A escória de aciaria LD, principal coproduto da conversão do ferro gusa em aço, se utilizada como agregado na produção de concreto, pode reduzir custos com a estocagem de resíduos e reduzir a extração predatória de agregados naturais. Para tal, este estudo utilizou a escória de aciaria LD em substituição ao agregado miúdo do concreto, a areia, em teores de 0, 25, 50 e 75 %, em massa. O desempenho mecânico do concreto se mostrou próximo ao de referência, com exceção do módulo de elasticidade, que foi significativamente reduzido. A durabilidade dos concretos foi avaliada quanto à resistividade elétrica superficial, absorção de água, índice de vazios permeáveis, resistência à carbonatação acelerada, resistência à migração de cloretos, envelhecimento acelerado e natural. Quanto à durabilidade, apesar de verificada a redução da resistividade do concretos com escória, a substituição parcial da areia não promoveu o aumento da migração de cloretos, o que se atribui a fixação de clores pela formação de sal de Friedel; no entanto, a instabilidade volumétrica da escória se mostrou um fenômeno que gera graves patologias ao material, de modo que os corpos de prova com maior teor de substituição, após 70 dias de envelhecimento acelerado, romperam por expansão. / The basic oxygen furnace (BOF) slag, the main co-product of the process pig iron conversion to steel, if used as an aggregate in the concrete production, can reduce costs with the waste storage and reduce the predatory extraction of natural aggregates. For this, in this study the BOF slag was used in substitution to the small aggregate of the concrete, the sand, in contents of 0, 25, 50 and 75% by mass. The mechanical performance of the concrete was similar to that of reference, with the exception of the elasticity modulus, which was significantly reduced. The durability properties of the concretes were evaluated for surface electrical resistivity, water absorption, permeable voids index, resistance to accelerated carbonation, resistance to chloride migration, accelerated and natural aging. Regarding the durability, despite the reduction of the resistivity of slag concrete, the partial replacement of the sand did not promote the increase of chloride migration, which is attributed to the fixation of chlorides by Friedel Salt formation. However, the volumetric instability of the slag was a phenomenon that causes serious pathologies to the material, so that the specimens with higher substitution content, after 70 days of accelerated aging, ruptured by expansion.

Abstract not available

An in-depth study has been carried out to investigate refractory degradation during continuous steel casting processes. Slag/refractory interactions have been investigated through a study of the wetting behaviour and gas generation phenomena at the slag/refractory interface at 1550oC using sessile drop experiments. The influence of carbon content and slag composition was investigated. Two different steel casting slags (slag1: MnO 50%, SiO2 25%, Al2O3 25%; and slag2: MnO 40%, SiO2 60%) have been studied along with yttria stabilized zirconia refractory substrates respectively containing 10%, 15% and 20% carbon. The gas generation has been measured using the Infrared gas analyser, and its influence has also been investigated by taking optical images at varying times. The total amount of gases emitted has shown the dependence on the compositions of refractory substrates and the existence of casting slags. Under the investigation of zirconia-carbon refractory, a new phenomenon that the gas generated can push the liquid slags away and minimise the contact of slags and refractory substrates has been proven.

The present thesis deals with the development of a new type of dynamic model for metallurgical reactors. It also covers some of the theoretical aspects of steelmaking that is necessary to include in such an application. The thesis consists of modeling work, high temperature experiments and cold model experiments. Two different aspects of slags in the oxygen steelmaking were investigated. In the first study, slag samples were equilibrated with copper at 1923K in order to study their capacities in capturing phosphorous. Some of the samples were liquid-solid mixtures. The solid phases in these samples were identified by SEM analysis. The identified phases were found to agree well with Thermocalc calculations while the amount of solid fractions didn’t. The phosphorous distribution between the different phases was examined. The phosphate capacities of the samples were evaluated. The MgO content didn’t show any appreciable impact on the phosphate capacity. Furthermore the activities of FeO in the liquid slag samples were calculated and were found to deviate positively from ideality. In the second study the foaming height of CaO-SiO2-FeO slags by the reaction with hot metal was investigated. It was found that the foaming height increased with increasing FeO content up to 20-25%. The foaming height was seen to decrease with increased viscosity. The present results indicated that simply using foaming index for converter slag might lead to wrong conclusion. Simulation experiments using cold model at room temperature were conducted. Cold model experiments were carried out in order to study the penetration depth due to an impinging gas jet on the surface of a liquid metal. The liquid alloy Ga-In-Sn was used to simulate steel. And an HCl solution was used to simulate the slag. A comparison with predictions of existing models was made and a new model parameter was suggested. The observation of the movement of metal droplets generated by the gas jet was also made. The low velocity of droplets suggested that the turbulent viscosity played important role and the droplets could have long resident time in the slag. Furthermore a study of the effect of gas flow rate on homogenization and inclusion removal in a gas stirred ladle was carried out. Both industrial trials and cold model experiments were conducted. As an auxiliary tool CFD was used to predict the mixing times and was found to agree well with both the model experiments and industrial data. The increase of flow rate of inert gas would not improve the mixing substantially at higher flow rates. The water model study showed also that the gas flow rate had negligible effect on the rate of inclusion removal. Both the experiments and CFD calculation strongly suggested that low gas flow rate should be applied in the ladle treatment. Lastly a new approach to a dynamic process model of 300 ton BOF converter was made. The main feature was to utilize the velocity vectors obtained by CFD simulation. In the standalone model, the steel melt domain was sliced into 1000 cells. Based on the imported velocity vectors from the CFD calculation, the mass transfer of carbon and phosphorus was calculated taking into account the slag metal reactions. The mass exchange between slag and metal was considered to be dominated by the metal droplet formation due to oxygen jet. The convergence of the model calculation and the promising comparison between the model prediction and the industrial data strongly suggested that the proposed approach would be a powerful tool in dynamic process control. However, more precise descriptions of other process aspects need to be included before the model can be practically employed in a dynamic controlling system. / <p>QC 20120829</p>

