Prediction of contaminant transport in concrete subjected to short cyclical wetting and drying processes is integrally bound to prediction of the moisture flux. The concrete is unsaturated and the non-linear contaminant and moisture fluxes are not described by simple constant diffusion methods. This thesis presents, and partially justifies, a thermodynamic model for prediction of moisture movement in concrete, at all moisture contents commonly encountered. The wetting process is examined with Nuclear Magnetic Resonance (NMR) images during a simple absorption (sorptivity) experiment. Diffusivity functions are derived via a novel analytical approach and a universal diffusivity is suggested. Water sorption and desorption isotherms are measured on large concrete samples. van Genuchten’s retention function is successfully used to model the results. The unrelia-bility of the water sorption method at high moisture contents is illustrated by comparison with Mercury Intrusion Porosimetry (MIP). The BJH method is exploited to provide a methodology for estimating the water sorption isotherm from MIP. Mualem’s conductivity model is assessed with the water retention and NMR results. This thorough validation of the model yields a tortuosity parameter that is different to that commonly assumed. An analytical relationship between the sorptivity and the saturated permeability suggests the experimental the long-term unsaturated permeability overesti-mates the unsaturated conductivity function, and as such should be used judiciously when predicting unsaturated flow processes. Mualem’s conductivity model is further exploited to provide unsaturated air and vapour functions that are experimentally justified. The thermodynamic description of water movement and the hydraulic functions that are developed in the thesis are incorporated into T r inCet , a transient heat and mass trans-fer model based on the Finite Element Method (FEM). The complex coupled behaviour of air, liquid, vapour and temperature are well handled under a variety of common cyclical boundary conditions. The thesis presents all necessary experimental results required for validation of a com-plex, but easily described, model for moisture movement. It covers disparate ground to provide a powerful numerical model of unsaturated moisture movement in concrete under short-term cyclical processes.

[Truncated abstract] This thesis describes the development of synthetic rock samples, representative of core samples from hydrocarbon reservoirs. The basic process consists of screening and sorting silica particles into discrete grain sizes, and then binding them together using a proprietary process known as CIPS, (Calcite In-situ Precipitation System). In the bonding process, the porosity of the system is substantially preserved, and the technique allows the manufacture of synthetic core samples with a tailor-made permeability. The produced samples were extensively characterised using a variety of analytic techniques to determine their porosity, permeability and pore size distribution. These analyses were a necessary pre-cursor to a major part of this thesis: the characterisation of the pore space by nuclear magnetic resonance (NMR) techniques. The synthetic core samples, covering a 7 times factor in grain sizes were examined using NMR, and this data formed the comparative basis for the NMR studies that followed. Two fundamental NMR questions were posed and answered in this thesis: 1. What is the effect of paramagnetic ions in the rock matrix on the NMR response? In pursuit of this question the CIPS process was extended to include co-precipitation of paramagnetic ions. A key feature is that the ions were deposited in predictable amounts at known sites (on the wall of the pore space). ... The NMR response in these double cores was then measured and examined to provide an answer to the question posed at the beginning of this paragraph. The significance of this work is that the physically distinct cores are a cylindrical analogue of adjoining sedimentary strata. By answering the question posed above, the thesis gives an indication of the vertical porosity resolution ultimately possible in an NMR logging tool. At present this ranges from 9” to 24” in the most favourable circumstances. This work suggests that the NMR signal carries porosity information at a much higher resolution, and that advanced numerical analysis of the NMR signature could realise the potential of greater stratigraphic resolution in NMR logging In addition to the research outlined above, the application of the CIPS technique to produce analogues of reservoir rocks, pioneered in this thesis, has stimulated similar research to be undertaken at other institutions, including the fabrication of synthetic reservoir cores containing clay particles (at CSIRO - the Commonwealth Scientific and Industrial Research Organisation) and a large scale application, formation of meter size blocks of CIPS bonded material, with separate strata, for laboratory studies of seismic waves (at Curtin University)

Thesis (Ph. D.). UM #74-17,941. / Title from document title page. Includes bibliographical references. Available in PDF format via the World Wide Web.

