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.

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.

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.

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.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The hydrophobicity can be understood as the soil water repellency, making it difficult to wetting the same. This phenomenon is associated with the coating of soil particles by hydrophobic organic substances. The local vegetation can contribute to hydrophobic organic compounds, via deposition or decomposition, but the hydrophobicity is also related to the existence metabolites of bacteria and microorganisms, burns, high pH, type of clay mineral and granulometric composition of the soil. The objective of this study was to determine the critical moisture for the occurrence of hydrophobicity and evaluate its relationship with the resistance of aggregates and the hydro-physical and chemical properties in different soils from southern Brazil. Soil samples were collected at different locations of southern Brazil. In selected places the vegetation was composed only of natural grassland. For the evaluation of soil sorptivity and aggregate stability, soil samples were collected (blocks) in the layers from 0.00 to 0.05, 0.05 to 0.10 and from 0.10 to 0.20 m. Samples were also collected with structure preserved, with metal cylinders to determine the water retention curve, bulk density, total porosity, macroporosity and microporosity. In the same layers were sampled deformed for the determination of particle size, limits of plasticity and liquidity and the chemical characterization, which was formed by analysis of organic carbon, acidity active, potential acidity, the saturation of Al3+, CTCpH7,0 and saturation bases. Clay activity was determined by the method of EMBRAPA and the Skempton. To measure a soil sorptivity, was used a micro tension infiltrometer. The hydrophobicity was evaluated by comparing values of water and ethanol sorptivity. PVAa, PVd, LVd and LVDf presented at different moistures the index of hydrophobicity and water-soil contact angle below the critical limit and were classified as slightly repellent. The VEo, CXe, GXd and SXe, showed high levels of hydrophobicity and water-contact angles in all layers in soil condition air dried soil. But the value of R decreased with increasing soil moisture and with a deeper profile. In subsurface layers, from the tension of 100 kPa was found that the index of hydrophobicity decreased and became close to 1. Except in the GXd, this showed a hydrophobicity index value above the critical limit at all moistures analyzed. Total porosity was positively correlated with the ethanol sorptivity, however, was not correlated with the water sorptivity. Hydrophobicity and water-soil contact angle showed negative correlation with organic matter content. The aggregate stability was not directly influenced by the hydrophobic compounds, no significant correlation was found between the geometric mean diameter and aggregate stability index with hydrophobicity and water-soil contact angle. The clay activity determined by the method of EMBRAPA showed high correlation with the occurrence of hydrophobicity in air dried soil. / A hidrofobicidade pode ser entendida como a repelência do solo à água, dificultando o molhamento do mesmo. Esse fenômeno está associado ao recobrimento das partículas do solo por substâncias orgânicas hidrofóbicas. A vegetação local pode contribuir com compostos orgânicos hidrofóbicos, via deposição ou por decomposição, porém a hidrofobicidade também é relacionada com a existência metabolitos de bactérias e microrganismos, incêndios, pH elevado, tipo de argilomineral e composição granulométrica do solo. O objetivo deste trabalho foi determinar a umidade crítica para a ocorrência da hidrofobicidade e avaliar sua relação com a resistência de agregados e com as propriedades químicas e físico-hídricas, em diferentes solos do sul do Brasil. As amostras de solo foram coletadas em diferentes locais do estado do Rio Grande do Sul, nos locais escolhidos a vegetação era constituída apenas de campo natural. Para a avaliação da sortividade e estabilidade de agregados, foram coletadas amostras indeformadas (blocos) nas camadas de 0,00 0,05; 0,05 0,10 e 0,10 0,20 m. Também foram coletadas amostras com estrutura preservada, com cilindros metálicos, para a determinação da curva de retenção de água, densidade do solo, porosidade total, macroporosidade e microporosidade. Nas mesmas camadas foram coletadas amostras deformadas para a determinação da composição granulométrica, limites de plasticidade e liquidez, e para a caracterização química, que se constituiu pelas análises de carbono orgânico, acidez ativa, acidez potencial, saturação por Al3+, CTCpH7,0 e saturação por bases. Foi determinada a atividade da argila pelo método da EMBRAPA e pelo de Skempton. Para medir a sortividade utilizou-se de um micro infiltrômetro de tensão. A hidrofobicidade foi avaliada comparando valores de sortividade da água e do etanol. O PVa, PVd, LVd e LVdf apresentaram, em diferentes umidades, o índice de hidrofobicidade e ângulo de contato água-solo inferiores ao limite crítico, sendo classificados como pouco repelentes. O VEo, CXe, GXd e SXE apresentaram elevado índice de hidrofobicidade e ângulos de contato água-solo em todas as camadas na condição de solo seco ao ar. Porém, o valor de R diminuiu com o aumento da umidade do solo e com o aprofundamento no perfil. Nas camadas subsuperficiais, a partir da tensão de 100 kPa verificou-se que o índice de hidrofobicidade decresceu e tornou-se próximo de 1, exceto no GXd, que apresentou um valor do índice de hidrofobicidade acima do limite crítico em todas as umidades analisadas. A porosidade total apresentou correlação positiva com a sortividade ao etanol, porém, não se correlacionou com a sortividade à água. A hidrofobicidade e o ângulo de contato água-solo apresentaram correlação negativa com o teor de matéria orgânica. A estabilidade dos agregados não foi diretamente influenciada pelos compostos hidrofóbicos, não sendo verificada correlação significativa entre o diâmetro médio geométrico e estabilidade de agregados com o índice de hidrofobicidade ou com o ângulo de contato água-solo. A atividade da argila determinada pelo método da EMBRAPA apresentou elevada correlação com a ocorrência de hidrofobicidade no solo seco ao ar.

