The adsorption of several homopolymer polypeptides on Al2O3 and SiO2 particles and surfaces was investigated to identify possible anchor and tail blocks for brush-forming block copolypeptides. Poly-L-(glutamic acid) (GLU) and poly-L-(aspartic acid) (ASP) were found to adsorb on positively charged and nearly neutral Al2O3, while the GLU did not adsorb on negatively charged SiO2. Poly-L-proline (PRO) adsorbed only slightly on the alumina, but showed high affinity adsorption on silica. These results are useful in designing a brush forming block copolymer with the GLU acting as the anchor block and the PRO as the tail block. An important finding in this work is that these unstructured polypeptides, or proteins that only have primary and secondary structure, have adsorption behavior that is similar to that of synthetic polymers. The complexation between a random copolymer of two amino acids, glutamic acid and tyrosine, and poly(ethylene oxide) (PEO) was studied using an in-situ adsorption experiment. It was shown that the adsorption of the random copolymer greatly increased the adsorption of PEO. It was found that the conformation of the copolymer on the surface was controlled by the ionic strength, and the conformation of the adsorbed PEO was controlled by the PEO molecular weight. Both of these factors affected the molar complexation ratio between the PEO and the tyrosine repeat units. The adsorption of two novel triblock copolymers, with PEO tails and anionic hydrophobic center blocks, was studied on alumina and silica surfaces. On silica the adsorption was due to the PEO tails, resulting in low adsorbed amounts. The adsorption was much greater on alumina, indicating either brush formation on the surface or the adsorption of micelles, which are present in solution. The effect of adsorbed polymer on the steric stabilization of alumina particles was studied using sedimentation and electrophoretic mobility experiments. These results do not show conclusively that the triblock copolymer adsorption led to particle stabilization. It is possible that better colloid stabilization of the alumina may be realized by changing the triblock composition to get greater extension and higher packing of the PEO tails. / Ph. D.

O processo de dissolução da alumina para produção de alumínio primário em condições industriais em cubas de Tecnologia VSS (Vertical Stud Soderberg) com alimentação lateral em batelada é bastante complexo, pois sofre interferência de muitas variáveis de processo como: temperatura e química de banho, propriedades físico-químicas da alumina, concentração inicial de alumina no banho, quantidade de alumina adicionada e massa de banho disponível para dissolução. Um bom controle de adição de alumina e variáveis de processo contribuem para garantia de uma melhor eficiência de corrente, menor consumo de energia e redução da quantidade de lama (alumina não dissolvida) formada que se deposita no fundo das cubas, comprometendo a passagem da corrente elétrica e consequentemente reduzindo a eficiência dos fornos. No presente trabalho foram realizados experimentos para determinação da concentração da alumina, temperatura do banho, temperatura da crosta, altura da cavidade das cubas e caracterização da lama. Os resultados mostram as principais variáveis que influenciam no processo de dissolução da alumina, o comportamento semelhante da concentração da alumina e diferença de temperatura do banho durante os intervalos de alimentação de 2:40 e 4:00 horas, a temperatura de entrada da alumina e as condições de perda de cavidade devido a deposição de lama no fundo das cubas. / The dissolution process of alumina on industrial conditions (side feeding VSS-Vertical Stud Soderberg technology) to aluminum production is very complex, because suffers interference from process variables such as: temperature and bath chemistry, physicochemical properties of alumina, initial alumina concentration in the bath, amount of alumina added and bath mass available. A good control of alumina addition and process variables will contribute to keep good the current efficiency, lower energy consumption and reduction of the amount of sludge (undissolved alumina) formed at the bottom that in the future will compromise the flow of the electric current that will consequently reduce the efficiency of the pots . This work, were carried out experiments to determine alumina concentration, bath temperature, crust temperature, high of the pots and sludge characterization. The results show the main variables that influence the dissolution process, the similar behavior of the alumina concentration, difference of the bath temperature during the feeding intervals of 2:40 and 4:00 hours, the inlet temperature of the alumina and the losses of cavity due the sludge deposition on the bottom.