In the present thesis a study on the thermal state of steelmaking ladles was undertaken. The transient hot wire method was verified for thermal conductivity measurements on metallurgical slags and applied to ladle slag measurements. Temperature measurements on ladles in an industrial environment were carried out. The emissivities of the outer and inner shells of steelmaking ladles were investigated. Two dynamic models were developed to predict the heat transfer and fluid flow in a preheating and teeming ladle. The gathered thermal conductivity values for ladle slag were used to study the effect of the slag layer on the top surface of the melt on heat transfer and fluid flow in a teeming ladle. In the first stage, the transient hot-wire method was verified to measure the thermal conductivity of metallurgical slags at steelmaking temperatures. A numerical model was developed, cold model experiments were conducted and test measurements using a high temperature experimental setup were carried out. To minimize natural convection and to obtain more reliable measurements, the crucible diameter, the hot-wire diameter, the applied current, the position of the wire in the crucible and the cooling on the upper surface of the crucible were studied. Investigations into the choice of sheathing material of the circuit exposed to the slag were also made. It was found that only certain materials were suitable for slag measurements depending on slag composition and temperature. The electrical resistivity of the hot wire was measured to make the thermal conductivity calculation more reliable. The wire diameter also played a major role due to the heat generation per surface area. The thermal conductivity should be derived from the values measured during the first seconds. In this initial stage, the effect of the natural convection as a function of the wire position in the crucible, the cooling on the top surface and the diameter of the crucible are negligible. A compromise has to be made in choosing the electrical current, since higher current results in higher sensitivity but at the same time in more natural convection. In the second stage, the thermal conductivities of four different ladle slags were measured at 1773 K, 1823 K, 1873 K and 1923 K using the transient hot wire method. Very good reproducibility was obtained. The thermal conductivity did not vary substantially with the variation of slag composition at 1873 K and 1923 K, at which the slag samples were all entirely liquid. The thermal conductivities were low. It was found that the precipitation of solid phase resulted in a considerable increase of thermal conductivity. In the third stage, a two dimensional model was developed in order to predict the temperature distribution in the ladle wall during the preheating process. The model calculated the heat transfer and the velocity field in the gas phase inside the ladle as well as the heat transfer in the solid walls during the preheating process. Measurements of the temperature profiles in an industrial ladle were carried out using an infrared thermography. The measurements were made both inside and outside the ladle. The model predictions were found to be in reasonably good agreement with the measured temperatures. It was found that the preheating time could be minimized when the working lining became thinner. The effect ofthe distance between the lid and the ladle was also studied by the model. The results indicated that there was no significant temperature change on the upper side wall of the ladle. On the lower side wall and bottom the temperature changed slightly. The temperature difference in the lower part of the ladle could be explained by the larger flame distance from the bottom layer. In the fourth stage, a two dimensional axisymmetric model was developed to predict the heat flux in a steelmaking ladle during the teeming process. The model predicts dynamically the flow fields in both the liquid phase and the gas phase along with the movement of the liquid upper surface. The model also predicts the temperature distributions in the liquid metal, gas phase and all layers in the ladle wall. Again, industrial measurements were performed using an infrared thermography, both inside the ladle after teeming and at the wall outside the ladle during the whole process sequence. The model predictions were found to be in agreement with the measured data. It was found that the heat transfer to the surrounding atmosphere and the conductivity of the highly insulating layer were the most important factors for the heat loss. The decrease of the thickness of the working lining was found to have limited effect on the total heat flux. In the fifth and final stage, the effect of the slag layer on the top surface of the melt, on fluid flow and on heat transfer in a teeming ladle was investigated theoretically. The two dimensional axisymmetric model developed in the fourth stage was used. To predict the effect of the slag layer a stationary heat conduction boundary condition including thermal conductivity and slag layer thickness was employed. Different calculations with differing thermal conductivity values for the slag layer were carried out. The calculations showed that the effect of the slag layer was insignificant. This could be explained by the similarity of the thermal conductivity of slag and gas phase. / <p>QC 20121010</p>

No description available.

