Highly glass-liquid-erosion-resistant electrically fused zirconia-corundum refractory material and method for producing the same

Abstract

The application relates to a high-glass-liquid-erosion-resistant electrically-fused zirconia-corundum refractory material and a preparation method thereof, and belongs to the technical field of inorganic nonmetallic refractory materials. The refractory material comprises synergistically modified electrically-fused zirconia-corundum aggregates, electrically-fused zirconia-corundum fine powder, 9,9-bis(4-hydroxy-3-tert-butylphenyl) fluorene, nano silicon dioxide, yttrium oxide and silica sol. The synergistically modified electrically-fused zirconia-corundum aggregates are obtained by constructing a polyphenol-zirconium coordination structure, a dynamic boric ester topological locking structure and a continuous network structure formed by in-situ hydrolysis and polycondensation of organosilicon on the surface of the electrically-fused zirconia-corundum aggregates, and a dense and stable interface barrier layer is further formed in the sintering process. Through the synergistic effect of the interface multiple synergistic network structure and the rigid aromatic reinforcing structure, the glass liquid erosion depth and the element diffusion degree are significantly reduced, the material density and the thermal shock resistance are improved, and the application is suitable for long-term stable service of high-temperature parts of float glass, photovoltaic glass and special glass kilns.

Description

Technical Field

[0001] This invention belongs to the technical field of inorganic non-metallic materials and high-temperature structural functional materials, specifically relating to an electrofused zirconia corundum refractory material with high resistance to glass melt erosion and its preparation method. Background Technology

[0002] Fused zirconia-corundum refractories, due to their high proportion of zirconia and corundum phases, possess excellent high-temperature strength, thermal shock resistance, and low porosity. They are widely used in critical components such as the melting, refining, and runner sections of float glass, photovoltaic glass, and specialty glass furnaces. Under prolonged exposure to high temperatures above 1500℃ and in environments with high alkali and high borosilicate glass melts, the material must withstand multiple destructive factors, including chemical erosion, penetration corrosion, and thermal stress cycling. Therefore, its resistance to glass melt erosion directly affects the furnace's service life and the stability of glass quality.

[0003] However, in actual service, molten glass easily penetrates along grain boundaries, microcracks, and residual pore channels in fused zirconia-corundum materials, reacting with localized zirconia or glass phases, leading to a loose interfacial structure, grain boundary debonding, and a gradually deepening erosion layer. Simultaneously, repeated thermal cycling promotes microcrack propagation, accelerates erosion layer peeling, and ultimately causes localized material failure. Existing technologies for improving erosion resistance mainly include increasing zirconia content, reducing porosity, or introducing small amounts of oxide stabilizers. However, these methods mostly involve adjusting component ratios or densification improvements, and are unlikely to effectively block the penetration path of molten glass at the interfacial structure level.

[0004] In recent years, interface structure regulation has gradually become a research hotspot in the field of refractory materials. However, most studies still focus on simple inorganic oxide doping or particle-scale composites, lacking technical solutions for constructing molecular-level synergistic network structures on the surface of fused zirconia alumina aggregates. Therefore, how to improve the long-term erosion resistance of fused zirconia alumina materials to molten glass without significantly increasing material cost and density through interface structure reconstruction and multi-mechanism synergistic enhancement remains a pressing technical problem to be solved in this field. Summary of the Invention

[0005] To overcome the problems of grain boundary penetration, loose interfacial structure, and continuous expansion of the erosion layer in fused zirconia-alumina refractories under long-term exposure to high-temperature molten glass, as described in the background art, this invention aims to provide a highly resistant fused zirconia-alumina refractories to molten glass erosion and its preparation method. This invention involves interfacial synergistic modification of the fused zirconia-alumina aggregate, constructing a polyphenol-metal coordination structure and a dynamic covalent topological locking structure on the aggregate surface. Furthermore, it introduces in-situ polycondensation of organosilicon to form a continuous inorganic network layer. Simultaneously, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene is added to the system, allowing it to embed into the interfacial structure during firing and participate in high-temperature structural reconstruction, thereby forming a dense and stable interfacial barrier layer. Combined with the synergistic effects of nano-silica, yttrium oxide, and silica sol, the overall density and high-temperature structural stability of the material are improved. Through the combined effect of the multi-synergistic interfacial network structure and the rigid aromatic reinforcing phase, this invention effectively inhibits the penetration of molten glass along grain boundaries and significantly reduces the thickness of the erosion layer, thereby improving the high-temperature resistance of fused zirconia-alumina refractories to molten glass erosion.

