Cambios físico-químicos de un refractario MgO-C después de servicio en horno de arco eléctrico

Tesis (Maestría en Ciencias de la Ingeniería Mecánica, con especialidad en Materiales) - U.A.N.L, 1992

The influence of B4C and MgB2 additions on the behavior of MgO-C bricks

Carbon-containing refractory materials have received great attention over the last years due to their importance in the steelmaking process. The oxidation of carbon present in refractory materials at temperatures above 500 degrees C is usually accompanied by the decrease of their mechanical strength and chemical resistance. Aiming to improve the oxidation resistance of carbon-oxide refractories, the use of materials known as antioxidants has been extensively studied. In this work we evaluated the performance of MgB2 and B4C antioxidants when incorporated into MgO-C bricks. We observed that the co-addition of metallic antioxidants and B4C or MgB2 leads to refractory bricks with enhanced hot modulus of rupture and resistance against oxidation and slag corrosion. However, the excessive addition of these antioxidants could impair the performance of the obtained bricks. Thus, when determining the optimum concentration of MgB2 and B4C to be added into MgO-C refractories, one must take into consideration this behavior. (c) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

A study of slag corrosion of oxides and oxide-carbon refractories during steel refining

The use of ceramic material as refractories in the manufacturing industry is a common practice worldwide. During usage, for example in the production of steel, these materials do experience severe working conditions including high temperatures, low pressures and corrosive environments. This results in lowered service lives and high consumptions of these materials. This, in turn, affects the productivity of the whole steel plant and thereby the cost. In order to investigate how the service life can be improved, studies have been carried out for refractories used in the inner lining of the steel ladles. More specifically, from the slag zone, where the corrosion is most severe. By combining thermodynamic simulations, plant trails and post-mortem studies of the refractories after service, vital information about the behaviour of the slagline refractories during steel refining and the causes of the accelerated wear in this ladle area has been achieved. The results from these studies show that the wear of the slagline refractories of the ladle is initiated at the preheating station, through reduction-oxidation reactions. The degree of the decarburization process is mostly dependent on the preheating fuel or the environment. For refractories without antioxidants, refractory decarburization is slower when coal gas is used in ladle preheating than when a mixture of oil and air is used. In addition, ladle preheating of the refractories without antioxidants leads to direct wear of the slagline refractories. This is due to the total loss of the matrix strength, which results in a sand-like product. Thermal chemical changes that take place in the slagline refractories are due to the MgO-C reaction as well as the formation of liquid phases from impurity oxides. In addition, the decrease in the system pressure during steel refining makes the MgO-C reaction take place at the steel refining temperatures. This reduces the refractory’s resistance to corrosion. This is a serious problem for both the magnesia-carbon and dolomite-carbon refractories. The studies of the reactions between the slagline refractories and the different slag compositions showed that slags rich in iron oxide lead mostly to the oxidation of carbon/graphite in the carbon-containing refractories. This leads to an increased porosity and wettability and therefore an enhanced penetration of slag into the refractory structure. If the slag contains high contents of alumina and or silica (such as the steel refining slag), reactions between the slag components and the dolomite-carbon refractory are promoted. This leads to the formation of low-temperature melting phases such as calcium-aluminates and silicates. The state of these reaction products during steel refining leads to an accelerated wear of the dolomite-carbon refractory. The main products of the reactions between the magnesia-carbon refractory and the steel refining slag are MgAl2O4 spinels, and calcium-aluminates, and silicates. Due to the good refractory properties of MgAl2O4 spinels, the slag corrosion resistance of the magnesiacarbon refractory is promoted.

An Experimental Study of Submerged Entry Nozzles (SEN) Focusing on Decarburization and Clogging

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high-viscous alumina-rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. Trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of the commercial SENs.

Key features of alumina/magnesia/graphite refractories for steel ladle lining

The corrosion resistance of resin bonded alumina/magnesia/graphite refractories containing different kinds of aggregates were investigated when submitted to the action of slags of several CaO/SiO2 ratios. The laboratory testing was performed by means of the rotary slag attack test. Specifically evaluated was the influence of alumina/carbon ratio and magnesia and silica contents on the refractories corrosion resistance. It was found that this property could be improved by increasing the refractory Al2O3/SiO2 ratio as well as by choosing the appropriate Al2O3/C ratio. © 2000 Elsevier Science Ltd.