De même degré d'importance que les paramètres de formulation, les conditions de consolidation sont des facteurs déterminants pour la durabilité des bétons conventionnels vibrés. Dans le cas des bétons autoplaçants (BAP), grâce à leur grande fluidité, la mise en place dans les coffrages a lieu par écoulement libre sous l'effet de leur poids propre. Leur consolidation se fait sans vibration grâce à leurs caractéristiques rhéologiques. Il est donc légitime de penser que, les caractéristiques rhéologiques des BAP peuvent avoir une influence importante sur les propriétés qui déterminent la durabilité. Cette thèse étudie les liens possibles entre les caractéristiques rhéologiques des BAP et leur durabilité vis-à-vis du transport des agents agressifs. Dix-sept formulations de BAP couvrant une large gamme de caractéristiques rhéologiques et se différenciant uniquement par leur dosage en adjuvants ont été étudiées à cet effet. Trois modèles rhéologiques classiques ont été mis en oeuvre pour la détermination des paramètres rhéologiques des bétons étudiés.L'essai de sorptivité et dans une moindre mesure l'essai de carbonatation accélérée ont été utilisés comme indicateur de durabilité vis-à-vis du transport des agents agressifs. La durabilité de la couche superficielle au contact respectivement avec le coffrage en bois et en PVC a été étudiée et les résultats ont été comparés à la durabilité du béton à cœur. Cette étude a été faite en tenant compte des échanges hydriques et de l'arrangement granulaire au droit du coffrage. D'autre part, l'étude de la durabilité de la couche superficielle dans des conditions de mise en place proches du chantier a été faite sur 6 poutres partiellement armées longues de 2 m ainsi que sur 3 bétons semi-autoplaçants légèrement vibrés.Les résultats montrent qu'il existe une corrélation forte entre la viscosité plastique du modèle Bingham modifié ou le coefficient de consistance du modèle Herschel-Bulkley et la sorptivité. Très probablement, la viscosité agit sur le volume relatif des pores capillaires de gros diamètres. L'étude spécifique de la couche superficielle a montré que sa sorptivité dépend du type de coffrage utilisé à cause des éventuels échanges hydriques opérés entre le béton et la surface du coffrage. De plus, l'arrangement granulaire au droit du coffrage est également influencé. Ainsi, la sorptivité de la couche superficielle au contact du PVC est proche mais inférieure à celle du béton à cœur. La sorptivité de la couche superficielle au contact du bois est significativement inférieure à celle de la couche superficielle au contact du PVC tout en restant corrélé avec la viscosité plastique du modèle Bingham modifié ou le coefficient de consistance du modèle Herschel-Bulkley. / Consolidation conditions are determining factors for the sustainability of conventional vibrated concrete as like as formulation parameters. In the case of self-consolidating concrete (SCC), due their fluidity, casting is done by free flow under the influence of their own weight. Consolidation in the forms is done without vibration due to their rheological characteristics. It is therefore reasonable to expect that the rheological characteristics of SCC would have a significant influence on the durability's properties. This thesis examines the possible links between the rheological characteristics of SCC and vis-à-vis durability's transport of aggressive agents. In total, Seventeen SCC mixtures covering a wide range of rheological properties were investigated. Three current rheological models were studied to determine the rheological parameters. In other hand, durability of cover concrete close of site conditions was studied on 6 partially reinforced beams and 3 semi-workable concrete vibrated slightly.Sorptivity test was used as indicator of vis-à-vis aggressive transport durability. The durability of the concrete cover layer in contact respectively with the wooden and PVC frame has been studied and the results were compared with the durability of interior bulk concrete. This study was made taking into account the exchange of water and aggregate arrangement against the formwork.Good correlation between initial plastic viscosity determined