As características das matérias-primas particuladas como tamanho, forma, área específica, entre outras, determinam não somente o desempenho final de um produto, mas também o processo de sua fabricação. Neste sentido, matérias-primas sintéticas são produzidas por meio de conversões químicas que têm como finalidade o controle da reprodutibilidade de características. Esta tese tem como objetivo o estudo de precursores sintetizados com matérias-primas nacionais de elevada pureza, quanto à área específica (AE), estrutura cristalina e morfologia das fases formadas durante as transformações térmicas de alguns hidróxidos (gibsita e pseudoboemita), sais (acetato e formato) e sulfatos duplos (de amônio e de sódio) de alumínio. As amostras sintetizadas e aquecidas foram caracterizadas por DRX, MEV, BET e análise térmica (TG, DTA e DSC), a fim de que fossem observadas as variações nas características das fases formadas. Observou-se que todos os precursores, à exceção do \"sulfato-Na\", evoluem termicamente resultando como produto final somente a a-alumina. No caso particular do \"sulfato-Na\", em que se apresenta resultados preliminares, verifica-se a formação, além da a- alumina, de B-alumina. Os hidróxidos e os sais de alumínio passam por uma seqüência de aluminas de transição que exibem valores de área específica elevados. Com relação à pseudoboemita, além da caracterização proposta no trabalho, foi estudada a influência do método de secagem e do tempo de envelhecimento da pseudoboemita nas características dos materiais sintetizados. Verificou-se que o método de secagem pode influenciar as temperaturas de transformações de fases das aluminas. Precursores secos por nebulização podem formar a fase a concomitantemente com a fase 0, o que não ocorre com os materiais secos ao ar. Já o tempo de envelhecimento influenciou no tamanho final das fibrilas de pseudoboemita. Tanto o método de secagem quanto o tempo de maturação afetam de forma determinante a organização das fibrilas que, por sua vez, estabelecem a distribuição de poros nos materiais produzidos. / Features of powdered raw materials like size, morphology, specific area, determine the product performance, besides the fabrication process product. In this direction, the synthetic raw materials are produced by means of chemical conversion to control the characteristics reprodutibility. This thesis has as objective the study of precursor\'s synthesized with national raw materials of raised pureness, by the study if the specific area (AE), crystalline structure and morphology of the phases formed during thermal transformation of some hydroxides as (aluminum hydroxides- gibbsite and pseudoboehmite; aluminum salts - acetate and formate and aluminum sulphates - sodium and amonium) produzed by high pure nacional raw materials. The sythetized and heated samples are examined by DRX, MEV, BET and thermal analysis (TG, DTA e DSC) to verify the characteristics variations in the formed phases. It\'s can be seen that every thermal treated precursors evolve to a-alumina. In the particular case of \"Na-sulfate\", the preliminary results present also B-alumina. The hydroxides and salts pass by a sequence of alumina transition, that show high specific area. In the case of pseudoboehmite, was also studied the influence of dried method and the aging of aqueous aluminum hydroxide gels in the characteristic of synthesized materials. It verified that the dried method can influence the temperature of the alumina phase\'s transitions. Dried precursors by spray drier can form the phase a and 0 together, this not occur with the others. The aging can influence in the pseudoboehmite microfibrils size. The dried method and the aging influence the organization microfibrils, and this one determines the pore distribution from the produced materials.

As características das matérias-primas particuladas como tamanho, forma, área específica, entre outras, determinam não somente o desempenho final de um produto, mas também o processo de sua fabricação. Neste sentido, matérias-primas sintéticas são produzidas por meio de conversões químicas que têm como finalidade o controle da reprodutibilidade de características. Esta tese tem como objetivo o estudo de precursores sintetizados com matérias-primas nacionais de elevada pureza, quanto à área específica (AE), estrutura cristalina e morfologia das fases formadas durante as transformações térmicas de alguns hidróxidos (gibsita e pseudoboemita), sais (acetato e formato) e sulfatos duplos (de amônio e de sódio) de alumínio. As amostras sintetizadas e aquecidas foram caracterizadas por DRX, MEV, BET e análise térmica (TG, DTA e DSC), a fim de que fossem observadas as variações nas características das fases formadas. Observou-se que todos os precursores, à exceção do \"sulfato-Na\", evoluem termicamente resultando como produto final somente a a-alumina. No caso particular do \"sulfato-Na\", em que se apresenta resultados preliminares, verifica-se a formação, além da a- alumina, de B-alumina. Os hidróxidos e os sais de alumínio passam por uma seqüência de aluminas de transição que exibem valores de área específica elevados. Com relação à pseudoboemita, além da caracterização proposta no trabalho, foi estudada a influência do método de secagem e do tempo de envelhecimento da pseudoboemita nas características dos materiais sintetizados. Verificou-se que o método de secagem pode influenciar as temperaturas de transformações de fases das aluminas. Precursores