Thermodynamic calculation and microstructure characterization of spinel formation in MgO–Al2O3–C refractories

In this paper, by simulating the gas phase conditions inside the MgO–Al₂O₃–C refractories during continuous casting process and combining with thermodynamic analysis, as well as SEM analysis, the gas-gas and gas-solid formation of MA spinel were clarified in carbon containing refractories. Thermodynamic calculations showed that gas partial pressure of CO, O₂ and Mg could meet the formation and stable existence conditions of MA spinel in MgO–Al₂O₃–C refractories under service environment, and nitrogen could not affect the formation of MA spinel at 1550 °C in the thermodynamic condition. The formation processes of MA spinel were analyzed experimentally under embedding carbon atmosphere. The carbon-coated alumina powders in MgO–Al₂O₃–C refractories prevented the direct contact between magnesia and alumina. Mg gas was formed by carbon thermal reaction, then reacted with alumina (gas-solid) and gas containing aluminum (gas-gas) to generate MA spinel. Through gas-gas or gas-solid reaction, the formation of MA spinel was effectively controlled. By means of SEM analysis, a two-layer structure with dense outer spinel layer and loose inner layer was formed in MgO–Al₂O₃–C refractories.     

Fracture behavior of low carbon MgO–C refractories using the wedge splitting test

The fracture behavior of low carbon MgO–C refractories containing various carbon sources were investigated by means of the wedge splitting test and microscopic fractographic analysis to evaluate quantitatively their thermal shock resistance in the present work. The results showed that the addition of various nanocarbons in MgO–C specimens can lead to more tortuous crack propagation path during the wedge splitting test and much better thermal shock resistance compared to the specimen with flaky graphite as carbon source; particularly, the specimen containing carbon nanotubes had the most outstanding thermal shock resistance. Also, it was suggested from the correlation analysis that the increase of the specific fracture energy and interface crack propagation as well as the decrease of the modulus of elasticity, coefficient of thermal expansion and transgranular crack propagation can contribute to an improvement of thermal shock resistance of MgO–C refractories.     

Effect of electromagnetic field on slag corrosion resistance of low carbon MgO–C refractories

Using MgO–C refractories containing 6% carbon and the slag with a basicity (CaO/SiO₂) of around 0.8, the melting slag resistance experiments of low carbon MgO–C refractories were carried out in induction furnace and resistance furnace, respectively. The microstructure of low carbon MgO–C refractories corroded by slag under the different conditions was analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDAX). The results show that in induction furnace having electromagnetic field (EMF), there are MgFe₂O₄ spinel with a little of Mn ions generated in the interfacial layer. Part of the solid solution is monticellite [CaMgSiO₄] containing a little MnO and FeO. While under the condition of EMF free, there is not MgFe₂O₄ spinel in the interfacial layer and the solid solution is monticellite (CaMgSiO₄). At a high temperature, EMF increases the diffusion coefficient of Fe^2+/3+ ions, which displaces Mg²⁺ and forms MgFe₂O₄ with a little of Mn ions. There are MgAl₂O₄ spinel in the penetration layers under the conditions of both EMF and EMF free. EMF speeds up corrosion of low carbon MgO–C refractories.     

Formation mechanism of whiskers in Al–MgAl2O4–MgO refractories at 1400 °C under N2 atmosphere

Al–MgAl₂O₄–MgO refractories were prepared using fused magnesia, metal Al, fused spinel and sintered high purity magnesia as raw materials. The phase composition and microstructure of Al–MgAl₂O₄–MgO refractories treated at 1400 °C under N₂ atmosphere were investigated by means of XRD, SEM and EDS. The results showed that magnesia (MgO) whiskers and MgAlON whiskers were formed on the surface and in the inner area of the Al–MgAl₂O₄–MgO refractories, respectively. The MgO whiskers grew preferentially along the axial direction, forming cylindrical shape MgO whiskers. Then the cylindrical MgO whiskers further absorbed Mg(g) and O₂(g), and grew along the radial direction to form the square columnar shape MgO whiskers. The MgAlON whiskers firstly grew in one-dimensional direction, forming whisker shape MgAlON, then some whisker shape MgAlON gradually developed and grew into two-dimensional flake shape MgAlON. The sintering and thermal shock resistance was significantly improved by the whiskers. The growth process of magnesia whiskers and MgAlON whiskers were dominated by a vapor-solid (VS) mechanism.     

