Inorganic geopolymers or simply geopolymers based on silico-aluminate are relatively novel materials with a wide range of potential applications. The mAln purpose of the present study was to experimentally investigate the compositionmicrostructure- property relationship of these new materials. These must be understood in order to optimise the performance of geopolymers. Geopolymers with different chemical compositions (Si:Al and Na:Al atomic ratios) were prepared by thermally assisted alkali-activation of metakaolinite at 70ºC. Metakaolinite was obtAlned by dehydroxylation of kaolinite at 750ºC for 6 hours. Measurements indicated that the compositions of geopolymers influence the microstructural character as well as the physical and mechanical properties of these materials. Geopolymers prepared with an atomic ratio of Si:Al = 1.04 and 1.25 are categorised as sodium-poly(sialate) (Na-PS) geopolymers. These materials were found to be composed of zeolite-A or zeolite-X in conjunction with amorphous geopolymer. These materials are relatively soft, with low density and high apparent porosity, and have low hardness and compressive strength. Geopolymers prepared with an atomic ratio of Si:Al = 1.50, 1.75 and 2.00 are categorised as sodium-poly(sialate-siloxo) (Na-PSS) geopolymers. The structure of these geopolymers is amorphous as observed by X-ray diffraction (XRD) with no evidence of zeolite formation. A broad amorphous hump in the X-ray diffraction patterns suggests that the Na-PSS geopolymers consist of disordered frameworks with short-range order. The thermal analysis of Na-PSS by means of thermogravitmetric-differential thermal analysis (TG-DTA) revealed that about 15% of the initial reaction water remAlns in the geopolymer framework. The DTA curves for Na-PSS show a single endothermic peak around 135ºC due to water evolution. / Na-PSS geopolymers exhibit substantial shrinkage and cracking after heating up to 950ºC. Geopolymers with aggregate also suffer extensive cracking due to heating although the shrinkage was less than that of geopolymers without aggregate Dilatometer results show that geopolymer pastes shrink about 2% below 300ºC and remAln dimensionally stable up to 800ºC. The coefficient of thermal expansion of geopolymers is comparable to that of Portland cement paste. The presence of aggregate was found to reduce the shrinkage of geopolymer by 50%. Quartz aggregate, however, limits the useful working temperature range of geopolymers to below 500ºC due to a sudden expansion of quartz at 574ºC. The thermal conductivity of geopolymers was measured using a hot-wire method. The results indicated that thermal conductivity of geopolymers was similar to those of Portland cement paste. As with Portland cement, the addition of quartz was found to increase the thermal conductivity. The compressive strength of Na-PSS geopolymers is significantly influenced by the hardness, apparent porosity and the atomic ratio of Si:Al. It was found that geopolymers with an atomic ratio of Si:Al = 1.5, Na:Al = 0.6 have the highest compressive strength and hardness. It was also observed that the addition of aggregate (quartz and granite) has negligible effect on the strength of geopolymers. The bond strength between geopolymer and aggregate was measured by using a tensile test. The results indicated that sandstone aggregate provides the strongest interfacial bond with geopolymer, followed by granite and quartz. The mechanical interlocking due to the rough surface of the sandstone was believed to be responsible for the relatively high interfacial bond strength. / The microstructural characterisation of Na-PSS by means of SEM (scanning electron microscopy) and TEM (transmission electron microscopy) revealed that the morphology of Na-PSS consists of aluminosilicate matrix, unreacted metakaolinite, pores and microcracks. The presence of microcracks observed by SEM and TEM are categorised as secondary microcracks formed during sample preparation. Computed Tomography Imaging (CT-Scan) results for as prepared geopolymers with and without the inclusion of aggregate did not reveal any resolvable cracks. Optical microscopy observations on polished and vacuum evacuated samples also shows the formation of cracks on the surface of geopolymers. The presence of unreacted metakaolinite was confirmed by energy dispersive spectroscopy (EDS), X-ray mapping and electron diffraction. It was also found that Na-PSS geopolymers prepared with Si:Al = 2.0, Na:Al = 1.0 are more homogeneous (less unreacted metakaolinite) than Na-PSS geopolymers prepared with Si:Al = 1.5, Na:Al = 0.6. SEM and TEM observations revealed that the interfacial zone between geopolymer paste and aggregate has the same chemical composition as the rest of the geopolymer matrix. As a result of this study there is a better understanding of the composition-microstructure-property relationship of geopolymers paving the way to the production of geopolymers with improved performance in a variety of applications.