[0006] The objective of this invention can be achieved through the following technical solutions: A highly resistant fused zirconia-corundum refractory material, comprising the following raw materials in parts by weight: 70-85 parts of synergistically modified fused zirconia-corundum aggregate; 10-20 parts of fused zirconia-corundum fine powder; 0.2-1.5 parts of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene; 0.5-3.0 parts of nano-silica; 0.2-2.0 parts of yttrium oxide; and 3-8 parts of silica sol. The synergistically modified fused zirconia-corundum aggregate is synthesized by synergistic modification of fused zirconia-corundum aggregate with gallic acid, catechol, phenylboronic acid, zirconium nitrate, and vinyltriethoxysilane through interfacial polyphenol-zirconia coordination reaction, dynamic borate ester bond construction, and in-situ hydrolysis and polycondensation reaction of organosilicon.

[0007] Optionally, the synergistically modified fused zirconia-corundum aggregate comprises the following raw materials in parts by weight: 85-95 parts of fused zirconia-corundum aggregate; 0.5-3.0 parts of gallic acid; 0.5-3.0 parts of catechol; 0.5-3.0 parts of phenylboronic acid; 0.2-2.0 parts of zirconium nitrate; and 0.5-4.0 parts of vinyltriethoxysilane.

[0008] Optionally, the preparation method of synergistically modified fused zirconia corundum aggregate includes the following steps: (1) The fused zirconia alumina aggregate is mixed with gallic acid and catechol, so that the polyphenols are adsorbed on the surface of the aggregate and form a polyphenol interface layer, thus obtaining polyphenol-coated fused zirconia alumina aggregate. (2) Add phenylboronic acid and zirconium nitrate to polyphenol-coated fused zirconium corundum aggregate to react, so that catechol and phenylboronic acid form a dynamic borate ester structure, and at the same time, the polyphenol hydroxyl group and zirconium ion undergo coordination reaction to construct a coordination-dynamic covalent composite network layer on the surface of the aggregate, and obtain coordination-topology locked composite aggregate. (3) Add vinyltriethoxysilane to the coordination-topology locked composite aggregate for hydrolysis and polycondensation reaction to form a continuous Si–O–Si network structure in situ on the aggregate surface. After drying, synergistically modified fused zirconia corundum aggregate is obtained.

[0009] Optionally, the reaction conditions in step (1) are as follows: dispersion in deionized water or ethanol-water mixed solvent system, stirring speed of 300-800 r / min, temperature of 30-50℃, reaction time of 1-2 h, and system pH controlled at 5.0-6.5.

[0010] Optionally, the reaction conditions in step (2) are: stirring at 40-70°C for 1.5-3 hours, stirring speed of 400-900 r / min, and pH of the system adjusted to 6.0-7.5 to promote polyphenol-zirconium coordination and borate ester bond formation.

[0011] Optionally, the reaction conditions in step (3) are as follows: hydrolysis and polycondensation reaction is carried out at 50-80°C for 2-4 hours, stirring speed is 300-700 r / min, and then drying is carried out at 100-120°C for 4-8 hours to fully solidify the organosilicon network.