Atmosphere and carbon effects on microstructure and phase analysis of in situ spinel formation in MgO–C refractories matrix

The effects of carbon, air and reducing atmospheres on microstructure and phase evolution of in situ MgAl₂O₄ spinel (S) formation in the matrix of MgO–C refractories were investigated by X-ray diffraction powder analysis (XRD) and scanning electron microscopy (SEM)/energy-dispersive spectroscopy (EDS) techniques. The formation of spinel started under 1000 °C in both air and reducing atmospheres. The morphology of in situ spinel and its formation mechanism were however different and dependent upon the atmosphere. The solid-state reaction was clarified to be the dominant mechanism of spinel formation in oxide atmosphere, while the gas–solid reaction was found to play a vital role in reducing atmosphere. Reaction of MgO and C in reducing atmosphere led to the formation of Mg_(g) which was found to be partially controlling the in situ spinel formation in the carbon containing samples fired in reducing environment. The results which were necessary are explained with emphasis on MgO–C refractories applications.     

Cr7C3: A potential antioxidant for low carbon MgO–C refractories

Magnesia carbon (MgO–C) refractory, one of the most commonly used refractories in the steelmaking system, relies on graphite to improve the thermal shock resistance and slag corrosion resistance. The oxidation of graphite carbon in a MgO–C brick usually leads to the destruction of the carbon network in the brick, which causes the structure of the brick to become loose and easily eroded. At present, metal powders, carbides, and borides are used as antioxidants to prevent the oxidation of carbon in MgO–C bricks. The metal carbide Cr₇C₃ can be prepared from aluminum chromium slag through a simple synthetic process and at a low cost. In this work, we investigated the oxidation resistance of low carbon MgO–C refractories with different amounts of Cr₇C₃ powder (1, 2, 3, and 4 wt%). The refractories with 3 wt% Cr₇C₃ powder showed optimal resistance to oxidation. The microstructure indicated that oxygen reacts with Cr₇C₃ preferentially over carbon to form chromium oxide and magnesium chromium spinel, blocking the pores and hindering oxygen diffusion. Carbon arising from the reduction of carbon monoxide by Cr₇C₃ can act as a supplementary carbon source. The better oxidation resistance also contributed to the improvements in slag corrosion and thermal shock resistance of the refractories.     

Improved thermal shock stability and oxidation resistance of low-carbon MgO–C refractories with introduction of SiC whiskers

This research focuses on the utilization of SiC whiskers synthesized from rice husk powders in low-carbon magnesia–carbon (MgO–C) refractories, and attempts to reduce the flake graphite content in refractories by adding synthesized SiC whiskers. The effect of the addition amount of SiC whiskers on the microstructure, mechanical properties, thermal shock stability and oxidation resistance of MgO–C refractories with different graphite content was studied. The results indicated that the introduction of SiC whiskers facilitated the generation and growth of ceramic phases in MgO–C refractories. By adding 1 wt% SiC whiskers, the graphite content could be reasonably reduced (from 5 wt% to 4 wt%), and the strength, thermal shock stability and oxidation resistance of refractories were enhanced by the synergistic effect of the introduced SiC whiskers and the generated ceramic phases, the CMOR, CCS, residual CCS, and oxidation resistance were increased by 44, 6, 12 and 27% respectively.     

Enhancement of oxidation resistance at 1000–1400 °C of low carbon Al2O3–C refractories with pre-synthesized SiCnw/Al2O3

The oxidation resistance of low carbon Al₂O₃–C refractories with the addition of SiC_nw/Al₂O₃ composite powders and the enhancement mechanisms were investigated. The oxidation resistance was evaluated by oxidation index (O.I.) and oxidation rate constant (k). The enhancement mechanisms of SiC_nw/Al₂O₃ on oxidation resistance were analyzed based on the phases and microstructures. The results showed that the SiC_nw/Al₂O₃ can improve the oxidation resistance of Al₂O₃–C refractories, the O.I. and k of A6 (6 wt% SiC_nw/Al₂O₃ addition) were 26.0% and 34.5% lower than those of reference sample A0, respectively. The oxidation resistance of refractories was improved in a range of 1000–1400 °C due to the introduction of SiC_nw/Al₂O₃. The enhancement mechanisms can be explained that SiC_nw is more susceptible to be oxidized due to its high specific surface area, which expanded the action temperature range of other antioxidants and itself. The mullite and dense protective layer generated during oxidation is also beneficial to impede the diffusion of O₂.     

