Improved thermal shock resistance of low-carbon Al2O3–C refractories fabricated with C/MgAl2O4 composite powders

The addition of C/MgAl₂O₄ composite powders can improve the thermal shock resistance of low-carbon Al₂O₃–C refractories attribute to the formation of microcracks in the agglomerated structure, thus consuming more thermal stress and strain energy. Moreover, C/MgAl₂O₄ composite powders additive promote the formation of short fibrous ceramic phases in the refractories, which suggest a bridging role in the interior of the refractories and increase its toughness. Furthermore, the C/MgAl₂O₄ composite powders also result in a remarkable enhancement of the slag corrosion resistance in the 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.     

Cyclic thermal shock resistance for MgAlON–MgO composites obtained with additions of spent MgO–C brick: Microstructure characteristics,thermal shock parameter and thermal shock mechanism

Thermal shock parameters (R, R''', R'''' and R_st) of MgAlON–MgO composites obtained with additions of spent MgO–C brick were calculated using measured mechanical properties and thermal expansion coefficient, determining their resistance to fracture initiation and crack propagation. The cyclic thermal shock experiments of MgAlON–MgO composites performed from 1398 K to ambient temperature indicate that as number of thermal shock cycle increases, retained strength ratio of MgAlON and MgAlON–4.2 wt%MgO sharply decrease and then keep constant, while that of MgAlON–10.5 wt%MgO and MgAlON–15.7 wt%MgO slowly decrease. The reason for the difference is that MgAlON and MgAlON–4.2 wt%MgO show low value of R''' and R'''', and high value of R and R_st. Moreover, precipitation of impurity containing Fe may play a positive role in improvement of thermal shock resistance of MgAlON–MgO composites. MgAlON?4.2 wt%MgO has the maximum retained strength (55 MPa) even after 5 thermal shock cycles, which is expected to be used in the metallurgical industry.     

Catalytic combustion synthesis of CNTs/MgO composite powders and the influences on the thermal shock resistance of low-carbon Al2O3–C refractories

Using MgC₂O₄, Mg powders as raw materials and Ni(NO₃)₂?6H₂O as a catalyst, CNTs/MgO composite powders were prepared by a catalytic combustion synthesis method. The CNTs/MgO composite powders were characterized by XRD, Raman spectroscopy, FESEM/EDS and HRTEM. The effects of catalyst content on the degree of graphitization and aspect ratio of the CNTs in composite powders were investigated. Moreover, the thermal shock resistance of low-carbon Al₂O₃–C refractories after adding the composite powder was investigated. The results indicated that the CNTs prepared with 1 wt% Ni(NO₃)₂?6H₂O addition had a higher degree of graphitization and aspect ratio. In particular, the aspect ratio could reach approximately 200. The growth mechanism of hollow bamboo-like CNTs in the composite powders was proven to be a V-L-S mechanism. The thermal shock resistance of Al₂O₃–C samples could be improved significantly after adding CNTs/MgO composite powders. In particular, compared with CM0, the residual strength ratio of Al₂O₃–C samples with added 2.5 wt% composite powders could be increased 63.9%.     

Thermal shock resistance of mullite–cordierite refractories

Abstract

The effect of aggregate size on the strength degradation of mullite-cordierite specimens subjected to thermal shock has been studied. Strength degradation of shocked specimens is shown to depend on the aggregate size, on the preshock strength of sintered specimens, and on cordierite content. Retained strength after shocking increased in specimens prepared from small aggregates owing to the higher initial strength. These specimens contained lower cordierite content as a result of the increased dissociation of cordierite brought about by decreasing the aggregate size.     

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.     

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.     

