Bentonite is the most preferred silicate-based binder in iron ore pelletizing. However, it is considered as an impurity due to its high SiO2 and Al2O3 content. The iron-making economy is adversely affected by the addition of bentonite or other silicate-based binders. In recent years, impurity-free alternative binders have been tested in order to replace bentonite or to lower the bentonite dosage. Organic binders yield good quality green and dry pellets. However, they fail to impart enough mechanical strength to the preheated and fired pellets as a result of insufficient slag bonding. Thus, they have not found widespread application in the industry. The addition of boron compounds into pellet mix is proposed as a potential solution to overcome the insufficient compressive strengths of preheated and fired pellets produced with organic binders. During the experiments, some organic binders and boron compounds were tested as alternative binders to bentonite either alone or in combination, for both magnetite and hematite pellets. The performances of the tested binders on pellet qualities: balling, wet pellet moisture content, drop number, pellet compressive strengths (wet - dry - preheated - fired), dustiness, porosity, mineralogy, morphology, chemical contents, reducibility and swelling index have been compared with the performances of reference bentonite binder. The results of the tests showed that, the quality of pellets are insufficient when organic binders or calcined colemanite used as binder alone. The former failed to provide sufficient preheated and fired pellet strengths, the latter failed in terms of wet and dry pellet quality. However, good quality wet, dry, preheated and fired pellets could be produced with combination of these two binders. Calcined colemanite addition into pellets made with organic binders was tested in different dosages (0.25-1.00%). Results showed that with increasing dosage of calcined colemanite both strengths of preheated and fired pellets increased linearly. It was found that as low as 0.50% calcined colemanite addition equally-performed on magnetite fired magnetite pellets at 1300oC when compared with the performance of the reference bentonite binder. However, its performance was better on hematite pellets in order to improve the pellet compressive strengths. In addition, stronger pellets could be produced at lower firing temperatures like 1100oC with the addition of calcined colemanite. The reason of the improved preheated and fired compressive strengths of pellets bonded with calcined colemanite was due to the physical melting of calcined colemanite at the contact point of iron oxide grains during thermal treatment. It was found that bentonite bonded pellets fired at 1300oC were more reducible than those of produced with calcined colemanite addition. Swelling indices of these pellets were determined in the industrially acceptable limits. The chemical and mineralogical analyses results showed that the combined binders did not contaminate the pellet composition since the organic binders burnt-out without residue and colemanite does not contain much impurity.

