yes / The present paper reports the testing of 12 alkali-activated mortars and a control ordinary portland cement (OPC) mortar. The main aim is to develop cementless binder activated by sodium silicate powder. An alkali quality coefficient combining the amounts of main compositions of source materials and sodium oxide (Na2O) in sodium silicate is proposed to assess the properties of alkali activated mortars, based on the hydration mechanism of alkali-activated pastes. Fly ash (FA) and ground granulated blast-furnace slag (GGBS) were employed as source materials. The ratio of Na2O-to-source material by weight for different mortars ranged between 0.038 and 0.164; as a result, alkali quality coefficient was varied from 0.0025 to 0.0365. Flow loss of fresh mortar, and shrinkage strain, compressive strength and modulus of rupture of hardened mortars were measured. The compressive strength development of alkali activated mortar was also compared with the design equations for OPC concrete specified in ACI 209 and EC 2. Test results clearly showed that the flow loss and compressive strength development of alkali-activated mortar were significantly dependent on the proposed alkali quality coefficient. In particular, a higher rate of compressive strength development achieved at early age for GGBS-based alkali-activated mortar and at long-term age for FA-based alkali-activated mortar. In addition, shrinkage strain and modulus of rupture of alkali-activated mortar were comparable to those of OPC mortar.

[pt] Em um reservatório de petróleo, a eficiência do deslocamento do óleo é bastante reduzida pela presença de fraturas e camadas de alta permeabilidade. Quando uma fase aquosa é injetada, esta flui preferencialmente por caminhos de baixa resistência, deixando grandes volumes do reservatório não afetados pelo processo de injeção. Uma alternativa para minimizar esse problema é bloquear as fraturas com um sistema líquido que forma um gel após algum tempo, forçando a fase aquosa a fluir pela matriz porosa. Os géis de silicato de sódio são uma das formulações que podem ser utilizadas para esse fim. No entanto, a cinética do processo de formação do gel de silicato é difícil de controlar, pois depende de muitas variáveis. Essa incerteza do processo de gelificação pode levar à formação de uma fase de gel fora da posição desejada, levando a diversos problemas, como perda de injetividade. Uma formulação líquida utilizando microcápsulas é uma proposta com um método inovador que tem como objetivo controlar o tempo de liberação do agente ativador e, consequentemente, melhorar o controle sobre o início do processo de gelificação. O primeiro passo no desenvolvimento desta técnica foi estudar a evolução da reologia do gel formado a partir do silicato de sódio com ácido clorídrico para avaliar a taxa de formação do gel em função de diferentes parâmetros do processo, como a concentração de Na-Si e HCl. Os resultados mostram que o processo de gelificação é função do pH da solução e que o tempo de gelificação é menor quanto maior a concentração de ácido clorídrico. No método proposto, a solução de ácido clorídrico é encapsulada e a gelificação só se inicia após o rompimento do invólucro da cápsula, que é desencadeado pela imposição de um gradiente de pressão osmótica. / [en] In an oil reservoir, the efficiency of oil displacement is greatly reduced by the presence of fractures and high permeability layers. When an aqueous phase is injected, it flows preferentially through low resistance paths, leaving large volumes of the reservoir not affected by the injection process. An alternative to minimize this problem is to block fractures with a liquid system that forms a gel after some time, forcing the water phase to flow through the porous matrix. Sodium silicate gels are one of the formulations that can be used for this purpose. However, the kinetics of the silicate gel formation process is difficult to control, since it depends on many different variables. This uncertainty of the gelation process in the subsurface may lead to the formation of a gel phase away from the desired position, leading to many different problems, such as loss of injectivity. A liquid formulation using microcapsules is proposed as an innovative method designed to control the release time of the activating agent and, consequently, to improve control over the start of the gelation process. The first step in the development of this technique was to study evolution of the rheology of the gel formed from sodium silicate with hydrochloric acid in order to evaluate the rate of the gel formation as a function of different process parameters, such as the concentration of Na-Si and HCl. The results show that the gelation process is a strong function of the solution pH and that the gelation time is shorter the higher the concentration of hydrochloric acid. In the proposed method, the hydrochloric acid solution is encapsulated and the gelation only starts after the bursting the capsule shell, which is triggered by imposing a gradient of osmotic pressure.