The present work focuses on mineral reactions and slag formation of LKAB olivine iron ore pellets (MPBO) subjected to reducing conditions in the LKAB experimental blast furnace (EBF). The emphasis is on olivine reactions with surrounding iron oxides. Many factors influence the olivine behaviour. The study was performed by use of micro methods; optical microscopy, micro probe analysis, micro Raman and Mössbuer spectroscopy and thremodynamic modeling. During manufacturing, in oxidising atmosphere at high temperature (1350°C), olivine alterations occur through slag formation and rim reactions with iron oxides and other additives. To be able to describe olivine behaviour in the rather complex blast furnace reduction process one has to consider factors such as reactions kinetics, reduction degree of iron oxides, vertical and horizontal position in the furnace and reactions with alkali. Samples were collected from the EBF both from in shaft probing during operation and from excavation following quenching of the EBF. The initial slag forming olivine consist of primary forsterite – (Mg1.9Fe0.1)SiO4 – with inclusions of hematite and an amorphous silica rich phase, a first corona with lamellae of magnesioferrite, olivine and orthopyroxene, a second corona of amorphous silica and magnesioferrite. During reduction in the upper shaft in the EBF (700-900°C) Fe3+ reduces to Fe2+. The amorphous silica in the second corona absorbs alkali, Al, Fe2+, Mg, and Ca and form glasses of varying compositions. The lamellae in the first corona will merge into a single phase olivine rim. With further reduction the glasses in the second corona will merge with the olivine rim forming an iron rich olivine rim and leaving the elements that do not fit into the olivine crystal lattice as small silicate glass inclusions. Diffusion of magnesium and iron between olivines and iron oxides increase with increasing temperature in the lower shaft of the EBF (750-1100°C). In the cohesive zone of the EBF (1100-1200°C) Fe2+ is not stable any longer and Fe2+ will be expelled from the olivine as metallic iron blebs, and the olivine will form a complex melt with a typical composition of alkali-Al2O3-MgO-SiO2. Alkali plays an important role in this final olivine consumption. The quench time for samples collected with probes and excavation are minutes respectively hours. A study of the quench rate’s effect on the phases showed no differences in the upper shaft. However, in the lower shaft wüstite separates into wüstite and magnetite when wüstite grows out of its stability field during slow cooling of excavated samples. There is also a higher alkali and aluminium deposition in the glass phases surrounding olivines in excavated pellets as a result of alkali and aluminium gas condensing on the burden in the EBF during cooling. Coating applied to olivine pellets was studied in the EBF with the aim to investigate its behaviour, particularly its ability to capture alkali. The coating materials were kaolinite, bauxite, olivine and limestone. No significant reactions were observed in the upper shaft. In the lower shaft a majority of the phases were amorphous and reflecting the original coating compositions. Deposition from the EBF gas phase occurs and kalsilite (KAlSiO4) is found in all samples; coating used for binding alkali is redundant from a quality perspective.

The aim of this thesis work is to increase the knowledge of phenomena taking place during the initial stage in a top blown converter. The work has been done in a few steps resulting in four different supplements. Water model experiments have been carried out using particle image velocimetry (PIV) technology. The system investigated was a fundamental top blown converter where an air jet was set to impinge on a water surface. The flow field of the combined blown case, where an air jet was introduced through a bottom nozzle, was also captured by the PIV. The work clearly showed that the flow field caused by an impinging top blown jet alone could not match that of the bottom blown case. The main re-circulation loop (or vortex) was investigated with respect to position and it was found that an increased flow rate pushes the center of the re-circulation loop downwards into the bath. However, for the top-blown case there is a point when the flow rate is too large to cause a distinguishable re-circulation loop since the jet becomes more plunging (i.e. penetrates deep into the bath) than impinging, with large surface agitation and splashing as a result.A numerical model with the same dimensions as the experimental system was then created. Three different turbulence models from the same family were tested: standard-, realizable- and a modified-(slight modification of one of the coefficients in order to produce less spreading of the air jet) k-ε turbulence model. It could be shown that for the family of k-ε turbulence models the difference in penetration depth was small and that the values corresponded well to literature data. However, when it comes to the position of the re-circulation loop it was shown that the realizable k-ε model produced better results when comparing the results to the experimental data produced from the PIV measurements, mentioned earlier.It was then shown how the computational fluid dynamics (CFD) model could be coupled to thermodynamics databases in order to solve for both reactions and transport in the system. Instead of an air-water system, a gas-steel-slag system was created using the knowledge obtained in the previous simulation step described above. Reactions between gas-steel, gas-slag, steel-slag and gas-steel-slag were considered. Extrapolation of data from a few seconds of simulation was used for comparison to experimental data from the literature and showed reasonable agreement. The overall conclusion was that it is possible to make a coupling of the Thermo-Calc databases and a CFD software to make dynamic simulations of metallurgical processes such as a top-blown converter.A parametric study was then undertaken where two different steel grades were tested; one with high initial carbon content (3.85 mass-%) and one with lower carbon content (0.5 mass-%). The initial silicon content was held constant at 0.84 mass-%. Different initial temperatures were tested and also some variation in initial dissolved oxygen content was tried. It was found that the rate of decarburization/desiliconization was influenced by the temperature and carbon concentration in the melt, where a high temperature as well as a high carbon concentration favors decarburization over desiliconization. It was also seen that the region affected by a lower concentration of alloys (or impurities) was quite small close to the axis where the impinging jet hits the bath. Add the oscillating nature of the cavity and it was realized that sampling from this region during an experiment might be quite difficult. / QC 20100720