O presente trabalho está relacionado com o desenvolvimento e análise do desempenho eletroquímico de eletrodos compósitos do tipo nonwoven também chamados de free-standing binder/metal-free electrodes, em eletrólito líquido orgânico que contem íons de lítio. Os eletrodos de excelente resistência mecânica, livre de metais e binder, e que podem conter vários miligramas dematerial eletroativo por cm3, são constituídos por substratos de fibras de carbono derivado de poliacrilonitrila, e a carga eletroativa composta por nanotubos de carbono de parede múltipla (NTC) e nanotubos de MnO2 (NT). Foram utilizados dois tipos de substrato (denominados aqui de feltro e tecido de carbono) de diferentes condutividades eletrônicas e geometrias tridimensionais. O recobrimento das fibras de carbono dos nonwovens com NTC foi realizado por decomposição química de vapor (CVD) mantendo-se constante as variáveis operacionais, o que resultou em NTC do mesmo tipo para todas as amostras e um bom controle da massa depositada. O MnO2 foi incorporado por eletrodeposição em eletrólito aquoso, esse método garantiu um bom controle de massa eletrodepositada de NT. Os eletrodos obtidos foram caracterizados estruturalmente empregando-se microscopia de varredura (MEV), difração de raios-X e microscopia Raman. Para análise de desempenho eletroquímico e mecanismo de armazenagem/conversão de energia nos eletrodos empregadas as técnicas de voltametria e cronopotenciometria cíclicas. Os resultados mostram que os eletrodos compósitos são híbridos, podem atuar como capacitores e eletrodos de baterias de íons lítio. As metodologias aplicadas se mostram extremamente reprodutíveis reprodutivas e controláveis. Depedendo das composições e combinações foi possível obter capacidades específicas associadas com armazenagem/estocagem de lítio em altas densidades de corrente (A/g) na janela de potencial de 0,005 - 3,5V vs Li/Li+ (por exemplo, 800 mAh/g em 1 A/g, taxa C-rate = 1,25C, 400 mAh/g em 2,66A/g, taxa C-rate = 5C). A eficiência faradaica para o primeiro ciclo carga/descarga variou entre 83% e 54%, dependendo da quantidade de MnO2 e da corrente aplicada. Foi observado que é possível melhorar ainda mais os resultados com adição de outros constituintes, como por exemplo, a adição de partículas de prata (<1 % em peso). Neste caso os eletrodos forneceram eficiência faradaica de 83%, 1.100 mAh/g em 1,7A/g, em taxa C-rate = 1,66C e 550 mAh/g em 2,8A/g em taxa C-rate = 5C). Em termos de capacitância os compósitos também se mostram muito positivos. Valores de capacitância da ordem de 180F/g foram facilmente obtidos em tempos de descarga de 58s e num intervalo de potencial em relação ao Li/Li+ (~3,05 V vs H2/H+) de 1,4 a 3,8V vs Li/Li+, o que permite gerar densidade de energia e potência da ordem de 63 Wh/kg e 3,6 kW/kg respectivamente. Os eletrodos estudados podem atuar como eletrodo em baterias de íons lítio e em dispositivos de capacitores, o que significa que pode ser útil para o desenvolvimento de sistemas híbridos de armazenamento/conversão de energia, particularmente, de sistemas híbridos bipolar bateria-supercapacitor. / The present work is correlated with the development and electrochemical analisys of a nonwoven kind of electrode, also called as free-standing binder/metal-free electrodes, into lithium-ion liquid organic electrolyte, whereas the constituents are the substrate made of carbon fiber derived from carbonization of polyacrylonitrile, and the electroactive material which are defective multi-walled carbon nanotubes (MWCNT) and MnO2 nanotubes. Two types of nonwoven substrates (here denominated felt and cloth) with different electronic conductivity and three-dimensional geometry were employed. MWCNT coating of the nonwoven carbon fibers was achieved with chemical vapor decomposition (CVD) of methanol at same growth conditions, which resulted in electrodes with same type of MWCNT and a good control of the deposited mass. MnO2 was incorporaded by electrodeposition in aqueous electrolyte and this methodology was found appropriate to provide electrodes with same MnO2 NT loading, although the structural phase of MnO2 was affect by nonwoven substrate type. The robusts electrodes able to support several miligrams of electroactive material per cm3 obtained were structurally characterized using scanning electron microscopy (SEM, TEM), X-ray diffraction and Raman microscopy. It was employed cyclic voltammetry at different scan rate and chronopotentiometry (discharge/charge curves at galvanostatic conditions) aiming the understanding of the electrochemical performance and mechanism of energy storage/conversion of MnO2/MWCNT coated nonwoven electrodes. The results show that the composite electrode is hybrid, can act like capacitor or lithium ion battery electrode. It can provide very high specific capacity associated with storage/extraction of Li same in elevated gravimetric current density of A/g in the potential window of 0.005-3.5V vs Li/Li+ (e.g 800 mAh/g at 1 A/g, rate = 1,25C, 400 mAh/g at 2,66A/g, rate = 5C). The Faradic efficiency measure during the first charge/discharge cycle was between 83% to 54% depending on amount of MnO2 constituent and applied current. It was also observed a gain in the electrochemical performance of MnO2/MWCNT coated nonwoven electrode with Ag nanoparticles addition (about 1% wt). With presence of Ag constituent into the composites nonwovens it was found for instance 83% of Faradic efficiency at 1st discharge/charge cycle, 1,100 mAh/g at 1,7A/g rate = 1,66C and 550 mAh/g at 2,8A/g rate = 5C. In terms of capacitance the nonwoven were able to provide values like 180 F/g during 58s in high voltage window (1.4-3.8V vs LI/Li+) which correspond to energy and power density of 63 Wh/kg e 3.6 kW/kg, respectively. The electrodes developed in the present study could therefore act both as an electrode for Li intercalation and for capacitors devices, which means that it can be useful for the development of hybrid energy storage/conversion systems, particularly, bipolar battery-supercapacitor hybrid single.

