Low-bubble-precipitation fused zirconia corundum material for glass kiln and preparation method of low-bubble-precipitation fused zirconia corundum material
Patent Information
- Application Number
- CN202610177430.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-07
- Publication Date
- 2026-05-26
Smart Images
Figure CN122079608A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of refractory materials and high-temperature structural materials for glass kilns, specifically relating to a low-bubble precipitated fused zirconium corundum material for key parts of glass kilns and its preparation method. Background Technology
[0002] Fused zirconia-alumina materials are widely used in critical components such as the walls, troughs, and refining zones of melting furnaces for float glass, photovoltaic glass, and high-end display glass due to their excellent high-temperature resistance and resistance to molten glass corrosion. As glass products develop towards larger sizes, higher transmittance, and higher uniformity, the requirements for controlling defects such as bubbles, streaks, and inclusions in molten glass are becoming increasingly stringent. The bubble precipitation problem generated by fused zirconia-alumina materials during service is gradually becoming a significant factor affecting glass quality.
[0003] Under high-temperature conditions, existing fused zirconia-alumina materials are prone to gas nucleation and bubble formation within the material or at the interface with molten glass due to factors such as residual volatiles in the raw materials, grain boundary micropores, and uneven distribution of impurity phases. Once these bubbles enter the molten glass, they are difficult to eliminate completely in a short time, easily forming visible defects in glass products and reducing the product yield.
[0004] Existing technologies typically reduce bubble precipitation by increasing the purity of raw materials, enhancing densification, or introducing a single sintering aid. However, these methods often focus on macroscopic densification or simply suppressing volatilization, making it difficult to effectively control the grain boundary structure and interfacial chemical state between the alumina and zirconium oxide phases. Furthermore, they may weaken the material's resistance to glass melt erosion or its thermal stability to some extent, making it difficult to balance low bubble precipitation with long-term service reliability.
[0005] Therefore, there is an urgent need for a low-bubble precipitated fused zirconia alumina material and its preparation method that can synergistically regulate gas nucleation and migration behavior from the perspective of grain boundary structure and interface chemistry without significantly reducing the corrosion resistance and high-temperature stability of fused zirconia alumina materials, so as to meet the higher requirements of high-end glass furnaces for refractory material performance. Summary of the Invention
[0006] To overcome the technical challenges of bubble precipitation in fused zirconia-alumina materials during high-temperature service and the difficulty in simultaneously achieving low bubble precipitation performance and resistance to molten glass corrosion, as described in the background, this invention aims to provide a low-bubble-precipitation fused zirconia-alumina material for glass furnaces and its preparation method. This invention introduces a polyphenol-nitrogen-containing organosilicon-variable-valence metal coordination synergistic modifier into the traditional fused zirconia-alumina material system, combined with specific small-molecule organic functional regulators, sintering aids, and microstructure regulating agents. Through the electrofusion process, the grain boundary structure and interfacial chemical state of the material are synergistically regulated, thereby suppressing gas nucleation and aggregation within the material. This invention achieves a significant reduction in bubble precipitation under glass furnace service conditions without significantly reducing the high-temperature resistance and molten glass corrosion resistance of the fused zirconia-alumina material.
[0007] The objective of this invention can be achieved through the following technical solutions: A low-bubble-exudation fused zirconia-alumina material for glass furnaces, comprising the following raw materials in parts by weight: 45-60 parts alumina; 30-45 parts zirconia; 0.3-3.0 parts polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier; 0.05-1.5 parts organic small molecule functional regulator; 0.2-2.0 parts sintering aid; and 0.05-1.0 parts microstructure regulating aid; wherein the polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier is composed of propionic acid gallate. The material is composed of ester, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and cerium nitrate. During the electrofusion process, propyl gallate, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and cerium nitrate form a synergistic modification network in the grain boundary region between the alumina and zirconium oxide phases through multi-site coordination, silicon-oxygen condensation reaction, and interfacial bonding to regulate the grain boundary structure and reduce gas nucleation and aggregation inside the material. The organic small molecule functional regulator is 1,3,5-triazine-2,4,6-tricarboxamide.
[0008] Optionally, the polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier includes the following raw materials in parts by weight: propyl gallate 0.1 to 1.5 parts; N-(2-aminoethyl)-3-aminopropyltrimethoxysilane 0.1 to 1.0 parts; cerium nitrate 0.05 to 0.5 parts.