Thesis (Ph. D.)--University of Oklahoma. / Bibliography: leaves 164-183.

Tamarindus indica L. é um componente natural amplamente consumido por humanos, apresentando propriedade antiinflamatória, antidiabética e antihepatotóxica. Além disso, como nós demonstramos previamente, o extrato apresenta atividade hipolipêmica e antioxidante. Neste trabalho, nós demonstramos o efeito do extrato de T. indica sobre mitocôndrias isoladas de fígado de rato. Na presença de Ca2+, o extrato causou um inchamento osmótico mitocondrial concentração-dependente, associado ao aumento da velocidade basal (V4), dissipação do potencial de membrana e liberação do Ca2+ pré-acumulado, os quais foram inibidos por ciclosporina A (CsA) e assim atribuídos a transição de permeabilidade da membrana mitocondrial (TPMM). A indução do inchamento osmótico mitocondrial foi prevenida por EGTA e vermelho de rutênio, indicando a dependência da TPMM de Ca2+. A oxidação de proteínas tiol mitocondrial, um mecanismo bem estabelecido como causador da TPMM, foi detectado. Entretanto, nenhuma alteração significante foi observada no estado redox de GSH. A oxidação de NAD(P)H e o acúmulo de espécies reativas de oxigênio produzidas pela mitocôndria foram observadas, em ambos os casos, foram prevenidas por CsA e/ou EGTA, indicando que são conseqüências da TPMM induzida pelo extrato de T. indica. Portanto, sem aparente envolvimento do estresse oxidativo no processo, sugerindo uma interação direta de compostos do extrato com grupos tiólicos de proteínas da membrana. O extrato de T. indica induziu uma depleção de ATP associada à TPMM, mostrando assim potencial para causar a morte celular por apoptose ou necrose, resultante da indução da TPMM por si ou pela depleção do ATP via TPMM. In vitro, o extrato apresentou capacidade scavenger de radicais livres, verificado pelo ensaio do DPPH, radical superóxido e radical hidroxil; e ainda foi capaz de diminuir a lipoperoxidação mitocondrial. Além disso, em baixas concentrações, o extrato mostrou uma propriedade quelante de Fe2+. / Tamarindus indica L. is a natural dietary component widely consumed by humans, presenting well established anti-inflammatory, anti-diabetic and anti-hepatotoxic properties. In addition, as we have previously demonstrated, extract presents hypolipemic and antioxidant activities. We show here the effects of T. indica extract on isolated rat liver mitochondria. In the presence of Ca2+, the extract caused mitochondrial concentration-dependent swelling, associated to, resting respiration increase (V4), membrane potential dissipation and release of pre-accumulated Ca2+, inhibited by cyclosporine A (CsA) and thus ascribable to mitochondrial permeability transition (MPT). This swelling induction was prevented by EGTA and ruthenium red, indicating strict dependence of MPT on Ca2+. Oxidation of mitochondrial membrane protein thiols, a well established mechanism causing MPT was detected. However, no significant change was observed in the GSH redox state, and the NADPH oxidation and accumulation of mitochondria-generated reactive oxygen species that was observed, were prevented by CsA and/or EGTA, indicating that they are consequence of the MPT induced by T. indica extract. Therefore, no apparent oxidative stress condition is involved as cause of this process suggesting that direct interaction with membrane protein thiol groups of the compounds responsible for MPT induction occurs. T. indica extract led to MPTassociated ATP depletion, thus showing the potential to cause cell death by apoptosis or necrosis resulting from MPT induction per se or from ATP depletion by MPT. In vitro, the extract presented free radical scavenging ability, as assessed by the 2,2-diphenyl-1- picrylhydrazyl (DPPH), superoxide radicals and radical hydroxyl assays, and led to decreased lipid peroxidation in mitochondria, as assessed by the thiobarbituric acid reactive substances (TBARS) assay. In addition, the extract showed an iron chelanting property in low concentrations.

