In well cementing, the cement slurry is exposed to the conditions far different than those of ordinary Portland cement (PC) used in construction. After placement, hardened cement paste should preserve integrity and provide zonal isolation through the life of the well. American Petroleum Institute (API) Class G cement is the most common cement type used in various well conditions. Class G cement has a high degree of sulfate resistance which makes it more stable than PC when subjected to the compulsive well conditions. Ground granulated blast furnace slag (GGBFS) blended cement has a long history of use in the construction industry, but is not extensively used in well cementing applications. This study presents an experimental program to investigate the applicability of CEM I and GGBFS blended cement pastes in the well cementing industry. Class G cement and blends of CEM I and GGBFS with the proportions (80:20), (60:40), (40:60) and (20:80) are prepared with same water/cement ratio (0.44) as restricted for Class G cement in API Specification 10A to be tested. The cement pastes are cured for ages of 1 day, 7 days and 28 days at 80

Slurry walls have been widely used for more than 25 years to control the migration of contaminants in the subsurface. In the USA, vertical barriers are mostly constructed of soil-bentonite using the slurry trench method of construction. In this method, sodium bentonite is mixed with water to form a viscous slurry that is pumped into a trench during excavation to maintain the trench stability. The stable trench is then backfilled with a mixture of soil and slurry having a consistency of high slump concrete. These barriers have been designed primarily for low permeability, generally less than 10&minus / 9 m/s. Some investigations have pointed toward improved performance using admixtures that would provide low permeability. In this study, Soma thermal power plant fly ash, granulated blast furnace slag, lime, and steel slag are used as admixture to improve the performance of slurry walls. Permeability, compressive strength, slump, compressibility properties of the mixtures were found and checked for the minimum requirements. According to the findings of this study, granulated blast furnace slag (GGBS), fly ash and steel slag can be used at certain percentages and curing periods as additive in cement-bentonite barrier wall construction. Permeability of specimens having fly ash decreases by increasing fly ash content. Mixtures having 50 % of GGBS type I with 5 % of lime and 9% bentonite content gave acceptable results in 28 days of curing time. Specimens including 50 % of GGBS type II with 5 % of lime and 9% bentonite content gave the higher permeability value in 28 days of curing time with respect to GGBS type I. In addition, most of the mixtures prepared by steel slag gave the acceptable permeability values in 28 days of curing period. Unconfined compressive strength of all mixtures increase by increasing curing time. Cc, Cr, Cv, kcon values were found from consolidation test results. Permeability values found from consolidation tests are 10 times to 100 times higher than flexible wall k results for the same effective stress of 150 kPa. Generally, mv values are decreasing with increasing curing time. As mv decreases, D increases.

In calcium aluminate cement (CAC) systems the hydration process is different than portland cement (PC) systems. The hydration products of CAC are subjected to conversion depending on temperature, moisture, water-cement ratio, cement content, etc. Consequently, strength of CAC system can be seriously reduced. However, presence of other inorganic binders or additives may alter the hydration process and improve various properties of CAC based composites. The objective of this study is to investigate the temperature effect on the behaviour of CAC based composite binders. Throughout this research, several combinations of CAC-PC, CAC-gypsum, CAC-lime, CAC-ground granulated blast furnace slag (CAC-GGBFS) were studied. These CAC based composite binders were subjected to seven different curing regimes and their strength developments were investigated up to 210 days. In addition, the mechanism of strength development was examined by XRD analyses performed at 28 and 210 days. Finally, some empirical relationships between strength-time-curing temperatures were formulated. Experimental results revealed that the increase in ambient temperature resulted in an increase in the rate of conversion, thereby causing drastic strength reduction, particularly in pure CAC mix. It has been observed that inclusion of small amount of PC, lime, and gypsum in CAC did not induce conversion-free CAC binary systems, rather they resulted in faster conversion by enabling rapid formation of stable C3AH6 instead of metastable, high strength inducing CAH10 and C2AH8. On the other hand, in CAC-GGBFS mixes, the formation of stable straetlingite (C2ASH8) instead of calcium aluminate hydrates hindered the conversion reactions. Therefore, CAC-GGBFS mixes, where GGBFS ratio was over 40%, did not exhibit strength loss due to conversion reactions that occurred in pure CAC systems.