This master thesis presents the effects of fly ash on the properties of alkali activated slag concrete, commonly referred as Geopolymer concrete (GPC). Cement manufacturer are major producers of CO2 which negatively affects the environment. Due to the increased construction activities and environmental concern, it is necessary to introduce alternative and eco-friendly binders for concrete. Slag and fly ash based concrete, which is by-product from industrial waste, is probably the best replacement for OPC concrete due to less or nil environmental issue. Most of the researchers have already concluded that slag and fly ash can be used as binders in concrete by activating them with alkali activator solution (e.g. by sodium silicate or sodium carbonate). In the present work concretes were produced by varying the proportion of slag to fly ash (40:60, 50:50, 60:40 & 80:20); amount of alkali activators (5, 10 & 14) and chemical modulus of sodium silicate (Ms) (0.25, 0.5 & 1).  Setting times and compressive strength values were evaluated. Results showed that decrease in fly ash content irrespective of % of alkali activators and alkali modulus (Ms), the compressive strength was increasing and setting time was getting shorter. The produced concretes showed increasing compressive strength with increase in % of alkali activator for Ms 0.5 and 1, while for Ms=0.25 the strength was decreasing with increase in % of alkali activators. From this it can be concluded that, Ms=0.5 was the optimum point below which the reaction got slower. Based on the initial investigations, mix S8:F2-SS10(1) and S8:F2-SS10(0.5) showed most promising results in terms of fresh and hardened concrete properties and were easy to handle. Consequently, the above mentioned mixture was chosen to be studied in more detail. The experimental program for these mixes included determination of slump flow, compressive strength (7, 14, 28 days) and shrinkage (drying and autogenous). The results shows that, strength increased with time and comparatively mix with Ms=0.5 showed higher compressive strength than mix with Ms=1, due to higher alkalinity of the pore solution. Mix with Ms=1 showed higher drying shrinkage compared to mix with Ms=0.5, which was explained by higher alkalinity of the solutions (Ms=0.5) leading to rapid formation of aluminosilicate gel. Autogenous shrinkage appeared to be higher for mix with Ms=0.5. This was associated with lower modulus which leads to densification of concrete microstructure at early ages. Pore diameter decrease and the water trapped in the pores exerted increasing tensile stress resulting for higher autogenous shrinkage.

Made available in DSpace on 2017-07-21T20:42:39Z (GMT). No. of bitstreams: 1 Josiane Carneiro Souza.pdf: 4154319 bytes, checksum: dcde979ba587a2471aa62c75df7e7827 (MD5) Previous issue date: 2012-12-19 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / The manufacture of metal parts by molding and molded by the process in the green sand (sand base crowded with clay) is widespread in industries for its low cost and operational flexibility. A major advantage is that the materials can be reused in new molding cycles. However, when the liquid metal comes in contact with the mold, causes disabling clay locally, generating inert materials that focus on the sand and limit long cycles of reuse. Thus, there are surplus sands by adding new primary materials and the consequent need for disposal to maintain the constant flow of materials. This excess is a liability that is usually discarded in landfills. This study sought a solution to this environmental waste, by reuse in the actual molding process using the sodium silicate (Na2SiO3.XH2O)/CO2, as binder. The properties obtained from samples with waste foundry sands (WFS) and with the new green sands were compared to verify the real potential for reuse WFS and the effect of its inert components and additives. For this purpose it was evaluated the mechanisms involved in the interaction with the green sand silicate before and after reaction with CO2 in the range of 0 to 20% (by weight) mixed. Mechanical properties were evaluated before and after gassing with CO2, both with WFS and with its primary components. In this study, for microstructural characterization techniques were used for X-ray diffraction, optical microscopy and MEV/ EDS. The results showed mutually dependent mechanical properties, the morphology of the silica gel coating on the sand grains, and the composition of the mixture used. / A fabricação de peças metálicas por fundição e moldadas pelo processo em areias a verde (areia base aglomerada com argila) é bastante difundida nas indústrias pelo seu baixo custo e flexibilidade operacional. Uma das grandes vantagens é que os materiais utilizados podem ser reutilizados em novos ciclos de moldagem. Porém, quando o metal líquido entra em contato com o molde, provoca a desativação da argila localmente, gerando materiais inertes que se concentram na areia e limitam ciclos longos de reuso. Com isto, surgem excedentes de areias pela adição de materiais primários novos e a consequente necessidade de descarte para manter o fluxo constante de materiais. Este excedente é um passivo que normalmente é descartado em aterros. Este trabalho buscou uma solução ambiental para este resíduo, por meio da reutilização no próprio processo de moldagem, utilizando silicato de sódio (Na2SiO3.XH2O)/CO2, como ligante. As propriedades obtidas de amostras com areias descartadas e com as areias a verde novas foram comparadas entre si para verificar o real potencial de reutilização da ADF e o efeito de seus componentes inertes e aditivos. Para esta finalidade avaliou-se os mecanismos envolvidos na interação da areia a verde com o silicato, antes a após reação com CO2, na faixa entre 0 a 20% (em peso) nas misturas. Propriedades mecânicas foram avaliadas antes e após a gasagem com o CO2, tanto com areia descartada de fundição (ADF) quanto com os seus componentes primários. Neste estudo, para caracterização microestrutural foram utilizadas técnicas de Difração de raios X, Microscopia Ótica e Microscopia Eletrônica de Varredura/EDS. Os resultados demonstraram dependência mútua entre as propriedades mecânicas; a morfologia do recobrimento da sílica gel sobre os grãos de areia; e a composição da mistura utilizada.