Refratários magnesianos de panela de aciaria: redução da oxidação inicial, formação da fase espinélio MgAl2O4 e resistência ao dano por choque térmico

A campanha dos refratários magnesianos aplicados como revestimento de trabalho de panelas de aciaria depende da soma de diversos fatores como resistência à corrosão, resistência à oxidação do carbono, estabilidade termomecânica, entre outros. A concepção microestrutural do refratário pode influenciar de forma benéfica ou deletéria no desempenho do refratário in situ. Nesta tese de doutorado os refratários magnesianos comerciais de panela de aciaria foram estudados sob três diferentes aspectos: redução da oxidação prematura do carbono, formação da fase espinélio de alumina e magnésio e resistência ao choque térmico e ao dano por choque térmico. Para reduzir a oxidação precoce do carbono foi desenvolvido um coating cerâmico que atua como uma eficiente barreira física, reduzindo o contato do oxigênio da atmosfera de aquecimento com o carbono presente no refratário. Como resultado reduz-se a oxidação prematura do carbono e eleva-se a vida útil do revestimento. A formação da fase espinélio de magnésia e alumina também influencia o desempenho termomecânico destes refratários, principalmente devido ao incremento volumétrico decorrente de sua formação. Nesta tese foram estudados os mecanismos de formação desta fase in situ, demonstrando experimentalmente o caminho preferencial que leva à formação desta fase mineralógica. O comportamento termomecânico dos refratários magnesianos foi determinado em função da resistência ao choque térmico (parâmetros R, R\'\'\') e quanto à resistência ao dano por choque térmico (parâmetro R\'\'\'\' e Rst). Estes parâmetros foram correlacionados com as respectivas características microestruturais destes refratários. Os resultados apresentados por esta tese de doutorado compõe uma importante ferramenta técnica para as indústrias produtoras de aço e de refratários por fornecer subsídio técnico e científico para fundamentar alterações em refratários já existentes e colaborar com o desenvolvimento de novos refratários de engenharia com elevado desempenho e maior vida útil.

Avaliação do molhamento da matriz de um concreto refratário (Al2O3-SiC-SiO2-C) por escórias sintéticas contendo distintos teores de MgO

O comportamento de espalhamento de quatro escórias sintéticas foi investigado pelo método da gota séssil, quando em contato com a matriz de um concreto refratário contendo alto teor de carbono e carbeto de boro como agente antioxidante. A evolução do molhamento do sólido foi monitorada a 1450, 1550 e 1650 ºC por 1800 s. Além disso, simulações termodinâmicas foram efetuadas, usando o programa FactSage®, visando promover um maior entendimento das reações químicas que podem ocorrer na interface dos materiais avaliados. Foi observado que a composição química do líquido afetou diretamente o espalhamento deste e quanto maior o teor de MgO na composição da escória, maiores foram os valores do ângulo de contato entre líquido e sólido. No entanto, em altas temperaturas e tempos prolongados, foram verificadas a formação de bolhas na superfície do líquido e a infiltração das escórias nos poros do refratário. Estes fatores afetaram negativamente e tornaram menos conclusivos os dados coletados nos ensaios propostos, apontando que ainda são necessários aperfeiçoamentos da técnica de molhabilidade para a avaliação de materiais complexos, tais como os concretos refratários.

Partial melt processing and electrical properties of Bi-Sr-Ca-Cu-o superconducting thick films on (100) MgO substrates

Superconducting thick films of Bi2Sr2CaCu2Oy (Bi-2212) on single-crystalline (100) MgO substrates have been prepared using a doctor-blade technique and a partial-melt process. It is found that the phase composition and the amount of Ag addition to the paste affect the structure and superconducting properties of the partially melted thick films. The optimum heat treatment schedule for obtaining high Jc has been determined for each paste. The heat treatment ensures attainment of high purity for the crystalline Bi-2212 phase and high orientation of Bi-2212 crystals, in which the c-axis is perpendicular to the substrate. The highest Tc, obtained by resistivity measurement, is 92.2 K. The best value for Jct (transport) of these thick films, measured at 77 K in self-field, is 8 × 10 3 Acm -2.

Numerical studies of gypsum plasterboard and MGO board lined LSF walls exposed to fire