secos por nebulização podem formar a fase a concomitantemente com a fase 0, o que não ocorre com os materiais secos ao ar. Já o tempo de envelhecimento influenciou no tamanho final das fibrilas de pseudoboemita. Tanto o método de secagem quanto o tempo de maturação afetam de forma determinante a organização das fibrilas que, por sua vez, estabelecem a distribuição de poros nos materiais produzidos. / Features of powdered raw materials like size, morphology, specific area, determine the product performance, besides the fabrication process product. In this direction, the synthetic raw materials are produced by means of chemical conversion to control the characteristics reprodutibility. This thesis has as objective the study of precursor\'s synthesized with national raw materials of raised pureness, by the study if the specific area (AE), crystalline structure and morphology of the phases formed during thermal transformation of some hydroxides as (aluminum hydroxides- gibbsite and pseudoboehmite; aluminum salts - acetate and formate and aluminum sulphates - sodium and amonium) produzed by high pure nacional raw materials. The sythetized and heated samples are examined by DRX, MEV, BET and thermal analysis (TG, DTA e DSC) to verify the characteristics variations in the formed phases. It\'s can be seen that every thermal treated precursors evolve to a-alumina. In the particular case of \"Na-sulfate\", the preliminary results present also B-alumina. The hydroxides and salts pass by a sequence of alumina transition, that show high specific area. In the case of pseudoboehmite, was also studied the influence of dried method and the aging of aqueous aluminum hydroxide gels in the characteristic of synthesized materials. It verified that the dried method can influence the temperature of the alumina phase\'s transitions. Dried precursors by spray drier can form the phase a and 0 together, this not occur with the others. The aging can influence in the pseudoboehmite microfibrils size. The dried method and the aging influence the organization microfibrils, and this one determines the pore distribution from the produced materials.

No description available.

Abstract: Oil pollution and spills cause serious damage to marine ecosystems and coastal environments. Currently, oily waters recuperated form a spill must be shipped onshore for treatment. This limits the volume of water that can be treated during a spill. There is a need to develop technologies to treat oily waters below 15 ppm (parts per million) at the site of the spill. Synthetic membrane technologies are widely used in water treatment and purification. They can offer an on-site solution to contaminated oily water treatment in oil production and spills. The suitability of a membrane for use in this application is determined by the type of material used in its fabrication. Compared to polymeric membranes, inorganic membranes are inert to microbiological degradation, offer high chemical and thermal resistance, and can easily be backflushed and cleaned once fouled. However, inorganic membranes consisting of metal oxides are heavier and more expensive than polymeric membranes, due to their bulky and brittle ceramic support layers. This limits their application when the overall weight of a process unit is of concern. A newly developed 2D/3D material, named twinned alumina nanosheets (TAN), has recently been used to make dynamic membranes. The nanoplatelets forming TAN have a length of 4 µm, a width of 1 µm, and a thickness of 100 nm. They have a very high permeability, a 0.2 µm-pore size and a porosity up to 88% due to their low nanosheet volume. These unique characteristics make TAN a very promising material to form membrane selective layers. However, they must be supported on a very open layer in order to take advantage of their high porosity. In this work, a composite membrane was produced with a selective layer of 2D/3D alumina nanoplatelets deposited onto stainless steel meshes and ceramic supports. The structure of the TAN in the selective layer was reinforced with binders. The main objective of this work was to verify the adhesion of the TANs onto the support. The crystallization of TAN was optimized to obtain an open 2D/3D structure. This structure was then deposited on a stainless-steel mesh. The mesh was pretreated by electrochemical etching to achieve a re-entrant surface. The mesh was immersed in an etching solution and placed parallel to a conductive graphite plate under a constant electric potential of 5V for 4 min. Aqueous solutions of silica sol and colloidal silver were tested as binding agents. They were deposited on the mesh with TAN and sintered for 4 hrs. Experiments were performed on testing stainless steel meshes with different opening sizes and comparing different calcination temperatures. The best sintering temperature was 800°C for a mesh with an opening size of 35µm. The synthesized membrane was challenged with a suspension of 10 ppm bentonite clay at a constant pressure of 100 mbar. The integral structure of a TAN membrane produced with a 2.5wt% silica binder was maintained after backflushing. The 2.5wt% silica membrane had a high flux and the particle filtration process for this membrane was modelled as pore constriction and intermediate blocking, indicating that backflushing provided the deep cleaning of pores. According to the SEM images, the 2.5wt% silica membrane preserved the integral structure of the TAN, while the pores tended