Enhanced oxidation resistance of low-carbon MgO–C refractories with Al3BC3–Al antioxidants: A synergistic effect

The synergistic effects of Al₃BC₃–Al antioxidants on optimizing the oxidation resistance of low-carbon MgO–C refractories were investigated. The results indicated that the oxidation index and rate constant of low-carbon MgO–C refractories with optimized Al₃BC₃–Al additions were 13% and 1.10 × 10⁻⁴ cm² min⁻¹ at 1400°C for 3 h, respectively, which is much lower than that of Al or Al₃BC₃ containing ones. Single Al₃BC₃ is not a suitable antioxidant for low-carbon MgO–C refractories; however, if Al₃BC₃ was initially protected and Al reacted as the antioxidant, enhanced oxidation resistance at high temperature can be achieved. The formation of dense MgO–MgAl₂O₄–Mg₃B₂O₆ layer contributed to superior oxidation resistance, and the temperature for the generation of this layer was as low as 1100°C due to liquid and vapor phase–assisted reactions with Al₃BC₃–Al. Furthermore, a self-repairing function was achieved at 1600°C with the combination of Al₃BC₃–Al additions in spite of the faster oxidation rate.     

Enhanced performance of low-carbon MgO–C refractories with nano-sized ZrO2–Al2O3 composite powder

Low-carbon MgO–C refractories are facing great challenges with severe thermal shock and slag corrosion in service. Here, a new approach, based on the incorporation of nano-sized ZrO₂–Al₂O₃ composite powder, is proposed to enhance the thermal shock resistance and slag resistance of such refractories in this work. The results showed that addition of ZrO₂–Al₂O₃ composite powder was helpful for improving their comprehensive performances. Particularly, the thermal shock resistance of the specimen containing 0.5 wt% composite powder was enhanced significantly which was related to the transformation toughening of zirconia and in-situ formation of more spinel phases in the matrix; also, the slag resistance of the corresponding specimen was significantly improved, which was attributed to the optimization of pore structure and formation of much thicker MgO dense layer.     

Influence of additives on nano-SiC whisker formation in alumina silicate–SiC–C monolithic refractories

This study describes the effect of additives on increasing cold crushing strength (CCS) and bulk density (BD) of alumina silicate–SiC–C monolithic refractories. Two series of carbon-containing monolithics were prepared from Iranian chamotte (sample A) and Chinese bauxite (sample B), as 65 wt.% in each case together with, 15 wt.% SiC-containing material regenerates (crushed sagger) and 10 wt.% fine coke (a total of 90% aggregate) and 10 wt.% resole (phenol formaldehyde resin) as binder. Different values of additives (such as silicon and ferrosilicon metal) are added to the mixture and BD, apparent porosity and CCS are measured after tempering at 200 °C for 2 h and firing at 1100 °C and 1400 °C for 2 h. At low temperature of 200 °C, Si and ferrosilicon contribute to the formation of stronger cross-linking in the resit structure and provide CCS values of as high as about 65 MPa. At 1400 °C, SiC whiskers of nano-sized diameter are formed due to the presence of Si and FeSi₂ and improve CCS values of as high as about 3–4 times in sample containing 6 wt.% ferrosilicon metal as additive.     

Effect of carbon content on the mechanical behavior of MgO–C refractories characterized by Hertzian indentation

The mechanical behavior of magnesia–carbon (MgO–C) refractory materials containing 4, 11, and 19 wt% carbon was investigated by Hertzian indentation tests. No microstructural changes were observed for the various carbon amounts. The slope during loading and the residual displacement after unloading were determined from indentation load–displacement curves. Indentation conditions were varied to study their influence on the mechanical behavior of the MgO–C. Repetitive contact fatigue tests were also conducted. The carbon content and indentation ball size ultimately affected the indentation mechanical behavior. The MgO–C containing 4 wt% carbon exhibited relatively hard and brittle behavior, while the MgO–C containing 19 wt% carbon exhibited a quasiplastic behavior, independent of ball radius indented on the MgO–C. Results indicated that carbon, in suitable amounts, provides the MgO–C with soft and ductile behavior in contact, wear, and impact environments.     

