Refractory material with high thermal shock resistance and preparation method thereof
By preparing compositions of refractory materials with high thermal shock resistance and surface coating treatment, the problem of poor thermal shock stability of traditional magnesia-carbon refractory materials has been solved, thereby improving the stability and service life of the materials in high-temperature equipment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-05
- Publication Date
- 2026-03-13
Smart Images
Figure CN121651897A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of refractory materials technology, specifically to a high thermal shock refractory material and its preparation method. Background Technology
[0002] High-temperature alloys have been widely used in many fields such as marine gas turbines, ultra-high critical rotors for thermal and nuclear power plants, marine engineering, and petrochemicals. They are also key materials for advanced aero engines. The thermal shock resistance of refractory materials used in high-temperature alloy smelting is one of the key factors affecting the purity of high-temperature alloys. It not only affects the performance of high-temperature alloys but also limits the service life of refractory materials, thus affecting alloy production.
[0003] In modern industrial production, high-temperature equipment and furnaces are widely used. During operation, they frequently experience drastic temperature changes. This so-called thermal shock condition can easily cause structural cracks or even breakage in refractory materials, thus affecting the stability and service life of the equipment. Traditional magnesia-carbon refractory materials can no longer meet the requirements. The poor thermal shock stability of magnesia-carbon refractory materials used in industry limits their practical application.
[0004] In summary, improving the thermal shock resistance of refractory materials is a technical problem that needs to be solved in the current industrial field. Therefore, the high thermal shock resistance refractory material and its preparation method of the present invention are of great significance in the field of refractory material technology. Summary of the Invention
[0005] In order to overcome the above-mentioned technical problems, the purpose of this invention is to provide a refractory material with high thermal shock resistance and its preparation method: solving the problem of poor thermal shock stability of existing refractory materials.
[0006] The objective of this invention can be achieved through the following technical solutions: In a first aspect, this application provides a refractory material with high thermal shock resistance, comprising the following components in parts by weight: 10-15 parts α-Al2O3 micro powder, 2-4 parts TiO2 micro powder, 3-5 parts hexagonal boron nitride whiskers, 8-12 parts fused magnesia, 25-35 parts fused white corundum, 15-25 parts microporous sintered corundum, 5-8 parts magnesium aluminum spinel, 2-4 parts silicon powder, 1-3 parts aluminum powder, 3-5 parts flake graphite, 3-6 parts zircon, 1-2 parts Y2O3 powder, 4-8 parts additives, 2-4 parts binder, and 5-10 parts coating slurry; The particle size of the α-Al₂O₃ micro powder is 1-5 μm; the particle size of the TiO₂ micro powder is 1-5 μm; the particle size of the magnesium aluminum spinel is 45-100 μm; the particle size of the silicon powder is ≤43 μm; the particle size of the aluminum powder is ≤74 μm; the particle size of the flake graphite is ≤74 μm; and the particle size of the Y₂O₃ powder is ≤43 μm.
[0007] In a preferred embodiment of the present invention, the fused magnesia is a mixture of fused magnesia particles with a particle size of 1-3 mm and fused magnesia fine powder with a particle size of ≤74 μm at a mass ratio of 65 g: 27-29 g.
[0008] In a preferred embodiment of the present invention, the fused white fused alumina is a mixture of fused white fused alumina aggregate with a particle size of 3-5 mm, fused white fused alumina aggregate with a particle size of 1-3 mm, and fused white fused alumina fine powder with a particle size of 75-100 μm in a mass ratio of 13g:10-30g:15-25g.
[0009] In a preferred embodiment of the present invention, the microporous sintered alumina is a mixture of microporous sintered alumina with a particle size of 3-5 mm, microporous sintered alumina with a particle size of 1-3 mm, and microporous sintered alumina with a particle size of ≤1 mm in a mass ratio of 13g:10-30g:11g.
[0010] In a preferred embodiment of the present invention, the zircon is a mixture of zircon sand with a particle size <125μm and zircon powder with a particle size ≤74μm in a mass ratio of 60g:40g.