This diploma thesis deals with the study of the binder mortar based on calcium sulphate. The theoretical part deals with the general theory of sulfate binders and anhydrite mortars. Further attention is paid to the standard requirements for these binders and mortars and the evaluation of the existing research at the THD Institute. The experimental part is devoted to research of anhydrite mortar for the production of self-leveling mixtures. The subject of the research was the design of a suitable activating agent, performing technological tests on designed anhydrite pastes and mortars and monitoring hydration.

No description available.

En France, les volumes de sédiments de dragage générés chaque année pour la maintenance des ports et des voies navigables sont estimés à environ 50 millions de mètres cubes. La gestion de ces sédiments représente un enjeu économique, social et environnemental pour les gestionnaires. Aujourd’hui, l’une des solutions privilégiées est le développement de la gestion à terre de ces matériaux, qui consiste à les réutiliser comme matières premières secondaires en substitution partielle ou totale de matières nobles. De nombreux travaux de recherche ont été effectués sur la problématique de la valorisation des sédiments de dragage et de curage et de nouvelles filières sont actuellement toujours à l’étude (ciments, enrochements pour travaux maritimes et fluviaux, bétons cellulaires, granulats artificiels, etc.). Ce travail de thèse s’inscrit dans un contexte d’économie circulaire et vise à permettre le développement d’une gestion durable et responsable des ressources naturelles non renouvelables. Ceci à travers la réutilisation des sédiments de dragage dans la formulation de matériaux composites traités par des liants thermodurcissables ou thermoplastiques. Ainsi, après un travail de synthèse bibliographique sur les principales propriétés des sédiments de dragage, les méthodes de formulation des mortiers polymères et les modalités d’intégration des matériaux alternatifs dans ces matrices sont été décrites. Les expérimentations portent plus particulièrement sur la formulation de matériaux à partir de polymères thermodurcissables (résines de type Epoxy ou Polyester) et thermoplastiques (plastiques recyclés issus du tri des déchets). La validation des performances techniques des formulations optimisées pour chacun des traitements a été effectuée pour des usages en revêtements de sols ou en granulats légers dans des bétons hydrauliques. Enfin, la dernière partie de la thèse a été consacrée à l’étude de l’acceptabilité environnementale des nouveaux matériaux à travers la réalisation des essais de lixiviation dynamique sur monolithes. Les travaux menés ont permis de démontrer la faisabilité technique et environnementale de la valorisation des sédiments en tant que charge minérale dans des matrices polymères, avec des taux d’incorporation de sédiments significatifs pouvant atteindre jusqu’à 80 %. Ce qui confirme l’intérêt de cette typologie de traitement pour la valorisation des sédiments de dragage. / In France, the volume of dredged sediments generated each year through maintenance of ports and waterways, is estimated at around 50M cubic meters. The management of these sediments represents an economic, social and environmental stake for the managers of the waterways. Today, one of the solution is the onshore management of these sediments, which consists on their reuse as secondary raw materials in partial or total substitution of natural materials for civil engineering applications such as sub-base road materials, embankments, concrete, bricks/tiles, and cement production. In this context this study was initiated in order to define a long-term value chain for dredging sediments for a sustainable and responsible management of natural resources. This through the valorization of dredged sediments in polymer matrix mortar formulations. Indeed, this research presents an innovative solution that preserves natural resources by promoting the use of local resources, such as dredged sediments. In order to achieve this objective, the study included several phases : the first part is devoted to the state of the art concerning dredged sediments, polymer mortars and the recovery of waste in polymer mortars. In the second part, we studied recovery of sediment in thermosetting matrix polymers (Epoxy-Polyester). In the third part we studied the possibilities of incorporating sediments in recycled thermoplastic matrix. The materials from this combination have been used as lightweight aggregates for mortar formulation. Finally, in the last part was devoted to environmental monitoring of new formulated materials. This is done through leaching tests carried out on crushed samples and monoliths, to ensure the environmental safety of these materials. The result obtained with the different formulations tested, show the technical and environmental feasibility of valorization of sediments as mineral filler in polymer mortars, with sediments incorporation rates range between 50 and 80%. Indeed, the use of a polymer matrix makes it possible to have better physico-mechanical and chemical results with cementitious matrix mortars.

No description available.