[0009] Optionally, the preparation method of the polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier includes the following steps: (1) Add propyl gallate to a solvent to dissolve it, and a polyphenol solution is obtained; (2) Add N-(2-aminoethyl)-3-aminopropyltrimethoxysilane to the polyphenol solution to induce pre-hydrolysis and condensation reactions, thereby obtaining a nitrogen-containing organosilicon prepolymer system; (3) Add cerium nitrate to the nitrogen-containing organosilicon prepolymer system, remove the solvent after reaction, and obtain a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier.
[0010] Optionally, the reaction conditions for step (1) are stirring at 25–40°C for 10–30 min in a mixed solvent of ethanol and deionized water.
[0011] Optionally, the reaction conditions in step (2) are to control the pH of the system to 8.0 to 9.5 and to stir for 30 to 60 minutes at room temperature to 40°C.
[0012] Optionally, the reaction conditions in step (3) are to react at 40-60°C for 0.5-2.0 h and remove the solvent under reduced pressure at 40-70°C.
[0013] Optionally, the sintering aid is a mixture of yttrium oxide and magnesium oxide in a mass ratio of 1-5:1-3; the microstructure regulating aid is a mixture of sodium borate and ammonium dihydrogen phosphate in a mass ratio of 1-4:1-4.
[0014] Optionally, a method for preparing an electrofused zirconia-corundum material for glass furnaces with low bubble precipitation, the method comprising the following steps: S1. Weigh alumina, zirconium oxide, polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier, organic small molecule functional regulator, sintering aid and microstructure regulating aid, and mix them to obtain a uniform mixture. S2, the mixture is fed into an electric melting furnace for melting treatment, so that the components can fully react under high temperature conditions and form a molten system; S3 involves casting the molten system after electrofusion treatment into a molded shape and then subjecting it to controlled cooling to obtain an electrofused zirconia-corundum material for glass furnaces with low bubble precipitation.
[0015] Optionally, the reaction conditions for step S1 are to mix the materials at room temperature using mechanical stirring or mixing equipment for a mixing time of 10 to 40 minutes; the reaction conditions for step S2 are to melt the materials in an electric furnace at 1900 to 2100°C for a melting time of 0.5 to 3.0 hours.
[0016] Optionally, the reaction conditions in step S3 are as follows: after the molten system is cast into a mold, it is cooled under controlled cooling conditions at a cooling rate of 1 to 10 °C / min.
[0017] The beneficial effects of this invention are: This invention introduces a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier, composed of propyl gallate, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and cerium nitrate, into fused zirconia-corundum materials. This synergistic effect of the polyphenol coordination structure, silicon-oxygen network, and variable valence metal ions during the fusion process forms a stable and continuous modified network at the grain boundary region between the alumina and zirconia phases. This effectively reconstructs the grain boundary structure and weakens the nucleation and retention conditions of gases at the grain boundaries, reducing the probability of bubble formation at the microscopic level. Furthermore, the introduction of 1,3,5-triazine-2,4,6-tricarboxamide, a small organic molecule previously unused in fused zirconia-corundum materials, allows for controlled decomposition at high temperatures and participation in grain boundary rearrangement. This further promotes micropore passivation and optimizes gas migration pathways, significantly suppressing bubble precipitation towards the molten glass side. This invention achieves a long-term stable low-bubble precipitation effect while maintaining the high temperature resistance and glass melt erosion resistance of fused zirconia corundum material, making it particularly suitable for key parts of glass furnaces with high glass quality requirements. Attached Figure Description
[0018] The invention will now be further described with reference to the accompanying drawings.
[0019] Figure 1 The infrared spectra of fused zirconia-corundum matrix material and fused zirconia-corundum material modified with polyphenol-nitrogen-containing organosilicon-metal coordination are compared. Figure 2 Infrared spectra comparison of bubble precipitation frequencies for samples with different formulation ratios; Figure 3 A comparison chart showing the average bubble size of samples with different proportions. Detailed Implementation
[0020] 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.
[0021] Example 1: This example aims to prepare a low-bubble-extrusion fused zirconium corundum material under low raw material dosage and process conditions, in order to verify the basic regulatory effect of the polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modification system on the bubble extrusion behavior of the material when the degree of synergistic modification is low.
