre de 5% par mois

Mesures dans des cibles epaisses de sulfates et d'oxydes, dans des cibles minces d'oxydes disposees sur des couches minces de carbone et dans des cibles epaisses de tetraborate de li dope par equiv. A 1% de ba, la ou ce sous forme de sulfate ou d'oxyde. Bon accord avec les previsions theoriques et avec les valeurs experimentales trouvees pour des elements voisins

¨This thesis focuses on evaluating the dual-modal Computed Tomography (CT) and Magnetic Resonance Imaging (MRI) capabilities of contrast agents. For such purposes a gadolinium based contrast agent is of high interest, due to its paramagnetic properties, which while present inside a magnetic field will hence interact with the protons spins of water (in tissue and fat) and shorten their the T1 relaxation time, thereby creating a positive image contrast in MRI. Furthermore, the X-ray Mass Attenuation Coefficient (MAC) of gadolinium is relatively high, thus suggesting its potential use, also as a CT contrast agent. Gadolinium nanoparticles (GdNPs) can be loaded into cells, such as macrophages, which offers the possibility to track cells inside entire organisms. In the first step the uptake of GdNPs inside cells was investigated, together with a test for toxicity. To show the potential of using GdNP loaded macrophages for functional imaging of inflammation, an acute allergic airway inflammation mouse model (mimicking asthma in humans) was used and analyzed by in-situ synchrotron phase contrast CT. In the first step this approach was evaluated using macrophages loaded with a clinical contrast agent containing barium sulphate (BaSO4), since this agent is known to provide high contrast in CT. In the ultimate step a combination of both BaSO4 and GdNP loaded macrophages was used in the same asthmatic mouse model and analyzed by dual modal Synchrotron phase contrast CT and Micro Magnetic Resonance Imaging (μ-MRI). Complementary results in terms of the biodistribution of injected macrophages could only be obtained by the combination of both synchrotron phase contrast CT and μ-MRI, where the first modality allows a detailed localization of clustered BaSO4 loaded macrophages, but fails to detect single macrophages, which could instead be indirectly observed by μ-MRI as an increase of the T1-contrast, coming from the soft tissue of mice injected with GdNP loaded macrophages.

Le sujet porte sur l'étude géochimique et métallogénique des minéralisations uranifères (gisement de bertholène) et de barytine-sulfures (gisement de Lacan et du nord du massif cristallin des Palanges).

Récupération du baryum à partir du milieu aqueux par flottation ionique utilisant des alkylbenzène-sulfonates de sodium. Récupération du gallium, par flottation ionique en utilisant des alkylsulfates de sodium en milieu acide, et des collecteurs à fonction oxine en milieu basique

Les mécanismes contrôlant l'extraction d'ions par flottation ionique à l'aide de tensioactifs ioniques à longue chaîne sont décrits à travers l'étude de la récupération du baryum par le laurylsulfate de NA. Mise au point d'un modèle, appliqué à la récupération du zirconium dans les solutions acides de nitrate d'uranyle

Barium sulfate scaling can cause many oilfield problems leading to loss of well productivity and well abandonment. Currently, diethylene triamine pentaacetic acid (DTPA) is used, along with synergist oxalic acid and potassium hydroxide, to remove the scale by dissolution. However, the chemical factors affecting this reaction are not known fully, leading to mixed results in terms of treatment effectiveness. This thesis investigates the effect of these factors, by analyzing the change in barite dissolution due to intrinsic factors like variations in formulation composition and extrinsic factors like presence of competing ions. The dissolution reaction is carried out, by taking the barite powder and chelant solution in a teflon round bottom flask and measuring the barite dissolved periodically, with an ICP-OES. The effect of different factors is studied by varying each factor individually and plotting the changes in solubilities. These lab tests show that solubility of barite (0.01mM in water), ideally, increases with increasing concentrations of chelating agents, even going as high as 239 mM. However experimental or field constraints lead to significant decrease in dissolution, especially at higher chelant concentrations. Thus, field tests to determine most effective chelant concentrations must precede treatment design. Lab tests also show that combination of DTPA with weaker chelating agents like ethylene diamine tetraacetic acid (EDTA), L-glutamic acid, N,N-diacetic acid (GLDA) or methyl glycine diacetic acid (MGDA) reduces barite dissolution and should be avoided during treatment design. Addition of synergists to the formulations, initially improves dissolution performance, especially for moderate chelant concentrations, but proves detrimental and hence must be avoided, over longer treatments. Finally, presence of competing ions in seawater, calcium sulfate and calcium carbonate, can significantly reduce barite dissolution and must be carefully studied for each formation-fluid system before design of treatments. Thus, this project sets a framework to identify the best chelant formulation and estimate its dissolution profile to ensure, a more informed treatment design for barite scale removal.