Orientador: José Luiz Pinheiro Melges / Resumo: A indústria do cimento Portland é responsável direta por uma carga de poluentes de significativo dano ambiental. Os Concretos Ativados Alcalinamente (CAA) são matrizes compostas por um ativador alcalino e um aglomerante alternativo. O material comumente utilizado para a ativação alcalina é o silicato de sódio, cuja fabricação também se mostra como ambientalmente nociva. O silicato de sódio, junto ao cimento Portland, podem ser dispensados, uma vez que a produção do ativador pode se dar através de um composto rico em silício (materiais pozolânicos no geral), sendo a cinza da casca de arroz (CCA) o instrumento de estudo do trabalho apresentado, e a soda cáustica como fornecedora de sódio (meio alcalino). Os concretos CAA foram definidos conforme o parâmetro ξ (CAA-ξ), que representa a relação molar entre SiO2 e Na2O, com as variações ξ = 1,2, ξ = 1,6 e ξ = 2,0, esta última representando o concreto ativado alcalinamente com maior taxa de CCA. Este trabalho tem como intuito a avaliação das propriedades mecânicas dos concretos CAA, comparando-as, em seguida, com duas tipologias de concreto com cimento Portland CPV-ARI, com distintos fatores água cimento (0,45 e 0,55). A variação na relação a/c teve como intuito a análise de duas referências com valores diferentes de fck. Os resultados demonstram que a resistência à compressão axial e diametral (sete dias de cura) para os concretos CAA se encontraram na faixa de 25 a 30 MPa, e de 1,5 a 3,5 MPA, respectivamente. Não foram observados... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The Portland cement industry is directly responsible for a load of pollutants of significant environmental damage. Alkali-Activated Concrete (AAC) is a matrix with prior activation and alternative binder. The catalyst material commonly used for prior activation is the sodium silicate, the manufacture of which is also environmentally harmful. Sodium silicate, together with Portland cement, can also be dispensed with, since the activator can be produced through a silicon-rich compound (pozzolanic materials in general), with the rice husk ash (RHA) being the instrument of study of the work presented, and caustic soda as a supplier of sodium. The AAC concretes were defined according to the parameter ξ (AAC- ξ), which represents the molar ratio of SiO2 and Na2O, with the variations ξ = 1.2, ξ = 1.6 and ξ = 2.0, the latter representing the AAC with higher RHA rate. This work intends to evaluate the mechanical properties of AAC, comparing them to two types of concrete with ordinary Portland cement with high early resistance, with different water cement factors (0.44 and 0.55). The variation in the water/binder mass ratio was intended to analyze two references with different values of compressive strength class. The results demonstrate that the axial and diametric compression strength (seven days cure) for the AAC concretes were in the range of 25 to 30 MPa, and of 1.5 to 3.5 MPA, respectively. There were no significant gains in the transition between the ages of 7 and 28 days, and 2... (Complete abstract click electronic access below) / Mestre

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2016. / Population growth in South Africa has led to a direct increase in electricity demand. Due to the abundance of coal in the country, most of the energy requirement is met through coal combustion. Although there is a vast coal resource, the natural high grade coal is mainly exported, while the low grade coal is exploited for electricity generation. The combustion of low grade coal during electricity production results in huge quantities of coal fly ash (CFA) that require careful disposal, due to its toxicity. Poor management of this waste constitutes serious human and environmental problems, such as respiratory diseases, contamination of soil, surface water and groundwater. This is in part due to the fact that only a small percentage of fly ash is utilised efficiently in the construction industry. Several studies have recently been conducted into the use of CFA as a starting material for the synthesis of zeolites and geopolymers, due to its high silicon and aluminium content. However, the synthesis of zeolites from CFA has been subject to criticism, because the synthesis of zeolites from the bulk CFA results in zeolite products that are mixed with non-reacted fly ash and toxic elements. On the other hand, pure phase zeolites can only be synthesised from CFA extracts, which results in a small yield of the zeolite products and a huge amount of solid waste. Therefore, this does not facilitate either the use of fly ash-based zeolites as catalysts in advanced chemical processes or scaling up of the synthesis process. This study seeks to make optimal use of CFA by developing a method for optimal extraction of Si and Al for the synthesis of ZSM-5 and faujasite zeolites, and use the resulting solid waste for the synthesis of geopolymers such that the resultant waste is minimised or completely eliminated. Two distinct processes are employed in this study to synthesise ZSM-5 or faujasite zeolite from CFA extracts, while the solid residue is transformed into a geopolymer. In the first process, an alkaline leaching method is employed for extraction of Si from CFA using 8 M NaOH at 150 0C for 24 h. It was found that the Si extract contained a certain amount of Al, enough for the synthesis of a high silica zeolite such as ZSM-5. However, the Si extract had to be treated with oxalic acid in order to remove the excess Na in the extract, since this could prevent the formation of ZSM-5. The obtained Si extract was then used as a feedstock for the synthesis of Zeolite ZSM-5 with NaOH and tetraethyl ammonium hydroxide (TEAOH) as mineralising and structure directing agents respectively. The obtained gel underwent hydrothermal synthesis at 160 °C for 72 h, while the solid residue obtained after Si extraction was used in the synthesis of geopolymer at 70 °C for 5 days. The obtained ZSM-5 and geopolymer products were characterised using ICP, XRD, SEM, FTIR and NMR techniques.

