There are still research gaps regarding the effects of key parameters such as water-to-cementitious materials ratio (w/cm), type of binder and pore structure characteristics on the response of concrete to special forms of sulfate attack: physical salt attack (PSA) and thaumasite sulfate attack (TSA). Hence, this study aims at developing an innovative type of concrete: nano-modified fly ash concrete, incorporating various dosages of nano-silica (NS) or nano-alumina (NA) and fly ash, and explores its efficiency in resisting various forms of sulfate attack.

Concrete structures are often exposed to sulfates, which are typically found in groundwater and soils, in agricultural run-off, in industrial facilities, and in other source points. These sulfates may attack concrete and significantly shorten the service life of concrete due to reactions between sulfate ions and concrete constituents. These reactions form expansive and deleterious compounds that lead to cracking and spalling of the concrete. This reaction is a function of the sulfate solution but also the physical, chemical, and mineralogical properties of the cement and supplemental cementitious materials (SCMs). It is widely understood that the addition of some fly ashes, by-products of coal combustion power plants, improve the sulfate resistance of the concrete but some fly ash additions actually reduce the sulfate resistance. This project aims to understand this relationship between fly ash and sulfate resistance. Using sulfate testing results on mortar previously obtained at The University of Texas at Austin, this research evaluated the mineralogical, chemical, and physical characteristics of fly ash and attempted to link these measured characteristics (or combinations thereof) to sulfate resistance of concrete. / text

The objective of this investigation was to assess the influence of the SO3 content on the durability and strength of portland cement. Four portland cements were used in this study. The cements had a variable tricalcium silicate, tricalcium aluminate, and alkali contents, as well as differences in the amount and form of calcium sulfates. The SO3 content of the cements was increased by replacing part of the cement by gypsum according to ASTM C 452-95. Mortar bars and cubes were prepared for the as-received as well as for the cements with an SO3 content of 3.0% and 3.6%. The durability of the as-received and doped cements was determined by measuring the length change of the mortar bars that were exposed to sodium sulfate environment. The compressive strength of the mortar cubes prepared for the same mixes was measured at different ages for sets of cubes cured both in sodium sulfate solution and in saturated lime solution. It was concluded at the end of this study that there is an optimum SO3 content for the lowest expansion that is different from that determined for the highest compressive strength. Optimum values also differed from one cement to another and from one age to another for the same cement. The results also indicate the dependence of SO3 content on tricalcium aluminate and alkali content of cements. In addition, for all cements examined in this study with alkali content of less than 0.60%, increasing the SO3 content above 3.0% had negative effects on durability assessed by strength or expansion measurements. For the cement with highest alkali and tricalcium aluminate content, increasing the SO3 content from 3.0% to 3.6% delayed the onset of strength drop; however, at 360 days the strength drop experienced by both doping levels was the same.

In an effort to make structures more sustainable and durable, supplementary cementitious materials are often used to replace cement. Ground granulated blast furnace slag, for instance, is an industrial by-product of iron refinement and is frequently used in concrete mixture design to not only reduce cost, but also increase later-age strength as well as durability. However, published literature indicates that slags with a high alumina content may have a detrimental effect when concrete is exposed to a sulfate environment. ASTM standard C989 does not suggest any information or guidelines regarding using slags with an alumina content between 11-18%. Therefore, the objective of this study was to fill in the gap of this standard by studying slags of variable alumina content as high as 16 percent. This study presents data collected for compressive strengths of mortar cubes exposed to lime and 5 percent sodium sulfate solution at ages of 7, 28, 91, and 182 days from the date of mixing as well as expansion data for mortar bar specimens exposed to 5 percent sodium sulfate solution up to 120 days. Slag replacement levels used here were 0, 30, 50, and 70%. Mortar bar specimens showing deterioration were analyzed using x-ray diffraction coupled with Rietveld refinement to assess the mechanism of deterioration. Cubes were stored in lime and sulfate solutions abiding by ASTM C1012 in order to analyze the resistance to sulfate attack. Sulfate resistance was measured in terms of decalcification of the CSH gel as well as expansion. The results suggest using high alumina slags at a low percentage adversely affects sulfate resistance since the acquired strength at 182 days fell below that of 28 day strength, which is often used in the industry as the parameter which constitutes whether a mixture is adequate. It was also seen that increasing alumina content of the slag resulted in increased expansion. X-ray diffraction analysis indicates that the mechanism of deterioration, of the control as well as the blended mortar, is due to secondary gypsum and secondary ettringite formation. Therefore, it is recommended that slags having a high alumina content should be further analyzed in laboratory tests to examine their performance especially if concrete will be subjected to a sulfate environment during its service life.