In the production of cement, to increase the cement/clinker ratio and decrease CO2 emission, the most important alternative is to produce mineral admixture incorporated cements (CEM II-III-IV-V) instead of portland cement (CEM I). These cements are usually produced by intergrinding the portland cement clinker and the mineral admixtures. However, the difference between grindabilities of the different components of such cements may cause significant effects on the particle size distribution and many other properties. For this reason, separate grinding of additives and clinker may be thought as an alternative. In this study, the effects of intergrinding and separate grinding on the particle size distribution and consequently on the strength of portland composite cements which contained natural pozzolan (trass), granulated blast furnace slag (GBFS) and limestone besides portland cement clinker were studied.

In recent years, scientific studies are carried out to find new refractory material. Having good mechanical properties under very high temperatures, refractories are widely used in industries like iron, steel, glass, cement and pottery. Researches are focused on monolithic refractory making because of their superior properties comparing to conventional firebrick refractories. Providing a mono-block body, having no joints makes the monolithic refractories more durable at elevated temperatures. Easier production and installation are two main points that people are choosing monolithic refractories, thus an economy is made. In this study, for monolithic refractory production, high alumina cement was used as binding material. It is known that the increase in alumina (Al2O3) content increases the high temperature resistance, so that crushed firebrick, having 85% Al2O3 was used as aggregate. Pozzolanic materials, which are silica fume, fly ash, ground granulated firebrick and ground granulated blast furnace slag, were added to improve physical and mechanical properties of mortar. With the addition of steel fibres, change in compressive strength and flexural strength was observed.Superplasticizer was used to understand its behaviour under high temperatures. Portland cement containing mortars were also prepared to make comparison with high alumina cement containing specimens. Specimens were prepared in 5x5x5 cm and 4x4x16 cm prisms. They were cured for one day at curing room, then heated to 105&deg / C and then heated to 1100&deg / C. Weight, size and ultrasound velocity change, compressive strength and flexural strength tests were done to determine physical and mechanical properties of the monolithic refractories, before and after heating. Heated and non-heated specimens were pulverized for microstructural investigation with X-Ray diffraction (XRD) method. Using high alumina cement with 50 &ndash / 60 % granulated blast furnace slag or granulated firebrick, by the weight of cement, and crushed firebrick as aggregate, a satisfactory monolithic refractory material was made. It was observed that, mechanical properties were decreased at the Portland cement used mortars after several times of heating and cooling cycles. Also, it was determined that the microstructure of the high alumina cement containing mortars did not deteriorate much at 1100&deg / C, as long as there was no change observed from the results.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Sulfate ions found in seawater, groundwater and wastewater are aggressive agents that can result in severe concrete degradation. They react with cement hydration products and depending on the associated cations present (magnesium, calcium, potassium, sodium, ammonium), their concentrations and the conditions of the environment, this can result in the formation of ettringite, gypsum or thaumasite, decalcification of C-S-H, processes which may cause expansion, cracking and loss of mass and strength.When high sulfate resistance is required, national and international standards prescribe the use of cement with high concentrations of granulated blast furnace slag (GBFS). By substituting GBFS for cement, lower amounts of clinker are required. In addition, the pozzolanic activity of GBFS takes up the CH released by the hydration of silicates (C3S e C2S), which then is not available to react with sulfate ions to form gypsum, resulting in a more dense paste with lower penetrability. GBFS is one of the few mineral admixtures that can be added to white Portland cement (WPC), a material with widespread usage in civil construction, particularly in cases where concrete is used as a finished surface for architectural impact. The substitution of GBFS for WPC offers technical and environmental gains as well as economic advantages due to the higher cost of WPC. This study investigated the sulfate resistance of WPC with 0%, 50% and 70% GBFS as a substitution for cement. A mix with 50% GBFS that was chemically activated with Na2SO4 (4% b/w of binder) was also studied. The performance of the blended cements was monitored by exposing the prepared mortar specimens to a solution of Na2SO4 (5%) for 2 years according to ASTM C1012/04 and using TG/DTA, DRX and SEM/EDX analyses of the paste samples. For comparison, the same blends prepared with high early strength Portland cement (PC) were also used. The results showed the benefits of the use of GBFS in both types of cement, with higher concentrations of slag resulting in improved sulfate resistance. The use of chemical activation reduced expansion when compared with mixtures without activation. For long-term exposure, all WPC blends showed lower expansion than the corresponding blends with PC. Microstructural analysis identified ettringite and gypsum as the main degradation products of the sulfate attack. / Os íons sulfato, encontrados na água do mar, em águas subterrâneas e em águas residuárias são agentes agressivos que podem levar a uma severa degradação do concreto. Ao reagirem com os produtos de hidratação do cimento, dependendo do tipo de cátion a que estão associados (magnésio, cálcio, potássio, sódio, amônio, etc.), da concentração e das condições do meio, podem levar à formação de etringita secundária, sulfato de cálcio, taumasita, descalcificação do C-S-H, podendo ocorrer expansão, fissuração, perda de massa e de resistência. Quando se faz necessário