Made available in DSpace on 2014-12-17T14:07:08Z (GMT). No. of bitstreams: 1 ManoelIQJ_DISSERT.pdf: 1658589 bytes, checksum: 30023fa8ec2e11231777b5b0249ad3cc (MD5) Previous issue date: 2013-05-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The oil wells cementing is a critical step during the phase of well drilling, because problems during the operation of slurry pumping and an incomplete filling of the annular space between the metal casing and the formation can cause the slurry loss. Therefore, the slurry adopted in primary cementing an oil well must be properly dosed so that these problems are avoided during its pumping. When you drill a well in a weak rock formation requires even more careful, because should be a limit of hydrostatic pressure exerted during cementation, that does not occur rock collapse. With the objective of performing the cementing of a well whose formation is weak or unconsolidated are employed lighter slurries. Thus, this study used slurries with sodium silicate and nano silica in concentrations of 0,1; 0,4; 0,7 e 1,0 gpc, in which the slurries with nano silica showed the rheological parameters higher concentrations of up to 0.7 gpc and for concentration of 1.0 the slurry with sodium silicate obtained the highest values, remaining above the limits for application in fields, mainly wells with low fracture gradient, because a significant increase in viscosity may result in an increase in pressure pumping in operations of secondary cementations. Furthermore, there was no decrease in strength with increasing concentration of additive. Then, it is possible use of these additives to formulate Lighter slurry / A cimenta??o de po?os de petr?leo ? uma das etapas mais criticas durante a fase de perfura??o de um po?o, pois problemas durante a opera??o de bombeio da pasta e um preenchimento incompleto do espa?o anular, entre o revestimento e a parede do po?o, podem causar a perda do mesmo. Portanto, a pasta adotada na cimenta??o prim?ria de um po?o de petr?leo deve ser calculada adequadamente para que sejam evitados estes problemas durante seu bombeamento. Ao se perfurar um po?o em uma forma??o rochosa fraca requer-se, ainda, mais cuidado, pois, em geral, deve existir um limite de press?o hidrost?tica exercida durante a cimenta??o, para que n?o haja o colapso da forma??o. Com o objetivo de se realizar a cimenta??o de um po?o cuja forma??o ? fraca ou inconsolidada s?o empregadas pastas leves. Desta forma, neste trabalho foram utilizadas pastas com silicato de s?dio e nano s?lica em concentra??es de 0,1; 0,4; 0,7 e 1,0 gpc, onde as pastas com nano s?lica apresentaram os par?metros reol?gicos superiores at? a concentra??o de 0,7 gpc e para a concentra??o de 1,0 gpc a pasta com silicato de s?dio obteve os maiores valores, ficando acima dos limites estabelecidos para aplica??o em campos, principalmente em po?os com baixo gradiente de fratura, pois o aumento significativo da viscosidade pode resultar no incremento da press?o de bombeio em opera??es de recimenta??o. Al?m disto, n?o foi observado em decr?scimo de resist?ncia mec?nica com aumento de concentra??o dos aditivos. Sendo poss?vel utiliza??o destes aditivos para formula??o de pastas leves