Geopolymers are a relatively new class of materials that have many broad applications, including use as substitute for ordinary Portland cement (OPC), use in soil stabilisation, fire resistant panels, refractory cements, and inorganic adhesives. Geopolymers are an alternative binder to Portland cement in the manufacture of mortars and concrete, as its three-dimensional alumino silicate network develops excellent strength properties. Use of geopolymers in place of ordinary Portland cement is also favoured owing to the possible energy and carbon dioxide savings. Geopolymer is typically synthesized by alkali activation of pozzolanas at moderate temperatures (< 1000C). The focus of the thesis is synthesis and characterization of geopolymers as construction materials. In this context, the role of compositional factors, such as, pozzolana type (fly ash, kaolinite, metakaolinite, ground granulated blast furnace slag, red soil), alkali (sodium hydroxide is used in this study) activator concentration, Si/Al (Si= silicon, Al = aluminium) ratio of the pozzolana and environmental factors, namely, curing period and temperature are examined. Besides synthesizing geopolymers that could be an alternate to concrete as construction material, sand-sized aggregates were synthesized using geopolymer reactions. This was done as river sand is becoming scarcer commodity for use as construction material. Several compositional and environmental factors were varied in geopolymer synthesis in order to identify the optimum synthesis conditions that yield geopolymers with maximum compressive strength. Besides varying external (compositional and environmental) factors, the role of internal microstructure in influencing the compressive strength of the geopolymer was examined. Micro-structure examinations were made using X-ray diffraction (XRD), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) studies. The studies on compositional and environmental factors in geopolymer synthesis brought out several interesting results. The results firstly brought out that amongst the pozzolanas studied, ASTM class F fly ash is most suited for maximum compressive strength mobilization upon geopolymer reactions. Moderate temperature (75-1000C) was adequate to mobilize large compressive strengths. Room temperature curing needed more than 7 days before the pozzolana-NaOH paste began to develop strength. Curing period of 56 days was needed for the geopolymer to develop significant strength (19.6MPa). A similar range of compressive strength could be developed by the pozzolana-NaOH paste upon curing for 3 days at 1000C. Likewise curing the pozzolana-NaOH paste at temperatures > 1000C led to reduction in compressive strength from shrinkage and breakage of bonds. A caustic soda (NaOH) concentration of 10 M was adequate to develop maximum compressive strength of the geopolymer. Caustic soda concentrations in excess of 10 M did not result in further improvement of strength. The Si/Al ratio also contributes to strength mobilization. The Si/Al ratio of the geopolymer was enhanced by mixing commercially obtained silica gel with the pozzolana. Maximum strength mobilization was observed at Si/Al ratio = 2.45 corresponding to 6.5 % silica gel addition to the pozzolana (on dry mass basis). Comparing compressive strengths of geopolymers with varying silica gel contents, geopolymer specimens with least water content and largest dry density did not exhibit maximum compressive strength indicating that the physico-chemical (bond strength, micro-structure) played a pivotal role than physical parameters (dry density, water content) in dictating the strength of the geopolymer. MIP results showed that bulk of the porosity in fly ash geopolymer specimens is contributed by macro pores and air voids. Geopolymerization leads to bulk consumption of cenospheres in fly ash and forms polymerized matrix with network of large pores. After geopolymerization, all the main characteristic peaks of Al–Si minerals observed in fly ash persisted, suggesting that no new major crystalline phases were formed. Presence of small amount of inorganic contaminants in fly ash can drastically reduce the strength of the fly ash geopolymer. For example, 5-20 % presence of red soil reduces the strength of fly ash geopolymer by 16 to 59 %. Presence of unreacted clay coupled with less porous structure is responsible for the reduction in compressive strength of fly ash geopolymer subjected to red soil addition. MIP studies with geopolymers also revealed that there is good bearing between compressive strengths and maximum intruded volume (from MIP test) of geopolymers. For example, fly ash geopolymer specimen exhibits highest total intruded volume (0.3908 cc/g) and largest compressive strength of 29.5 MPa, while red soil geopolymer specimen exhibit least intruded volume (0.0416 cc/g) and lowest compressive strength (5.4 MPa). Further, analysis showed that specimens with larger airvoids+macropores volume had larger compressive strength, suggesting that geopolymers with more porous microstructure develop larger compressive strength. All geopolymer specimens exhibited tri-modal nature of pores i.e. macro-pore mode (entrance pore radius: 25-5000 nm), mesopore mode (entrance pore radius: 1.25 to 25 nm) and air void mode (entrance pore radius >5000 