[0011] In a preferred embodiment of the present invention, the additive consists of MgAl2O3 and Ca. 12 Al 14 O 33 It is obtained by ball milling and calcining alumina mixed in a ratio of 40-45g: 10-15g: 24-32g.
[0012] In a preferred embodiment of the present invention, the coating slurry is prepared by ball milling ZrB2 powder with a particle size of 1-5 μm, SiC powder with a particle size of 0.5-2 μm, TaSi2 powder with a particle size of 1-3 μm, anhydrous ethanol, and polyvinyl butyral in a ratio of 50-70 g: 10-20 g: 5-15 g: 140-240 mL: 2-3 g in a ball mill jar for 12-24 h; the polyvinyl butyral is produced by Sinopharm Chemical Reagent Co., Ltd.
[0013] In a preferred embodiment of the present invention, the hexagonal boron nitride whiskers are prepared by the following steps: Boric acid, melamine, and deionized water were added to a three-necked flask equipped with a stirrer and a thermometer. The mixture was stirred at 85°C for 3-4 hours, then allowed to cool naturally to 25°C and stand for 6-8 hours. The mixture was then filtered, and the filter cake was placed in a freeze dryer at -30°C and freeze-dried for 1-2 hours. The cake was then transferred to a high-temperature tube furnace under a nitrogen atmosphere and heat-treated at 1000-1400°C for 1-4 hours. After cooling naturally to 25°C, hexagonal boron nitride whiskers were obtained.
[0014] In a preferred embodiment of the present invention, the ratio of boric acid, melamine and deionized water is 5-10g: 5-10g: 500mL.
[0015] In a preferred embodiment of the present invention, the binder is prepared by the following steps: Phenol and formaldehyde solutions were added to a three-necked flask equipped with a stirrer and thermometer, and stirred for 30 minutes. Tetraethyl orthosilicate was added and stirring was continued for another 30 minutes. Carbon black and mixed acid were added to a beaker and stirred for 30 minutes. The mixture was then placed in a 90°C water bath for 3 hours and washed 2-3 times with deionized water. The mixture was dried in a 60°C vacuum drying oven for 24 hours. Anhydrous ethanol was added to the beaker and ultrasonically vibrated for 1 hour. The mixture was then added to the three-necked flask, and NaOH solution was added. The mixture was heated to 90°C and reacted at a constant temperature for 2-3 hours. The pH was adjusted to 6-6.5 with acetic acid solution, and the mixture was dehydrated under vacuum. Ethylene glycol was added and stirred for 30 minutes to obtain the binder.
[0016] In a preferred embodiment of the present invention, the ratio of phenol, formaldehyde solution, tetraethyl orthosilicate, carbon black, mixed acid, anhydrous ethanol, NaOH solution, and ethylene glycol is 100-150g: 110-150mL: 6-42mL: 3-16g: 400mL: 30mL: 50mL: 20mL; the formaldehyde solution has a mass fraction of 37%; the mixed acid is a mixture of 98% concentrated sulfuric acid and 58-68% concentrated nitric acid at a volume ratio of 3:1; the NaOH solution has a molar concentration of 1mol / L; and the acetic acid solution has a mass fraction of 36%.