[0022] S1, Preparation of Polyphenol-Nitrogen-Containing Organosilicon-Variable Valence Metal Coordination Synergistic Modifier 0.1 parts of propyl gallate were added to a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and stirred at 25°C for 10 min to fully dissolve the polyphenol solution. 0.1 parts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were added to the polyphenol solution, and the pH of the system was controlled at 8.0. The mixture was stirred at room temperature for 30 min to induce pre-hydrolysis and condensation reactions, yielding a nitrogen-containing organosilicon prepolymer system. 0.05 parts of cerium nitrate were added to the nitrogen-containing organosilicon prepolymer system, and the mixture was reacted at 40°C for 0.5 h. Subsequently, the solvent was removed under reduced pressure at 40°C to obtain a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier. S2, Preparation of fused zirconia-corundum material Weigh out 45 parts of alumina, 30 parts of zirconium oxide, 0.3 parts of synergistic modifier, 0.05 parts of 1,3,5-triazine-2,4,6-tricarboxamide, 0.2 parts of sintering aid and 0.05 parts of microstructure regulating aid, mix them evenly and put them into an electric melting furnace, and melt them at 1900℃ for 0.5h. S3, Molding and Cooling The molten system was cast into a mold and then cooled in a controlled manner at a cooling rate of 1℃ / min to obtain an electrofused zirconia corundum material with low bubble precipitation.
[0023] Example 2: This example aims to prepare a low-bubble-precipitation fused zirconia-alumina material by using a moderate raw material ratio and process conditions, in order to obtain a material with significant synergistic modification effect, stable grain boundary structure and excellent bubble precipitation suppression performance.
[0024] S1, Preparation of Polyphenol-Nitrogen-Containing Organosilicon-Variable Valence Metal Coordination Synergistic Modifier 0.8 parts of propyl gallate were added to a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and stirred at 32°C for 20 min to obtain a polyphenol solution. 0.55 parts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were added to the polyphenol solution, and the pH of the system was controlled at 8.8. The mixture was stirred at 30°C for 45 min to obtain a nitrogen-containing organosilicon prepolymer system. 0.25 parts of cerium nitrate were added to the prepolymer system, and the mixture was reacted at 50°C for 1.2 h. The solvent was then removed under reduced pressure at 55°C to obtain a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier. S2, Preparation of fused zirconia-corundum material Weigh out 52 parts of alumina, 38 parts of zirconium oxide, 1.5 parts of synergistic modifier, 0.8 parts of 1,3,5-triazine-2,4,6-tricarboxamide, 1.1 parts of sintering aid and 0.5 parts of microstructure regulating aid, mix them and put them into an electric melting furnace, and melt them at 2000℃ for 1.5h. S3, Molding and Cooling The molten system was cast into a mold and then subjected to controlled cooling at a rate of 5°C / min to obtain an fused zirconia-alumina material with excellent low-bubble precipitation properties; from Figure 1 Infrared spectral comparisons show that the unmodified fused zirconia alumina material mainly exhibits characteristic absorption peaks of inorganic oxides such as Al-O and Zr-O. The overall spectrum is dominated by metal-oxygen bond vibrations in the low wavenumber region, with no obvious absorption characteristics of organic functional groups. After synergistic modification with polyphenols, nitrogen-containing organosilicon, and variable-valence metal coordination, the material shows obvious CH stretching vibration absorption peaks at 2920 cm⁻¹ and 2850 cm⁻¹, and absorption peaks related to ester and amide groups near 1720 cm⁻¹ and 1650 cm⁻¹. At the same time, the characteristic absorptions of Si-OC and Si-O-Si in the 1250–1100 cm⁻¹ region are enhanced, indicating that the organosilicon and polyphenol structures have been successfully introduced into the system. The main absorption peaks of Al-O and Zr-O still exist before and after modification, with only changes in peak shape and intensity. This indicates that the synergistic modification process did not destroy the main crystal phase structure of fused zirconia alumina, but mainly acted on the grain boundaries and interface regions, which is conducive to achieving synergistic improvement of material performance.
[0025] Example 3: This example aims to prepare fused zirconia corundum material with low bubble precipitation under conditions of high dosage of synergistic modifier and organic small molecule functional regulator and strong electrofusion conditions, in order to evaluate the stability of the effect of this technical solution on grain boundary structure regulation and bubble precipitation suppression under the strengthening process conditions.
[0026] S1, Preparation of Polyphenol-Nitrogen-Containing Organosilicon-Variable Valence Metal Coordination Synergistic Modifier 1.5 parts of propyl gallate were added to a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and stirred at 40°C for 30 min. 1.0 part of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane was added to the resulting solution, and the pH of the system was controlled at 9.5. The mixture was stirred at 40°C for 60 min. 0.5 parts of cerium nitrate were added to the system, and the reaction was carried out at 60°C for 2.0 h. The solvent was then removed under reduced pressure at 70°C to obtain a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier.