碩士
萬能科技大學
材料科學與工程研究所在職專班
105
In this study, Polystyrene (PS) / barium sulfate (BaSO4) / styrene-butadiene-styrene copolymer (SBS) composites were prepared by melt compounding and mixed with barium sulphate in different content.The mixture was kneaded at a temperature of 180-260 ℃ through a twin-screw extruder. The samples were prepared by injection molding and tested according to ASTM standards. We examined mechanical and physical properties of different compounding. We discussed melt index analysis, tensile property test, flexural strength test, impact strength, the results revealed the use of barium sulfate (BaSO4) can the processing required flow index can be adjusted by the ratio. Adjustment of BaSO4 / SBS proportions can obtain different mechanical properties of the materials. In accordance with different needs, such as the tensile properties of good circumstances can choose PS / SBS 5% of its BaSO4 addition of 10-20%, bending strength of good circumstances can choose PS / BaSO4 / SBS ratio of 45/50 / 5, good impact strength can be used in the case of PS / SBS 10% of its BaSO4 can choose to add 10-30%, so the compounding can be adjusted according to different requirements in response to the need of material industry.

Το θειικό βάριο είναι ένα κρυσταλλικό στερεό το οποίο απαντάται ως ορυκτό. Οι χρήσεις του στην βιομηχανία είναι πολλές, καθώς χρησιμοποιείται σε ένα ευρύ φάσμα εφαρμογών από την κατασκευή πυράντοχων βαφών έως την βιομηχανία παραγωγής πετρελαίου για την αποφυγή αύξησης της πίεσης κατά την διάρκεια των γεωτρήσεων. Ωστόσο, κατά τη χρήση του στην άντληση πετρελαίου, η χρήση του έχει ως αποτέλεσμα το σχηματισμό επικαθίσεων οι οποίες είναι δύσκολο να απομακρυνθούν λόγω της μικρής τους διαλυτότητας. Για την απομάκρυνση των επικαθίσεων θειικού βαρίου δεν είναι δυνατόν να χρησιμοποιηθούν κοινά οξέα, καθώς το θειικό βάριο αφενός είναι δυσδιάλυτο σε αυτά αλλά παράλληλα δημιουργούν σοβαρά προβλήματα διάβρωσης του εξοπλισμού (σωληνώσεις, reservoir αποθήκευσης νερού). Για την αντιμετώπιση των καθαλατώσεων αυτού του είδους, χρησιμοποιούνται υδατοδιαλυτές ενώσεις οι οποίες προστίθενται στα ρευστά στα οποία λαμβάνει χώρα καταβύθιση του θειικού βαρίου και έχουν την ικανότητα να παρεμποδίσουν ή να επιβραδύνουν το σχηματισμό του θειικού βαρίου. Ενώσεις αυτού του τύπου είναι οι πολύ-φωσφονικές, πολυηλεκτρολύτες όπως τα πολύ-καρβοξυλικά, πολυσουλφονικά οξέα κ.τ.λ., με ορισμένες από αυτές να είναι αρκετά δραστικές και να μπορούν να περιορίσουν σε μεγάλο βαθμό τον σχηματισμό επικαθίσεων του θειικού βαρίου. Στην παρούσα εργασία μελετήθηκε η κινητική της καταβύθισης του θειικού βαρίου σε υδατικά υπέρκορα διαλύματά του, στα οποία η αναλογία πλεγματικών ιόντων Ba:SO4 1:1 στους 25οC, απουσία και παρουσία πρόσθετων. Πραγματοποιήθηκαν πειράματα αυθόρμητης καταβύθισης για την εύρεση του εύρους της μετασταθούς ζώνης με την τεχνική “free drift”. Από την συσχέτιση του χρόνου επαγωγής που μετρήθηκε, συναρτήσει του υπερκορεσμού και βάσει της κλασσικής θεωρίας της πυρηνογένεσης υπολογίσθηκε ότι η επιφανειακή ενέργεια του θειικού βαρίου ήταν 17,4 mJ•m-2. Η τιμή αυτή, η οποία είναι σημαντικά διαφορετική από τις τιμές οι οποίες αναφέρονται στην βιβλιογραφία, αντανακλά τη σημασία του τρόπου παρασκευής των υπέρκορων διαλυμάτων στις μετρήσεις αυτές. Στη σταθερή περιοχή των υπέρκορων διαλυμάτων, και προκειμένου να διερευνηθεί ο μηχανισμός κρυσταλλικής ανάπτυξης του θειικού βαρίου, έγινε σειρά πειραμάτων στα οποία μετρήθηκε ο ρυθμός κρυσταλλικής ανάπτυξης του θειικού βαρίου σε κρυσταλλικά φύτρα θειικού βαρίου. Στα υπέρκορα διαλύματα, η αναλογία πλεγματικών ιόντων Ba:SO4 1:1 στους 25oC. Οι μετρήσεις αυτές πραγματοποιήθηκαν με την τεχνική διατήρησης σταθερού του υπερκορεσμού κατά την διάρκεια της