assegurar uma elevada resistência ao sulfato, a normalização nacional e internacional, dentre outras recomendações, especifica o uso de cimento com elevados teores de escória de alto-forno. Além da redução da quantidade de clínquer ocasionada pela substituição do cimento por escória, a atividade pozolânica da mesma consome o CH liberado pela hidratação dos silicatos (C3S e C2S), que não fica disponível para reagir com os sulfatos e formar sulfato de cálcio, e promove a densificação da matriz, reduzindo a penetrabilidade do meio. A escória é também uma das poucas adições que podem ser incorporadas no cimento Portand branco (CPB), que vem se tornando uma nova tendência dentro do contexto da construção civil, quando se opta por concreto aparente em obras com forte apelo arquitetônico. Além das vantagens técnicas e ambientais, a substituição do cimento branco por escória possibilita a redução do custo bastante elevado do CPB. Neste estudo, investigou-se a resistência ao sulfato de sódio do CPB com teores de substituição de escória de alto-forno de 0%, 50% e 70%. Também foi investigada uma mistura com 50% de escória ativada quimicamente por Na2SO4 (em teor de 4% em massa do material aglomerante). O desempenho dos cimentos foi avaliado pela exposição de argamassas em solução de 5% de Na2SO4 por dois anos, de acordo com a ASTM C1012/04 e através de análise de DRX, TG/DTA e MEV/EDS em pastas. Para comparação foram investigadas as mesmas misturas compostas com cimento Portland de alta resistência inicial, CPV-ARI. Os resultados mostraram os benefícios do uso da escória em ambos os cimentos, sendo que o acréscimo do seu teor aumentou a resistência ao ataque por sulfatos. A ativação química reduziu a expansão comparativamente às misturas sem ativador. A longo prazo, todas as misturas com o CPB apresentaram menor expansão do que aquelas com CPV-ARI. A análise da microestrutura identificou a etringita e o sulfato de cálcio como os principais produtos de degradação por sulfato de sódio.

A crescente preocupação ambiental e a atual crise energética fazem com que indústrias, de um modo geral, intensifiquem esforços para maximização de processos de produção e reutilização de subprodutos gerados. Na siderurgia a produção do aço é realizada por meio da extração do minério de ferro adicionando-se fundentes, gerando como subproduto uma ganga em forma de escória de alto forno. Na presente pesquisa foram compostas misturas de concreto compactado com rolo CCR visando o emprego como base de pavimentos, utilizando três diferentes materiais de granulometria miúda: areia natural, areia industrial e escória granulada de alto forno (com dimensão máxima de 4,8 mm) nas quantidades de 50 % e 100 %; para fins de análise da influência destas diferentes areias foram confeccionados corpos de prova cilíndricos e prismáticos moldados na umidade ótima e no ramo seco da curva de compactação. Foram investigados parâmetros referentes à umidade de compactação, massa específica, resistências à tração indireta e à tração na flexão, módulos de elasticidade por pulso ultrassônico, além de módulos de elasticidade estáticos obtidos a partir de curvas tensão-deformação e por analogia de Möhr (medida de flecha em vigotas em flexão). Visando avaliar a aplicabilidade dos CCR estudados, em especial aquele com escória, foi utilizado o programa computacional MnLayer (para análise de tensões em pavimentos asfálticos) empregando camada de base rígida em CCR para estruturas de pavimentos sujeitos à ação de cargas do tráfego de veículos rodoviários, portuários e aeroportuários, observando a influência dos três tipos de agregados miúdos no nível de tensões da camada cimentada, o que depende em grande parte do módulo de elasticidade da camada de base. Observou-se queda nas resistências dos CCR quando da incorporação de 50 % ou 100 % de escória granulada; por outro lado, essas misturas apresentaram ganhos de resistência em idades mais avançadas em comparação a misturas que empregaram areias natural ou industrial. O módulo de elasticidade dos CCR, com a presença da escória, parcial ou total como fração areia, em geral decresceu à exceção de seu emprego em conjunto com areia natural. As misturas com escória granulada, do ponto de vista de análise mecanicista, resultaram em exigências de maiores espessuras do material, o que não pode fazer tal mistura economicamente viável em qualquer situação, para os casos de misturas com 100 % de escória granulada de alto forno e com fração mista de areia natural e escória. / The increasing environmental concerns as well as energy sources shortage leads industry to consider both optimization of production processes and sustainable use and disposal of its by-pass products. In siderurgical steel manufactures the most common by-pass product is the blast furnace slag with emphasis to its granulated shape. This study considered the evaluation of rolled compacted concretes (RCC) mixtures containing natural or industrial sands as well as such slags at 50% and 100% (with maximum diameter of 4.8 mm) as candidates for pavement base layers. The analysis considered laboratory compaction tests in order to verify the influence of such sands on concrete physical parameters as bulk density and optimum moisture content. Evaluation of mechanical parameters as indirect tensile strength, flexural strength, ultrasonic modulus of elasticity and static modulus of elasticity were carried out as part of the study. Through mechanistic analysis using the elastic layered theory-based computational program MnLayer it was possible to verify implications of each RCC mixture design on pavement thickness and tensile stresses in cemented base layers, in consideration of highway, harbor and airport vehicles. Loss of resistance was verified for RCC mixtures at 50% and 100% slag sand; on the other hand such mixtures have improved its strengths at advanced ages (180 days) compared to the other sands. The modulus of elasticity also decreased for mixtures containing slag sands with exception to the blend of natural and slag sand. Under the mechanistic stand point slag sand mixtures requires thicker base layers in pavements that could lead, depending on several factors, to less cost-effective results in the case of 100% slag sands mixtures and blend (50%-50%) natural and slag sands mixtures.