Made available in DSpace on 2015-05-14T12:56:02Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1910042 bytes, checksum: 8e8a3485e33886a2a24c8a6a9e1630e9 (MD5) Previous issue date: 2014-02-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Immersion of natural enamel caries (NEC) in quinoline has been important for determining lesion size and mapping areas with different pore sizes, but quantitative volumetric data of the infiltration are not available. Here we provide first quantitative volumetric data of the volume infiltrated by quinoline (mostly < 50% of pore volume were infiltrated) in histological layers (including dark zone) of ground sections of NEC lesions (n = 20) and report that a parameter related to permeability predicted 60% of the variance of the volumetric infiltration. Distance from the original enamel surface was inversely related to the infiltrated volume. In most lesions the translucent zone was not the lesion front. Real-time 2D mapping of transport processes after immersion in quinoline revealed an early outward water flow and a late inward quinoline penetration, both following prisms paths parallel to the main axis of ground sections. New events of the nature of transport processes in ground sections of NEC lesions reported here can be explored to improve efficiency of both remineralizing agents and resin infiltrants for treatment of NEC. / A imersão em quinolina de lesões naturais de cárie em esmalte tem sido importante para determinar o tamanho da lesão e áreas com diferentes tamanhos de poros. No entanto, dados volumétricos quantitativos resultantes da infiltração desta substância não estão disponíveis na literatura. Sendo assim, o presente trabalho objetivou apresentar os primeiros dados quantitativos volumétricos do infiltrado por quinolina (na maioria das amostras < 50 % do volume de poros foram infiltrados) em camadas histológicas (incluindo zona escura) de cortes por desgaste de lesões cariosas naturais em esmalte (n = 20). Além disto, verificou-se que um parâmetro relacionado à permeabilidade previu 60 % da variância da infiltração volumétrica. A distância da superfície do esmalte original foi inversamente relacionada com o volume infiltrado. Na maioria das lesões, a zona translúcida não foi o front da lesão. Mapeamento em 2D em tempo real de processos de transporte após a imersão em quinolina, através de microscopia de luz polarizada, revelou primeiramente um fluxo de água para o exterior e uma conseguinte penetração por quinolina, ambos seguindo a trajetória dos prismas paralelamente ao eixo principal dos cortes por desgaste. Novos eventos da natureza dos processos de transporte em cortes por desgaste aqui relatados podem ser explorados para melhorar a eficiência de ambos os agentes remineralizantes e infiltrantes de resina para tratamento de lesões cariosas.

Made available in DSpace on 2015-05-14T12:56:03Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 946361 bytes, checksum: 1766fac9ee5a060f38a21f6c3c424890 (MD5) Previous issue date: 2014-03-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aim of this study was to compare artificial carious enamel lesions induced with an acid gel containing large amounts of organic matter and artificial carious lesions induced by an acidic solution (with little organic constituent) regarding organic volume and permeability (&#61537;d). Thirty teeth (twenty third molar and ten molars with inactive white spot lesions) were divided into three groups. In order to induce artificial caries, ten teeth were exposed to an acid gel containing hydroxyethylcellulose 2% and 50 mM lactic acid at pH 