The diffusion behavior of guest molecules introduced in porous materials has been studied. Diffusion studies in such porous materials may help for elucidating the structural properties, transport mechanism and/or surface barriers of the zeolite structure. The focus of this work is on diffusion in nanoporous materials with complex pore spaces. First a short introduction in the basics of diffusion and the PFG NMR technique (Pulsed Field Gradient Nuclear Magnetic Resonance) is described. In the following two chapters the diffusion in hierarchical pore spaces or, to be more precise, zeolites with generated mesopores, which traverse the microporous bulk phase, are investigated. The hierarchical pore spaces consists in the first case of micro- and mesopores and in the second case of micro-, meso- and macropores. The diffusion behavior in these materials has been investigated revealing diffusion acceleration in the mesoporous samples, as compared to the purely microporous material. In the next chapter the diffusion behavior in glass samples with different porosity and their complementary pore space is investigated. Diffusion with full loaded pore spaces and surface diffusion, where the molecules were only able to diffuse along the pore walls, has been explored. The aim was to find out to what extent the diffusion in two complementary pore spaces is correlated. In the last chapter, the effect of an inorganic binder on the transport in zeolite pellets has been studied. First the diffusion behavior in binderless zeolite beads in comparison with the zeolite powder employed for their production has been explored. The particular interest was to find out up to which extent the diffusion patterns observed with the powder samples could again be recognized in the beads. In a second study the transport characteristics within binderless molecular sieves have been investigated, with the purpose to reveal differences in the diffusion behavior in comparison with their binder-containing counterparts.

We are today experiencing an increasing demand for high energy density storage devices like the lithium-ion battery for applications in portable electronic devices, electric vehicles (EV) and as interim storage for renewable energy. High capacity retention and long cycle life are prerequisites, particularly for the EV market. The key for a long cycle life is the formation of a stable solid-electrolyte interphase (SEI) layer on the surface of the negative electrode, which typically forms on the first cycles due to decomposition reactions at the electrode-electrolyte interface. More control over the surface layer can be gained when the layer is generated prior to the battery operation. Such a layer can be tailored more easily and can reduce the loss of lithium inventory considerably. In this context, water-soluble electrode binders, e.g. sodium carboxymethyl cellulose (CMC-Na) and poly(acrylic acid) (PAA), have proven themselves exceptionally useful. Since the binder is a standard component in composite electrodes anyway, its integration into the electrode fabrication process is easily accomplished. This thesis work investigates the parameters that govern binder distribution in elec-trode coatings, control the stability and electrochemical performance of the elec-trode and that determine the composition of the surface layer. Several commonly used electrode materials (graphite, silicon and lithium titanate) have been applied in order to study the impact of the binder on the electrode morphology and the differ-ent electrode-electrolyte interfaces. The results are correlated with the electrochemi-cal performance and with the SEI composition obtained by in-house and synchro-tron-based photoelectron spectroscopy (PES). The results demonstrate that the poor swellability of these water-soluble binders leads to a protection of the active material, given that the surface coverage is high and the binder evenly distributed. Although on the laboratory scale electrode formu-lations with a high binder content are common, they have little practical use in commercial devices due to the high content of inactive material. As the binder con-tent is decreased, complete surface coverage is more difficult to achieve and the binder distribution is more strongly coupled to the particle-binder interactions during the preparation process. Moreover, it is demonstrated in this thesis how these inter-actions are related to the surface area of the electrode components applied, the surface composition and the electrochemistry of the electrode. As a result of the smaller binder contents the benefits provided by CMC-Na and PAA at the electrode surface are compromised and the performance differs less distinctly from electrodes fabricated with the conventional binder, i.e. poly(vinylidene difluoride) (PVdF). Composites of alloying and conversion materials, on the other hand, typically em-ploy binders in larger amounts. Despite the frequently noted resiliency to volume expansion, which is also a positive side effect of the poor swellability of the binder in the electrolyte, the protection of the surface and the formation of a more stable interface are the major cause for the improved electrochemical behaviour, com-pared to electrodes employing PVdF binders.