[0012] Optionally, a method for preparing an electrofused zirconia-corundum refractory material with high resistance to molten glass erosion includes the following steps: S1, the synergistically modified fused zirconia alumina aggregate, fused zirconia alumina fine powder, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, nano-silica and yttrium oxide are dry-mixed according to the proportions and mixed evenly to obtain a uniform mixture; S2, add silica sol to the obtained uniform mixture for wet mixing, so that the components are fully dispersed and form a plastic preform mixture; S3. The resulting mixture is shaped, dried, and then fired at high temperature to obtain an fused zirconia corundum refractory material with high resistance to glass melt erosion.

[0013] Optionally, the reaction conditions in step S1 are a dry mixing time of 10–30 min and a mixing speed of 20–60 r / min.

[0014] Optionally, the reaction conditions for step S2 are as follows: the amount of silica sol added is 3-8% of the total mass of the mixture, the wet mixing time is 5-20 min, and the mixing temperature is 20-40℃.

[0015] Optionally, the reaction conditions for step S3 are: molding pressure of 50-200 MPa, drying temperature of 100-150°C, drying time of 12-48 h, firing temperature of 1550-1700°C, and holding time of 3-8 h.

[0016] The beneficial effects of this invention are: This invention constructs a polyphenol-zirconium coordination structure and a dynamic borate ester topological locking structure on the surface of fused zirconia-corundum aggregate, and combines this with in-situ polycondensation of organosilicon to form a continuous and dense inorganic network layer. This creates a stable three-dimensional synergistic barrier structure at the microscopic interface. Simultaneously, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene is introduced, which undergoes structural reconstruction during the high-temperature sintering stage to form a high-carbon residual rigid reinforcing phase. This blocks the penetration path of molten glass along grain boundaries and micropore channels at the molecular scale, significantly reducing the erosion rate and eroded layer thickness, improving interfacial bonding strength and structural integrity, and maintaining excellent crack propagation resistance and spalling stability under repeated thermal cycling conditions. This enables the material to achieve long-term stable service in a high-temperature molten glass environment. Attached Figure Description

[0017] The invention will now be further described with reference to the accompanying drawings.

[0018] Figure 1 The infrared spectra of fused zirconia-corundum aggregate and synergistically modified fused zirconia-corundum aggregate are compared. Figure 2 For samples with different proportions. Detailed Implementation

[0019] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.

[0020] Example 1: This example aims to verify that even when all components and process parameters are at their lower limits, the present invention can still form an effective interface synergistic network structure and possess the ability to resist glass melt erosion.

[0021] Preparation process S1, Preparation of synergistically modified fused zirconia-corundum aggregate 85 parts of fused zirconia-corundum aggregate were weighed and added to deionized water. The mixture was dispersed at 300 r / min, heated to 30℃, and the pH of the system was adjusted to 5.0. 0.5 parts of gallic acid and 0.5 parts of catechol were added, and the mixture was reacted for 1 h to allow polyphenols to adsorb onto the aggregate surface and form a polyphenol interface layer, thus obtaining polyphenol-coated fused zirconia-corundum aggregate. Subsequently, 0.5 parts of phenylboronic acid and 0.2 parts of zirconium nitrate were added to the system, and the mixture was reacted at 40℃ and 400 r / min for 1.5 h. The pH was adjusted to 6.0 to allow catechol and phenylboronic acid to form a dynamic borate ester structure. At the same time, the polyphenol hydroxyl groups underwent a coordination reaction with zirconium ions, resulting in a coordination-topologically locked composite aggregate. 0.5 parts of vinyltriethoxysilane were added, and the mixture was hydrolyzed and polycondensed at 50℃ and 300 r / min for 2 h. The mixture was then dried at 100℃ for 4 h to obtain synergistically modified fused zirconia-corundum aggregate.

[0022] S2, Mix Weigh out 70 parts of synergistically modified fused zirconia-corundum aggregate, 10 parts of fused zirconia-corundum fine powder, 0.2 parts of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 0.5 parts of nano-silica, and 0.2 parts of yttrium oxide. Dry mix for 10 min at a speed of 20 r / min. Add silica sol to the mixture so that the silica sol accounts for 3% of the total mass of the mixture. Wet mix at 20℃ for 5 min to obtain a plastic blank mixture. S3 Forming and Firing The mixture was molded under 50 MPa pressure, dried at 100℃ for 12 h, and then fired at 1550℃ and held for 3 h to obtain a highly resistant fused zirconia-corundum refractory material to glass melt erosion.