Analysis on microcrystalline graphite and properties of MgO–C refractories with microcrystalline graphite

The composition and microstructure of microcrystalline graphite were studied by X-ray diffraction, differential thermal analysis–thermogravimetry, SEM and energy dispersive analysis in this paper. The chemical composition of ash in microcrystalline graphite was also analysed in the study. The microcrystalline graphite was introduced in MgO–C refractories fabrication to investigate the influence of microcrystalline graphite on the main properties of MgO–C refractories. The oxidation resistance, thermal shock resistance, hot bending strength and expansion rate of MgO–C samples with microcrystalline graphite and flake graphite were investigated in this study. It is indicated that the proper addition amount of microcrystalline graphite in MgO–C refractories should be no more than 4?wt-%.     

Properties of MgO–Fe–C refractories as linings of vanadium-extraction converter

For the purpose to extend the service life of MgO–C bricks used as linings of vanadium-extraction converters, MgO–Fe–C bricks with different carbon content were designed and the properties of this novel refractory were investigated by comparing to the traditional MgO–C bricks. The results showed that the poor service life of MgO–C bricks was due to the poor sinterability of the oxidized layer at 1400 °C, whereas the oxidized layer of MgO–Fe–C brick was well sintered due to the oxidation of Fe particles in the oxidized layer and formation of MgO–FeO_ss in air atmosphere. Excellent oxidation resistance and corrosion resistance against vanadium containing slag were also obtained due to the increase of compactness of oxidized layer and concentration of FeO in the oxidized layer compared to MgO–C bricks, and it is considered that MgO–Fe–C brick is a favorable substitute of MgO–C refractory to be used as linings of vanadium-extraction converters.     

Effect of bimodal microstructure on high-temperature properties of nano-reinforced Al2O3–MgO–C refractories

The beneficial effects of adding nanostructured expandable graphite (EG) hybridized yttrium aluminium garnet (EG\YAG) powder as a composite reinforcement in improving the oxidation resistance, hot-strength, and microstructure development in Al₂O₃–MgO–C refractories were studied. The refractory components reinforced with EG\YAG exhibited more than 60% of oxidation resistance enhancement and as high as 200% increase in hot-strength performance over the standard refractories, formulated without EG\YAG. Correlating the damage parameter (D_E) calculations based on ultrasonic measurements with residual strength data (R_c, R_b) showed that there was a progressive increase in R_c and R_b values with consistent reduction in the oxidative damage of EG\YAG reinforced refractories. Analysis indicated that these beneficial features were majorly ascribed to the in-situ development of bimodal microstructure with EG\YAG sintered framework throughout the refractory interior in these new class of reinforced systems. Additionally, the mechanism of toughening and implications of these results to materials design are discussed.     

Microstructure and mechanical properties of multi-walled carbon nanotubes containing Al2O3–C refractories with addition of polycarbosilane

Carbon nanotubes (CNTs) are a promising reinforcement for fabricating Al₂O₃–C refractories. However, CNTs are prone to agglomerate or react with antioxidants or reactive gaseous phases such as Al (g), Si (g) and SiO (g), etc. at high temperatures. To overcome the problems above, polycarbosilane (PCS) and multi-walled carbon nanotubes (MWCNTs) were firstly mixed with micro-alumina powder in a liquid medium and then incorporated into Al₂O₃–C refractories. Then the microstructure and mechanical properties of Al₂O₃–C refractories fired in the temperature range from 800 °C to 1400 °C were investigated in this work. The results showed that the MWCNTs were well dispersed in the specimens with addition of PCS in contrast to the specimens without PCS due to the PCS adsorption on the surface of MWCNTs during the mixing process. And the mechanical properties, such as cold modulus of rupture (CMOR), flexural modulus (FM), forces and displacements of Al₂O₃–C refractories with PCS were much higher than those without PCS, which was attributed to more homogeneous dispersion of MWCNTs, more residual MWCNTs as well as different morphologies of ceramic whiskers. Meanwhile, the oxidation resistance of Al₂O₃–C refractories with PCS was improved greatly, which was supposed that the in situ formed SiC_xO_y coating prevented the oxidation of MWCNTs to some extent.     

