Effect of nanocarbon sources on microstructure and mechanical properties of MgO–C refractories

A study of microstructural evolution, mechanical and thermo-mechanical properties of MgO–C refractories, based on graphite oxide nanosheets (GONs), carbon nanotubes (CNTs) and carbon black (CB), was carried out by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS), three-point bending and thermal shock tests. Meanwhile, these results were compared to the conventional MgO–C refractory containing 10 wt% flaky graphite prepared under the same conditions. The results showed that higher cold modulus of rupture was obtained for the composition containing GONs, and the composition containing CNTs exhibited larger displacement after coking at 1000 °C and 1400 °C. Also, the addition of nanocarbons led to an improvement of the thermal shock resistance; in particular, both compositions containing CNTs and CB had higher residual strength ratio, approaching the thermal shock resistance of the reference composition containing 10 wt% flaky graphite, as it was associated with the presence of nanocarbons and in-situ formation of ceramic phases in the matrix.     

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.     

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.     

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-%.     

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.     

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.     

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.     

Slag resistance mechanism of MgO–Mg2SiO4–SiC–C refractories containing porous multiphase aggregates

The slag resistance of MgO–SiC–C (MSC) refractories should be improved because of the mismatch in the thermal expansion coefficient between the aggregates and matrix, as well as the defects caused by the affinity between periclase and slag. In this study, MgO–Mg₂SiO₄–SiC–C (MMSC) refractories were prepared using porous multiphase MgO–Mg₂SiO₄ (M-M₂S) aggregates to replace dense fused magnesia aggregates. Compared to MSC, the slag penetration index of MMSC decreased by 43.5%. The structure of the porous aggregates increased the surface roughness, and the multiphase composition of the aggregates decreased the mismatch of the thermal expansion coefficient with the matrix, thus reducing debonding between the aggregates and matrix. The aggregates and matrix in the MMSC formed an interlocking structure, which bound them more tightly to improve the slag resistance. The slag viscosity at different depths from the initial slag/refractory interface was calculated using the Ribond model. The M-M₂S aggregates increased Si_xO_y^z− in the slag, which increased the slag polymerization and slag viscosity. The aggregates and matrix in the MMSC reacted with the slag to form high melting point phases, which reduced the channel of the slag. In addition, the penetration depth and velocity derived from the Washburn Equation were modified for the CaO–SiO₂–Al₂O₃–MgO–FeO slag and magnesia based refractory to accurately evaluate slag penetration.     

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.     

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.     

Formation of hollow MgO-rich spinel whiskers in low carbon MgO–C refractories with Al additives

MgO–C refractories with different carbon contents have been developed to meet the requirement of steel-making technologies. Actually, the carbon content in the refractories will affect their microstructure. In the present work, the phase compositions and microstructure of low carbon MgO–C refractories (1 wt% graphite) were investigated in comparison with those of 10 wt% and 20 wt% graphite, respectively. The results showed that Al₄C₃ whiskers and MgAl₂O₄ particles formed for all the specimens fired at 1000 °C. With the temperature up to 1400 °C, more MgAl₂O₄ particles were detected in the matrix and AlN whiskers occurred locally for high carbon MgO–C specimens (10 wt% and 20 wt% graphite). However, the hollow MgO-rich spinel whiskers began to form locally at 1200 °C and grew dramatically at 1400 °C in low carbon MgO–C refractories, whose growth mechanism was dominated by the capillary transportation from liquid Al at these temperatures.     