[0027] S2, Preparation of fused zirconia-corundum material Weigh out 60 parts of alumina, 45 parts of zirconium oxide, 3.0 parts of synergistic modifier, 1.5 parts of 1,3,5-triazine-2,4,6-tricarboxamide, 2.0 parts of sintering aid and 1.0 parts of microstructure regulating aid, mix them and melt them at 2100℃ for 3.0h. S3, Molding and Cooling The molten system was cast into a mold and then cooled in a controlled manner at a cooling rate of 10℃ / min to obtain an electrofused zirconia corundum material with low bubble precipitation.
[0028] Comparative Example 1: This comparative example aims to compare and verify the contribution of the synergistic effect of the polyphenol-nitrogen-organosilicon-variable valence metal coordination synergistic modification system to the low bubble precipitation performance by using only propyl gallate for single modification while keeping the other raw material ratios and process conditions unchanged.
[0029] S1, Preparation of a single polyphenol modifier 0.8 parts of propyl gallate were added to a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and stirred at 32°C for 20 min to obtain a polyphenol solution; then the solvent was removed under reduced pressure at 55°C to obtain a single polyphenol modifier. S2, Preparation of fused zirconia-corundum material Weigh out 52 parts of alumina, 38 parts of zirconium oxide, 1.5 parts of polyphenol single modifier, 0.8 parts of 1,3,5-triazine-2,4,6-tricarboxamide, 1.1 parts of sintering aid and 0.5 parts of microstructure regulating aid, mix them and put them into an electric melting furnace, and melt them at 2000℃ for 1.5h. S3, Molding and Cooling The molten system was cast into a mold and then cooled in a controlled manner at a cooling rate of 5°C / min to obtain fused zirconia corundum material.
[0030] Comparative Example 2: This comparative example aims to compare and verify the effect of the synergistic effect of the polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modification system on grain boundary structure regulation and low bubble precipitation performance, while keeping the other raw material ratios and process conditions unchanged.
[0031] S1, Preparation of a single nitrogen-containing organosilicon modifier N-(2-aminoethyl)-3-aminopropyltrimethoxysilane was added to a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and the pH of the system was controlled at 8.8. The mixture was stirred at 30°C for 45 min to allow it to undergo pre-hydrolysis and condensation reactions. The solvent was then removed under reduced pressure at 55°C to obtain a nitrogen-containing organosilicon single modifier. S2, Preparation of fused zirconia-corundum material Weigh out 52 parts of alumina, 38 parts of zirconium oxide, 1.5 parts of nitrogen-containing organosilicon single modifier, 0.8 parts of 1,3,5-triazine-2,4,6-tricarboxamide, 1.1 parts of sintering aid and 0.5 parts of microstructure regulating aid, mix them and put them into an electric melting furnace, and melt them at 2000℃ for 1.5h. S3, Molding and Cooling The molten system was cast into a mold and then cooled in a controlled manner at a cooling rate of 5°C / min to obtain fused zirconia corundum material.
[0032] Comparative Example 3: This comparative example aims to compare and verify the contribution of 1,3,5-triazine-2,4,6-tricarboxamide to low bubble precipitation performance without adding organic small molecule functional regulators, while keeping the synergistic modifier and its preparation process unchanged.
[0033] S1, Preparation of Polyphenol-Nitrogen-Containing Organosilicon-Variable Valence Metal Coordination Synergistic Modifier 0.8 parts of propyl gallate were added to a mixed solvent of ethanol and deionized water in a volume ratio of 1:1, and stirred at 32°C for 20 min to obtain a polyphenol solution. 0.55 parts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane were added to the polyphenol solution, and the pH of the system was controlled at 8.8. The mixture was stirred at 30°C for 45 min to obtain a nitrogen-containing organosilicon prepolymer system. 0.25 parts of cerium nitrate were added to the prepolymer system, and the mixture was reacted at 50°C for 1.2 h. The solvent was then removed under reduced pressure at 55°C to obtain a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier. S2, Preparation of fused zirconia-corundum material Weigh out 52 parts of alumina, 38 parts of zirconium oxide, 1.5 parts of synergistic modifier, 1.1 parts of sintering aid and 0.5 parts of microstructure regulating aid, mix them and put them into an electric melting furnace, and melt them at 2000℃ for 1.5h. S3, Molding and Cooling The molten system was cast into a mold and then cooled in a controlled manner at a cooling rate of 5°C / min to obtain fused zirconia corundum material.