4.5 (Gel; n = 10) while the other ten teeth a demineralizing solution (0,1 mM lactic acid, 11.7 mM of calcium, chloroform 0.5% v/v, 6 mM phosphate, pH 4.5) (Solution; n = 10). As a control group, the teeth containing white spot lesions were also analyzed (Natural Caries, n = 10). Three points were analyzed in each sample at the surface layer in each lesion at 50&#956;m intervals. The results obtained in each of the three groups were compared with theoretical mathematical found values in the literature as a way to standardize the comparison. Finally, variations in organic volume (Ratio &#61538;) and permeability (Ratio &#61537;d) in relation to predicted values were compared between groups. For variable Ratio &#61538;, there was a significant difference between the gel and solution [p<0.0001, ANOVA; Effect Size (ES)=1.84] and between solution and the natural caries (p=0.001, ANOVA; ME=0.46). Similarly, the values of Ratio &#61537;d between Gel/Solution (p<0.0001, Mann-Whitney, ES=0.96) and Solution/Natural caries (p<0.0001; Mann-Whitney; ME=1.15) differed significantly. There was no statistically significant difference between the groups Gel and Natural Caries for Ratio &#61538; (p=0.585, ANOVA, ES=0.30) and the Ratio &#61537;d (p=0.940, Mann-Whitney, ES=0.01). It was concluded that, as in natural decay, the surface layer of artificial carious enamel lesions created with organic acid gel showed higher organic matter and lower permeability compared to those induced in acidic solution. / O objetivo deste estudo foi comparar lesões cariosas artificiais de esmalte induzidas com gel ácido contendo grande quantidade de matéria orgânica e lesões cariosas artificiais induzidas com solução ácida com pouco constituinte orgânico, quanto ao volume orgânico e à permeabilidade (&#61537;d). Trinta dentes (vinte terceiros molares inclusos e dez molares com lesão de mancha branca inativa) foram distribuídos em três grupos. Com o intuito de se induzir cárie artificial, dez dentes inclusos foram expostos a um gel ácido de hidroxietilcelulose 2% e ácido lático 50 mM com pH 4,5 (Gel; n=10) e os outros dez a uma solução desmineralizante (0,1 mM de ácido lático, 11,7 mM de cálcio, clorofórmio 0,5% v/v e 6 mM de fosfato, com pH 4,5) (Solução; n=10). Como grupo controle, os dentes contendo lesões de mancha branca também foram analisados (Cárie Natural; n=10). De cada amostra analisou-se três pontos da camada superficial da lesão, em intervalos de 50 &#956;m. Os pontos analisados em cada um dos três grupos foram comparados com valores teóricos estabelecidos matematicamente na literatura, como forma de padronizar as comparações. E, por fim, as variações de volume orgânico (Razão &#61538;) e permeabilidade (Razão &#61537;d) em relação a valores previstos foram comparadas entre os grupos. Para a variável Razão &#61538;, houve diferença significante entre os grupos Gel e Solução [p<0,0001, ANOVA; Magnitude do efeito (ME)=1,84] e entre Solução e Cárie Natural (p=0,001; ME=0,46; ANOVA). Da mesma forma, os valores da Razão &#61537;d do cruzamento Gel/Solução (p<0,0001, Mann-Whitney; ME=0,96) e Solução/Cárie Natural (p<0,0001, Mann-Whitney; ME=1,15) diferiram de maneira significativa. Não houve diferença estatisticamente significante entre os grupos Gel e Cárie Natural para a Razão &#61538;&#61472;(p=0,585; ANOVA; ME=0,30) e a Razão &#61537;d (p=0,940; Mann-Whitney; ME=0,01). Concluiu-se que, semelhantemente à cárie natural, a camada superficial das lesões cariosas artificiais de esmalte criadas com gel ácido apresentaram maior volume orgânico e menor permeabilidade, comparadas às induzidas em solução ácida.