καταβύθισης. Ως παράμετρος παρακολούθησης της εξέλιξης της κρυσταλλικής ανάπτυξης χρησιμοποιήθηκε η ειδική αγωγιμότητα των υπέρκορων διαλυμάτων, η οποία εμετρείτο με τον αντίστοιχο αισθητήρα, το σήμα από τον οποίο, ενεργοποιούσε αυτόματο τιτλοδότη για την προσθήκη αντιδραστηρίων κατάλληλης συγκέντρωσης. Οι μετρήσεις του ρυθμού κρυσταλλικής ανάπτυξης έδειξαν παραβολική εξάρτηση από τον υπερκορεσμό των αντίστοιχων διαλυμάτων ενώ δεν παρουσιάστηκε εξάρτηση του ρυθμού από την συγκέντρωση των φύτρων για τις συγκεντρώσεις κρυστάλλων μεταξύ 0,026 – 0,19 mg.L. Η εξάρτηση του ρυθμού κρυσταλλικής ανάπτυξης του θειικού βαρίου από τον υπερκορεσμό των αντίστοιχων διαλυμάτων έδειξε ότι ο μηχανισμός καθορίζεται από την επιφανειακή διάχυση των δομικών μονάδων. Οι αναστολείς που χρησιμοποιήθηκαν για την μελέτη στην επίδραση της παρουσίας τους στα υπέρκορα διαλύματα στο ρυθμό της κρυσταλλικής ανάπτυξης φύτρων θειικού βαρίου ήταν το βενζοϊκό- 1,3,5 τρις φωσφονικό οξύ (BTP) και το άμινο τρις-μεθυλενοφωσφονικό οξύ (AMP). Η κυριότερη διαφορά των δυο ενώσεων έγκειται στη μοριακή τους γεωμετρία: Το πρώτο χαρακτηρίζεται από σχετική ακαμψία των δεσμών ενώ το δεύτερο από ευκινησία . Κατά τη διάρκεια των πειραμάτων αυτών διαπιστώθηκε ότι η παρουσία των αναστολέων στα υπέρκορα διαλύματα είχε σημαντική επίδραση (αύξηση) στη διαλυτότητα του θειικού βαρίου, ενώ ταυτόχρονα παρατηρήθηκε μείωση των ρυθμών κρυσταλλικής ανάπτυξης. Το AMP βρέθηκε ότι ήταν περισσότερο αποτελεσματικό στην αναστολή της καταβύθισης του θειικού βαρίου, προκαλώντας μείωση στο ρυθμό σε ποσοστό μεγαλύτερο του 90% σε συγκεντρώσεις της τάξης των 30 ppm. Το BTP ήταν και αυτό αρκετά αποτελεσματικό, παρατηρήθηκε όμως ότι η αποτελεσματικότητα της παρουσίας του ήταν αρκετά υψηλή (>50%) σε χαμηλές (10 ppm) και σε υψηλές συγκεντρώσεις (>50 ppm) συγκεντρώσεις, ενώ στις ενδιάμεσες συγκεντρώσεις η αποτελεσματικότητά του ήταν σημαντικά μικρότερη. Επιπλέον, το AMP είχε ανασταλτική δράση στο ρυθμό καταβύθισης του θειικού βαρίου τόσο σε αλκαλικές (pH=9,5) όσο και σε όξινες (pH=3,6) τιμές pH στα υπέρκορα διαλύματα. Η αποτελεσματικότητα του AMP ήταν αρκετά υψηλή, μεγαλύτερη από 70%, σε συγκεντρώσεις >30 ppm.
Barium sulfate is a crystalline solid encountered as mineral and precipitated in numerous applications from analytical chemistry to the of fire resistant paints up to the oil industry to avoid the pressure increase during the drilling. However, in oil industry form deposits which are difficult to remove due to the low solubility. The removal of barium sulfate scale deposits is not possible through the use of common acids, because the solubility of this salt does not change significantly with increasing acid concentration. Moreover the use of mineral acids result in the severe corrosion of the metal parts of the equipment involved (pipes, water storage reservoir). Alternative descaling and scale prevention techniques have been desighed and are widely applied. In these techniques, a number of compounds have been used which, when added at very low concentrations in scale prone aquatic media result in the inhibition or cancellation of the formation of barium sulfate scale deposits. In these compounds which include poly-phosphonates or polyelectrolytes with sulfonated or carboxyl functional groups, have shown impressive results. The issue of structure of the additive molecules both in solution but most important upon adsorption on the surface of the nuclei of the crystalline deposit forming under the favorable friving force created by the solution supersaturation, is very important for obtaining a better understanding of the factors underlying the efficiency of inhibition of inorganic scale formation. In the present work, we investigate the kinetics of precipitation