[0023] Example 2: This example aims to verify that under the recommended median conditions, the interface cooperative network structure is most complete, and the material density and erosion resistance reach the best balance.

[0024] Preparation process S1, Preparation of synergistically modified fused zirconia-corundum aggregate 90 parts of fused zirconia-corundum aggregate were weighed and dispersed in deionized water at 500 r / min. The temperature was raised to 40℃ and the pH was adjusted to 5.8. 1.5 parts of gallic acid and 1.5 parts of catechol were added and reacted for 1.5 h to obtain polyphenol-coated fused zirconia-corundum aggregate. 1.5 parts of phenylboronic acid and 1.0 part of zirconium nitrate were added and reacted at 55℃ and 600 r / min for 2 h. The pH was adjusted to 6.8 to obtain coordination-topological locking composite aggregate. 2.0 parts of vinyltriethoxysilane were added and hydrolyzed and polycondensed at 65℃ and 500 r / min for 3 h. Then, the mixture was dried at 110℃ for 6 h to obtain synergistically modified fused zirconia-corundum aggregate. Figure 1Infrared spectral comparisons show that the unmodified fused zirconia-corundum aggregate mainly exhibits Zr–O and Al–O lattice vibration characteristic peaks in the 650–400 cm⁻¹ region, with only weak adsorbed water hydroxyl peaks in the high wavenumber region, resulting in a relatively simple overall spectrum. The modified sample shows a significantly enhanced broad peak near 3400 cm⁻¹, indicating the introduction of polyphenolic hydroxyl structures. Aromatic ring framework vibration peaks appear near 1600 cm⁻¹ and 1500 cm⁻¹, while a broad and strong absorption band forms in the 1100–1000 cm⁻¹ region, corresponding to the Si–O–Si network structure. Furthermore, a B–O-related vibration peak appears around 900 cm⁻¹. These newly added and enhanced peaks indicate that a coordination and silicon-oxygen synergistic network structure has been successfully constructed on the aggregate surface, significantly altering the interface structure. S2, Mix Weigh out 78 parts of synergistically modified fused zirconia-corundum aggregate, 15 parts of fused zirconia-corundum fine powder, 0.8 parts of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 1.5 parts of nano-silica, and 1.0 parts of yttrium oxide. Dry mix for 20 min at a speed of 40 r / min. Add silica sol to make it account for 5% of the total mass of the mixture and wet mix at 30℃ for 12 min. S3, Shaping and Firing Molded under 120 MPa pressure, dried at 120℃ for 24 h, and then fired at 1650℃ and held for 5 h, a dense fused zirconia corundum refractory material was obtained.

[0025] Example 3: This example aims to verify that, under the upper limits of composition and process parameters, the system of the present invention can still maintain the stability of the interface structure and further improve the resistance to erosion.

[0026] Preparation process S1, Preparation of synergistically modified fused zirconia-corundum aggregate 95 parts of fused zirconia-corundum aggregate were weighed and dispersed in deionized water at 800 r / min. The temperature was raised to 50℃ and the pH was adjusted to 6.5. 3.0 parts of gallic acid and 3.0 parts of catechol were added and reacted for 2 h to obtain polyphenol-coated fused zirconia-corundum aggregate. 3.0 parts of phenylboronic acid and 2.0 parts of zirconium nitrate were added and reacted at 70℃ and 900 r / min for 3 h. The pH was adjusted to 7.5 to obtain coordination-topological locking composite aggregate. 4.0 parts of vinyltriethoxysilane were added and hydrolyzed and polycondensed at 80℃ and 700 r / min for 4 h. Then, the mixture was dried at 120℃ for 8 h to obtain synergistically modified fused zirconia-corundum aggregate. S2, Mix Weigh out 85 parts of synergistically modified fused zirconia-corundum aggregate, 20 parts of fused zirconia-corundum fine powder, 1.5 parts of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 3.0 parts of nano-silica, and 2.0 parts of yttrium oxide. Dry mix for 30 min at a speed of 60 r / min. Add silica sol to make it account for 8% of the total mass of the mixture and wet mix at 40℃ for 20 min. S3, Shaping and Firing Molded under 200 MPa pressure, dried at 150°C for 48 hours, and then fired at 1700°C and held for 8 hours, yielded a highly resistant fused zirconia-corundum refractory material to glass melt erosion.