Orientador: Keizo Yukimitu / Resumo: Este trabalho visa o estudo da eficiência do uso da cinza de bagaço de cana-de-açúcar (CBC) como defloculante para materiais cerâmicos do tipo porcelanato, disponibilizada pela indústria Villagres, em comparação ao aditivo defloculante atualmente utilizado mesma, o silicato de sódio. O estudo do reaproveitamento deste material residual de origem orgânica na indústria cerâmica tem motivações que envolvem causas de disponibilidade, sustentabilidade, inovação e rentabilidade, motivações essas que, para este estudo em específico, foram fomentadas por resultados bastante promissores obtidos através de um estudo prévio envolvendo algumas destas mesmas variáveis citadas, em termos de redução do tempo de escoamento, e consequentemente, viscosidade. Materiais argilosos (argilominerais) fazem parte de grande parte da composição de massas cerâmicas. Durante o seu processo de moagem via úmida, observa-se nas argilas uma interação superficial de atração pelas forças de Van der Waals. Para que esta interação diminua e consequentemente a viscosidade da barbotina, utiliza-se aditivos defloculantes à base de sódio. O silicato de sódio é capaz de promover a troca catiônica dos cátions bivalentes. Conforme o decorrer do projeto, foram testadas diferentes formulações e metodologias nas instalações da indústria de porcelanato Villagres, com adições de silicato de sódio e/ou CBC aos materiais cerâmicos, e assim medir das viscosidades das misturas com o equipamento Copo de Ford para que fosse anali... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

No description available.

The effects of corrosion inhibitors on water quality and the distribution system were studied. This dissertation investigates the effect of inhibitors on iron surface roughness, copper surface roughness, and copper release. Corrosion inhibitors included blended poly/ortho phosphate, sodium orthophosphate, zinc orthophosphate, and sodium silicate. These inhibitors were added to a blend of surface water, groundwater, and desalinated brackish water. Surface roughness of galvanized iron, unlined cast iron, lined cast iron, and polyvinyl chloride was measured using pipe coupons exposed for three months. Roughness of each pipe coupon was measured with an optical surface profiler before and after exposure to inhibitors. For most materials, inhibitor did not have a significant effect on surface roughness; instead, the most significant factor determining the final surface roughness was the initial surface roughness. Coupons with low initial surface roughness tended to have an increase in surface roughness during exposure, and vice versa, implying that surface roughness tended to regress towards an average or equilibrium value. For unlined cast iron, increased alkalinity and increased temperature tended to correspond with increases in surface roughness. Unlined cast iron coupons receiving phosphate inhibitors were more likely to have a significant change in surface roughness, suggesting that phosphate inhibitors affect stability of iron pipe scales. Similar roughness data collected with new copper coupons showed that elevated orthophosphate, alkalinity, and temperature were all factors associated with increased copper surface roughness. The greatest increases in surface roughness were observed with copper coupons receiving phosphate inhibitors. Smaller increases were observed with copper coupons receiving silicate inhibitor or no inhibitor. With phosphate inhibitors, elevated temperature and alkalinity were associated with larger increases in surface roughness and blue-green copper (II) scales.. Otherwise a compact, dull red copper (I) scale was observed. These data suggest that phosphate inhibitor addition corresponds with changes in surface morphology, and surface composition, including the oxidation state of copper solids. The effects of corrosion inhibitors on copper surface chemistry and cuprosolvency were investigated. Most copper scales had X-ray photoelectron spectroscopy binding energies consistent with a mixture of Cu2O, CuO, Cu(OH)2, and other copper (II) salts. Orthophosphate and silica were detected on copper surfaces exposed to each inhibitor. All phosphate and silicate inhibitors reduced copper release relative to the no inhibitor treatments, keeping total copper below the 1.3 mg/L MCLG for all water quality blends. All three kinds of phosphate inhibitors, when added at 1 mg/L as P, corresponded with a 60% reduction in copper release relative to the no inhibitor control. On average, this percent reduction was consistent across varying water quality conditions in all four phases. Similarly when silicate inhibitor was added at 6 mg/L as SiO2, this corresponded with a 25-40% reduction in copper release relative to the no inhibitor control. Hence, on average, for the given inhibitors and doses, phosphate inhibitors provided more predictable control of copper release across changing water quality conditions. A plot of cupric ion concentration versus orthophosphate concentration showed a decrease in copper release consistent with mechanistic control by either cupric phosphate solubility or a diffusion limiting phosphate film. Thermodynamic models were developed to identify feasible controlling solids. For the no inhibitor treatment, Cu(OH)2 provided the closest prediction of copper release. With phosphate inhibitors both Cu(OH)2 and Cu(PO4)·2H2O models provided plausible predictions. Similarly, with silicate inhibitor, the Cu(OH)2 and CuSiO3·H2O models provided plausible predictions.

