Fly ash has been used extensively to control deleterious alkali-silica reaction in concrete. The majority of fly ashes can be used to control ASR induced expansion. Fly ashes with high CaO contents are less effective at reducing expansion and fly ashes with high alkali contents can be counter active. Class C fly ashes are less effective at reducing the pH of the pore solution because they are less pozzolanic. The pozzolanic reaction in Class F fly ashes enhances the ability for the hydration products to bind alkalis. This prevents the availability of these alkalis for ASR. This project aims to characterize fly ash in a way that best predicts how it will perform in concrete with an emphasis on ASR. Fly ashes with a variety of chemical compositions were evaluated using a range of analytical and characterization techniques. Research data from several universities were used to correlate their long term data with this project’s accelerated tests. This research aimed at evaluating the mineralogical, chemical, and physical characteristics that most affect the ability of a given fly ash to prevent ASR-induced expansion and cracking. / text

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This thesis broadly addresses the issue of materials sustainability in the production of Portland cement concrete. Two methods are presented, both aimed at achieving more sustainable concrete through the use of waste and recycled materials. The first method involves utilizing reclaimed asphalt pavement (RAP) as an aggregate in structural concrete, and the second method involves utilizing waste quarry fines as partial replacement of Portland cement in concrete mixes. Many efforts have been made in recent years to justify the use of RAP aggregates in concrete. All previous efforts appear to unanimously report a reduction in concrete performance with varying proportions of RAP usage. The poor performance of RAP aggregates in concrete is attributed mainly to a larger, more porous interfacial transition zone (ITZ) and to the cohesive failure of the asphalt. It is hypothesized that the detrimental impact on the ITZ is attributable to organic compounds leached from the asphalt in the high pH pore solution. This study proves the presence of organic compounds in the pore solution and demonstrates that there is an apparent retardation of cement hydration. This study also attempted to pretreat the RAP in a sodium hydroxide (NaOH) solution to pre-leach the organic compounds. The pretreatment demonstrated that organic compounds were leached and that NaOH modified the asphalt surface chemistry. However, only a marginal improvement in compressive strength was observed by completing the pretreatment. Replacement of Portland cement by filler products is a practice aimed at reducing the carbon footprint of concrete, such as is common with Type IL Portland limestone cement. This study investigates the impact of replacing cement with seven different quarry fines materials. The quarry fines were used to replace cement at 5% to 20% by volume in either cement paste or mortar samples that were then analyzed for various physicochemical properties. It was found that all the quarry fines had detrimental impact on the hydration kinetics of cement pastes. The inclusion of quarry fines was also found to cause varying degrees of reduction in mortar compressive strength. While further analyses of the quarry fines are required, quarry fines 2, 5 and 7 did display encouraging signs to suggest the potential for use as a filler material in blended cements. / Master of Science / This thesis broadly addresses the issue of sustainability in the cement and concrete industry. Sustainability is a significant problem for the cement and concrete industry due to the large amount of carbon emissions produced in the manufacturing process of Portland cement. One method to reduce the carbon footprint of concrete is to use recycled aggregates, and reclaimed asphalt pavement (RAP) is investigated in this thesis as a recycled aggregate option. Previous studies have shown that the use of RAP in concrete results in poor mechanical performance when compared to conventional concrete. In this thesis, the RAP was pretreated by soaking it in sodium hydroxide (NaOH) to see if any improvement is noted. It was determined that the pretreatment resulted in marginal improvements in concrete performance. Another method to reduce the carbon footprint of concrete is through the use of substitutions of Portland cement. In this thesis, quarry fines from around Virginia were investigated for potential as substitutive material. Quarry fines are a by-product from quarrying operations and are often considered a waste material because they have limited applications. This study analyzed the performance of cementitious materials prepared with various substitutive percentages of quarry fines and found that, in general, the inclusion of quarry fines resulted in a decrease of mechanical performance. In total, seven quarry fines were tested and only two showed potential for use as a substitution in Portland cement concrete. These two investigations are essential in reaching the goal of reducing the carbon footprint of the cement and concrete industry.