of barium sulfate from supersaturated solutions both in the absence and in presence of additives was investigated. The kinetics of crystal growth were investigated using the seeded growth techiwue at sustained supersaturation. The molar ratio of total barium : sulfate (Ba:SO4) in the supersaturated solutions was 1:1 and all experiments were done at 25oC in the absence and presence of additives. The width of the metastable zone for the barium sulfate system was determined from spontaneous precipitation experiments involving unstable supersaturated solutions with the “free drift” technique. From the dependence of the inhibition times preceding precipitation on the solution supersaturation and using the classical nucleation theory (CNT) models the surface energy of the precipitated phase was estimated. The kinetics of crystallization of barium sulfate were investigated in stable supersaturated solutions which were seeded with well-aged and characterized barium sulfate crystals prepared from slow mixing of equimolar barium chloride and sodium sulfate solutions. The molar ratio Ba:SO4 was in these experiments 1:1. The rates of crystal growth were measured at conditions of constant supersaturation using a specific conductivity probe, which through the synchronized burettes of an automatic titrator triggered the addition of equimolar barium chloride and sodium sulfate solutions. The added titrants had the appropriate composition to compensate for the respective quantities transferred to the solid phase forming. The rate of titrants addition yieleded the rates of crystal growth at the respective conditions. The measured crystal growth rates showed parabolic dependence on the solution supersaturation suggesting the prevalence of a surface diffusion controlled mechanism. Moreover, the independence of the measured crystal growth rates (moles precipitated per unit time and seed crystals surface area) on the mass of the seed crystals. Confirmed that crystal growth took place exclusively on the seed crystals. The effect of the presence of benzene-1,3,5-triyltris phosphonic acid (BTP) and amino-tris(methylenephosphonic) acid (AMP) in the supersaturated solutions on the rates of crystal growth of barium sulfate was investigated by measurements of the respective crystal growth rates at sustained supersaturation as in the additives free solutions. The main structural difference of the two molecules tested is that the former has a flat conformation because of the aromatic ring while the latter has a significantly higher freedom of motion. The presence of the test additives in the supersaturated solutions had a significant effect on the solubility of barium sulfate. The modified solubilities were calculated from measurements of the concentrations of free Ba2+ and SO42- ions concentrations and solution supersaturations were calculated accordingly. The presence of the test additives resulted in the significant reduction of the respective crystal growth rates. The presence of AMP in the ssupersaturated solutions caused reduction of the crystal growth rates as high as 90% at 30 ppm. BTP was efficient as well in inhibiting barium sulfate crystallization. However, it was found that rates were reduced by more than 50% at concentrations as low as 10 ppm and high concentrations in the range of 50 ppm. At intermediate concentration (20-30 ppm) the efficiency of BTP in the reduction of crystal growth of barium sulfate was significantly lower. AMP inhibited barium sulfate scale not only at alkaline pH (pH=9,5) values and at acidic values (pH=3,6). At pH=3,6 and for AMP conentrations of 30 ppm the rates of crystal growth of barium sulfate were reduced by 70% with respect to the values in its absence.