In situ hot elastic modulus evolution of MgO–C refractories containing Al,Si or Al–Mg antioxidants

Metals and alloys (such as Al, Si, Al–Mg and Al–Si) are commonly added to MgO–C refractory bricks as antioxidants due to their effectiveness to prevent carbon oxidation (in the 600–1400 °C range) and their low cost. These additives act at different temperatures and react with refractory components and gases in the environment, inducing significant changes in the resultant microstructure and affecting the overall thermo-mechanical performance of these products. This work addresses the evaluation of physical properties, cold and hot mechanical resistance, as well as in situ hot elastic modulus (E) measurements in the temperature range of 30–1400 °C for MgO–C bricks containing antioxidants (Al, Si or Al–Mg alloy) in a reducing atmosphere. Cured and fired samples of the designed formulations were evaluated throughout 1 or 2 heating-cooling cycles. Despite the improved mechanical behavior (higher cold crushing strength and hot modulus of rupture) of the antioxidant-containing formulations, compared to the additive-free MgO–C sample, the interaction of the selected additives with the refractory components and CO_(g) led to a generation of phases (i.e., Al₄C₃, Al₂O₃, SiC, SiO₂, MgAl₂O₄) that could not be well accommodated in the microstructure. Consequently, the in situ E drop was observed during cooling (mainly below 600 °C) of the antioxidant-containing sample due to crack and flaw formations. Si and Al–Mg were the most promising antioxidants, whereas the Al-containing composition showed the highest E damage level after two heating/cooling cycles up to 1400 °C for cured samples. Based on the elastic modulus profiles with the temperature, the results also indicated the best working conditions for these ceramic materials.     

In situ synthesis and interfacial bonding mechanism of SiC in MgO–SiC–C refractories

Adding SiC directly to MgO–C refractories possesses the disadvantages of low dispersion and interfacial bonding strength. Herein, the in situ synthesized SiC was introduced into the MgO–SiC–C refractories to maintain the original excellent performance of MgO–C refractories and reduce the carbon dissolution in molten steel. With the increase of Si and C content in raw materials, the morphology of SiC changed from whisker to network, whose growth mechanism was vapor–solid and vapor–liquid–solid. The network structure and uniform distribution of SiC improved the thermal shock resistance of MgO–SiC–C refractories. According to the analysis of molecular dynamics simulation by Materials Studio software, SiC strengthened the relationship between periclase and graphite to enhance the structure of the compound.     

Mechanism of in-situ formation of spinel and its effect on the mechanical properties of Al2O3–C refractories

This work looked at the in-situ formation mechanism of magnesia alumina spinel in Al₂O₃–C refractories with magnesia addition at different firing temperatures. A comprehensive study on the mechanical properties of Al₂O₃–C refractories was performed in comparison to traditional analogs. The magnesia alumina spinel was in-situ formed at the firing temperature of 1150 °C in Al₂O₃–C refractories. With the increase of the firing temperature, the Al₂O₃ phase was gradually dissolved in spinel phase to form aluminum rich spinel phase, resulting in a decrease in its lattice constant due to the defects formation. The formed spinel phase was homogenously distributed and bonded well with corundum, improving the interfacial bond, load transferring capacity and crack propagation resistance. The formation of spinel phase also enhanced the sintering of the alumina matrix owing to the solid solution of alumina in the spinel. Therefore, the mechanical properties such as cold modulus of rupture and hot modulus of rupture in Al₂O₃–C refractories achieved a substantial enhancement compared with traditional refractories.     

Nanocarbon containing low carbon Al2O3–C refractories: Comparison between N220 and N990 nanocarbons

Continuous casting process is the majorly used solidification process in steel fabrication. The refractories used in this process are most commonly made up of alumina-carbon-based compositions. Generally, these functional refractories consist of about 30% residual carbon after coking. Improvements in steel industries, such as attaining clean steel and ultralow-carbon steel, require alumina-carbon refractories with low carbon content. In the present work, low carbon-containing Al₂O₃–C refractories are studied by using two different grade nanocarbons, namely, N220 and N990 with varying amounts, along with fixed 3-wt% graphite in the batch composition. The physical, mechanical, and thermomechanical properties along with the oxidation resistance are evaluated and compared. Phase analysis and microstructural developments at different temperatures were also characterized. Optimized compositions of both the nanocarbons are further studied for hot strength and oxidation resistance measurement. Based on all the obtained results, one batch composition is finalized for the thermal shock and corrosion testing. All the results are compared against a reference batch composition containing 25% graphite as a carbon source. The formation of in situ ceramic phases like aluminum carbide in nanocarbon-containing compositions provides a dense compact microstructure that improves strength, helps to inhibit oxidation, and contributes to corrosion resistance.