Three epoxy-coated reinforcing steel (ECR) types removed from job sites, one shipped directly from the coater's plant, three commercial corrosion inhibitors, and one ECR plus a corrosion inhibitor were evaluated as reinforcing steel corrosion protection systems against chloride induced corrosion. The three corrosion inhibitors were calcium nitrite, an aqueous mixture of esters and amines, and a mixture of alcohol and amine. The ECR was tested in two groups, 0% and 1% coating damage. Corrosion protection performance was evaluated by the amount of visually observed blister surface area, for the ECR, and corroded surface area, for the tested corrosion inhibitors. Results of the ECR testing demonstrated that coating debondment and corrosion of ECR is directly related to the amount of damage present in the coating, as well as coating thickness. For the bare steel tested with and without corrosion inhibitors, the results showed that corrosion increases with increasing chloride concentrations. Corrosion inhibition characteristics were demonstrated only by the calcium nitrite corrosion inhibitor. A corrosion protection evaluation test was developed for concrete corrosion inhibitor admixtures. The test solution is a simulated concrete pore water. Corrosion is accelerated by evaluating the temperature to field conditions of 40 C. The test consists of a 7 day pretreatment period followed by a 90 day test period. The corrosive sodium chloride is added to the solution containing the bare or epoxy-coated reinforcing steel specimens after the 7 day pretreatment period. In addition, the solution is periodically saturated with oxygen. / Master of Science

Corrosion of reinforcing steel in concrete exposed to chloride-laden environments is a well-known and documented phenomenon. The need for cost effective systems for protection against corrosion has become increasingly clear since the first observations of severe corrosion damage to interstate bridges in the 1960's. As one potential solution to the mounting problem of corrosion deterioration of structures, corrosion-inhibiting admixtures have been researched and introduced into service. This report conveys the results of a three-part laboratory study of corrosion inhibiting admixtures in concrete. The commercial corrosion inhibiting admixtures for concrete have been analyzed by three evaluation methods, including: • Conventional concrete corrosion cell prisms under ponding, • Black steel reinforcing bars immersed in simulated concrete pore solutions, • Electrochemical screening tests of special carbon steel specimens in electrochemical corrosion cells containing filtered cement slurry solution. The purposes of the study include: • Determining the influence of a series of commercially available corrosion inhibiting admixtures on general concrete handling, performance and durability properties not related to corrosion. • Determining the effectiveness of corrosion inhibiting admixtures for reduction or prevention of corrosion of reinforcing steel in concrete, relative to untreated systems, under laboratory conditions. • Conducting a short-term pore solution immersion test for inhibitor performance and relating the results to those of the more conventional long-term corrosion monitoring techniques that employ admixtures in reinforced concrete prisms. • Determining whether instantaneous electrochemical techniques can be applied in screening potential inhibitor admixtures. Concrete properties under test included air content, slump, heat of hydration, compressive strength, and electrical indication of chloride permeability. Monitoring of concrete prism specimens included macro-cell corrosion current, mixed-cell corrosion activity as indicated by linear polarization, and ancillary temperature, relative humidity, and chloride concentration documentation. Simulated pore solution specimens were analyzed on the basis of weight loss and surface area corroded as a function of chloride exposure. Electrochemical screening involved polarization resistance of steel in solution. Results include corrosion potential, polarization resistance and corrosion current density. / Master of Science

La durabilité des ouvrages en béton armé est étroitement liée à la composition des matériaux dont ils sont formés, et plus particulièrement aux propriétés de ces derniers. Cette durabilité est caractérisée par des indicateurs parmi lesquels se trouve le coefficient de diffusion des chlorures. Ceux-ci pénètrent le béton et interagissent avec les ions composant la solution interstitielle (contenue dans les pores) ainsi que les composants de la matrice cimentaire. Il existe peu de travaux dans la littérature qui décrivent toutes ces interactions ioniques de façon simultanée et encore moins leur prise en compte dans l’étude et la modélisation des transferts. Ce travail de thèse présente une étude des interactions multi-espèces se produisant lors du transfert des ions chlorure. Pour ce faire, l’évolution de la composition de la solution interstitielle, de plusieurs pâtes de ciment contenant diverses additions minérales, est étudiée. La solution interstitielle des pâtes de ciment est extraite suite à un