[0034] Performance testing: 1. Test method for bubble precipitation behavior The fused zirconia-corundum materials prepared in the examples and comparative examples were processed into samples of uniform size, cleaned, and placed in a high-temperature molten glass simulation device, allowing the sample surface to directly contact the molten glass. A constant-temperature holding test was conducted under set high-temperature conditions, and the bubble precipitation on the sample surface and its adjacent molten glass area was continuously observed throughout the holding process. By recording the bubble precipitation frequency per unit time, the persistence of bubble appearance, and the trend of bubble size changes, the ability of different materials to suppress bubble precipitation was compared and evaluated.
[0035] 2. Test method for the degree of contamination in molten glass The example and comparative samples were placed in molten glass under the same conditions for high-temperature contact tests. After the tests, the samples were removed, and the molten glass after contact was observed and sampled for analysis. By comparing whether there were obvious residual bubbles, turbidity, or increased inclusions in the molten glass, the impact of different materials on the cleanliness of the molten glass during service was evaluated, thus reflecting the degree of influence of materials on glass quality in actual use.
[0036] 3. High-Temperature Service Stability Test Method The example and comparative samples were subjected to prolonged isothermal treatment in a high-temperature furnace to simulate the continuous operation of a glass furnace. During and after treatment, the samples were visually inspected to observe for surface blistering, localized peeling, structural loosening, or other abnormal changes. By comparing the stability performance of different samples under prolonged high-temperature exposure, the suitability of the material for long-term service in a glass furnace was evaluated.
[0037] 4. Test methods for adaptability of glass furnace start-up and shutdown conditions The example and comparative samples were placed in a high-temperature furnace and subjected to multiple heating and cooling cycles according to the glass furnace start-up and shutdown conditions. After each cycle, the samples were observed, and the presence of obvious cracking, damage, or performance degradation was recorded. By comparing the integrity retention of different samples under multiple thermal start-up and shutdown conditions, the impact of the synergistic modification system and the organic small molecule functional regulator on the service reliability of the materials was evaluated.
[0038] Table 1 Performance Test Results
[0039] As shown in Table 1, the fused zirconia-alumina materials prepared in Examples 1-3 are significantly superior to the comparative materials in terms of bubble precipitation behavior, glass melt cleanliness, and high-temperature service stability. Figure 2 Example 2 exhibits the best overall performance, with a bubble precipitation frequency of 2 bubbles / 10 min, significantly lower than the 7 bubbles / 10 min of Example 1 and the 4 bubbles / 10 min of Example 3, and even further lower than the 17 bubbles / 10 min, 14 bubbles / 10 min, and 10 bubbles / 10 min of Comparative Examples 1, 2, and 3, respectively. This indicates that the introduction of the synergistic modification system and the organic small molecule functional regulator can significantly reduce the bubble precipitation level of the material under glass furnace service conditions.
[0040] From the perspective of bubble size control effect Figure 3 The average bubble size in Example 2 was only 0.4 mm, significantly smaller than that in Example 1 (1.3 mm) and Example 3 (0.7 mm). In contrast, the average bubble size in the comparative materials was generally larger, reaching 3.0 mm in Comparative Example 1, 2.5 mm in Comparative Example 2, and 1.8 mm in Comparative Example 3. These results demonstrate that the combined action of the synergistic modifier and small organic molecules not only reduces the number of bubbles but also effectively inhibits bubble growth, thereby reducing the impact of bubbles on the quality of the molten glass.
[0041] In terms of glass melt contamination and service stability, the glass melt in Example 2 remained clear and transparent during the test, demonstrating very stable high-temperature service stability and excellent start-stop adaptability. While Examples 1 and 3 showed slight turbidity, they still maintained stable high-temperature service and good start-stop adaptability overall. In contrast, the comparative materials all exhibited varying degrees of turbidity during the test, with Comparative Examples 1 and 2 showing significant turbidity. Their high-temperature service stability and start-stop adaptability were only average or poor, indicating significant performance degradation.
[0042] In summary, by introducing a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier into fused zirconia corundum material, and by using 1,3,5-triazine-2,4,6-tricarboxamide for functional regulation, the frequency and size of bubble precipitation can be significantly reduced. At the same time, the cleanliness of the glass melt can be improved and the stability of the material under high-temperature service and start-up and shutdown conditions can be enhanced. Among them, the raw material ratio and process conditions used in Example 2 show the best comprehensive performance.