nm). The micro pores (entrance pore radius < 1.25 nm) do not contribute to porosity of the geopolymer specimens. Sand particles prepared from geopolymer reactions (FAPS or fly ash geopolymer sand) predominated in medium sized (2mm to 0.425 mm) sand particles. Their particle size distribution characteristics (uniformity coefficient and coefficient of curvature) classified them as poorly graded sand (SP). Dissolution, followed by polymerization reactions led to dense packing of the Si–O–Al–O– units that imparted specific gravity of 2.59 to FAPS particles which is comparable to that of river sand (2.61). Dissolution in strongly alkaline medium imparted strongly alkaline pH (12.5) to the FAPS particles. The river sand is characterized by much lower pH (7.9). Despite being characterized by rounded grains, the FAPS particles mobilized relatively high friction angle of (35.5o) than river sand (∅ = 28.9o). The river sand-mortar (RS-M) and fly ash geopolymer sand-mortar (FAPS-M) specimens developed similar 28-day compressive strengths, 11.6 to 12.2 MPa. Despite its higher water content, FAPS-mortar specimens developed similar compressive strength and initial tangent modulus (ITM) as river sand-mortar specimens. The FAPS-M specimen is more porous (larger intruded volume) with presence of larger fraction of coarser pores. Total porosity is majorly contributed by macro-pores (67.92%) in FAPS-M specimen in comparison to RS-M specimen (macro-pores = 33.1%). Mortar specimens prepared from FAPS and river sand exhibit similar pH of 12.36 and 12.4 respectively. FAPS-mortar specimens have lower TDS (1545 mg/L) than river sand-mortar specimens (TDS = 1889 mg/L). The RS-M and FAPS-M specimens exhibit leachable sodium levels of 0.001 g Na/g RS-M and 0.007 g Na/g-FAPS-M respectively in the water leach tests. The larger leachable sodium of FAPS-M specimen is attributed to residual sodium hydroxide persisting in the FAPS even after washing. The ultra-accelerated mortar bar test (UAMBT) shows that the percentage expansion of FAPS-M and RS-M specimens are comparable and range between 0.07 to 0.08 %.

La nécessité de construire de manière durable, rationnelle et écologique incite à l’innovation et la recherche d’alternatives, telles que la géopolymérisation et l’activation alcaline, qui suscitent un intérêt croissant. Dans ce sens, ces technologies permettent de valorise rdes matières premières à plus faible impact environnemental pour le développement d’une nouvelle famille de matériaux. Cependant, ces mécanismes réactionnels sont complexes et il est encore nécessaire de lever plusieurs verrous avant leur implémentation : la confusion entre les deux processus, l’absence d’approches de formulation rationnelles, la méconnaissance de certaines vulnérabilités, etc. La thèse s’intègre dans cette dynamique et a pour objectif une meilleure connaissance des géopolymères et des matériaux alcali-activés. Le cadre de travail est le développement de coulis d’injection. Un programme expérimental basé sur une sélection de compositions est établi afin de caractériser leurs principales propriétés. Les différences entre les deux processus de structuration sont relevées à travers une étude physico-chimique (DRX, RMN) et liées aux évolutions macroscopiques au jeune âge. Un travail d’optimisation de formulation est mené afin de répondre à des critères d’application et définir les paramètres influençant le comportement rhéologique et mécanique des coulis. Une méthodologie basée sur l’analyse micromécanique et l’homogénéisation multi-échelles a permis d’évaluer le module élastique des matériaux et peut servir de plateforme pour une analyse globale du comportement mécanique. Enfin, une étude de la durabilité est entamée en évaluant la sensibilité au séchage et à la lixiviation en milieu acide. / The need for more durable, rational and ecological constructions encourages innovation and the search for alternatives, such as geopolymerization and alkali-activation, with a growing interest. These technologies allow the use of resources with a lower environmental impact in developing a new class of materials. However, both reaction mechanisms are complex and some issues need further investigation before a proper implementation: the confusion between these processes, the absence of a rational design approach, the lack of knowledge concerning some mechanisms of degradation, etc. The present thesis joins this dynamic and aims at a better understanding of geopolymers and alkali activated materials to design soil injection grouts. An experimental program has been established based on selected mix designs to study their main properties. The differences between both structuration processes were determined through a physicochemical study (XRD, NMR). They were correlated to the macroscopic phenomena observed at early age. An optimization of the mixtures was carried to satisfy the application criteria and define the parameters controlling the rheological and mechanical behavior of the grouts. Using a micromechanical characterization and multiscale homogenization, a methodology has been designed to determine the elastic modulus of the materials.This can be used as a first tool to analyze the global mechanical behavior. Finally, the sensitivity to drying and exposure to acid environments was assessed.