Made available in DSpace on 2015-05-14T12:56:03Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2756793 bytes, checksum: 52c334e99949464b4e3237ddf1e202c6 (MD5) Previous issue date: 2014-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The transport of materials through the tooth enamel is conventionally derived from the diffusion process, which leads to a number of limitations, because the pores of the enamel are extremely small, requiring a certain extension, as occurs in adhesive techniques by the etching process. An alternative method to this technique is the electrokinetic flow (EKF), which promotes the unidirectional flow of substances through the pores of the enamel by applying an external electric field. Based on this premise it was promoted the infiltration of a composite resin with low viscosity (Icon DMG, Hamburg, Germany) on the surface of 20 extracted human teeth by EKF, using an electric field (1.5V) in two stages: (1) infiltration of potassium chloride 0.1M (KCl) during 3h and (2) infiltration of the resin during 2h. Longitudinal histological sections of &#8776; 100&#956;m were analyzed by fluorescence microscopy and polarized light microscopy associated with the "polscopesingle"system, after 24h of dehydration and along 50, 100, 150, 200, 250, 300, 350, 400, 450 and 500&#956;m deep. Electric voltage (&#956;A) presented to be positive during infiltration. Images from Fluorescence Microscopy revealed fluorescence of the infiltrated enamel areas for all samples, from the surface to the dentin-enamel junction (DEJ), indicating the formation of a hybrid layer with average depth of 1627.66 &#956;m and a standard deviation of 284.20 &#956;m. The records of the phase delay during dehydration of the infiltrated and non-infiltrated areas did not present changes in the infiltrated area. It was observed that the water was replaced by the resin (p<0.000001), with high effect size (>0.8). Based on these results, it was concluded that the EKF resulted in infiltration of the resin into the enamel nanochannels. / O transporte de materiais através do esmalte dentário é limitado já que convencionalmente depende do processo de difusão, em virtude do volume nanométrico dos poros do esmalte. Um método alternativo pode ser o uso do Fluxo Eletrocinético (FEC), que promove o fluxo unidirecional de substâncias através dos poros do esmalte pela aplicação de um campo elétrico externo. Por conseguinte, este estudo promoveu a infiltração de resina fluida na superfície de 20 dentes humanos extraídos através do FEC, utilizando um campo elétrico de 1,5 volt em duas etapas: (1) infiltração de Cloreto de Potássio (KCl) 0,1M por 3h (2) infiltração da resina Icon (DMG, Alemanha) por 2h. Cortes histológicos por desgaste com &#8776; 100&#956;m foram analisados por Microscopia de Fluorescência (MF) e por Microscopia de Luz Polarizada (MLP) associada ao sistema single polscope , durante a desidratação das amostras por um período de 24h e analisando pontos histológicos a 50, 100, 150, 200, 250, 300, 350, 400, 450 e 500&#956;m a partir da superfície de áreas infiltradas e não infiltradas. A variação da corrente elétrica (mA) mostrou-se positiva durante a infiltração. As imagens da MF demonstraram fluorescência do esmalte na região infiltrada desde a superfície até a junção amelo-dentinária (JAD), indicando a formação de uma camada híbrida com profundidade média de 1627,66 &#956;m e desvio padrão de 284,20 &#956;m. Comportamentos distintos foram identificados para as áreas infiltrada e não infiltrada durante a desidratação. A área não infiltrada perdeu água, conforme verificado através da redução do retardo de fase. A área infiltrada não perdeu água, uma vez que o retardo manteve-se constante, sugerindo que a água fracamente aderida foi substituída pela resina durante a infiltração. As diferenças estatísticas entre os pontos histológicos das duas áreas foram calculadas através do teste de Mann-Whitney, com nível de significância de 5%, confirmando que a água foi substituída pela resina (p< 0,000001), com alta magnitude do efeito (>0,8). Portanto, pode-se concluir que a utilização do FEC resultou na infiltração da resina nos nanocanais do esmalte, formando camada híbrida de grande profundidade.