Application of Cr3C2/C composite powders synthesized via molten-salt method in low-carbon MgO–C refractories

High-performance and low-carbon MgO–C refractories are important refractories for smelting ultra-low carbon steel and clean steel. Based on this, Cr₃C₂/C composite powders were synthesized by the molten-salt method, and used as an additive to prepare low-carbon MgO–C refractories under nitrogen atmosphere. The phase, morphology and oxidation kinetics of Cr₃C₂/C composite powders were studied. In addition, the effect of Cr₃C₂/C composite powders on the morphology, mechanical properties, thermal shock resistance, and corrosion resistance of MgO–C refractories was investigated. The results indicated that the Cr₃C₂/C composite powders exhibited superior oxidation resistance than flake graphite. Moreover, the Cr₃C₂/C composite powders were introduced into the MgO–C refractories. Compared with the sample without Cr₃C₂/C composite powders, the introduction of 1 wt% Cr₃C₂/C composite powders significantly improved the thermomechanical properties and corrosion resistance of the material, its CMOR, CCS before and CCS after thermal shock were 9.06 MPa, 50.40 MPa and 32.60 MPa, respectively, and the corrosion index was significantly reduced from 44.6% to 26.5%.     

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.     

MgO–CaZrO3-based refractories for cement kilns

Two series of refractory materials have been designed taking into account the phase equilibrium relationships to obtain MgO–CaZrO₃–Ca₂SiO₄–Ca₃Mg(SiO₄)₂ or MgO–CaZrO₃–Ca₃Mg(SiO₄)₂–c-ZrO₂ as final crystalline phases. Specimens have been fabricated by reaction sintering of natural dolomite and zircon and with dead burned magnesia aggregates. Different relationships between the proportion and sizes of the fines and the aggregates have been explored.The microstructure of the materials has been characterized in terms of density, crystalline phases and phase distribution and morphology. A combination of X-ray diffraction (XRD) analyses and reflected light optical microscopy and scanning electron microscopy with microanalysis have been used. The phases present in the materials are those expected from the phase equilibrium relationships in the quaternary system. The optimum microstructures, i.e. minimum porosity and adequate matrix content to constitute the bonding between the aggregates are found for initial matrix fractions higher than those for non-reactive systems.The mechanical behaviour has been determined in terms of the room temperature dynamic Young's modulus, E, and the three point bending modulus of rupture, MOR, at 25 and 1100 °C. Additionally, the work of fracture, WOF, has been calculated from the load–displacement curves of stable fracture tests.For optimum starting mixtures, materials with E (60–80 GPa), MOR (4–6 and ～10 MPa at 25 and 1100 °C, respectively) and WOF (40–70 J m^?2) values in the range of those of other magnesia-based refractories have been obtained.     

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.     

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.     

Raw materials,microstructure, and properties of MgO–C refractories: Directions for refractory recipe development

A range of steel making vessels and continuous casting components use graphite containing MgO-C refractories that work from ambient to 1600 °C or higher. In the current study, a detailed review on the key importance behind the rightful selection of raw material quality in the development of MgO-C refractories with improved high-temperature microstructure stability is provided. Special cases of carbon\ceramic reinforcements (SiC, nanocarbon, EG, CNT’s, Zircon, Titania) are also included in this review study with the combination of regular raw materials used in refractory formulation such as magnesia, graphite, resin binder, antioxidant additives, and alloys thereof. Additionally, the material design concept based on strength factor (f_s) has been applied to implicate the raw material quality analysis in the development of carbon containing refractory recipe exhibiting satisfactory hot-strength performance with the recyclable MgO-C grog over the commercially available carbon\ceramic reinforcements is discussed.     

Influence of ceramic phase content and its morphology on mechanical properties of MgO–C refractories under high temperature nitriding

To evaluate the influences of ceramic phase content and its morphology on the mechanical properties of MgO–C refractories, pre-prepared Si powder-phenolic resin loaded with Fe₂O₃ was introduced to prepare MgO–C refractories via catalytic nitridation. The effects of nitriding temperature and Fe₂O₃ content on the phase composition, microstructure evolution and properties of MgO–C refractories were studied and compared. The results show that the increase of the nitriding temperature was conducive to the in-situ formation of the ceramic phases, and a new phase of Mg₂SiO₄ was formed at temperatures ≥1450 °C. Both the increase in nitriding temperature and the addition of catalyst could inhibit the growth of α-Si₃N₄ to promote the formation of β-Si₃N₄ and MgSiN₂. In addition, the formation of excessive ceramic phases caused samples after nitriding to expand violently and form more porous, thereby reducing the physical properties of MgO–C refractories.     

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.