Com o intuito de valorizar resíduos localmente disponíveis foi selecionada como principal matéria prima desta pesquisa, uma cinza de fundo proveniente da queima de carvão mineral para geração de energia em uma usina termoelétrica do Estado. Uma vez que este resíduo ainda não possui destinação que lhe agregue valor, o mesmo é amplamente utilizado no preenchimento de cavas de extração de carvão ou então permanece em bacias de sedimentação, criando assim um panorama suscetível a problemas ambientais além de gerar elevados custos para seu transporte. Neste âmbito surgem com grande destaque o desenvolvimento de ligantes álcali-ativados, dentre estes os geopolímeros, que por utilizarem diversos materiais provenientes de resíduos industriais na sua produção apresentam grande redução na emissão de CO2 e no consumo energético quando são comparados ao cimento Portland. Estes materiais consistem na ativação alcalina de aluminossilicatos amorfos (precursor), sendo estes na maioria das vezes resíduos ou subprodutos industriais. Sendo assim, o presente trabalho teve por objetivo otimizar traços, com base em cinza de fundo, para a produção de ligantes e argamassas geopoliméricas. O método experimental proposto se encontra dividido em diferentes fases subsequentes à seleção e caracterização das matérias primas: (1) síntese de sistemas geopoliméricos em pasta, (2) otimização dos geopolímeros em pasta e (3) produção de argamassas geopoliméricas com verificação das propriedades mecânicas e de absorção de água. A partir da análise dos resultados observou-se que o teor de Na2O = 15% com uma concentração de silicatos solúveis no ativador (expresso como a relação molar SiO2/Na2O) igual a 1 (sistema CF-15-1,0), se mostrou ideal para as misturas com cinza de fundo. A adição de silicatos solúveis propiciou um incremento de resistência aos sistemas produzidos no geral, atingindo em alguns casos o acréscimo de até 40% na resistência aos 28 dias. Quando avaliados diferentes tamanhos de partículas a partir do beneficiamento mecânico das cinzas, observou-se que um diâmetro médio de 7 μm é o mais adequado. Com relação aos sistemas binários e híbridos testados quando comparados aos seus referenciais moldados apenas com cinza de fundo, nenhuma combinação foi capaz de superar as resistências dos referenciais. Quando produzidas argamassas geopoliméricas a partir das combinações com outros resíduos (lodo de anodização do alumínio e catalizador de equilíbrio - resíduo proveniente do processo de craqueamento catalítico em leito fluidizado de frações pesadas do petróleo) e cimento Portland, houveram quedas na resistência à compressão de maneira generalizada. A argamassa utilizada como referência (CF-15-1,0) se mostrou a matriz mais densa e consequentemente atingiu o maior desempenho mecânico com menor absorção de água por capilaridade. / In order to valorise locally available residues, bottom ash (BA) from a thermo-electrical plant was selected as the main material within the project presented here. BA does not have any commercial value and normally it is used to refill old coal mines or it is disposed in extended basins increasing the environmental impact as well as the cost related to its transport. Also there exist convincing interests in the development of non-conventional binders, i.e. alkali-activated cements (geopolimers), which can be a feasible pathway to the valorization of different industrial wastes. When alkali-activated concrete is produced under optimal conditions, it can exhibits similar or even higher mechanical performance and durability when compared to traditional Portland cement concrete. These materials are based on aluminosilicate mineral (precursor) chemically activated by an alkaline solution (activator). Thus, this project is focused in the optimization dosage of bottom ash based geopolymers in pastes and the subsequent mortars production and assessment. Mechanical performance and some permeability properties of the developed geopolyemrs were assessed. The results showed that 15% of Na2O in respect to the bottom ash with 1,0 SiO2/Na2O molar ratio as activator produced more suitable geopolymeric paste. This material was used as a reference system for the development of the proposed project. Also mechanical treatement applied to the BA reduced x% the mean particle size obteining 7 μm and this improved up to ~95% the mechanical performance of the produced geopolymers. The inclusion of Portland cement as a secondary precursor did not have significant effect under the compressive strength when compared to the BA-based systems. Furthermore, the use of other sorces of aluminosilicates, such as aluminium anodizing sludge and spent fluid cracking catalyst, also did not presented any improvement in the analysed geopolimeric systems. BA-based systems activated at 15% of Na2O using an alkali activator solution with a Ms of 1.0 showed the lowest permability and higher mechanical performance.