Made available in DSpace on 2014-12-17T14:07:07Z (GMT). No. of bitstreams: 1 IrantecioMF_DISSERT_Parcial.pdf: 354207 bytes, checksum: e43a8d49123a8e937d996a1e4e80ba39 (MD5) Previous issue date: 2012-09-28 / Lightweight oilwell cement slurries have been recently studied as a mean to improve zonal isolation and sheath-porous formation adherence. Foamed slurries consisting of Portland cement and air-entraining admixtures have become an interesting option for this application. The loss in hydrostatic pressure as a consequence of cement hydration results in the expansion of the air bubbles entrapped in the cement matrix, thus improving the sheath-porous formation contact. Consequently, slurries are able to better retain their water to complete the hydration process. The main objective of the present study was to evaluate the effect of the addition of an air-entraining admixture on the density, stability and permeability of composite slurries containing Portland cement and diatomite as light mineral load. Successful formulations are potential cementing materials for low fracture gradient oilwells. The experimental procedures used for slurry preparation and characterization were based on the American Petroleum Institute and ABNT guidelines Slurries containing a pre-established concentration of the air-entraining admixture and different contents of diatomite were prepared aiming at final densities of 13 to 15 lb/gal. The results revealed that the reduction of 15 to 25% of the density of the slurries did not significantly affect their strength. The addition of both diatomite and the air-entraining admixture increased the viscosity of the slurry providing better air-bubble retention in the volume of the slurry. Stable slurries depicted bottom to top density variation of less than 1.0 lb/gal and length reduction of the stability sample of 5.86 mm. Finally, permeability coefficient values between 0.617 and 0.406 mD were obtained. Therefore, lightweight oilwell cement slurries depicting a satisfactory set of physicochemical and mechanical properties can be formulated using a combination of diatomite and air-entraining admixtures for low fracture gradient oilwells / Atualmente, busca-se a formula??o de pastas de cimento leves para prevenir o fraturamento de forma??es de baixa resist?ncia ou depletadas e combater a perda de circula??o, com boa ader?ncia e isolamento hidr?ulico entre cimento e meio poroso. O cimento espumado composto pela mistura de cimento com incorporador de ar ? um material alternativo para essa aplica??o. A perda de press?o hidrost?tica durante o processo de hidrata??o causa expans?o das bolhas de g?s, mantendo o grau de contato cimento-meio poroso, diferentemente do que ocorre apenas com o uso do cimento tradicional. A ader?ncia entre o cimento e o meio poroso (forma??o rochosa) faz com que haja estabilidade da pasta, impedindo a perda de ?gua do cimento no estado fresco para o meio. O presente trabalho tem como objetivo estudar a estabilidade e a permeabilidade de comp?sitos ciment?ceos contendo diatomita (carga leve) e incorporador de ar, verificando se o uso desses aditivos ? vi?vel para cimentos projetados para ambientes de baixo gradiente de fratura. A metodologia empregada no trabalho consiste na prepara??o e avalia??o de pastas comp?sitas, por meio de procedimentos adotados pelo American Petroleum Institute e pela Associa??o Brasileira de Normas T?cnicas. Partiu-se de uma dosagem fixa do incorporador de ar e variou-se a concentra??o de diatomita. As densidades calculadas foram 13,0 lb/gal, 14,0 lb/gal e 15,0 lb/gal, com o intuito de observar a contribui??o do fator ?gua/cimento na estabiliza??o das espumas geradas pela adi??o do incorporador de ar em rela??o a uma pasta padr?o, sem incorporador de ar. Os resultados revelaram que as pastas tiveram suas densidades reduzidas entre 15% e 25%, com a adi??o do incorporador de ar e diatomita e boa resist?ncia mec?nica. O aumento da viscosidade nas formula??es com diatomita proporcionou maior reten??o das bolhas, visto que houve redu??o acentuada da migra??o de ar para a superf?cie do cimento durante cura em repouso. Observou-se que pastas est?veis apresentaram varia??o entre o valor de densidade de fundo e topo de 0,96 lb/gal e rebaixamento de topo de 5,86 mm, al?m de baixos coeficientes de permeabilidade (0,617 mD a 0,406 mD). Concluiu-se que ? poss?vel formular pastas ciment?ceas espumadas de baixa densidade com propriedades mec?nicas e reol?gicas satisfat?rias, al?m de boa estabilidade e baixa permeabilidade, a partir de uma combina??o de cimento, diatomita e incorporador de ar. Os materiais resultantes s?o adequados visando ? cimenta??o de po?os de petr?leo com forma??es de baixa resist?ncia ou depletadas / 2020-01-01

No description available.