Flexible ultrafine nearly stoichiometric polycrystalline SiC fibers with excellent oxidation resistance and superior thermal stability up to 1900 °C

Flexible ultrafine SiC fibers with superior high-temperature stability and excellent oxidation resistance are regarded as one of the most promising materials for high-temperature applications. However, excess oxygen and carbon in the ultrafine SiC fibers limit their thermal stability due to decomposition of the SiC_xO_y phase. In the present work, flexible ultrafine nearly stoichiometric polycrystalline SiC fibers were fabricated by combining the electrospinning technique and polymer-derived ceramic method. The ultrafine SiC fibers exhibited superior high-temperature stability and oxidation resistance. The retention rates of tensile strength were 90.0 %, 94.2 % and 86.4 % after heat treatment in argon at 1800 °C, 1900 °C and 2000 °C, respectively. TG results of the fibers showed little weight loss of only 1.52 % at 1900 °C in Ar and the weight gain of only 4.1 % up to 1500 °C in air. Such improved thermal stability was achieved through sintering at high temperature for elimination of excess oxygen and carbon with Al doped as the sintering aid to restrain the grain coarsening. The ultrafine SiC fibers still exhibited excellent flexibility without obvious damage when they were heated by the butane blowtorch flame of about 1100 °C in air. Furthermore, the infrared thermography illustrated that the ultrafine SiC fiber membrane also had good thermal insulation performance. The outstanding mechanical properties and thermal stability of ultrafine SiC fibers suggest their potential applications at the high temperature and harsh environment.     

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.     

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.     

Thermal shock resistance of magnesia–chrome refractories—experimental and criterial evaluation

Eleven commercially available magnesia–chrome refractories have been tested. Their basic properties have been determined along with bending strengths at 20,950 and 1400 °C, linear thermal expansion coefficients at 950 °C and 1400 °C, Young's modulus by the static method and the work of fracture at 950 °C. Young's modulus was determined within the temperature range 20–1000 °C, in the process of heating and cooling. The values of thermal shock resistance R_st and R₄ were calculated and correlated to thermal shock resistance (TSR). It has been demonstrated that the R_st criterion is a useful tool to forecast TSR, no matter whether the value of the E modulus is determined by the static or dynamic method. The values of Young's modulus obtained by various methods at 20 °C and 950 °C have been compared. It has been proven that Young's modulus dependence on temperature is a specific feature of a given material.     

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-%.     

Enhancement of thermal shock and slag corrosion resistance of MgO–ZrO2 ceramics by doping CeO2

The purpose of this paper was to develop ceramics materials with high thermal shock resistance and corrosion resistance for preparing gas blowing components. In this paper, MgO-rich MgO–ZrO₂ ceramics were obtained by using MgO powder and ZrO₂ powder as starting materials and CeO₂ as an additive. Changes in the properties in terms of thermal shock resistance, mechanical properties, and slag corrosion-resistance with chemical compositions were examined correlated to microstructure and phase changes. Especially, the effect of doping CeO₂ on phase transition of zirconia in MgO-rich system was discussed. The results showed that doping amount of CeO₂ significantly improved properties of MgO–ZrO₂ ceramics. Especially when doping amount of CeO₂ was 2 wt%, residual strength ratio was enhanced over 100% after thermal shock testing. In samples doped with CeO₂, ZrO₂ was stable in cubic or tetragonal form due to complete solution of CeO₂, which was important reason for the improvement of various properties of MgO–ZrO₂ ceramics.     

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.     

Mechanical and thermal shock properties of size graded MgO–PSZ refractory

The effects of the mixture of coarse powder with fine PSZ powder on the thermal-mechanical properties of 10 Mg–PSZ samples were studied. The size graded specimens were injection-molded using 3.5 m% MgO–ZrO₂ powders. The physical properties of the ZrO₂ samples and five thermal shock parameters were measured and calculated. These properties included density (ρ), porosity (p), the ratio of m/(t+c+m) phase, fracture toughness (K_IC), strength (σ_f), Young's modulus (E), shear modulus (G), Poisson's ratio (ν), and the thermal expansion (α) between ambient temperature to 1100°C. The toughness and thermal shock resistance of the PSZ are controlled by the states of porous microstructure which can be represented by a parameter (nominal largest tolerable length of defects) a_t. The PSZ samples show two types of thermal shock behavior differentiated by comparing the value of a_t to the characteristic length L_f of the defects in the sintered PSZ. The states of the defects, i.e. porosity, are the microstructural evidence to explain the relationship between the thermal shock properties.     