essai de migration par pressage et analysée par chromatographie ionique. Par ailleurs, l’évolution de la microstructure de ces matériaux suite au transfert des chlorures est caractérisée par porosimétrie à intrusion de mercure (PIM) et microscopie électronique à balayage (MEB). Ceci a permis de mettre en évidence les modifications provoquées par la diffusion des ions chlorures. Dans un second temps, et afin de simuler le transfert des chlorures dans la matrice cimentaire, un modèle de transfert multi-espèces est développé. Dans ce sens, plusieurs modèles de transfert mono et multi-espèces, sous l’effet d’un champ électrique ou non, en régime stationnaire et transitoire ont été développés auparavant. L’objectif de cette partie numérique est d’étendre ces modèles à la prise en compte de l’ensemble des ions composant la solution interstitielle ainsi que leurs interactions multi-espèces conduisant à la précipitation de composés à base de chlore et à la dissolution des hydrates. La formulation mathématique des phénomènes étudiés est établie à partir de la loi de conservation de masse et les équations de la thermodynamique. Les conditions initiales et aux limites sont adaptées pour tenir compte à la fois de la composition chimique réelle de l’eau de mer et de celle de la solution interstitielle. Les résultats obtenus permettent de mettre en exergue l’effet de ces phénomènes sur la composition chimique de la solution interstitielle ainsi que sur le transfert des chlorures. / The durability of the reinforced concrete structures is closely related to the composition of their materials and, particularly to their properties. This durability is characterized by indicators among which we quote the diffusion coefficient of chlorides. These ionic species penetrate through the concrete and interact with the other species present in the interstitial solution (contained in concrete pores) as well as the cementitious matrix components. In the literature, there is a lake of data describing simultaneously these ionic interactions, especially their consideration in the study or modeling the ionic transport phenomena. This work focuses on the study of multispecies interactions that occur during the chloride transfer. To this purpose, the evolution of pore solutions chemistry of hardened cement pastes manufactured with different mineral additions is investigated. This solution is extracted, before and after migration test, using a specific press and analyzed by ionic chromatography. Furthermore, the microstructure evolution of these cement pastes is characterized by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). This allows highlighting the modification caused by chloride penetration. Secondly, for the modeling of chloride transport in cement based materials, a multispecies transport model is developed. In this context, several mono and multispecies transport models, under an electrical field or not, in transitory or steady state were developed previously. The aim of this numerical study is to extend these models in order to consider the ions present in the interstitial solution and their multispecies interactions leading to the precipitation of new chloride compound and the dissolution of some hydrates. The mathematical formulation of the phenomena studied was established from the principle of mass conservation and the thermodynamic equations. Initial and boundary conditions were adopted to take into account both the chemical composition of sea water and that of pore solution. Results highlight the effect of these phenomena on the pore solution chemistry and the chloride transport.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2016-10-03T11:31:01Z No. of bitstreams: 2 Dissertação - Plínio Ferreira Pires - 2016.pdf: 6131513 bytes, checksum: 8fa6643740293050fba973c250df0e54 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-10-03T11:31:21Z (GMT) No. of bitstreams: 2 Dissertação - Plínio Ferreira Pires - 2016.pdf: 6131513 bytes, checksum: 8fa6643740293050fba973c250df0e54 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2016-10-03T11:31:21Z (GMT). No. of bitstreams: 2 Dissertação - Plínio Ferreira Pires - 2016.pdf: 6131513 bytes, checksum: 8fa6643740293050fba973c250df0e54 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2016-07-27 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The carbonation phenomenon consists in a physicochemical process which reduces the alkalinity of concrete. Carbonation can destabilize the protective layer of the steel, leaving it susceptible to corrosion, which is one of the most significant and costly causes of deterioration in reinforced concrete. Accordingly, chemical analysis of the pore solution has been held for about 60 years, but few studies are focused on types of concrete containing mineral additions subjected to carbonation, due to the difficulty of obtaining the pore solution, given its structure densification under these conditions. Depending on the concrete composition, the natural carbonation process can take several years to present sufficient analyzable data, therefore, most of the studies on this topic use accelerated tests to simulate this phenomenon. However, even