[0027] Comparative Example 1: This comparative example aims to verify the effect of only "polyphenol-zirconium coordination" single modification on fused zirconia corundum aggregate.

[0028] Preparation process S1, Preparation of synergistically modified fused zirconia-corundum aggregate 90 parts of fused zirconia-corundum aggregate were weighed and dispersed in deionized water at 500 r / min. The temperature was raised to 40℃ and the pH was adjusted to 5.8. 1.5 parts of gallic acid and 1.5 parts of catechol were added and reacted for 1.5 h to obtain polyphenol-coated fused zirconia-corundum aggregate. 1.0 part of zirconium nitrate was added and reacted at 55℃ and 600 r / min for 2 h. The pH was adjusted to 6.8 to allow the polyphenol hydroxyl groups to coordinate with zirconium ions. The mixture was then dried at 110℃ for 6 h to obtain fused zirconia-corundum aggregate modified only by polyphenol-zirconia coordination. S2, Mix Weigh out 78 parts of the above-mentioned single modified fused zirconia alumina aggregate, 15 parts of fused zirconia alumina fine powder, 0.8 parts of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 1.5 parts of nano-silica and 1.0 parts of yttrium oxide, dry mix for 20 min at 40 r / min; add silica sol to make it account for 5% of the total mass of the mixture, and wet mix at 30℃ for 12 min; S3, Shaping and Firing Molded under 120 MPa pressure, dried at 120℃ for 24 h, and then fired at 1650℃ and held for 5 h, the fused zirconia-corundum refractory material was obtained.

[0029] Comparative Example 2: This comparative example aims to verify the effect of "organosilicon in-situ hydrolysis and polycondensation" as the sole modification of fused zirconia-corundum aggregate.

[0030] Preparation process S1, Preparation of synergistically modified fused zirconia-corundum aggregate 90 parts of fused zirconia-corundum aggregate were weighed and dispersed in deionized water at 500 r / min. The temperature was raised to 40℃. 2.0 parts of vinyltriethoxysilane were added and hydrolyzed and polycondensed at 65℃ and 500 r / min for 3 h. Then the mixture was dried at 110℃ for 6 h to obtain fused zirconia-corundum aggregate modified only by in-situ hydrolysis and polycondensation of organosilicon. S2, Mix Weigh out 78 parts of the above-mentioned single modified fused zirconia alumina aggregate, 15 parts of fused zirconia alumina fine powder, 0.8 parts of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, 1.5 parts of nano-silica and 1.0 parts of yttrium oxide, dry mix for 20 min at 40 r / min; add silica sol to make it account for 5% of the total mass of the mixture, and wet mix at 30℃ for 12 min; S3, Shaping and Firing Molded under 120 MPa pressure, dried at 120℃ for 24 h, and then fired at 1650℃ and held for 5 h, the fused zirconia-corundum refractory material was obtained.

[0031] Comparative Example 3: This comparative example aims to verify the effect of not adding 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene while keeping the synergistically modified aggregate of Example 2 unchanged.