Generation of wastes in the form of liquid, solid or gas is inevitable in any industry.Industrial Solid Waste is the waste that is generated from an industrial or manufacturing process and includes the waste generated from non-manufacturing activities as well.Most of these wastes fall under the category of Ashes, Slagsor Sludges. For the present work, three types of secondary lead slag, two types of granulated blast furnace slag (GBS) or iron slag and four types of steel slags were procured and studied.An elaborate study on various characteristics of the slags has been performed. Based on the results, all the possible applications for the individual slags are considered. The performance of the secondary lead slag as an embankment material was analyzed. The slope stability for various conditionswas analyzed using Geo5 and experimentally determined strength parameters. It was found that the material can be used safely for embankment constructions.The CBR values were very good in the range for both GBS and steel slag,thus repeated load triaxial test are done to determine the resilient modulus. k1-k3model was adopted and the regression coefficients were determined. Based on the results the pavement design is done using KENPAVE software. An exercise has been performed to determine the quantity of the conventional material that could be saved, considering the type and size of the pavement. For the aggregate sized steel slag, the tests were done to find the suitability of the material for various applications like, as railway ballast, concrete aggregate, gabion and rip rap stones. And the tests result shows the material to be suitable for these applications and is expected to perform well. Study on morphological parameters reveals that the size and gradation of any material plays an important role in its mechanical behavior, however in the case of slags, this could be tailor made by using appropriate crushers, as per the requirements.

L'objet des travaux réalisés dans cette thèse concerne la mise en oeuvre d'un éco-liant à base de co-produits industriels : une cendre volante papetière et un laitier moulu, pour la fabrication de mortiers secs. Cet éco-liant a été élaboré pour remplacer partiellement le ciment comme constituant de matériaux traditionnels d'une part, et recycler en grande quantité l'un des deux déchets industriels, la cendre volante papetière tout en intégrant les notions d'économie circulaire et d'éco-conception d'autre part. La littérature fait état de nombreux travaux sur les différents types de cendres et de laitiers mettant en avant les caractéristiques, la minéralogie, la réactivité de ces cendres volantes papetières et des laitiers moulus. Ces deux coproduits avec environ 20% de SiO2 et 50% de CaO (% pondéraux), ont une composition chimique très proche de celle d'un ciment et développent des propriétés pouzzolaniques qui peuvent suppléer celles du ciment. Leur valorisation comme matériau liant est alors envisageable. Une complète connaissance des propriétés physico-chimiques, structurelles et minéralogiques de la cendre volante papetière et du laitier moulu a conduit à une étude exploratoire de formulations. Des mélanges à partir de 72% de cendres volantes papetières et de 28% de laitier moulu ont été étudiés en se référantà la formulation de base d'un mortier pour en optimiser la teneur en eau et le niveau d'énergie de compactage. Un matériel spécifique pour compacter les éprouvettes prismatiques de dimensions 4x4x16cm3 de mortier a été utilisé. L'effet de l'ajout de trois types d'activateurs i.e. chlorure de calciumCaCl2, métasilicate de sodium Na2O3Si et carbonate de sodium Na2CO3, et d'une faible quantité deciment i.e. 5% et 10% a été analysé mettant en relation la résistance mécanique et la microstructure desmélanges. Deux formulations optimales ont fait l'objet d'analyses relatives à la minéralogie, auxrésistances mécaniques à 2, 7 et 28 jours de cure, à la microstructure avec des images MEB,distributions des pores et à la durabilité. Compte-tenu des résultats satisfaisants obtenus, une approcheà l'échelle semi-industrielle de fabrication de blocs 15x15x15 cm3 à partir des deux formulationsretenues a été menée et discutée. Les premiers résultats montrent un grand intérêt pour la fabricationde pavés et de produits dérivés pour l'aménagement de zones piétonnes ou à circulation réduite. / The aim of this thesis is the development of an eco-binder based on industrial co-products : a wastepapery ash and a ground granulated blast-furnace slag, for the manufacture of dry mortars. On the one hand,this eco-binder was developed to replace partially cement as a constituent of traditional materials, andon the other hand to recycle in large quantities one of these two industrial wastes ; wastepaper fly ashwith considering all the notions of circular economy and eco-design. From literature, there are numerousand relevant research works on the different types of ash and slag, highlighting the characteristics, themineralogy, the reactivity of the wastepaper fly ash and ground granulated blast-furnace slags in details.These two co-products with about 20 wt.