with full control of the laboratory environment, it is not possible to reproduce the randomness of the variables responsible for the degradation that occur in real situations. This study aims to evaluate the process of natural carbonation in 36 different types of concrete or analysis conditions, which cover a wide range of characteristics and properties of concrete that represent the various service situations of the structures, after about 14 years of exposure, in typical urban environment. The results are presented for types of concrete with and without mineral additions (silica fume, rice husk ash, metakaolin, fly ash and blast furnace slag); three water/binder (0.40, 0.55 and 0.70) and two curing conditions (dry-cured and moist-cured). The study was conducted by the application of simplified models of carbonation and statistical analysis on an extensive experimental database (over 2000 measurements) obtained by eight evaluations of carbonation carried at different ages, through 14 years of natural exposure prototypes of concrete beams. In addition, chemical analysis of pH, ionic strength and conductivity of the pore solution - obtained through innovative method - were conducted in both the carbonated layer and the non-carbonated layer of concrete. The results indicate that the empirically-analytical model proposed by Tuutti, has an excellent representativity of carbonated depth over time. The use of a coefficient of carbonation, from Tuutti’s model, calculated from early ages, can generate mistaken conclusions: underestimating the dry-cured concrete and overestimating the moist-cured concrete. In the overall analysis of the natural carbonation coefficients obtained by ANOVA showed that the water/binder ratio is the most significant factor, followed by curing type and, finally, the type of addition. The best performances as the carbonation are observed to the lower water/binder concretes, subjected to wet cure. Under the method used to obtain the pore solution, it was possible to compare the difference between the chemical properties of non-carbonated and carbonated layers of each type of concrete analyzed. / O fenômeno da carbonatação consiste em um processo físico-químico que leva à redução de alcalinidade do concreto. Isto pode desestabilizar a camada protetora do aço, deixando-o passível de corrosão, que é uma das mais importantes e onerosas causas de deterioração do concreto armado. Nesse sentido, a análise química da solução do poro tem sido realizada há cerca de 60 anos, contudo raros trabalhos focam em concretos submetidos à carbonatação contendo adições minerais, dada a dificuldade de se obter a solução devido à densificação na estrutura porosa nessas condições. Dependendo da composição do concreto, o processo de carbonatação natural pode levar vários anos para apresentar dados passíveis de análise, diante disso, a maioria dos estudos nesse tema utilizam ensaios acelerados para simular tal fenômeno, contudo, mesmo com todo controle do ambiente de laboratório, não se pode reproduzir a aleatoriedade das variáveis que ocorre em situações reais de degradação. Este trabalho tem como objetivo avaliar o processo de carbonatação natural em 36 diferentes concretos ou condições de análise, os quais cobrem uma ampla faixa de características e propriedades dos concretos, representando as mais diversas situações de serviço para as estruturas, após cerca de 14 anos de exposição, em ambiente típico urbano. São, portanto, apresentados resultados de concretos sem e com adições minerais (sílica ativa, cinza de casca de arroz, metacaulim, cinza volante e escória de alto-forno); três relações água/ligante (0,40; 0,55 e 0,70) e duas condições de cura (seca e úmida). O estudo se deu por meio de aplicações de modelos simplificados de carbonatação e análises estatísticas em um extenso banco de dados experimentais (mais de 2000 medidas) obtido por oito avaliações da frente de carbonatação realizadas em diferentes idades, durante 14 anos de exposição natural de protótipos de vigas de concreto. Foram realizadas também análises químicas de pH, força iônica e condutividade da solução do poro, obtida através de método inovador, tanto da camada carbonatada quanto da camada não carbonatada dos concretos. Os resultados indicam que o modelo empírico-analítico, proposto por Tuutti, possui excelente representatividade da profundidade carbonatada ao longo do tempo. A utilização de um coeficiente de carbonatação, do modelo de Tuutti, calculado a partir de idades iniciais pode gerar conclusões equivocadas: subestimando os concretos sem cura e superestimando os de cura úmida. A análise global dos coeficientes de carbonatação, obtidos pela ANOVA, demonstrou que a relação água/ligante é o fator mais significativo, seguido do tipo de cura e, por último, o tipo de adição. Os melhores desempenhos quanto à carbonatação são observados para os concretos de menor relação água/ligante, submetidos à cura úmida. De acordo com o método empregado para obtenção da solução do poro, foi possível comparar a diferença entre as propriedades químicas da camada não carbonatada e a carbonatada, para toda a família de concretos analisada.