[0032] Preparation process S1, Preparation of synergistically modified fused zirconia-corundum aggregate 90 parts of fused zirconia-corundum aggregate were weighed and dispersed in deionized water at 500 r / min. The temperature was raised to 40℃ and the pH was adjusted to 5.8. 1.5 parts of gallic acid and 1.5 parts of catechol were added and reacted for 1.5 h to obtain polyphenol-coated fused zirconia-corundum aggregate. 1.5 parts of phenylboronic acid and 1.0 part of zirconium nitrate were added and reacted at 55℃ and 600 r / min for 2 h. The pH was adjusted to 6.8 to obtain coordination-topological locking composite aggregate. 2.0 parts of vinyltriethoxysilane were added and hydrolyzed and polycondensed at 65℃ and 500 r / min for 3 h. Then, the mixture was dried at 110℃ for 6 h to obtain synergistically modified fused zirconia-corundum aggregate. S2, Mix Weigh out 78 parts of synergistically modified fused zirconia alumina aggregate, 15 parts of fused zirconia alumina fine powder, 1.5 parts of nano silica and 1.0 parts of yttrium oxide, dry mix for 20 min at a speed of 40 r / min; add silica sol to make it account for 5% of the total mass of the mixture, and wet mix at 30℃ for 12 min. S3, Shaping and Firing Molded under 120 MPa pressure, dried at 120℃ for 24 h, and then fired at 1650℃ and held for 5 h, the fused zirconia-corundum refractory material was obtained.

[0033] Performance testing: 1. Static Erosion Test Method for Molten Glass The samples from each embodiment and comparative example were processed into cubic specimens with dimensions of 30mm × 30mm × 30mm. A cylindrical groove with a diameter of 20mm and a depth of 20mm was machined in the center of each specimen. Glass material with the same composition as industrial float glass was used and filled into the groove until it was full. The specimens were placed in a high-temperature silicon molybdenum rod furnace and heated to 1600℃ at a heating rate of 5℃ / min. The temperature was maintained in air for 72 hours, and then cooled to room temperature with the furnace. After cooling, the specimens were cut along the longitudinal center, ground and polished, and the maximum erosion depth and average erosion thickness of the molten glass along the grain boundary direction were measured under a metallographic microscope. At least 5 measurement points were selected for each sample, and the average value was taken. The smaller the erosion depth, the better the resistance to molten glass erosion.

[0034] 2. Methods for analyzing the microstructure and elemental distribution of interfaces After the etching test, the cross-sections of the samples were progressively sanded and then polished with diamond. The microstructure of the etched layer, transition layer, and unetched areas was then observed under a scanning electron microscope. Grain boundary structure, glass phase penetration, and interface compactness were observed at magnifications ranging from 500 to 5000x. Simultaneously, energy dispersive spectroscopy (EDS) was used to perform line and area scan analyses of elements such as Si, Na, Zr, and Al within the etched area. The diffusion depth of glass melt elements into the matrix was compared among the samples to evaluate interfacial barrier capacity and structural stability.

[0035] 3. Test methods for bulk density and apparent porosity The Archimedes method was used to determine the bulk density and apparent porosity. The samples were processed into blocks of 50 mm × 50 mm × 50 mm, dried at 110 °C to constant weight, and the dry weight (m1) was recorded. The samples were then boiled in boiling water for 2 hours to allow the pores to fully absorb water. After cooling to room temperature, the saturated mass (m2) and the suspended mass (m3) in water were measured. Higher bulk density and lower apparent porosity indicate better material compactness, which is beneficial for improving resistance to glass melt penetration.

[0036] 4. Thermal shock resistance test method After firing, the samples were processed into strips measuring 25mm × 25mm × 150mm. The samples were placed in a 1000℃ resistance furnace for 30 minutes, then quickly removed and immersed in 20℃ clean water for cooling within 5 seconds, completing one thermal shock cycle. After each cycle, the surface cracks of the sample were observed and the mass was measured. The cycle was repeated in the above manner until a through crack appeared or the mass loss exceeded 5%. The maximum number of cycles the sample withstood was recorded. A higher number of cycles indicates better thermal shock resistance of the material.