En los últimos años, el análisis numérico de problemas acoplados, como los procesos de degradación de materiales y estructuras relacionados con los efectos medioambientales, ha cobrado especial importancia en la comunidad científica de la mecánica del hormigón. Problemas de este tipo son por ejemplo el ataque químico, el efecto de altas temperaturas o la retracción por secado.Tradicionalmente, los análisis acoplados existentes en la literatura se han realizado a nivel macroscópico, considerando el material como un medio continuo y homogéneo. Sin embargo, es bien conocido que el origen de la degradación observada a nivel macroscópico, a menudo es debida a la interacción entre los áridos y el mortero, sobre todo cuando se dan cambios de volumen diferenciales entre los dos componentes. Esta es la razón por la que el análisis mesomecánico está emergiendo como una herramienta potente para estudios de materiales heterogéneos, aunque actualmente existen escasos modelos numéricos capaces de simular un problema acoplado a esta escala de observación.En esta tesis, la aplicabilidad del modelo meso-mecánico de elementos finitos, desarrollado en el seno del grupo de investigación durante los últimos quince años, se extiende al análisis de problemas acoplados higro-mecánicos y químico-mecánicos, con el fin de estudiar la retracción por secado y el ataque sulfático externo en muestras de hormigón. La generación numérica de mesogeometrías y mallas de elementos finitos con los áridos de mayor tamaño rodeados de la fase mortero se consigue mediante la teoría de Voronoï/Delaunay Adicionalmente, con el fin de simular las principales trayectorias de fisuración, se insertan a priori elementos junta de espesor nulo, equipados con una ley constitutiva basada en la mecánica de fractura no lineal, a lo largo de todos los contactos entre árido y matriz, y también en algunas líneas matriz-matriz.La aportación principal de esta tesis es, conjuntamente con la realización de análisis acoplados sobre una representación mesoestructural del material, la simulación no solo de la formación y propagación de fisuras, sino también la consideración explícita de la influencia de éstas en el proceso de difusión.Los cálculos numéricos se realizan mediante el uso de los códigos de elementos finitos DRAC y DRACFLOW, previamente desarrollados en el seno del grupo de investigación, y acoplados mediante una estrategia staggered. Las simula-ciones realizadas abarcan, entre otros aspectos, la evaluación del compor-tamiento acoplado, el ajuste de parámetros del modelo con resultados experimentales disponibles en la bibliografía, diferentes estudios del efecto de los áridos en la microfisuración inducida por el secado y las expansiones debidas al ataque sulfático, así como el efecto simultáneo de los procesos gobernados por difusión y cargas de origen mecánico. Los resultados obtenidos concuerdan con observaciones experimentales de la fisuración, el fenómeno de spalling y la evolución de las deformaciones, y muestran la capacidad del modelo para ser utilizado en el estudio de problemas acoplados en los que la naturaleza heterogénea y cuasi-frágil del material tiene un papel predominante.

Numerous agents and mechanisms are known to affect the durability of a concrete structure during its service life. Examples include freezing and thawing, corrosion of reinforcing steel, alkali-aggregate reactions, sulfate attack, carbonation, and leaching by neutral or acidic ground waters. Among these, external sulfate attack was first identified in 1908, and led to the discovery of sulfate resistant Portland cement (SRPC). Besides SRPC, another way of coping with the problem of sulfate attack is the use of pozzolans either as an admixture to concrete or in the form of blended cements This study presents an investigation on the sulfate resistance of blended cements containing different amounts of natural pozzolan and/or low-lime fly ash compared to ordinary Portland cement and sulfate resistant Portland cement. Within the scope of this study, an ordinary Portland cement (OPC) and five different blended cements were produced with different proportions of clinker, natural pozzolan, low-lime fly ash and limestone. For comparison, a sulfate resistant Portland cement (SRPC) with a different clinker was also obtained. For each cement, two different mixtures with the water/cement (w/c) ratios of 0.485 and 0.560 were prepared in order to observe the effect of permeability controlled by water/cement ratio. The performance of cements was observed by exposing the prepared 25x25x285 mm prismatic mortar specimens to 5% Na2SO4 solution for 78 weeks and 50mm cubic specimens for 52 weeks. Relative deterioration of the specimens was determined by length, density and ultrasonic pulse velocity change, and strength examination at different ages. It was concluded that depending on the amount and effectiveness of the mineral additives, blended cements were considered to be effective for moderate or high sulfate environments. Moreover, the cement chemistry and w/c ratio of mortars were the two parameters affecting the performance of mortars against an attack. As a result of this experimental study it was found out that time to failure is decreasing with the increasing w/c ratio and the effect of w/c ratio was more important for low sulfate resistant cements with higher C3A amounts when compared to high sulfate resistant cements with lower C3A amounts.