This research studies the green geopolymer incorporated with phase change material (PCM) for energy saving in buildings. First class F fly ash (FA) based-geopolymer binder was studied. In order to improve the mechanical properties, low calcium slag (SG) was added to the FA to produce geopolymer. The effect of different factors including SG content (at different relative amounts FA/SG = 0/100, 25/75, 50/50, 75/25 and 100/0), NaOH solution at different concentrations (7.5, 10 and 15 M), various curing times (1, 2, 4, 7, 14 and 28 days) and curing temperatures (25 (ambient), 45, 60, 75 and 90°C) was investigated. The unit weight and uniaxial compressive strength (UCS) of the geopolymer specimens were measured. Scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) and X-ray diffraction (XRD) were also performed to characterize the microstructure and phase composition of the geopolymer specimens. The results show that the incorporation of SG not only improves the strength of the geopolymer specimens but also decreases the initial water content and thus the NaOH consumption at the same NaOH concentration required for geopolymer production. In addition, the inclusion of SG increases the unit weight of the geopolymer specimens, simply because SG has a much greater specific gravity than FA. The results also show that the strength of the FA/SG-based geopolymer develops rapidly within only 2 days and no obvious gain of the strength after 7 days. The optimum curing temperature (the curing temperature at which the maximum UCS is obtained) at a FA/SG ratio of 50/50 is around 75°C. Second, FA-based geopolymer concrete was synthesized and the effect of different factors including sodium silicate to sodium hydroxide (SS/SH) ratio, aggregate shape, water to fly ash (W/FA) ratio, curing time, water exposure and PCM inclusion on the compressive strength of the geopolymer concrete specimens cured at different ambient temperatures was studied. The results show that the UCS of the specimens increases with higher SS/SH and W/FA ratios up to a certain level and then starts to decrease at higher ratios. The results also indicate that a major portion of the strength of the specimens cured at ambient temperatures develops within the first four weeks. In addition the strength of the FA-based geopolymer concrete is slightly decreased with water exposure and PCM incorporation. Third, the mechanical and thermal properties of geopolymer mortar synthesized with FA and different amount of PCM were studied and the effect of incorporated PCM on the unit weight and UCS of geopolymer mortar was evaluated. SEM imaging was performed to identify the change of micro structure of the geopolymer mortar after incorporation of PCM. The thermal properties of the geopolymer mortar containing different amount of PCM were also characterized using differential scanning calorimetry (DSC) analysis. In addition model tests were performed using small cubicles built with geopolymer mortar slabs containing different amount of PCM to evaluate the effectiveness of geopolymer mortar wall with incorporated PCM in controlling the heat flow and internal temperature. The results indicate that both the unit weight and UCS of the geopolymer mortar decrease slightly after PCM is incorporated, mainly due to the small unit weight and low strength and stiffness of the PCM, respectively. However, the compressive strength of geopolymer mortar containing up to 20% PCM is still sufficiently high for applications in buildings. The results also show that the incorporation of PCM leads to substantial increase of heat capacity and decrease of thermal conductivity of the geopolymer mortar and is very effective in decreasing the temperature inside the cubicles. Finally, a numerical study on the thermal performance of geopolymer with incorporated PCM was carried out. In order to simulate the heat transfer through geopolymer containing PCM, a simplified method was first presented. The influence of phase transition was linked to the energy balance equation through variable specific heat capacity of the PCM-geopolymer. The thermal properties of the geopolymer containing PCM for the numerical analysis were determined using DSC and guarded heat flow (GHF) tests. The simplified method was validated based on the good agreement between the numerical and experimental results. With the validated model, the effect of various factors including the specific heat capacity, thermal conductivity and wall thickness on the thermal performance of PCM-geopolymer walls was studied. Then a modified numerical method was proposed for simulating the whole thermal transfer processes and the simulation results were used to conduct the economic evaluation of PCM-geopolymer walls for energy savings in buildings.

Charles University in Prague Faculty of Pharmacy in Hradec Králové Department of Pharmaceutical Technology Student: Šárka Hávová Supervisor: PharmDr. Jitka Mužíková, Ph.D. Title of diploma thesis: A study of compaction process and properties of tablets with hypromellose and α-lactose monohydrate Thesis studied the co-processed dry binder RetaLac® from the aspect of his compressibility and dissolution of the active ingredient from tablets. RetaLac® contains α-lactose monohydrate and hypromellose in the identical proportion. The same parameters were tested in the corresponding physical mixtures of FlowLac® 100 with various types of hypromellose (Metolose® 100 SR, Metolose® 4000 SR, Metolose® 100 000 SR) and compared with the substance RetaLac® . Compressibility was evaluated by means of the energy profile of compression and tensile strength of tablets. Salicylic acid was used as the model active ingredient. Dissolution testing was performed using the method of the rotating basket.