[0017] Secondly, this application provides a method for preparing a refractory material with high thermal shock resistance, comprising the following steps: Step 1: Weigh out the following components by weight: 10-15 parts α-Al2O3 micro powder, 2-4 parts TiO2 micro powder, 3-5 parts hexagonal boron nitride whiskers, 8-12 parts fused magnesia, 25-35 parts fused white corundum, 15-25 parts microporous sintered corundum, 5-8 parts magnesium aluminum spinel, 2-4 parts silicon powder, 1-3 parts aluminum powder, 3-5 parts flake graphite, 3-6 parts zircon, 1-2 parts Y2O3 powder, 4-8 parts additives, 5-10 parts anhydrous ethanol, 2-4 parts binder, and 5-10 parts coating slurry. Step 2: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill and dry mix for 30 min to obtain aggregate; add hexagonal boron nitride whiskers to anhydrous ethanol and stir magnetically for 10 min, add binder and continue stirring for 1 h, add the above aggregate, mix and stir for 15 min, acclimate at 25℃ for 12 h, press under a 150MPa cold press, transfer to a drying oven and cure at 60℃, 120℃ and 180℃ for 12 h respectively, hold at 1500-1650℃ for 2-4 h under argon atmosphere, and cool with the furnace to 25℃ to obtain refractory material; Step 3: Apply the coating slurry to the surface of the refractory material with a thickness of 80-200μm. Transfer it to an oven and dry it at 60℃ for 12 hours. Place it in a high-temperature tube furnace, introduce argon gas, and heat it to 800-1000℃ at a heating rate of 10℃ / min. Hold it at this temperature for 1-2 hours, then cool it to 700℃ at a cooling rate of 5℃ / min. Cool it to 25℃ in the furnace and place it in a vacuum sintering furnace for gaseous silicon infiltration treatment. Introduce argon gas and heat it to 1000℃ at a heating rate of 10℃ / min. Then heat it to 1450-1550℃ at a heating rate of 5℃ / min and hold it for 1-2 hours. Cool it to 25℃ in the furnace to obtain a refractory material with high thermal shock resistance.
[0018] The beneficial effects of this invention are: This invention discloses a high thermal shock resistant refractory material and its preparation method. The method involves ball milling a mixture of α-Al₂O₃ micropowder, TiO₂ micropowder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y₂O₃ powder, and additives to obtain aggregate. Hexagonal boron nitride whiskers are added to anhydrous ethanol and stirred, a binder is added and stirred, the aggregate is added and stirred, then the mixture is bound, pressed, cured, sintered, and cooled to obtain the refractory material. A protective coating is prepared on the surface of the refractory material using a slurry coating method combined with subsequent gaseous silicon infiltration treatment, resulting in the high thermal shock resistant refractory material. The composite of α-Al₂O₃ micropowder and TiO₂ micropowder results in the sequential formation of CaTiO₃ and Mg at the magnesia grain boundaries. 1+x Al 2(1-x) Ti xO4 acts as a "pinning" agent, increasing grain size, density, and reducing the coefficient of thermal expansion, thus improving the material's thermal shock resistance. Zircon decomposes in situ during high-temperature sintering, generating ZrO2 and SiO2. This process, accompanied by a volume effect, introduces numerous uniformly distributed microcracks within the material, effectively passivating, deflecting, and branching the main cracks generated by thermal stress, absorbing and dissipating their energy. Hexagonal boron nitride whiskers, as the core toughening component, significantly improve the material's fracture toughness and impact resistance through whisker pull-out, bridging, and crack deflection mechanisms. Zircon oxide, stabilized by Y2O3 and derived from zircon decomposition, undergoes a martensitic transformation under stress-induced conditions, producing… Volume expansion applies compressive stress to the crack tip, thereby preventing further crack propagation. The introduction of microporous sintered corundum and flake graphite, through their own micropores and layered structure, further reduces the elastic modulus of the material and provides a stress buffer layer, enhancing the material's adaptability to rapid temperature changes. A protective coating is prepared on the material surface using a slurry coating method combined with gaseous silicon infiltration. The silicon in the coating reduces the channels for oxygen diffusion inward, lowers the overall thermal expansion coefficient of the coating, improves the density of the coating, and increases the bonding strength between the coating and the substrate, giving the coating good resistance to high-temperature oxidation and thermal shock. The synergistic effect of multiple toughening mechanisms improves the material's thermal shock resistance.