Fire resistance of cold-formed light gauge steel frame (LSF) wall systems is enhanced by lining them with single or multiple layers of wall boards with varying thermal properties. These wall boards are gypsum plasterboards or Magnesium Oxide (MgO) boards produced by different manufacturers. Thermal properties of these boards appear to show considerable variations and this can lead to varying fire resistance levels (FRL) for their wall systems. Currently FRLs of wall systems are determined using full scale fire tests, but they are time consuming and expensive. Recent research studies on the fire performance of LSF wall systems have used finite element studies to overcome this problem, but they were developed based on 1-D and 2-D finite element platform capable of performing either heat transfer or structural analysis separately. Hence in this research a 3-D finite element model was developed first for LSF walls lined with gypsum plasterboard and cavity insulation materials. Accurate thermal properties of these boards are essential for finite element modelling, and thus they were measured at both ambient and elevated temperatures. This experimental study included specific heat, relative density and thermal conductivity of boards. The developed 3-D finite element model was then validated using the available fire tests results of LSF walls lined with gypsum plasterboard, and is being used to investigate the fire performance of different LSF wall configurations. The tested MgO board exhibited significant variations in their thermal properties in comparison to gypsum plasterboards with about 50% loss of its initial mass at about 500 ºC compared to 16% for gypsum plasterboards. Hence the FRL of MgO board lined LSF wall systems is likely to be significantly reduced. This paper presents the details of this research study on the fire performance of LSF wall systems lined with gypsum plasterboard and MgO board including the developed 3-D finite element models, thermal property tests and the results.

Trap-State Dynamics in Visible-Light-Emitting ZnO:MgO Nanocrystals

Oleate-capped ZnO:MgO nanocrystals have been synthesized that are soluble in nonpolar solvents and which emit strongly in the visible region (450−600 nm) on excitation by UV radiation. The visible emission involves recombination of trap states of the nanocrystalline ZnO core and has a higher quantum yield than the band gap UV exciton emission. The spectrally resolved dynamics of the trap states have been investigated by time-resolved emission spectroscopy. The time-evolution of the photoluminescence spectra show that there are, in fact, two features in the visible emission whose relative importance and efficiencies vary with time. These features originate from recombination involving trapped electrons and holes, respectively, and with efficiencies that depend on the occupancy of the trap density of states.

Reduction in magnetic field induced broadening of the resistive transition in laser‐deposited YBa2Cu3O7−x thin films on MgO

The magnetic field induced broadening of the normal to superconducting resistive transition of YBa2Cu3O7−x thin films laser deposited on (100) MgO substrates for field oriented parallel to the c axis is found to be significantly reduced in comparison with that found previously in single crystals and in films deposited on SrTiO3. This reduction in broadening is associated with a high density of defects which, while causing a slight decrease in Tc and an increase in the zero‐field transition width, seems to provide strong vortex pinning centers that reduce flux creep

Enhancement of uniaxial magnetic anisotropy in Fe thin films grown on GaAs(001) with an MgO underlayer

The understanding and control of anisotropy in Fe films grown on cubic systems such as GaAs and MgO has been of interest from the point of view of applications in devices. We report magnetic anisotropy studies on Fe/GaAs(001) and Fe/MgO/GaAs(001) prepared by pulsed laser deposition. In Fe/GaAs(001), magneto optical Kerr effect (MOKE) measurements revealed a dominant uniaxial anisotropy for Fe thickness less than 20 monolayers (ML) and this was confirmed by ferromagnetic resonance (FMR) studies. Multiple steps in the hysteresis loops were observed for Fe films of thickness 20 and 25 ML. Whereas, in Fe/MgO/GaAs(001), even at 25 ML of Fe, the uniaxial anisotropy remained dominant. The anisotropy constants obtained from FMR spectra have shown that the relative strength of uniaxial anisotropy is higher as compared to the cubic anisotropy constant in the case of Fe/MgO/GaAs(001). (C) 2011 American Institute of Physics. doi:10.1063/1.3556941]

Bio-inspired route for the synthesis of spherical shaped MgO:Fe3+ nanoparticles: Structural, photoluminescence and photocatalytic investigation

MgO:Fe3+ (0.1-5 mol%) nanoparticles (NPs) were synthesized via eco-friendly, inexpensive and simple low temperature solution combustion route using Aloe vera gel as fuel. The final products were characterized by SEM, TEM and HRTEM. PXRD data and Rietveld analysis revealed the formation of cubic system. The influence of Fe3+ ion concentration on the structure morphology, UV absorption, PL emission and photocatalytic activity of MgO:Fe3+ NPs were investigated. The yellow emission with CIE chromaticity coordinates (0.44, 0.52) and average correlated color temperature value was found to be 3540 K which corresponds to warm light of NPs. The control of Fe3+. on MgO matrix influences the photocatalytic decolorization of methylene blue (MB) under UV light. The enhanced photocatalytic activity of MgO:Fe3+ (4 mol%) was attributed to dopant concentration, effective crystallite size, textural properties, decreased band gap and capability for reducing the electron hole pair recombination. Further, the trends of inhibitory effect in the presence of different radical scavengers were explored. These findings open up new avenues for the exploration of Fe-doped MgO in eco-friendly water applications and in the process of display devices. (C) 2015 Elsevier B.V. All rights reserved.