Geopolymers (GPs) are a special class of inorganic polymers with unique properties. Their 3-D amorphous structure and properties are often attributed to SiO2/Al2O3 molar ratios. However; contradictory results reported in literature on the structure and properties, do not conclusively support these reported findings. Furthermore, alternative processing methods are necessary for synthesizing pure geopolymers without impurities often found in precursor material. A rigorous study on chemical composition and processing parameters as well as alternative processing methods are necessary for advancing GPS in various engineering applications. The effects of H2O/(SiO2 + Al2O3) and SiO2/Al2O3 molar ratios , as well as precursor material on the density, open porosity, microstructure and the thermal and mechanical properties in K and Na activated geopolymers is investigated. X-ray diffraction, Nuclear Magnetic Resonance as well as alcohol immersion to determine density and open porosity is utilized for structural characterization. Thermogravimetric analysis and Thermomechanical analysis are used to investigate thermal behavior. Thermal conductivities and mechanical properties were measured using Thermal Constant analysis and compression testing respectively. Conclusive results demonstrate that the amount of water used to process GPs is the governing factor affecting their structure while SiO2/Al2O3 molar ratio plays no significant role. The K- and Na-activated samples have similar amounts of residual water after aging for 21 days at ambient conditions. In addition, the effects of the initial water content, SiO2/Al2O3 ratio, and alkaline activator (Na or K) on the thermal and mechanical properties of GPs, indicate that the dominant factor controlling thermal conductivity is H2O/(SiO2 + Al2O3) ratio used in processing, and to a lesser degree, the type of activation ion (Na or K). The SiO2/Al2O3 ratio did not have an effect on thermal conductivity. However, GPs compressive strengths are strongly affected by H2O/(SiO2 + Al2O3) ratio, especially at higher water ratio. At high and intermediate H2O/(SiO2 + Al2O3) ratios, liquid/solid ratio is the most important factor controlling the strength of GPs. At low H2O/(SiO2 + Al2O3) ratios, SiO2/Al2O3 ratio also plays an important role. Finally, partial geopolymer synthesis was possible using pure SiO2 and Al(OH)3 precursors, providing a possible low temperature alternative to other aluminosilicate precursors.

Made available in DSpace on 2015-05-14T12:56:02Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1595008 bytes, checksum: 8cb0cd919ceaad29b00aa94f0f9a23ca (MD5) Previous issue date: 2013-11-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aim of this study was to evaluate the adhesive characteristics of two kinds of geopolymers (G1 and G2) among five well known cements used in Dentistry: two conventional self-cure cements zinc phosphate (FZ), glass ionomer (IV) and three resin -based cements, one of them with light cure RelyX Veneer (RV) whereas the other two are dual cements RelyX ARC (RA) and RelyX U200 (RU), which is a self-adhesive product. Before the execution of the experiments themselves, forty-five non-carious molars were selected for afterwards analysis. The teeth were sectioned along the cervical line, and the crown was split along the mesial-distal line, creating 90 halves of teeth crowns. Each one was placed inside of the lumen of a segment of a regular 25mm PVC pipe. Once that was done, self-cure acrylic resin was poured into the pipes until the full submersion of the half crowns. Each block was transversally sliced, creating specimens in the shape of 2 mm thick discs. Thereupon, conic cavities were drilled into the dentin using a diamond bur. Ten samples were used for each cement and each geopolymer was used in twenty samples. These materials were inserted into these cavities, avoiding their overfill. Randomized 24h storage under relative wetness and room temperature for the selfcure cements and one sample of each geopolymer (G1u and G2u) was set. As a matter of comparison, other ten samples of the geopolymer (G1s and G2s) were stocked in a dry room, for the same period of time, so that it could be possible to analyze its adhesion without the wetness influence. Afterwards, the push-out experiments were made in a universal testing machine. The results were made under the ANOVA and Tukey tests, which showed that the best adhesive strength were showed by G2S and followed by G1S. Among the resin cements, RV obtained the best performance. G1u and G2u showed the lowest adhesive levels, without any relevant statistical differences between them. The conclusion is that the geological cements mechanical characteristics are promising, although they re very susceptible to wetness. The rational application of geopolymers in Dentistry must face an correction of is hidrosolubility, so that its clinical usage can reach a good effectiveness. / O objetivo deste trabalho foi avaliar as características adesivas de dois tipos de geopolímero (G1 e G2) frente a cinco cimentos odontológicos de uso consagrado: dois convencionais fosfato de zinco (FZ), ionômero de vidro (IV) e três resinosos, sendo um deles fotopolimerizável Relyx Veneer® (RV) , e os demais, dual - Relyx ARC® (RA) e Relyx U200® (RU), este último, autocondicionante. Previamente à execução dos ensaios, quarenta e cinco molares hígidos foram selecionados para estudo. Os elementos dentários foram seccionados na linha cervical, e a coroa foi dividida no sentido mésio-distal, gerando noventa hemi-coroas, que foram posicionadas na luz de um cano de PVC de 25mm de diâmetro. Nesse momento, elas foram incluídas em resina acrílica auto-polimerizável. Cada artefato foi desgastado, gerando um corpo de prova em forma de disco com 2mm de espessura. Em seguida, foram feitos preparos cavitários cônicos em dentina. Para cada cimento comercial, dez amostras foram utilizadas, e para os geopolímeros, vinte. Os compostos foram inseridos nesses preparos, evitando-se o extravasamento. Arbitrou-se um tempo de estocagem de 24 horas em condições de umidade relativa em temperatura ambiente para os cimentos comerciais e uma amostra de cada geopolímero (G1u e G2u). Para efeitos comparativos, outras dez amostras de cada geopolímero (G1s e G2s) foram armazenadas em ambiente seco durante o mesmo período, de modo a se conhecer suas adesões sem influência da umidade. A partir daí, foram executados ensaios de push-out em uma máquina universal. Os resultados foram submetidos aos testes de ANOVA e Tukey, que mostraram que as melhores resistências adesivas foram apresentadas por G2s, seguida por G1s. Dentre os cimentos convencionais, RV teve o melhor desempenho. G1u e G2u mostraram os níveis de adesão mais baixos, não tendo diferenças estatísticas entre si. Conclui-se que as características mecânicas dos cimentos geológicos se mostraram promissores, apesar de bastante susceptíveis à ação da umidade. O uso odontológico mais racional dos geopolímeros deve passar pela correção de seu caráter hidrossolúvel, de modo a se alcançar uma aplicabilidade clínica mais efetiva.