[0037] Table 1 Performance test results of each sample

[0038] As shown in Table 1, Example 2 exhibits the best performance across all performance indicators. Figure 2 The erosion depth of the glass melt was 3.2 mm, which was significantly lower than 4.8 mm in Example 1 and 3.6 mm in Example 3, and significantly better than 6.5 mm in Comparative Example 1, 6.0 mm in Comparative Example 2, and 4.5 mm in Comparative Example 3. At the same time, the element diffusion depth of its erosion layer was only 45 μm, while that of Example 1 and Example 3 was 85 μm and 60 μm, respectively, while that of Comparative Example 1 and Comparative Example 2 reached 140 μm and 120 μm, respectively, and that of Comparative Example 3 was 75 μm. This shows that the interface synergistic network structure constructed under the recommended median conditions can effectively block the diffusion of active elements in the glass melt into the matrix and significantly improve the interface barrier ability.

[0039] In terms of density, Example 2 had the highest bulk density of 3.74 g·cm⁻³, while Examples 1 and 3 had 3.62 g·cm⁻³ and 3.71 g·cm⁻³, respectively. Comparative Examples 1 and 2 had only 3.48 g·cm⁻³ and 3.52 g·cm⁻³, respectively, and Comparative Example 3 had 3.65 g·cm⁻³. Regarding apparent porosity, Example 2 had the lowest at 12.6%, while Examples 1 and 3 had 15.8% and 13.4%, respectively. Comparative Examples 1 and 2 increased to 18.9% and 17.6%, respectively, and Comparative Example 3 had 14.9%. These data indicate that the synergistic effect of the modified structure and 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene significantly promoted the sintering densification process, reduced pore connectivity channels, and thus improved the overall density of the material.

[0040] Regarding thermal shock resistance, Example 2 withstood 28 cycles, significantly higher than Example 1's 18 cycles and Example 3's 24 cycles, and also superior to Comparative Example 1's 12 cycles, Comparative Example 2's 14 cycles, and Comparative Example 3's 20 cycles. This indicates that the synergistic network structure can effectively suppress crack propagation and improve interfacial bonding strength and structural integrity. In particular, Comparative Example 3, without the addition of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, showed an increase in erosion depth from 3.2 mm in Example 2 to 4.5 mm, and a decrease in the number of thermal shock cycles from 28 to 20. This further demonstrates that this small organic molecule participates in interfacial structural reconstruction and plays a key reinforcing role during high-temperature sintering.

[0041] In summary, this invention constructs a synergistic interface system of polyphenol-zirconium coordination structure, dynamic borate ester topological locking structure, and organosilicon continuous network structure, and introduces 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene to form a high-temperature reinforcing phase. This results in materials that are significantly superior to single-modification systems in terms of erosion depth, element diffusion inhibition, compactness, and thermal shock resistance. Among these, Example 2 exhibits the best overall performance under median conditions, fully verifying the effectiveness and superiority of the technical solution of this invention.

Claims

1. A highly resistant fused zirconia-corundum refractory material to molten glass corrosion, characterized in that, The refractory material comprises the following raw materials in parts by weight: 70-85 parts of synergistically modified fused zirconia-corundum aggregate; 10-20 parts of fused zirconia-corundum fine powder; 0.2-1.5 parts of 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene; 0.5-3.0 parts of nano-silica; 0.2-2.0 parts of yttrium oxide; and 3-8 parts of silica sol. The synergistically modified fused zirconia-corundum aggregate is synthesized by synergistic modification of fused zirconia-corundum aggregate with gallic acid, catechol, phenylboronic acid, zirconium nitrate, and vinyltriethoxysilane through interfacial polyphenol-zirconia coordination reaction, dynamic borate ester bond construction, and in-situ hydrolysis and polycondensation reaction of organosilicon.

2. The fused zirconia-corundum refractory material with high resistance to molten glass erosion according to claim 1, characterized in that, The synergistically modified fused zirconia-corundum aggregate comprises the following raw materials in parts by weight: 85-95 parts fused zirconia-corundum aggregate; 0.5-3.0 parts gallic acid; 0.5-3.0 parts catechol; 0.5-3.0 parts phenylboronic acid; 0.2-2.0 parts zirconium nitrate; and 0.5-4.0 parts vinyltriethoxysilane.

