Journal of the Chinese Ceramic Society, Volume. 52, Issue 6, 2094(2024)
Influence of Impurities in Ordinary Sintered Magnesia Aggregates on Thermal Shock Resistance and High Temperature Fracture Behavior of MgO-C Refractory
Introduction MgO-C refractories are extensively utilized as lining materials for smelting equipment (i.e., converters, ladles, and electric arc furnaces) due to their excellent resistance to slag erosion and thermal shock. Nevertheless, under high scrap ratio smelting conditions, MgO-C refractories are subjected to mechanical stress due to the introduction of scrap steel and thermal stress caused by frequent fluctuations in service temperatures, resulting in a substantial reduction in their operational lifespan. It is thus crucial to further enhance the mechanical properties and thermal shock resistance of MgO-C refractories. In recent years, effective approaches on the composition and structural design of materials are explored, which include the construction of nanostructure matrices, light-weighting and strengthening of magnesia-based aggregates, the introduction of novel additives, and the optimization of secondary carbon in binders. Among them, calcium magnesium aluminate (CMA) aggregates as a novel porous aggregate have attracted much attention. At elevated temperatures, it induces a partial liquid phase within the material matrix, effectively mitigating internal thermal stresses, repairing micro-cracks resulting from thermal shock, and facilitating the formation and growth of spinel whiskers. Consequently, a substantial enhancement in both toughness and thermal shock resistance of the material is achieved. In fact, ordinary sintered magnesia aggregates contain certain impurity phases, such as merwinite (with a melting point of 1 550 ℃) and andradite (with a melting point of 1 170 ℃). When conventional fused magnesia aggregates partially are substituted with ordinary sintered magnesia aggregates in the preparation of MgO-C refractories, localized liquid phases can be generated within the matrix at high temperatures, which may serve a similar function to CMA aggregates. Compared to CMA aggregates, ordinary sintered magnesia aggregates are more affordable, resulting in a substantial reduction in production expenses and facilitating the efficient utilization of low-grade magnesia. In this paper, ordinary sintered magnesia aggregates were selected to partially substitute conventional fused magnesia aggregates in the preparation of MgO-C materials. The microstructure evolution, mechanical properties, thermal shock resistance, and high-temperature fracture behavior of MgO-C refractories containing ordinary sintered magnesia aggregates were investigated.Methods MgO-C refractories were prepared via substituting 10% of ordinary sintered magnesia aggregates (w(MgO)=93.33%, w(SiO2)=1.72%, w(CaO)=3.12%, and w(CaO)/w(SiO2)=1.81, w is mass fraction) for conventional fused magnesia aggregates (w(MgO)=97.35%, w(SiO2)=0.5%, w(CaO)=1.12%, and w(CaO)/w(SiO2)=2.24) with a flake graphite as carbon source, metallic silicon powder and boron carbide as antioxidants, and thermosetting phenolic resin as a binder. After thoroughly blending the aforementioned materials, bar-shaped specimens with the sizes of 140 mm×25 mm×25 mm and standard brick specimens with the sizes of 230 mm×110 mm×70 mm were shaped at 150 MPa and then cured at 200 ℃ for 24 h. The cold modulus of rupture (CMOR) of the bar-shaped specimens, treated at different temperatures (i.e., 200, 1 000, 1 400 ℃ and 1 600 ℃) in a coke bed was measured by a model XD-117A three-point bending test machine. The microstructure and elemental composition of the specimens were determined by a model Nova Nano 400 field emission scanning electron microscope, combined with a model IE 350 PentaFET X-3 energy dispersive spectrometer. The bar-shaped specimens (140 mm×25 mm×25 mm) coked at 1 400 ℃ were selected for thermal shock test by an oil quenching method. Namely, these specimens were initially heated in a coke bed at 900 ℃ for 30 min, followed by quenching in an oil bath. After undergoing three thermal shock cycles, the residual strength index (CMOR after thermal shocks/CMOR before thermal shocks) of specimens was calculated. Subsequently, the