The objective of the present thesis is to optimize the electric arc furnace (EAF) practice from an environmental view point. Two aspects that meet the requirements of the secondary steelmaking industries today, viz. Mo alloying with maximum retainment of the alloying element in molten steel and optimization of foaming by carbonate addition with a view to optimize the energy need of the process. Both these aspects would also have a significant impact on the process economy. Iron molybdate (Fe2MoO4) has been synthesized from commercial grade materials and proposed as a new potential precursor for steel alloying with Mo. The thermal stabilities of different molybdates, viz. Fe2MoO4, CaMoO4 and MgMoO4, were studied using thermogravimetry analysis (TGA). It was found that Fe2MoO4 is the most stable one and doesn’t evaporate in Ar atmosphere when heating up to 1573 K. The synthesis of Fe2MoO4 requires high temperature (1373 K) and long holding time (up to 16 hours). In a view of this, the possibilities for in-situ formation of Fe2MoO4 and CaMoO4 from their precursor mixtures were studied with the aid of high-temperature X-ray diffraction (XRD) and TGA analysis. Laboratory and industrial trials on steel alloying with Mo were conducted using precursor mixtures as sources of Mo. It was found that the mixture, which contains FeOx, MoO3 and C (Fe2MoO4 precursor), can provide the Mo yield up to 98 % at both the laboratory as well as industrial trials. The Mo yields even in the case of C+MoO3 and C+MoO3+CaO mixtures were around 93 % in these trials. The higher yield for the MoO3+C+FeOx mixture was attributed to the stabilization of Mo in the precursor (marked by the decrease in the Gibbs energy of Mo) and the readiness to dissolve in the steel bath. The heat effect of the slag foaming with carbonates addition was studied at 1623 and 1673 K with the aid of thermal analysis technique with a new crucible design. Experiments were conducted by adding limestone and dolomite pieces of defined shapes (together with iron sinkers) in molten slag and monitoring the temperature changes accompanying the decomposition of carbonates. It was found that the decomposition energies for dolomite and limestone for the studied slag composition are in the range 56-79 % of theoretical values, which is linked to the energy saving effect of slag foaming. No influence of sample shape on decomposition energy was found both for limestone and dolomite. The kinetics of slag foaming by limestone particles was studied at 1773 K with the aid of X-ray imaging system. A model was proposed to describe the decrease in foam height with time on the basis of CaO shell formation during decomposition reaction. The energy impact of limestone and raw dolomite addition was examined in a 100-ton EAF. It was found that, in the case of addition of carbonates after the scrap is completely molten; the endothermic heat effects for limestone and dolomite (2255 and 2264 kJ/kg respectively) were only 70 % from theoretical values. This is indicative of the resistance to heat transfer due to increased foaming. / QC 20100914

The influence of supplementary materials such as slag, metakaolin and limestone in steam-cured ternary and quaternary cement blends on physical and chemical hydration mechanisms was studied by analyzing the evolution of non-evaporable water content, hydration products and compressive strength. The role of limestone in hydration reactions of cement was also investigated. These properties were studied through the use of differential thermal and thermogravimetric analyses, as well as the loss-on-ignition, X-ray diffraction and compressive strength tests at 1, 3, 7, and 28 days. Research findings revealed that it is possible to replace up to 40% cement with other materials and still achieve compressive strengths similar to mixtures with a 25% cement replacement at 0.34 w/b ratio. Additionally, ternary limestone mixtures exhibited superior mechanical properties to ternary metakaolin mixtures. Lastly, limestone powder was determined to behave as inert filler, accelerating hydration at early ages through heterogeneous nucleation.