to fill with silica at higher silica concentrations. The effective pore size of the 2.5wt% silica membrane was estimated to be the smallest, which is approximately 0.53 μm. The 7.5wt% silica membrane had half the permeate flux of the other membranes, because of the high concentration of binder filling the pores of the TAN selective layer. The SiO 2 binder had a positive effect in reinforcing the TAN particles. The flux of the membrane did not increase after backflushing indicating that the selective layer of the membrane was securely bound to the stainless steel mesh. The membrane exhibited flux decline between backflushings indicating that particles were retained on its surface. SEM images taken after the filtration showed that this membrane completely released bentonite particles form its pores. Tests were also performed with a membrane having two TAN coatings on the wire mesh. This reduced the flux but did not improve the retention of fine particles. Colloidal silver was found to be a poor binding agent as particles were released particles from its selective layer. Silica was a highly successful binding agent while colloidal silver was not. TAN was also successfully deposited onto ceramic supports. It was also retained on top of the membrane after backflushing. The results of this work demonstrate that TANs reinforced and bound with silica are a promising type of material to form membrane selective layers. These layers have an open pore structure with a three-dimensional channel connectivity on both stainless steel and ceramic supports. The selective layer was successfully bound to the stainless steel supports. If the pore size of this membrane were to be reduced, it would meet the requirements for use at the site of an oil spill to treat contaminated waters as it does not need the heavier supports found in traditional ceramic membranes. Résumé: La pollution et les déversements d'hydrocarbures causent de graves dommages aux écosystèmes marins et aux environnements côtiers. À l'heure actuelle, les eaux huileuses récupérées d'un déversement doivent être expédiées à terre pour leur décontamination. Ceci limite le volume d’eau contaminé qui peut être traité. Il est nécessaire de développer des technologies permettant de traiter les eaux huileuses en dessous de 15 ppm (parties par million) sur le site du déversement. Les technologies membranaires sont largement utilisées dans le traitement et la purification de l'eau. La possibilité de se servir d’une membrane dans cette application est déterminée par les matériaux utilisés dans sa fabrication. Comparées aux membranes polymères, les membranes inorganiques sont inertes vis-à-vis de la dégradation microbiologique, offrent une résistance chimique et thermique élevée et peuvent facilement être rincées et nettoyées une fois encrassées. Cependant, les membranes inorganiques constituées d'oxydes métalliques sont plus lourdes et plus coûteuses que les membranes polymères, en raison de leurs couches de support en céramique volumineuses et cassantes. Cela limite leur application lorsque le poids total d'une unité de traitement est préoccupant. Un matériau 2D/3D récemment développé, appelé TAN (Twinned Alumina Nanosheets), a récemment été utilisé dans la formation de membranes dynamiques. Les nano-plaquettes formant les TAN ont une longueur de 4 µm, une largeur de 1 µm et une épaisseur de 100 nm. Ils ont une très haute perméabilité, une taille de pores de 0,2 µm et une porosité allant jusqu'à 88% en raison du faible volume des nanofeuilles. Ces caractéristiques uniques font du TAN un matériau très prometteur pour la formation de couches sélectives de membranes. Cependant, ils doivent être déposes sur une couche très ouverte afin de tirer parti de leur grande porosité. Au cours de ce travail, une membrane composite a été réalisée avec une couche sélective de nanoplaques d’alumine 2D / 3D (TAN) déposées sur deux types de supports; des mailles en acier inoxydable et des supports en céramique. La structure du TAN dans la couche sélective a été renforcée avec des liants. L'objectif principal de ce travail était de vérifier l'adhérence des TAN sur le support. La cristallisation des TAN a été optimisée pour obtenir une structure 2D/3D ouverte. Cette structure a ensuite été déposée sur un treillis en acier inoxydable. Les mailles ont été prétraitées pour obtenir une surface réentrante. Le maillage a été immergé dans une solution de gravure et placé parallèlement à une plaque de graphite conductrice sous un potentiel électrique constant de 5 V pendant 4 min. Des solutions aqueuses de sol de silice et d’argent colloïdal ont été testées en tant que liants. Ils ont été déposés sur la maille et frittés pendant 4 heures. Des expériences ont été effectuées sur des mailles en acier inoxydable avec différentes tailles d’ouverture et températures de calcination. La meilleure température de frittage était de 800 ° C pour un treillis ayant une taille d'ouverture de 35 µm. La membrane synthétisée a été mise à l’essai avec une suspension de 10 ppm d'argile bentonite à une pression constante de 100 mbar. La structure intégrale de la membrane couche de TAN produite avec un liant à 2,5wt% de silice a été maintenue après les tests de perméabilité. La structure 3D poreuse a tendance à se remplir de silice à des concentrations de silice supérieures à 2,5wt%. La taille effective des pores de la membrane produite avec 2,5wt% de liant de silice a été estimée à 0,53 µm. Le flux de la membrane n'a