One hundred billion tons of mine solid waste are estimated to be produced worldwide each year. In Canada, the mining and oil industries produce the most solid and semi-solid waste in the country, with more than a billion tons each year. In the earlier days of mining, the initial practices that were used to contain these waste materials consisted of surface storage, river dumping or just simple abandonment, while the more recent practices include dam impoundment and underground waste fill. These methods however can potentially cause environmental hazards and geotechnical problems. Against this context and as a result of stricter environmental regulations, cemented paste backfilling has been developed as a solution. This relatively new technology uses the produced waste tailings to backfill the mine stopes, greatly reducing their environmental impact while offering proper structural support in an efficient manner. However, the cost of cemented paste backfill (CPB) is greatly impacted by the binder content which can constitute up to 75% of its total cost. Additionally, the binder is usually mostly composed of ordinary Portland cement, and its production is highly energy-intensive and generates a large volume of carbon dioxide (CO₂). Indeed, it is estimated that the cement industry accounts for approximately 7% of the global anthropogenic CO₂ emissions, which is expected to increase on an annual basis. All of these factors have compelled the mining industry to seek alternatives for cement to enhance CPB strength, in hopes of reducing its carbon footprint. Against this context, this study investigates the effect of the addition of nanoparticles, namely nano silica (SiO₂) and nano-calcium carbonate (CaCO₃), on the strength development of CPB cured at a constant room temperature and in non-isothermal conditions. Nanoparticles have been studied and used as chemical admixtures in different cementitious materials with promising results; non-isothermal curing conditions better reflect the in-situ thermal curing conditions of CPB. Thus, numerous different laboratory tests and analyses, including uniaxial compressive strength (UCS), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) tests, thermogravimetric/derivative thermogravimetric (TG/DTG) analyses and electrical conductivity monitoring, have been conducted on CPB samples with or without nanoparticles, and cured at room temperatures or under non-isothermal conditions. The non-isothermal conditions replicate the development of temperature in two different sizes of CPB structures in the field. The results show that CPB that contains nanoparticles show a higher UCS over the entire period of curing in all of the tested conditions. The mechanical performance is further enhanced when tested under higher temperatures in non-isothermal temperature profiles. Most of the strength increase takes place at the early ages (3 days) of the testing. The reason for the improvement in the mechanical strength is linked to accelerated binder hydration and the nucleating and filler effects of the nano-material, which is corroborated by results obtained through microstructural analyses and EC monitoring. The use of natural gold tailings affects the mechanical performance of CPB and the accelerating effect of the nanoparticles due to sulphate attacks. Overall, these promising findings can help to contribute to reducing the carbon footprint of mining activities, and improve the efficiency and cost-effectiveness of mine backfilling processes.

<p>Aminoglycoside antibiotics are commonly used to treat bacterial infections but are highly susceptible to chemical modification, leading to resistance. Chemical modification can be hindered through the use of small molecule inhibitors that target bacterial enzymes involved in resistance, most notably kinases. Current methods for the discovery of small molecule inhibitors of kinases and related “kinase-like” enzymes are limited in throughput and utilize slow, tedious, and expensive assays. This thesis is focused on the development of highly versatile and scaleable kinase and “kinase-like” screening platforms for the discovery of small molecule inhibitors of these drug targets. The work begins with the validation of a matrix-assisted laser desorption/ionization tandem mass spectrometry (MALDI-MS/MS) platform utilizing phosphorylation of kanamycin, an aminoglycoside antibiotic, by aminoglycoside phosphotransferase 3ʹIIIa (APH 3ʹIIIa) as a model system. Using a product-to-substrate signal ratio as an internal standard, the assay was used to functionally screen over 200 compounds, combined into mixtures to enhance assay throughput. Moreover, the assay was used to determine inhibitory dissocation constants for newly discovered modulators. Throughput was further increased to a novel dual-kinase assay targeting a bacterial enzyme, APH 3ʹIIIa and a human kinase, protein kinase A (PKA), which was validated using the previous small molecule library. Alternative assay development platforms were also studied using imaging mass spectrometry of reaction microarrays and the fabrication of sol-gel derived bioaffinity chromatography columns. The MS-based kinase assays developed herein are highly amenable to high throughput screening, and have the potential to be extended to other important therapeutic targets.</p> / Doctor of Philosophy (PhD)