by the Bingham modified model or consistency coefficient determined by the Herschel-Bulkley model of SCC and the sorptivity measured during the first hours of testing is established. It is likely that the initial plastic viscosity or consistency coefficient has a marked influence on the volume of the largest capillary pores of concrete, which can significantly affect durability. The specific study of the concrete cover showed that its sorptivity depends on the type of formwork used because of water exchanges made between the concrete surface. Aggregate arrangement against the formwork was also modified. Sorptivity of the concrete cover of PVC is near but below that of the interior bulk concrete. Sorptivity of the concrete cover against wooden frame is significantly less than over of against PVC while being correlated with the plastic viscosity of modified Bingham or consistency coefficient of Herschel-Bulkley model.

Résumé : De même degré d’importance que les paramètres de formulation, les conditions de consolidation sont des facteurs déterminants pour la durabilité des bétons conventionnels vibrés. Dans le cas des bétons autoplaçants (BAP), grâce à leur grande fluidité, la mise en place dans les coffrages a lieu par écoulement libre sous l’effet de leur poids propre. Leur consolidation se fait sans vibration grâce à leurs caractéristiques rhéologiques. Il est donc légitime de penser que les caractéristiques rhéologiques des BAP peuvent avoir une influence importante sur les propriétés qui déterminent la durabilité. Cette thèse étudie les liens possibles entre les caractéristiques rhéologiques des BAP et leur durabilité vis-à-vis du transport des agents agressifs. Dix-sept formulations de BAP couvrant une large gamme de caractéristiques rhéologiques et se différenciant uniquement par leur dosage en adjuvants ont été étudiées à cet effet. Trois modèles rhéologiques classiques ont été mis en œuvre pour la détermination des paramètres rhéologiques des bétons étudiés. L’essai de sorptivité et dans une moindre mesure l’essai de carbonatation accélérée ont été utilisés comme indicateur de durabilité vis-à-vis du transport des agressifs. La durabilité de la couche superficielle au contact respectivement avec le coffrage en bois et en PVC a été étudiée et les résultats ont été comparés à la durabilité du béton à cœur. Cette étude a été faite en tenant compte des échanges hydriques et de l’arrangement granulaire au droit du coffrage. D’autre part, l’étude de la durabilité de la couche superficielle dans des conditions de mise en place proches du chantier a été faite sur 6 poutres partiellement armées longues de 2 m ainsi que sur 3 bétons semi-autoplaçants légèrement vibrés. Les résultats montrent qu’il existe une corrélation forte entre la viscosité plastique du modèle Bingham modifié ou le coefficient de consistance du modèle Herschel-Bulkley et la sorptivité. Très probablement, la viscosité agit sur le volume relatif des pores capillaires de gros diamètres. L’étude spécifique de la couche superficielle a montré que sa sorptivité dépend du type de coffrage utilisé à cause des éventuels échanges hydriques opérés entre le béton et la surface du coffrage. De plus, l’arrangement granulaire au droit du coffrage est également influencé. Ainsi, la sorptivité de la couche superficielle au contact du PVC est proche mais inférieure à celle du béton à cœur. La sorptivité de la couche superficielle au contact du bois est significativement inférieure à celle de la couche superficielle au contact du PVC tout en restant corrélé avec la viscosité plastique du modèle Bingham modifié ou le coefficient de consistance du modèle Herschel-Bulkley. / Abstract : Consolidation conditions are determining factors for the sustainability of conventional vibrated concrete as like as formulation parameters. In the case of self-consolidating concrete (SCC), due to their fluidity, casting is done by free flow under the influence of their own weight. Consolidation in the forms is done without vibration due to their rheological characteristics. It is therefore reasonable to expect that the rheological characteristics of SCC would have a significant influence on the durability’s