% SiO2 and 50 wt.% CaO have a chemical composition veryclose to that of a cement and develop pozzolanic properties that can replace those of cement. Theirvalorization as a binder material is then possible. A complete knowledge of the physicochemical, structuraland mineralogical properties of wastepaper fly ash and ground granulated blast-furnace slag led to anexploratory study of formulations for dry mortars. The mixtures containing 72 wt.% of wastepaper fly ashand 28 wt.% of ground granulated blast-furnace slag were investigated with reference to the formulationof a standard mortar to optimize the water content and compaction energy level. A specific equipment forcompacting prismatic specimens with dimensions 4x4x16 cm3 was used. The effect of adding three types ofactivators i.e. calcium chloride CaCl2, sodium metasilicate Na2O3Si and sodium carbonate Na2CO3, anda small amount of cement i.e. 5 wt.% and 10 wt.% was analyzed. The relation between mechanical strengthand the microstructure of the mixtures has been detailed and discussed. Two optimal formulations wereimplemented and, mineralogy, mechanical strength at 2, 7 and 28 days of curing, microstructure withSEM images, pore distributions and durability have been considered and analyzed. Taking into accountthe satisfactory results obtained, a semi-industrial approach to manufacture 15x15x15 cm3 blocks fromthe two selected formulations was conducted and discussed. The first results show a great interest in themanufacture of blocks of pavement and derived products for the construction of pedestrian or reducedtraffic areas.

The aim of this study was to assess the strength, durability properties and corrosion resistance of concrete samples using supplementary cementitious blended materials. In this investigation, three supplementary concrete materials (SCMs) were used together with ordinary Portland Cement (OPC) to form cementitious blends at different proportions. The supplementary materials are silica fume (SF), ground granulated blast furnace slag (GGBS) and fly ash (FA). Sixteen (16) different proportions of the cementitious blends were produced. Tests carried out on concrete samples include slump test, compressive strength, oxygen permeability, sorptivity, porosity, chloride conductivity test, resistance to chloride and sulphate attack. The electrode potentials of tested samples were also observed using electrochemical measurements. Concrete specimens prepared with 10%, 20%, 30%, 40%, up to 60% of blended cements replacement levels were evaluated for their compressive strength at, 7, 14, 28, 90 and 120 days while the specimens were evaluated for durability tests at 28, and 90 days respectively. The results were compared with ordinary Portland cement concrete without blended cement. Voltage, and temperature measurements were also carried out to understand the quality of concrete. The corrosion performance of steel in reinforced concrete was studied and evaluated by electrochemical half-cell potential technique in both sodium chloride, and magnesium sulphate solutions respectively. The reinforced concrete specimens with centrally embedded 12mm steel bar were exposed to chloride and sulphate solutions with the 0.5 M NaCl and MgSO4 concentrations respectively. An impressed voltage technique was carried out to evaluate the corrosion resistance of the combination of quaternary cementitious blended cement, so as to get the combination with optimum performance. Improvement of strength, durability, and corrosion resistance properties of blended concrete samples are observed at different optimum percentages for binary, ternary and quaternary samples. The effect of cementitious blends is recognized in limiting the corrosion potential of the tested SCM concrete samples. Generally, the cementitious blends with limited quantity of SF to 10% have the potential to produce satisfactory concrete. These should however be used for low cost construction, where high quality concrete is not required. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)