Water resistance and thermal stability of hybrid lignocellulosic filler–PVC composites

In this study, composites based on polyvinyl chloride (PVC), pulp fiber (PF), and wood flour (WF) were made by injection molding. The effects of two variable factors, namely the filler form and filler loading level, on the composite physical properties were examined. The result clearly showed that the major part of water absorption was due to water absorption of PF. It was found that the water absorption in the lignocellulosic material base composites is significantly higher than the neat PVC. Besides, the water absorption increased sharply with increasing cellulosic filler loadings in the composites. In case of hybrid composites, the rate of water uptake correlated with percentage weight of WF, lower WF (higher PF) loadings in composites exhibit higher rate of absorption. The higher onset of degradation temperature indicates the improved thermal stability of the samples. In other words, the result clearly illustrates that the thermal property of the composites increases after using PF and further increases after addition of WF.     

Effects of andalusite aggregate pre-fired at different temperatures on volume stability and oxidation resistance of Al2O3–SiC–C castables

In the present work, the effects of the pre-firing temperature of andalusite aggregates (5–3 mm) on the conversion of andalusite as well as the volume stability and oxidation resistance of the Al₂O₃–SiC–C castables were investigated. The phases of the andalusite aggregates were tested via X-ray diffraction, and their microstructures as well as those of the castables were characterized via scanning electron microscopy. The linear expansion of the castables decreased with increase in the pre-firing temperature of andalusite, as less residual andalusite in the pre-fired aggregates lowered its transformation in the castables during firing at high temperatures. Moreover, the higher amounts of SiO₂-rich glass produced by andalusite pre-fired at high temperatures and secondary mullite generated between andalusite and the matrixes were both favorable to the production of castables with denser structure. This prevented the diffusion of O₂ into the castables and improved their oxidation resistance.     

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%.     

Oxidation resistance and thermal cycling properties of the SiCnws–SiC coating on the C/SiC composites

SiC coatings reinforced with SiC nanowires were prepared on carbon/silicon carbide (C/SiC) composites through chemical vapor reaction route and chemical vapor deposition (CVD). The SiC nanowires were introduced to mainly improve the interface bonding properties of the coating and C/SiC composites. The microstructure, phase composition, thermal cycling, and bonding strength of the SiCnws–SiC coating were investigated. After nine thermal cycles, the weight loss of the SiCnws–SiC-coated C/SiC composites was only 4.6 wt.%. Tensile test results show that the tensile strength of the SiCnws–SiC-coated C/SiC composites was more than 4.5–4.6 MPa. The introduction of SiC nanowires effectively improved interface bonding strength, thus enhancing the thermal cycling and mechanical properties of the coating.     

Mullite–zirconia–zircon composites: Properties and thermal shock resistance

In the refractory field mullite and zirconia are the basis of materials used in the glass industry or when high chemical stability and corrosion resistance are necessary. In this work various mullite–zirconia/zircon compositions were investigated to improve the thermal shock (TS) resistance of dense composites produced by slip casting and sintering at 1600 °C. Zircon (SiZrO₄) acts as bonding phase and its thermal decomposition adds zirconia and silica to the material. Resultant composites were characterized by density and dilatometric measurements, XRD and SEM techniques. TS behavior was tested by quenching in water with quenching temperature differentials ΔT from 400 to 1200 °C. The degree of damage after the TS was experimentally evaluated through the variation of the elastic modulus E which is measured by the excitation technique. The severity of the TS test and the effect of the number of thermal cycles on E for each ΔT employed were determined.The tested materials retained their original mechanical properties for temperatures below a critical temperature ΔT_c near 600 °C. Materials quenched from ΔT of 1000 °C showed as much as 30% reduction in E indicating the important microstructure damage. The TS resistance improved with increasing zircon addition to 35 wt% in agreement with the behavior predicted from R parameter for crack initiation.