bar-shaped specimens after thermal shock test were further heated in the coke bed at 1 600 ℃ for 3 h, and then the recovery strength index (the change of CMOR after reheating to 1 600 ℃/CMOR after thermal shocks) of MgO-C specimens was calculated. In addition, the standard brick specimens were processed into the wedge splitting specimens (100 mm×100 mm×70 mm), and heated in the coke bed at 1 000 ℃. Subsequently, high-temperature wedge splitting tests were conducted at 1 000 ℃ and 1 400 ℃ for 30 min, respectively. The specimens were surrounded in alumina crucibles filled with coke in a high-temperature furnace to establish a reducing atmosphere. Fracture parameters such as the nominal notch tensile strength (σNT), specific fracture energy (Gf), characteristic length (lch) and thermal shock resistance (Rst), were calculated to further quantitatively characterize the thermal shock resistance of specimens.Results and discussion Ordinary sintered magnesia aggregates remain intact in MgO-C refractories coked at 1 000 ℃. However, the impurities within some ordinary sintered magnesia aggregates dissolve and diffuse into the surrounding matrix as the temperature increases to 1 400 ℃, disintegrating the aggregates into a porous structure. In addition, Mg2SiO4 particles and whiskers, as well as SiC whiskers also appear in the matrix due to the introduction of silica powder. The dissolution and diffusion of impurities increase as the temperature further increases to 1 600 ℃, generating Mg2SiO4 particles and SiC whiskers in the matrix. These structural changes in MgO-C refractories at high temperatures enhance the strength, even the high-temperature flexural strength, and improve the thermal shock resistance of MgO-C refractories.The results of high-temperature wedge splitting test show that MgO-C specimens containing ordinary sintered magnesia aggregates exhibit an equivalent peak load to those of the control specimens, while their fracture displacements significantly enlarge. As evident from various fracture parameters, MgO-C specimens containing ordinary sintered magnesia aggregates exhibit higher Gf, lch, and Rst at 1 000 ℃ and 1 400 ℃, indicating that the introduction of ordinary sintered magnesia aggregates effectively reduces the material brittleness due to improving the thermal shock resistance of specimen Also, the specimens containing ordinary sintered magnesia aggregates exhibit a higher proportion of cracks along the aggregate-matrix interface in the crack propagation path. The enhancement of fracture toughness and thermal shock resistance of MgO-C refractories with ordinary sintered magnesia aggregates addition can be attributed to the stress relief provided by the porous structure of ordinary sintered magnesia, the promotion of sintering at 1 400 ℃ by the formation of liquid phases, and the formation of whiskers in the matrix.Conclusions The addition of ordinary sintered magnesia effectively enhanced the thermal shock resistance of MgO-C refractories due to the porous structure of ordinary sintered magnesia aggregate and its ability to form a liquid phase at high temperatures, thereby reducing the overall thermal expansion rate of the specimens. MgO-C specimens containing ordinary sintered magnesia aggregates exhibited higher Gf, lch, and Rst at 1 000 ℃ and 1 400 ℃ due to the higher porosity of the ordinary sintered magnesia aggregates, effectively mitigating the stress concentration. At 1 400 ℃, the impurities in the ordinary sintered magnesia aggregates dissolved and diffused into the matrix to form a liquid phase network that was conducive to absorbing stress at crack tips. The formation of this liquid phase promoted the whiskers formation and slowed down the crack propagation.
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WANG Chao, LI Yawei, XU Xiaofeng, CHEN Qilong, WANG Guanzheng. Influence of Impurities in Ordinary Sintered Magnesia Aggregates on Thermal Shock Resistance and High Temperature Fracture Behavior of MgO-C Refractory[J]. Journal of the Chinese Ceramic Society, 2024, 52(6): 2094
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Received: Sep. 15, 2023
Accepted: --
Published Online: Aug. 26, 2024
The Author Email: Yawei LI (liyawei@wust.edu.cn; xuxiaofeng@wustedu.cn)