Les bétons autoplaçants (BAP) se distinguent des bétons ordinaires (BO) ou vibrés, par leurs propriétés à l’état frais. Ils sont capables de s’écouler sous leur propre poids, quelque soit le confinement du milieu, et restent homogènes au cours de l’écoulement. Pour parvenir à ce cahier de charge, les BAP sont formulés différemment des BO. En général, ils possèdent un même dosage en ciment et en eau que les BO ainsi qu’un volume de sable assez proche. L’apport de la pâte (ciment + eau + adition) est privilégié au détriment des gravillons. L’objectif du travail de recherche présenté dans cette thèse porte sur l’effet de l’attaque sulfatique externe sur les bétons autoplaçants. Pour cela quatre types de bétons autoplaçants à base de ciments, de granulats concassés et d’adjuvants ont été confectionnés. Chaque béton a subit quatre protocoles différents d’attaque sulfatique externe à savoir l’immersion totale, l’immersion-séchage à 105°C, l’immersion-séchage à 60°C et l’exposition des éprouvettes à un brouillard salin. Ces ambiances visent à reproduire de manière accélérée les différentes sources de pollutions capables de générer des attaques sulfatiques externes. A terme de six mois d’exposition des échantillons en béton et en mortier, il a été possible de dresser les principales conclusions reposant sur des études macroscopiques et microscopiques des échantillons testés. Trois comportements différents des bétons ont pu êtres distingués : bétons résistent à l’attaque sulfatique externe, bétons endommagés suite à cette attaque et bétons endommagés par la précipitation des sels et non par une réaction sulfatique externe. En conclusion, cette recherche a permis d’identifier les protocoles accélérés les plus adaptés aux études de la durabilité des bétons et de classer les bétons autoplaçants confectionnés avec des granulats concassés selon leurs résistants aux attaques sulfatiques externes (pollutions industrielles ou construction sur des sols gypseux). / The aim of the presented research in this thesis focuses on the effect of external sulfate attack on the durability of self-compacting concrete. For that, four types of concretes based on Aigerian cement, crushed aggregates and plasticizers have been made. Each type of concrete has undergone four different protocols of external sulfate attack which are the total immersion, the immersion 1drying at 105 CC, the immersion 1drying at 60 CC and the exposure of specimens to a salt spray. These environments are designed to reproduce the different accelerated sources of pollution that can generate external sulfate attack. A term of six months of exposure of the samples in concrete and mortar, it was possible to draw the main conclusions based on macroscopic and microscopie studies of the sam pies tested. Three different behaviors of concrete have been distinguished: concrete resistant to external sulfate attack, concrete damaged after tis attack and concrete damaged by salt precipitation and not by external sulfate reaction.

L’attaque sulfatique externe est un processus de dégradation au cours duquel les propriétés mécaniques et la composition chimique d’un matériau cimentaire vont être fortement affectées par la pénétration de sulfates en solution. La réponse à ce problème repose en partie sur la maîtrise de la composition des ciments. A ce titre, la capacité d’un ciment CEM I à former de l’ettringite lors de l’ASE et donc, par extension, d’être considéré comme résistant ou pas face aux sulfates, peut être évaluée par la formule de Sadran qui prend en compte les taux du C3A et C3S. Nous avons mis en place une méthode de caractérisation pour analyser le comportement de ciments CEM I de différents indices de Sadran. L’analyse s’appuie sur une méthodologie permettant une caractérisation globale de la dégradation. La teneur en C3A plus que l’indice de Sadran détermine le type de dégradation d’un ciment. La méthode de suivi et d’analyse utilisée sur les CEM I a été appliquée pour l’étude de ciments composés CEM V afin de comparer leur comportement avec celui de ciments résistants aux sulfates. Un essai incluant un pré conditionnement thermique, pour l’accélération de la dégradation, a été choisi et les résultats obtenus ont été comparés à ceux de l’essai développé précédemment au GeM. Il a été démontré que le pré conditionnement thermique ne permet pas une accélération significative de la dégradation. De plus, le séchage mis en place modifie la microstructure des échantillons de mortiers CEM V ; il ralentit la progression des sulfates et donc allonge le temps de réponse. L’adsorption des sulfates par les C-S-H fait l’objet de la dernière partie de cette thèse, tout en ouvrant sur des perspectives. / During external sulphate attack the mechanical properties and the chemical composition of a cementitious material are strongly affected by the penetration of sulphate in solution. The answer to this problem lies partly in the control of the composition of the cements. The ability of CEM I cements to form ettringite during external sulfate attack and therefore to be considered resistant, or not, to sulphates, can be evaluated by the formula of Sadran which considers the rates of C3A and C3S. We set up a characterization method to analyze the behavior of CEM I cements with different Sadran indexes. Two degradation mechanisms were observed, marked by either expansive phase precipitation or leaching. The monitoring and analysis method used on the CEM I cements has been applied to the study of CEM V blended cements in order to compare their behavior with that of sulphate resistant cements. A test including a thermal pre-conditioning was chosen and the results obtained were compared with those of the test previously developed at GeM. It has been shown that thermal pre-conditioning does not allow a significant acceleration of degradation. The adsorption of sulphates by C-S-H, as well as the loss of calcium, is the subject of the last part of this thesis, while opening up perspectives. The first results showed that sulphate fixation by C-S-H increases with the concentration of the sulphate solution.