3. The fused zirconia-corundum refractory material with high resistance to molten glass erosion according to claim 1 or 2, characterized in that, The preparation method of the synergistically modified fused zirconia corundum aggregate includes the following steps: (1) The fused zirconia alumina aggregate is mixed with gallic acid and catechol, so that the polyphenols are adsorbed on the surface of the aggregate and form a polyphenol interface layer, thus obtaining polyphenol-coated fused zirconia alumina aggregate. (2) Add phenylboronic acid and zirconium nitrate to polyphenol-coated fused zirconium corundum aggregate to react, so that catechol and phenylboronic acid form a dynamic borate ester structure, and at the same time, the polyphenol hydroxyl group and zirconium ion undergo coordination reaction to construct a coordination-dynamic covalent composite network layer on the surface of the aggregate, and obtain coordination-topology locked composite aggregate. (3) Add vinyltriethoxysilane to the coordination-topology locked composite aggregate for hydrolysis and polycondensation reaction to form a continuous Si–O–Si network structure in situ on the aggregate surface. After drying, synergistically modified fused zirconia corundum aggregate is obtained.

4. The fused zirconia-corundum refractory material with high resistance to molten glass erosion according to claim 3, characterized in that, The reaction conditions for step (1) are as follows: dispersion is carried out in a deionized water or ethanol-water mixed solvent system, stirring speed is 300-800 r / min, temperature is 30-50℃, reaction time is 1-2 h, and pH of the system is controlled at 5.0-6.

5.

5. The fused zirconia-corundum refractory material with high resistance to molten glass erosion according to claim 3, characterized in that, The reaction conditions for step (2) are: stirring at 40-70°C for 1.5-3 hours, stirring speed of 400-900 r / min, and pH of the system adjusted to 6.0-7.5 to promote polyphenol-zirconium coordination and borate ester bond formation.

6. The fused zirconia-corundum refractory material with high resistance to molten glass erosion according to claim 3, characterized in that, The reaction conditions for step (3) are as follows: hydrolysis and polycondensation reaction is carried out at 50-80°C for 2-4 hours, stirring at 300-700 r / min, followed by drying at 100-120°C for 4-8 hours to fully solidify the organosilicon network.

7. A method for preparing an electrofused zirconia-corundum refractory material with high resistance to molten glass erosion, characterized in that, The preparation method includes the following steps: S1, the synergistically modified fused zirconia alumina aggregate, fused zirconia alumina fine powder, 9,9-bis(4-hydroxy-3-tert-butylphenyl)fluorene, nano-silica and yttrium oxide are dry-mixed according to the proportions and mixed evenly to obtain a uniform mixture; S2, add silica sol to the obtained uniform mixture for wet mixing, so that the components are fully dispersed and form a plastic preform mixture; S3. The resulting mixture is shaped, dried, and then fired at high temperature to obtain an fused zirconia corundum refractory material with high resistance to glass melt erosion.

8. The method for preparing a highly resistant fused zirconia-corundum refractory material to molten glass corrosion according to claim 7, characterized in that, The reaction conditions for step S1 are a dry mixing time of 10–30 min and a mixing speed of 20–60 r / min.

9. The method for preparing a highly resistant fused zirconia-corundum refractory material to molten glass corrosion according to claim 7, characterized in that, The reaction conditions for step S2 are as follows: the amount of silica sol added is 3-8% of the total mass of the mixture, the wet mixing time is 5-20 min, and the mixing temperature is 20-40℃.

10. The method for preparing a highly resistant fused zirconia-corundum refractory material to molten glass corrosion according to claim 7, characterized in that, The reaction conditions for step S3 are: molding pressure of 50-200 MPa, drying temperature of 100-150℃, drying time of 12-48 h, firing temperature of 1550-1700℃, and holding time of 3-8 h.

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