[0019] In the preparation of high thermal shock resistant refractory materials, hexagonal boron nitride whiskers were first prepared. Boric acid and melamine reacted, and the amino groups produced by the hydrolysis of melamine formed a boron-nitrogen organic precursor through hydrogen bonding and coordination with the borate ions in boric acid. Under controlled reaction conditions and nitrogen protection, high-temperature pyrolysis occurred, and the melamine partially decomposed first, providing nitrogen and carbon sources and generating nitrogen-containing gases. The boric acid partially dehydrated to generate boron oxide. The gaseous nitrogen-containing substances and solid boron oxide synthesized hexagonal boron nitride. The specific precursor structure formed by freeze-drying guided the growth of hexagonal boron nitride in the form of whiskers, resulting in hexagonal boron nitride whiskers. Hexagonal boron nitride whiskers have a small coefficient of thermal expansion, high thermal conductivity, and low elastic modulus, exhibiting excellent thermal shock stability. The anisotropy of hexagonal boron nitride whiskers leads to the presence of microcracks during material preparation. The unique lamellar structure of hexagonal boron nitride whiskers can hinder crack propagation and can itself play a role in crack deflection and crack bridging, thereby improving the thermal shock resistance of the material.
[0020] In the preparation of high thermal shock refractory materials, a binder was first prepared. Phenol and formaldehyde were mixed and subjected to a condensation reaction under the catalysis of NaOH alkaline catalyst. The hydrogens at the ortho or para positions of the phenolic hydroxyl groups of phenol added to the carbonyl groups of formaldehyde to generate hydroxymethylphenol, which further condensed to form a phenolic resin prepolymer. Tetraethyl orthosilicate was hydrolyzed, and the resulting silicic acid condensed with the hydroxymethyl groups in the phenolic resin prepolymer to form Si-OC covalent bonds, yielding a phenolic hybrid prepolymer. Carbon black was heated with a mixed acid to introduce oxygen-containing functional groups onto the carbon black surface, improving its hydrophilicity and dispersibility in polar systems. The oxidized carbon black was washed and dried, then ultrasonically vibrated in ethanol to form a nanoscale dispersion slurry. The dispersed carbon black was added to the phenolic hybrid prepolymer for cross-linking and curing. The oxygen-containing functional groups on the carbon black surface interacted with the hydroxymethyl or silanol groups in the resin. To form a stronger interfacial bond, ethylene glycol is added to improve the flexibility and processability of the binder preform, resulting in a binder. Phenolic resin is an excellent carbon precursor; introducing Si into the phenolic resin molecular chain improves its oxidation resistance and thermal stability. Carbon black, acting as a "seed" and fixing the carbon skeleton, intertwines with the glassy carbon generated by resin pyrolysis to form a denser, continuous, and robust carbon network, improving the high-temperature strength of the material. The optimized carbon network effectively hinders the slippage of oxide grain boundaries, enhances the thermal conductivity of the material, and thus rapidly disperses thermal stress, improving thermal shock resistance. Uniformly dispersed nano-carbon black particles, after resin carbonization, can act as nano-reinforcing points, effectively pinning, deflecting, and branching microcracks, improving thermal shock resistance and fracture toughness. Adding ethylene glycol improves the rheology of the binder slurry and the flexibility of the preform, reducing the risk of cracking during drying and sintering. Attached Figure Description
[0021] The invention will now be further described with reference to the accompanying drawings.