An electrophoretic deposition (EPD) process of micro-quartz (MQ) powder is applied to carbon fibers (CFs) with the aim to enhance their interfacial bond to cementitious matrices and to investigate its influence on the microstructural and mechanical properties of the CFs itself. The electrophoretic mobility of the MQ particles with negative charge in aqueous media was confirmed by potential sweep experiments and zeta-potential measurements. High amounts of MQ were successfully deposited onto the fiber surface, as proven by scanning electron microscopy. Single-fiber tension tests and thermogravimetric analysis showed that EPD treatment had little impact on the tensile properties and thermal stability of the modified fibers. However, storing the CFs in cement pore solution impaired temperature stability of untreated and modified fibers. X-ray diffraction and Raman spectroscopy reveal specific changes of CF's microstructure upon EPD treatment and immersion in pore solution. Single-fiber pullout tests showed that the pullout resistance of MQ-modified CFs was enhanced, relative to untreated CFs. This augmentation can be explained by an enhanced interlocking mechanisms between CF and matrix due to the deposited quartz particles on the CF surface.

<p>Hydrated portland cement provides the solid adhesive matrix necessary to bind aggregate (sand and gravel) into concrete. The hydration reaction requires water, however the products of the reaction limit further diffusion of water to unreacted cement. Superabsorbent polymer (SAP) hydrogel particles absorb mixing water, then subsequently desorb when the relative humidity drops, serving as internal water reservoirs within the cement matrix to shorten diffusion distances and promote the hydration reaction in a process called internal curing. Internally cured cementitious mixtures exhibit an increased degree of hydration and reduced shrinkage and cracking, which can increase concrete service life. Increased service life can, in turn, reduce overall demand for portland cement production, thereby lowering CO2 emissions.</p> <p>This dissertation addresses practical implementation questions key to the translation of SAP hydrogel internal curing technology to from the benchtop to the field in transportation applications, including: (1) What effects do mix design adjustments made to increase mixture flow when using SAP have on cementitious mixture properties? and (2) What effect do cementitious binder characteristics have on SAP performance?</p> <p>The addition of SAP to a cementitious mixture changes the mixture’s flow behavior. Flow behavior is an important aspect of concrete workability and sufficient flow is necessary to place well consolidated and molded samples. Often, additional water is added to mixtures using SAP to account for the absorbed water, however cementitious mixture workability is often tuned using high range water reducing admixtures (e.g., polycarboxylate ester-based dispersants). Fresh and hardened properties of mortars were characterized with respect to flow modification method (using the mortar flow table test; compressive strength at 3, 7, and 28 days; flexural strength at 7 and 28 days; and microstructural characterization of 28-day mortars). At typical doses, it was found that the addition of extra water lowers the resulting compressive and flexural strength, while high range water reducing admixtures administered at doses to achieve sufficient mortar flow did not compromise compressive or flexural strength.</p> <p>The SAPs used in cement are generally poly(acrylamide-acrylic acid) hydrogels and are not chemically inert in high ionic-load environments, such as cement mixtures. The behavior of an industrial SAP formulation with characterized across five different cement binder compositions with respect the cement hydration reaction (using isothermal calorimetry, thermogravimetric analysis of hydration product fraction, and scanning electron microscopy (SEM)/energy dispersive x-ray spectroscopy (EDS) microstructural analysis), the absorption behavior of the SAP, and the fresh and hardened properties of SAP-cement composites (mortar flow and compressive and flexural strength). The change in properties induced by the addition of SAP was similar across ASTM Type I cements from three manufacturing sources, suggesting that SAP internal curing can be implemented predictably over time and geography. Excitingly, in analysis of cement systems meeting different ASTM standards (Type III and Type I with 30% replacement by mass with ground blast furnace slag), synergistic and mitigating reaction behaviors were observed, respectively, in Type III and slag cement, suggesting that further study of SAP with these cement systems could be of particular interest.</p>

The topic of this work is the monitoring of the effect of zinc on the hydration process in Portland mixed cement (specifically with the addition of finely ground granulated blast-furnace slag, high temperature fly ash and fluidized bed combustion filter ash). How much zinc and at what time it remains in the pore solution during hydration. Activation energy of a mixture of cement with zinc in the form of soluble salts (Zn(NO3)2.6H2O and ZnCl2) and insoluble oxide (ZnO) by isothermal calorimetry was also investigated. The XRF method has shown composition during hydration. The zinc retardation effect was investigated by isothermal calorimetry and activation energy was calculated using this method. The XRF and ICP-OES methods were used to measure the zinc content of the pore solution. And the amount of portlandite was monitored by the DTA and XRF method.