properties. This thesis examines the possible links between the rheological characteristics of SCC and durability’s transport of aggressive agents. In total, seventeen SCC mixtures covering a wide range of rheological properties were investigated. Three current rheological models were studied to determine the rheological parameters. In other hand, durability of cover concrete close to site conditions was studied on 6 partially reinforced beams and 3 semiworkable concrete vibrated slightly. Sorptivity test was used as indicator of aggressive transport durability. The durability of the concrete cover layer in contact respectively with the wooden and PVC frame has been studied and the results were compared with the durability of interior bulk concrete. This study was made taking into account the exchange of water and aggregate arrangement against the formwork. Good correlation between initial plastic viscosity determined by the Bingham modified model or consistency coefficient determined by the Herschel-Bulkley model of SCC and the sorptivity measured during the first hours of testing is established. It is likely that the initial plastic viscosity or consistency coefficient has a marked influence on the volume of the largest capillary pores of concrete, which can significantly affect durability. The specific study of the concrete cover showed that its sorptivity depends on the type of formwork used because of water exchanges made between the concrete surface. Aggregate arrangement against the formwork was also modified. Sorptivity of the concrete cover of PVC is near but below that of the interior bulk concrete. Sorptivity of the concrete cover against wooden frame is significantly less than over of against PVC while being correlated with the plastic viscosity of modified Bingham or consistency coefficient of HerschelBulkley model.

Preplaced aggregate concrete (PAC) is produced by grouting high workability cement based grouts among the voids of compacted coarse aggregate mass. Because of its low shrinkage, PAC has been used for many repair jobs like; tunnel lines, dams and bridge piers. Moreover, it has been used for underwater construction. Grout has a major effect on the properties of produced PAC and well defined grout controls the properties of resulted PAC. The effect of types and amount of powder materials, admixtures, sand and water content on the properties of fresh and hardened grout for the production of PAC have been investigated. Tests on hardened grout and PAC properties have also been carried out to investigate the most important effects. A correlation between hardened properties of grout and PAC has also been analyzed. Grout rheology using four different gradation sands at two different cement-sand and at different w/c ratios ratios has been identified experimentally; no added chemical admixtures or mineral additives had first employed, then superplasticizer (SP) was added at 2% and 1%, and finally a combination of 1% SP and pulverized fuel ash (Pfa) at 20% of the cement weight was employed for all mixes. Grout tests have included two point workability tests by the Viskomat NT, flow time funnel test, Colcrete flow meter test, and water bleeding test. After that, eighteen grout mixes with high workability were produced using three different sands at three w/c ratios and two c/s ratios with 1% SP and Pfa at 20% of the cement weight were designed. Eighteen hardened grout and PAC then produced and their compressive strength and sorptivity were tested. Grout rheology can be defined by the rheology of cement paste employed and the internal distance between sand particles. The effect of sand surface texture on grout rheology is important at very low internal distances. Fresh grout yield stress is the most important property which gives the same degree of sensitivity for all grouts regardless the material type and content used in the mix. There are strong relations between compressive strength of grout and PAC, but less correlation between them in sorptivity test because of the effect high quantity of coarse aggregate of PAC. Sorptivity of PAC is low comparing with different kinds of concrete suggesting its advantage for underwater construction.