pas augmenté après le rinçage, indiquant que la couche sélective de la membrane était liée de manière sûre au maillage en acier inoxydable. La membrane présentait un déclin de flux entre les rinçages indiquant que des particules étaient retenues à sa surface. Les images au microscope à balayage prises après la filtration ont montré que cette membrane libère complètement les particules de bentonite de ses pores. Des essais ont également été réalisés avec une membrane comportant deux revêtements TAN sur le treillis métallique. Cela réduit le flux mais n'améliore pas la rétention des particules fines. L'argent colloïdal s'est avéré être un agent de liaison médiocre car des particules sont libérées de sa couche sélective. La silice était un liant très efficace, contrairement à l'argent colloïdal. Le TAN a également été déposé avec succès sur des supports en céramique. Il est également resté sur la membrane après le rinçage à contre-courant. Les résultats de ce travail démontrent que les TAN renforcés avec un liant de silice sont un type de matériau prometteur pour former des couches sélectives, avec des structures à pores ouverts possédant une connectivité de canal tridimensionnelle, sur des supports en acier inoxydable et en céramique. La couche sélective a été liée avec succès au support en acier inoxydable. Si la taille des pores de cette membrane devait être réduite, elle pourrait être utilisée sur le site d'un déversement d'hydrocarbures pour traiter les eaux contaminées car elle ne nécessite pas les supports plus lourds que l'on trouve dans les membranes de céramique traditionnelles.

The densification mechanisms of polycrystalline α-alumina by spark plasma sintering are highly contradictory, with different research groups suggesting diffusion to dislocation controlled mechanisms to be rate controlling. The specific objective of this work was to investigate densification mechanisms of α-alumina during the intermediate and final stages of sintering by SPS, analyze the microstructural development and establish sintering trajectories. In addition, zirconia and yttria were added in different weight percentages to study the effect of solute concentration on the densification kinetics of spark plasma sintered alumina. The present work adopts a different approach from the classical method adopted previously to analyze the sintering kinetics and densification mechanisms of alumina in SPS, although existing models for hot pressing were adopted for the basic analysis. The densification behavior was investigated in the temperature range 1223-1573 K under applied stresses of 25, 50 and 100 MPa and grain sizes between 100 and 250 nm. The SEM micrographs reveal equiaxed grains with no abnormal grain growth in the dense samples. The ‘master sintering curve’ shows grain size to be primarily dependent on density, irrespective of the applied stresses or temperature. The stress exponent of 1 along with an inverse grain size exponent of 3 and activation energy of 320-550 kJ mol-1 suggests Al3+ grain boundary diffusion as the rate controlling densification mechanism in alumina. The densification rates are marginally slower in compositions with 0.1% Y2O3 and ZrO2 content possibly due to the smaller grain sizes used in this study which leads to faster rates compared to earlier reports. However, higher Y2O3 and ZrO2 content led to decrease in densification rate by more than an order of magnitude possibly due to presence of a second phase which increases the effective path length for diffusion, thereby reducing the densification rates. Presence of Y2O3 and ZrO2 in the compositions with 0.1% Y2O3 and ZrO2 were confirmed by TEM studies. The Y3Al5O12 (YAG) phase developed between 1223 and 1273 K and suppressed densification and grain growth in alumina. In spite of higher temperatures required for alumina-YAG and alumina-zirconia composites to attain density ~99%, the alumina grain size in the composites was smaller than that in pure alumina due to the Zener drag effect. The stress exponents obtained for Y2O3 and ZrO2 composites at both the concentrations yield a value of n~ 2, which indicates a change in densification mechanism from pure alumina. The higher stress dependence of these composites could be due to presence of solute and second phase formation, both of which retard densification rates. The inverse grain size exponents obtained are between 1 and 2; both stress exponent and grain size exponent values suggest an interface reaction controlled diffusion mechanism occurring in these composites, independent of the Y2O3 and ZrO2 content. Higher activation energies are obtained with the Y2O3 and ZrO2 composites of higher content, respectively, due to presence of second phase particles at grain boundaries. The presence of solutes at grain boundaries hinders grain boundary diffusion of alumina, leading to interface reaction controlled process; this is confirmed by superimposing standard aluminum grain boundary and lattice diffusion data on to stress-densification rate data obtained in this work. A comparison of stress exponents using current experimental data adopting the present and the classical approaches show a wide difference in their values indicating a change in the rate controlling diffusion path, necessitating a review of the assumptions made on the basic equations used in previous SPS studies.

Typescript (photocopy). / Digitized by Kansas Correctional Industries

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