Com o intuito de valorizar resíduos localmente disponíveis foi selecionada como principal matéria prima desta pesquisa, uma cinza de fundo proveniente da queima de carvão mineral para geração de energia em uma usina termoelétrica do Estado. Uma vez que este resíduo ainda não possui destinação que lhe agregue valor, o mesmo é amplamente utilizado no preenchimento de cavas de extração de carvão ou então permanece em bacias de sedimentação, criando assim um panorama suscetível a problemas ambientais além de gerar elevados custos para seu transporte. Neste âmbito surgem com grande destaque o desenvolvimento de ligantes álcali-ativados, dentre estes os geopolímeros, que por utilizarem diversos materiais provenientes de resíduos industriais na sua produção apresentam grande redução na emissão de CO2 e no consumo energético quando são comparados ao cimento Portland. Estes materiais consistem na ativação alcalina de aluminossilicatos amorfos (precursor), sendo estes na maioria das vezes resíduos ou subprodutos industriais. Sendo assim, o presente trabalho teve por objetivo otimizar traços, com base em cinza de fundo, para a produção de ligantes e argamassas geopoliméricas. O método experimental proposto se encontra dividido em diferentes fases subsequentes à seleção e caracterização das matérias primas: (1) síntese de sistemas geopoliméricos em pasta, (2) otimização dos geopolímeros em pasta e (3) produção de argamassas geopoliméricas com verificação das propriedades mecânicas e de absorção de água. A partir da análise dos resultados observou-se que o teor de Na2O = 15% com uma concentração de silicatos solúveis no ativador (expresso como a relação molar SiO2/Na2O) igual a 1 (sistema CF-15-1,0), se mostrou ideal para as misturas com cinza de fundo. A adição de silicatos solúveis propiciou um incremento de resistência aos sistemas produzidos no geral, atingindo em alguns casos o acréscimo de até 40% na resistência aos 28 dias. Quando avaliados diferentes tamanhos de partículas a partir do beneficiamento mecânico das cinzas, observou-se que um diâmetro médio de 7 μm é o mais adequado. Com relação aos sistemas binários e híbridos testados quando comparados aos seus referenciais moldados apenas com cinza de fundo, nenhuma combinação foi capaz de superar as resistências dos referenciais. Quando produzidas argamassas geopoliméricas a partir das combinações com outros resíduos (lodo de anodização do alumínio e catalizador de equilíbrio - resíduo proveniente do processo de craqueamento catalítico em leito fluidizado de frações pesadas do petróleo) e cimento Portland, houveram quedas na resistência à compressão de maneira generalizada. A argamassa utilizada como referência (CF-15-1,0) se mostrou a matriz mais densa e consequentemente atingiu o maior desempenho mecânico com menor absorção de água por capilaridade. / In order to valorise locally available residues, bottom ash (BA) from a thermo-electrical plant was selected as the main material within the project presented here. BA does not have any commercial value and normally it is used to refill old coal mines or it is disposed in extended basins increasing the environmental impact as well as the cost related to its transport. Also there exist convincing interests in the development of non-conventional binders, i.e. alkali-activated cements (geopolimers), which can be a feasible pathway to the valorization of different industrial wastes. When alkali-activated concrete is produced under optimal conditions, it can exhibits similar or even higher mechanical performance and durability when compared to traditional Portland cement concrete. These materials are based on aluminosilicate mineral (precursor) chemically activated by an alkaline solution (activator). Thus, this project is focused in the optimization dosage of bottom ash based geopolymers in pastes and the subsequent mortars production and assessment. Mechanical performance and some permeability properties of the developed geopolyemrs were assessed. The results showed that 15% of Na2O in respect to the bottom ash with 1,0 SiO2/Na2O molar ratio as activator produced more suitable geopolymeric paste. This material was used as a reference system for the development of the proposed project. Also mechanical treatement applied to the BA reduced x% the mean particle size obteining 7 μm and this improved up to ~95% the mechanical performance of the produced geopolymers. The inclusion of Portland cement as a secondary precursor did not have significant effect under the compressive strength when compared to the BA-based systems. Furthermore, the use of other sorces of aluminosilicates, such as aluminium anodizing sludge and spent fluid cracking catalyst, also did not presented any improvement in the analysed geopolimeric systems. BA-based systems activated at 15% of Na2O using an alkali activator solution with a Ms of 1.0 showed the lowest permability and higher mechanical performance.

