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.

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.

A fundamental step in the further developments of comprehensive modelling of the diffusive processes in liquids requires the possibility of obtaining reliable and accurate experimental data of the diffusion and thermodiffusion coefficients of multicomponent liquid systems. In the present work, we perform an experimental investigation of the diffusive properties of binary and ternary liquid systems. Two experimental techniques, the ‘Open Ended Capillary’ technique and the ‘Transient Interferometric Technique’ have been developed. Those techniques have been used for the experimental characterization of several systems composed of 1,2, 3,4-Tetrahydrnaphtalene, Isobutylbenzene and Dodecane at ambient temperature. Those particular species were selected as a simplified multicomponent system modelling the fluids contained in natural crude oils reservoirs. <p>For each of these techniques, experimental set-ups were designed, implemented and calibrated. The procedures for identifying the ternary diffusion coefficients from the measured compositions fields were studied in details. <p>The Open Ended Capillary Technique was applied under gravity condition to study isothermal diffusion binary and ternary systems. Difficulties related to a new procedure for interpreting the data collected at short times of the experiments are highlighted and its implication in the generalization of the technique for the study of multicomponent systems is discussed.<p>The Transient Interferometric Technique was used to perform an experimental study of three binary systems under gravity conditions. It was also applied for the investigation of ternary systems under microgravity condition in the frame of the DSC on SODI experiment, which took place aboard the International Space Station in 2011. The experimental results are reported and the analysis of the accuracy of the technique is presented. The TIT is the first technique ever providing accurate experimental measurements of the complete set of diffusion and thermodiffusion coefficients for ternary liquid systems.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Yes / In this paper, we will consider the selective maintenance problem for multistate series systems with stochastic dependent components. In multistate systems, the health state of a component may vary from perfect functioning to complete failure. The stochastic dependence (S-dependence) between components is discussed and categorized into two types in multistate context. First, the failure of a component can immediately cause complete failures of some other components in the system. Second, as components deteriorate, the reduced working performance rate of a multistate component affects the state as well as the degradation rate of its subsequent components in series structure. The system reliability is evaluated using an approach based on stochastic process. A cost-based selective maintenance model is developed for the multistate system with S-dependent components to maximize the total system profit, which includes the production gain and loss in the next mission as well as possible maintenance costs for the system. Analyses of systems with independent and dependent components are provided. It is observed that ignoring S-dependence in the system may lead to alternative maintenance decision making and an optimistic estimation of the system performance.

Directed assembly of molecular solids continues to attract widespread interest with its fundamental application in a wide range of commercial settings where control of the crystalline state of materials corresponds with product performance. These arenas include pharmaceuticals, personal care formulations, foods, paints and pigments and explosives. In recent times, the assembly of multicomponent organic systems has achieved considerable impetus with the widespread interest in co-crystal systems. However, cogent assembly (or engineering) of multicomponent materials is still in its infancy. Considerable advances in crystal design have been made through consideration of intermolecular ‘synthons’ – identifiable motifs utilising hydrogen bonds – but the translation of other molecular information (conformation, chirality, etc.) into solid state properties (e.g. long-range (translational) symmetry, crystal chirality) remains poorly understood. In this study, we have attempted to evaluate the influence of a chiral centre adjacent to molecular synthons to identify potential translation of information into the solid form. We have compared the co-crystallisation of nicotinamide with both the racemic mixture of malic acid against that with an enantiomerically pure form of the acid (L-malic acid). As well as DL-phenyllactic acid and L-phenyllactic acid. iii It is apparent that recognition between enantiomeric molecular forms play a significant role in the assembly of these systems. This mechanism can be considered independently from the H-bonding networks supporting the hetero-molecular interactions (e.g. acid-amide recognition). Discrimination and control of such interactions may play a role in transmitting chiral molecular information into solid state multi-component assemblies. In order to develop an understanding of co-crystal formation in chiral and achiral forms with intermolecular interactions, the CSD and crystal structures were obtained to do the analysis of how co-crystals pack. This study has also investigated the use of boronic acids. The aim of this study was to investigate the modification of the hydrogen bonding environment within the hydrogen bonded multi-component systems of boroxines. The study also attempted to determine how the starting materials drive the systems between the boronic acid co-crystal and the boroxine adduct.

Directed assembly of molecular solids continues to attract widespread interest with its fundamental application in a wide range of commercial settings where control of the crystalline state of materials corresponds with product performance. These arenas include pharmaceuticals, personal care formulations, foods, paints and pigments and explosives. In recent times, the assembly of multicomponent organic systems has achieved considerable impetus with the widespread interest in co-crystal systems. However, cogent assembly (or engineering) of multicomponent materials is still in its infancy. Considerable advances in crystal design have been made through consideration of intermolecular ‘synthons’ – identifiable motifs utilising hydrogen bonds – but the translation of other molecular information (conformation, chirality, etc.) into solid state properties (e.g. long-range (translational) symmetry, crystal chirality) remains poorly understood. In this study, we have attempted to evaluate the influence of a chiral centre adjacent to molecular synthons to identify potential translation of information into the solid form. We have compared the co-crystallisation of nicotinamide with both the racemic mixture of malic acid against that with an enantiomerically pure form of the acid (L-malic acid). As well as DL-phenyllactic acid and L-phenyllactic acid. iii It is apparent that recognition between enantiomeric molecular forms play a significant role in the assembly of these systems. This mechanism can be considered independently from the H-bonding networks supporting the hetero-molecular interactions (e.g. acid-amide recognition). Discrimination and control of such interactions may play a role in transmitting chiral molecular information into solid state multi-component assemblies. In order to develop an understanding of co-crystal formation in chiral and achiral forms with intermolecular interactions, the CSD and crystal structures were obtained to do the analysis of how co-crystals pack. This study has also investigated the use of boronic acids. The aim of this study was to investigate the modification of the hydrogen bonding environment within the hydrogen bonded multi-component systems of boroxines. The study also attempted to determine how the starting materials drive the systems between the boronic acid co-crystal and the boroxine adduct.

This diploma thesis focuses on the syhnthesis of multicomponent ceramic system based on Ca-(Mn,Co)-O. The thesis is devided in theoretical and experimental part. The theoretical part is describing ceramic materials for thermoelectric application, preparation and synthesis of these materials and their processing. The experimental part is dealing with synthesis of ceramic powder which is processed to the porous ceramics. The properties of prepared porous ceramics are observed.