Claims
1. A fused zirconia-corundum material for glass furnaces with low bubble precipitation, characterized in that, The fused zirconia-corundum material comprises the following raw materials in parts by weight: 45-60 parts alumina; 30-45 parts zirconia; 0.3-3.0 parts polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier; 0.05-1.5 parts organic small molecule functional regulator; 0.2-2.0 parts sintering aid; and 0.05-1.0 parts microstructure regulating aid; wherein the polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier is composed of propyl gallate and N-(2-aminoethyl) The material is composed of 3-aminopropyltrimethoxysilane and cerium nitrate. During the electrofusion process, propyl gallate, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and cerium nitrate form a synergistic modification network in the grain boundary region between the alumina and zirconium oxide phases through multi-site coordination, silicon-oxygen condensation reaction and interfacial bonding, so as to regulate the grain boundary structure and reduce gas nucleation and aggregation inside the material. The organic small molecule functional regulator is 1,3,5-triazine-2,4,6-tricarboxamide.
2. The fused zirconia-corundum material for glass furnaces with low bubble precipitation according to claim 1, characterized in that, The polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier comprises the following raw materials in parts by weight: propyl gallate 0.1-1.5 parts; N-(2-aminoethyl)-3-aminopropyltrimethoxysilane 0.1-1.0 parts; cerium nitrate 0.05-0.5 parts.
3. The method for preparing a low-bubble-precipitation fused zirconia-corundum material for a glass furnace according to claim 1 or 2, characterized in that, The preparation method of the polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier includes the following steps: (1) Add propyl gallate to a solvent to dissolve it, and a polyphenol solution is obtained; (2) Add N-(2-aminoethyl)-3-aminopropyltrimethoxysilane to the polyphenol solution to induce pre-hydrolysis and condensation reactions, thereby obtaining a nitrogen-containing organosilicon prepolymer system; (3) Add cerium nitrate to the nitrogen-containing organosilicon prepolymer system, remove the solvent after reaction, and obtain a polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier.
4. The fused zirconia-corundum material for glass furnaces with low bubble precipitation according to claim 3, characterized in that, The reaction conditions for step (1) are: stirring at 25-40°C for 10-30 minutes in a mixed solvent of ethanol and deionized water.
5. The fused zirconia-corundum material for glass furnaces with low bubble precipitation according to claim 3, characterized in that, The reaction conditions for step (2) are to control the pH of the system to be 8.0 to 9.5 and to stir for 30 to 60 minutes at room temperature to 40°C.
6. The fused zirconia-corundum material for glass furnaces with low bubble precipitation according to claim 3, characterized in that, The reaction conditions for step (3) are to react at 40-60°C for 0.5-2.0 h and remove the solvent under reduced pressure at 40-70°C.
7. The fused zirconia-corundum material for glass furnaces with low bubble precipitation according to claim 1, characterized in that, The sintering aid is composed of yttrium oxide and magnesium oxide in a mass ratio of 1-5:1-3; the microstructure regulating aid is composed of sodium borate and ammonium dihydrogen phosphate in a mass ratio of 1-4:1-4.
8. A method for preparing an electrofused zirconia-corundum material for a glass furnace with low bubble precipitation, characterized in that, The preparation method includes the following steps: S1. Weigh alumina, zirconium oxide, polyphenol-nitrogen-containing organosilicon-variable valence metal coordination synergistic modifier, organic small molecule functional regulator, sintering aid and microstructure regulating aid, and mix them to obtain a uniform mixture. S2, the mixture is fed into an electric melting furnace for melting treatment, so that the components can fully react under high temperature conditions and form a molten system; S3 involves casting the molten system after electrofusion treatment into a molded shape and then subjecting it to controlled cooling to obtain an electrofused zirconia-corundum material for glass furnaces with low bubble precipitation.
9. The method for preparing a low-bubble-precipitation fused zirconia-corundum material for a glass furnace according to claim 8, characterized in that, The reaction conditions for step S1 are as follows: mixing is carried out at room temperature using mechanical stirring or mixing equipment for a mixing time of 10 to 40 minutes; the reaction conditions for step S2 are as follows: melting is carried out in an electric melting furnace at 1900 to 2100°C for a melting time of 0.5 to 3.0 hours.
10. The method for preparing a low-bubble-precipitation electrofused zirconia-corundum material for a glass furnace according to claim 8, characterized in that, The reaction conditions for step S3 are as follows: after the molten system is cast into a mold, it is cooled under controlled cooling conditions at a cooling rate of 1 to 10 °C / min.