Com o intuito de valorizar resíduos localmente disponíveis foi selecionada como principal matéria prima desta pesquisa, uma cinza de fundo proveniente da queima de carvão mineral para geração de energia em uma usina termoelétrica do Estado. Uma vez que este resíduo ainda não possui destinação que lhe agregue valor, o mesmo é amplamente utilizado no preenchimento de cavas de extração de carvão ou então permanece em bacias de sedimentação, criando assim um panorama suscetível a problemas ambientais além de gerar elevados custos para seu transporte. Neste âmbito surgem com grande destaque o desenvolvimento de ligantes álcali-ativados, dentre estes os geopolímeros, que por utilizarem diversos materiais provenientes de resíduos industriais na sua produção apresentam grande redução na emissão de CO2 e no consumo energético quando são comparados ao cimento Portland. Estes materiais consistem na ativação alcalina de aluminossilicatos amorfos (precursor), sendo estes na maioria das vezes resíduos ou subprodutos industriais. Sendo assim, o presente trabalho teve por objetivo otimizar traços, com base em cinza de fundo, para a produção de ligantes e argamassas geopoliméricas. O método experimental proposto se encontra dividido em diferentes fases subsequentes à seleção e caracterização das matérias primas: (1) síntese de sistemas geopoliméricos em pasta, (2) otimização dos geopolímeros em pasta e (3) produção de argamassas geopoliméricas com verificação das propriedades mecânicas e de absorção de água. A partir da análise dos resultados observou-se que o teor de Na2O = 15% com uma concentração de silicatos solúveis no ativador (expresso como a relação molar SiO2/Na2O) igual a 1 (sistema CF-15-1,0), se mostrou ideal para as misturas com cinza de fundo. A adição de silicatos solúveis propiciou um incremento de resistência aos sistemas produzidos no geral, atingindo em alguns casos o acréscimo de até 40% na resistência aos 28 dias. Quando avaliados diferentes tamanhos de partículas a partir do beneficiamento mecânico das cinzas, observou-se que um diâmetro médio de 7 μm é o mais adequado. Com relação aos sistemas binários e híbridos testados quando comparados aos seus referenciais moldados apenas com cinza de fundo, nenhuma combinação foi capaz de superar as resistências dos referenciais. Quando produzidas argamassas geopoliméricas a partir das combinações com outros resíduos (lodo de anodização do alumínio e catalizador de equilíbrio - resíduo proveniente do processo de craqueamento catalítico em leito fluidizado de frações pesadas do petróleo) e cimento Portland, houveram quedas na resistência à compressão de maneira generalizada. A argamassa utilizada como referência (CF-15-1,0) se mostrou a matriz mais densa e consequentemente atingiu o maior desempenho mecânico com menor absorção de água por capilaridade. / In order to valorise locally available residues, bottom ash (BA) from a thermo-electrical plant was selected as the main material within the project presented here. BA does not have any commercial value and normally it is used to refill old coal mines or it is disposed in extended basins increasing the environmental impact as well as the cost related to its transport. Also there exist convincing interests in the development of non-conventional binders, i.e. alkali-activated cements (geopolimers), which can be a feasible pathway to the valorization of different industrial wastes. When alkali-activated concrete is produced under optimal conditions, it can exhibits similar or even higher mechanical performance and durability when compared to traditional Portland cement concrete. These materials are based on aluminosilicate mineral (precursor) chemically activated by an alkaline solution (activator). Thus, this project is focused in the optimization dosage of bottom ash based geopolymers in pastes and the subsequent mortars production and assessment. Mechanical performance and some permeability properties of the developed geopolyemrs were assessed. The results showed that 15% of Na2O in respect to the bottom ash with 1,0 SiO2/Na2O molar ratio as activator produced more suitable geopolymeric paste. This material was used as a reference system for the development of the proposed project. Also mechanical treatement applied to the BA reduced x% the mean particle size obteining 7 μm and this improved up to ~95% the mechanical performance of the produced geopolymers. The inclusion of Portland cement as a secondary precursor did not have significant effect under the compressive strength when compared to the BA-based systems. Furthermore, the use of other sorces of aluminosilicates, such as aluminium anodizing sludge and spent fluid cracking catalyst, also did not presented any improvement in the analysed geopolimeric systems. BA-based systems activated at 15% of Na2O using an alkali activator solution with a Ms of 1.0 showed the lowest permability and higher mechanical performance.