The influence of tricalcium silicate content of cement on concrete durability has long been a topic of discussion in the literature. The objective of this investigation was to determine whether increasing tricalcium silicate content of cement has a negative effect on concrete sulfate durability. Several mill certificates were reviewed to select cements with similar tricalcium aluminate content and variable tricalcium silicate contents. Cements selected for this study were randomly labeled as cements C, D, D2, E, and P. The following properties were assessed for the as-received cements: Blaine fineness, particle size distribution, chemical oxide content, and mineralogical content. Three different methods were employed to determine the mineralogical composition of the as-received cements: Bogue calculation, internal standard method, and Rietveld refinement analysis. Despite the attempt to select cements with similar composition, it was determined that the as-received cements had compositional differences other than their C3S content. These cements had a variable tricalcium aluminate and alkali content, as well as differences in the amount and form of calcium sulfates. In order to eliminate these variances, doped cements were prepared by increasing the C3S content of the as received cements to 69 % by Bogue calculation. Durability of as-received cements and doped cements was assessed through several measurements including length change, compressive strength, and phase transformation in sodium sulfate solution. For as-received cements, compressive strength of mortar cubes stored in saturated lime solution was evaluated as well. Semiquantitative x-ray diffraction analysis and scanning electron microscopy observations were performed on mortar bars to evaluate the relative amounts and morphology of the hydrated phases. It was concluded at the end of this study that cements with high tricalcium silicate content generally have poor durability in sodium sulfate environment. All the cements experienced higher expansion with increased C3S content. High C3S content combinedwith high C3A content was particularly detrimental to mortar resistance to sodium sulfate attack.

Fosfogesso é um resíduo sólido da produção de ácido fosfórico pelas indústrias de fertilizantes. A produção anual deste material no mundo é de cerca de 180 milhões de toneladas, e isto causa problemas com a sua armazenagem. O fosfogesso tem sido estudado para uso como material de construção de bases e sub-bases de pavimentos. O fosfogesso tem pouca durabilidade frente à ação da água quando sujeito somente à estabilização mecânica. O cimento Portland é então adicionado ao fosfogesso, resultando em misturas mais estáveis. A reação do aluminato tricálcico contido no cimento e dos sulfatos presentes no fosfogesso poderia conduzir à formação de cristais de etringita e à expansão subseqüente. O objetivo desta pesquisa é avaliar a influência do tipo de cimento na expansibilidade das misturas de fosfogesso e cimento para uso na construção de pavimentos. Analisou-se o comportamento expansivo de corpos de prova compactados com diferentes proporções de fosfogesso e cimento, variando-se o tipo de cimento, energia de compactação e período de cura. Para todos os cimentos usados nesta pesquisa, considerando-se o período de 84 dias de cura, a maior parte da expansão ocorreu nos primeiros 28 dias. A influência do tipo de cimento na expansão das misturas de fosfogesso e cimento é significante, mas o teor de aluminato tricálcico não é a única explicação para o comportamento de expansão observado neste estudo, visto que os resultados experimentais indicam que quantidades crescentes de aluminato tricálcico conduzem a menores expansões, fato que contraria a expectativa inicial desta pesquisa. / Phosphogypsum is a solid by-product resulting from the phosphoric acid process for manufacturing fertilizers. The annual worldwide production of this material is about 180 million de tons and it causes problems with its disposal. The phosphogypsum has been studied for use in pavement base and sub-base materials. Phosphogypsum has poor durability when subjected to mechanical stabilization only in wet conditions. The addition of stabilizing materials, such as Portland cement, is one method of overcoming this deficiency. The chemical reaction between tricalcium aluminate present in Portland cement and sulfate ions supplied by phosphogypsum could lead to the formation of ettringite and subsequent expansion. The objective of this research is to evaluate the influence of Portland cement type on the expansion of cement-stabilized phosphogypsum mixtures for use as pavement construction. The expansion behavior was analyzed through compacted specimens composed by different phosphogypsum and cement proportions, varying the cement type, compaction energy and curing period. For all cements used in this research, most of expansion occurred within the first 28 days in relation to the 84 days of curing. There is a significant influence of cement type on the expansion of the cement-stabilized phosphogypsum mixtures, but the aluminate tricalcium content is not the only explanation for the expansion behavior observed in this study. The experimental results show that an increasing amount of tricalcium aluminate yields lower expansion, fact that thwarts the initial expectation of this research.