This thesis describes research carried out to investigate techniques for (i) rapidly assessing the reactivity of fly ash; and (ii) evaluating its interaction with air-entraining admixtures (AEAs), both with regard to use in concrete. The materials considered for the project included, 54 fly ashes from 8 UK sources, and an additional three materials from Bangladesh, covering a range of fineness, loss-on-ignition (LOI) and production conditions (run-of-station, carbon removed, air-classified, co-combustion, oxy-fuel technology); Portland Cements (PCs) from five UK sources with various properties (strength classes 32.5 R, 42.5 N and 52.5 N); laboratory grade hydrated and quick limes; and three commercial AEAs and a standard laboratory grade reagent (surfactant). The research examining fly ash reactivity considered activity index tests to BS EN 450 (BSI, 2005c) as the reference and investigated tests covering fly ash properties/providing measures of fly ash behaviour to rapidly assess this. These included (i) fly ash fineness (45 µm sieve residue, or LASER particle size distribution (PSD) parameters), LOI and flow properties; (ii) accelerated curing of PC and lime-based mortars (iii) lime consumption by fly ash when combined with PC in paste or suspension (Frattini) or from a saturated lime solution; (iv) various measures of fly ash chemical composition (based on oxide/mineralogical analysis); and (v) a quicklime slaking test. The test results were validated by strength tests with 100 mm concrete cube. Results of the above indicated good correlations between fly ash fineness, mortar flow/water requirement and (pozzolanic) activity index (standard or accelerated curing). However, fly ash reactivity and fresh properties appeared to be influenced by the properties of the test PC (e.g. chemical composition and fineness) and there is a need to take this into account during assessment. Generally, finer fly ashes gave better flow; however, there is an optimum fineness (d90 ~40 µm) for best performance, and which is similar to the fineness of the test PC. Strong correlations between the accelerated and standard cured PC-based mortar indicate the latter can be used to estimate the former taking account of the fly ash properties. In view of eliminating the effect of PC properties on reactivity, mortar tests with laboratory grade hydrated lime suggested potential for this. However, for better assessment, this approach requires further work to address issues relating to slower rates of strength gain and increased time requirements, although high temperature conditions were used for curing. Measuring Ca(OH)2 consumption from fly ash/PC paste or suspension agreed with the behaviour in mortar, but needs special instruments (e.g. TGA or XRF). A similar approach with saturated lime did not work well, despite several measures being taken to try and improve this. The oxide and mineralogical analysis results of fly ash did not give good correlations with activity index, but improved when a factor combining them with fineness was considered. The test results were validated in concrete and with air-classified fly ashes from single sources which gave clear trend/behaviour. The lime slaking test was found to be ineffective for identifying fly ash reactivity. The reactivity assessment results were validated by carrying out concrete strength tests. In general, more consistent trends were obtained for fly ash from single source as noted with mortar earlier. Methods adopted/developed to assess the interaction of fly ash with AEA included (i) the foam index test; (ii) acid blue 80 (AB80) dye adsorption test (spectroscopic method); and (iii) methylene blue test. High variability in foam index test results between different operators were noted, which reflected differences in the degree of shaking applied and difficulties in identification of the test end point. Adoption of an automatic shaker and determination of suitable test conditions reduced this by more than 50%. Reliable test procedures were also established for the AB80 dye adsorption method. The results obtained from these tests gave very good correlations with fly ash specific surface area and the AEA dose required (both with commercial AEAs and standard reagent) for achieving target air contents in mortar and concrete. The methylene blue dye test also gave good correlations with these parameters, but was less effective for low LOI fly ashes. Between laboratory tests were carried out at three UKQAA members and considered, LOI, fineness (45 µm sieve and LASER PSD), and activity index. The results gave good agreement with those obtained at the Concrete Technology Unit for this work and again emphasized the role of fly ash fineness on its reactivity. Overall, fly ash fineness was found to be the best means of rapidly assessing its reactivity. Some of the other methods considered gave promising behaviour but require further refinements. Therefore, it is suggested that in addition to 45 µm sieve residue, other types of fineness measurement (e.g. sub 10 µm quantities, d50 and d90) can be considered suitable alternatives to activity index. Similarly, foam index tests with the automatic shaker or the AB80 test method could both be used as fly ash physical requirement tests, or in production control for air-entrained concrete.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Soil hydrophobicity can be conceptually defined as soil repellency to water and is associated with the covering of soil particles by hydrophobic organic substances which interact with mineral particles and pores in a complex way, making soil wetting difficult. The objectives of this study were to: (i) determine the biochemical composition of vegetation, physical and chemical properties of soil organic matter fractions and their relationships to the occurrence and degree of soil hydrophobicity; (ii) analyze the effects of hydrophobic compounds at different intensities on sorptivity and water retention curve; (iii) measure and monitor the effects of variation of soil temperature and water content on the variability of the degree of soil hydrophobicity during a drying cycle. Soil samples were collected from different soil classes in the Rio Grande do Sul and Santa Catarina States, southern Brazil. From the 0-5, 5-10 and 10-15 cm soil layers, undisturbed samples (in blocks) were collected for the determination of sorptivity while preserved samples were collected using core samplers (volume of 47 cm³) for the evaluation of water retention curve, soil bulk density, total porosity, macroporosity and microporosity. From these layers, deformed samples were also collected for soil chemical and physical characterization. However, part of the samples used for the determination of water retention curves were previously subjected to sequential chemical extraction with acetone and a solution of isopropanol:ammonia to remove hydrophobic compounds. Soil carbon analysis consisted of determination of total organic carbon, physical (> 53μm and <53μm), and chemical (fulvic and humic acids and humin) fractions. Water and ethanol sorptivity was determined using tension micro-infiltrometer. Hydrophobicity was evaluated by comparing water and ethanol sorptivity values and soil-water contact angle was calculated from the hydrophobicity index. The effect of temperature was measured using PVC cylinder (785 cm³) constructed with disturbed samples from different soils, wetted and dried under different temperatures (20, 45 and 70 °C) and the hydrophobicity was determined using the water droplet penetration time method. Hydrophobicity had an intimate relationship with soil organic carbon content, mainly organic compounds accumulated in physical fractions <53 μm and chemical fraction humin, indicating that hydrophobic compounds are highly recalcitrant and are strongly associated with silt and clay fractions, forming stable organo-mineral complexes, and at the same time, covering all or part of surfaces of mineral particles or aggregates. The existence of these hydrophobic compounds caused changes in sorptivity and soil-water contact angle, directly affecting capillary and soil water retention curve, and reduced the volume of water retained at lower potentials. The heating of the soil at temperatures at or below 45 °C did not alter the intensity of hydrophobicity but there were changes when soil temperature exceeded 70 °C or when the soil moisture was drastically reduced. / A hidrofobicidade do solo pode ser conceitualmente definida como a repelência do solo à água e está associada ao recobrimento das partículas do solo por substâncias orgânicas hidrofóbicas, que interagem de forma complexa com os poros e partículas minerais, dificultando o molhamento do solo. Os objetivos deste trabalho foram: (i) determinar a composição bioquímica da vegetação, das frações físicas e químicas da matéria orgânica e suas relações com a ocorrência e grau de hidrofobicidade; (ii) analisar os efeitos dos compostos hidrofóbicos em diferentes intensidades na sortividade e na curva de retenção de água; (iii) avaliar e monitorar os efeitos da variação da temperatura e do conteúdo de água na variação do grau de hidrofobicidade do solo ao longo de um ciclo de secagem. Foram coletadas amostras de solo de diferentes classes de solos existentes no Estado do Rio Grande do Sul e Santa Catarina. Nas camadas de 0 5, 5 10 e 10 15 cm foram coletadas amostras indeformadas (blocos), para a avaliação da sortividade e amostras com estrutura preservada, com cilindros metálicos (47 cm³), para a determinação da curva de retenção de água, densidade do solo, porosidade total, macroporosidade e microporosidade. Nessas camadas também foram coletadas amostras deformadas para a caracterização química e física dos solos. No entanto, parte das amostras utilizadas na determinação da curva de retenção de água foram previamente submetidas a uma extração química sequencial com acetona e uma solução de isopropanol:amônia para remoção dos compostos hidrofóbicos. A análise do carbono constou da determinação do carbono orgânico total e da determinação das frações físicas (>53μm e <53μm) e químicas (Ácidos Fúlvicos, Ácidos Húmicos e Humina). A sortividade da água e do etanol foram determinadas com um micro-infiltrômetro de tensão. A hidrofobicidade foi avaliada comparando valores de sortividade da água e do etanol. O ângulo de contato água-solo foi calculado a partir do índice de hidrofobicidade. O efeito da temperatura foi mensurado em cilindros de PVC (785 cm³) construídos com amostras desagregadas dos diferentes solos. As amostras foram umedecidas e secas sob diferentes temperaturas (20, 45 e 70°C), sendo a hidrofobicidade determinada simultaneamente pelo método do tempo de penetração da gota de água. A hidrofobicidade apresentou uma íntima relação com o teor de carbono orgânico do solo, principalmente com os compostos orgânicos acumulados na fração física <53 μm e na fração química da Humina, indicando que os compostos hidrofóbicos provavelmente apresentam elevada recalcitrância e estão fortemente associados às frações silte e argila, formando complexos organo-minerais estáveis, ao mesmo tempo em que recobrem total ou parcialmente a superfície de agregados ou partículas minerais. A existência desses compostos hidrófobos causa alterações na sortividade e no ângulo de contato água-solo, afetando diretamente a capilaridade e a curva de retenção do solo, reduzindo o volume de água retido nos menores potenciais. O aquecimento do solo à temperaturas inferiores a 45 °C não causa modificações na intensidade da hidrofobicidade, que é alterada somente quando a temperatura do solo excede a 70 °C ou quando a umidade do solo é acintosamente reduzida.