[0022] Figure 1 This is a schematic diagram showing the results of the number of water quenching tests on the thermal shock resistance of the high thermal shock refractory materials in Examples 1-3 and Comparative Examples 1-3 of this invention. Detailed Implementation
[0023] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0024] Example 1: This embodiment describes a method for preparing a refractory material with high thermal shock resistance, including the following steps: Step S1: Add 5g boric acid, 5g melamine and 500mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Mix and stir at 85℃ for 3h, cool naturally to 25℃, let stand for 6h, filter, place the filter cake in a freeze dryer at -30℃, freeze dry for 1h, transfer to a high temperature tube furnace under nitrogen atmosphere, heat treat at 1000℃ for 1h, cool naturally to 25℃, and obtain hexagonal boron nitride whiskers; Step S2: Add 100g of phenol and 110mL of 37% formaldehyde solution to a three-necked flask equipped with a stirrer and thermometer, mix and stir for 30min, add 6mL of tetraethyl orthosilicate, and continue stirring for 30min; add 3g of carbon black, 400mL of 98% concentrated sulfuric acid and 58% concentrated nitric acid in a volume ratio of 3:1 to a beaker and mix and stir for 30min, place in a constant temperature water bath at 90℃ for 3h, wash twice with deionized water, dry in a vacuum drying oven at 60℃ for 24h, add 30mL of anhydrous ethanol to a beaker and sonicate for 1h, add to the above three-necked flask, add 50mL of 1mol / L NaOH solution, heat to 90℃, react at a constant temperature for 2h, adjust the pH to 6 with 36% acetic acid solution, dehydrate under vacuum, add 20mL of ethylene glycol and mix and stir for 30min to obtain the binder; Step S3: Add 50g of ZrB2 powder with a particle size of 1μm, 10g of SiC powder with a particle size of 0.5μm, 5g of TaSi2 powder with a particle size of 1μm, 140mL of anhydrous ethanol and 2g of polyvinyl butyral to a ball mill jar, mix and ball mill for 12h to obtain coating slurry. Step S4: Weigh out the following components by weight: 10 parts α-Al2O3 micro powder, 2 parts TiO2 micro powder, 3 parts hexagonal boron nitride whiskers, 8 parts fused magnesia, 25 parts fused white corundum, 15 parts microporous sintered corundum, 5 parts magnesium aluminum spinel, 2 parts silicon powder, 1 part aluminum powder, 3 parts flake graphite, 3 parts zircon, 1 part Y2O3 powder, 4 parts additives, 5 parts anhydrous ethanol, 2 parts binder, and 5 parts coating slurry. The α-Al₂O₃ micro powder has a particle size of 1 μm, the TiO₂ micro powder has a particle size of 1 μm, the fused magnesia consists of fused magnesia particles with a particle size of 1 mm and fused magnesia fine powder with a particle size ≤74 μm, mixed in a mass ratio of 65 g: 27 g; the fused white corundum consists of fused white corundum aggregate with a particle size of 3 mm, fused white corundum aggregate with a particle size of 1 mm, and fused white corundum fine powder with a particle size of 75 μm, mixed in a mass ratio of 13 g: 10 g: 15 g; and the microporous sintered corundum consists of microporous sintered corundum with a particle size of 3 mm. The mixture consists of microporous sintered corundum with a particle size of 1 mm and microporous sintered corundum with a particle size ≤ 1 mm, mixed in a mass ratio of 13g:10g:11g; magnesium aluminum spinel with a particle size of 45μm; silicon powder with a particle size ≤ 43μm; aluminum powder with a particle size ≤ 74μm; flake graphite with a particle size ≤ 74μm; zircon, consisting of zircon sand with a particle size < 125μm and zircon powder with a particle size ≤ 74μm, mixed in a mass ratio of 60g:40g; Y₂O₃ powder with a particle size ≤ 43μm; and additives consisting of MgAl₂O₃ and Ca. 12 Al 14 O 33 Alumina is obtained by ball milling and calcining a mixture of 40g:10g:24g. Step S5: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill and dry mix for 30 min to obtain aggregate; add hexagonal boron nitride whiskers to anhydrous ethanol and stir magnetically for 10 min, add binder and continue stirring for 1 h, add the above aggregate, mix and stir for 15 min, acclimate at 25℃ for 12 h, press under a 150MPa cold press, transfer to a drying oven and cure at 60℃, 120℃ and 180℃ for 12 h respectively, hold at 1500℃ for 2 h under argon atmosphere, and cool to 25℃ with the furnace to obtain refractory material; Step S6: Apply the coating slurry to the surface of the refractory material with a coating thickness of 80 μm, transfer it to an oven and dry it at 60°C for 12 h, place it in a high-temperature tube furnace, introduce argon gas, heat it to 800°C at a heating rate of 10°C / min, hold it at that temperature for 1 h, cool it to 700°C at a cooling rate of 5°C / min, cool it to 25°C with the furnace, place it in a vacuum sintering furnace for gaseous silicon infiltration treatment, introduce argon gas, heat it to 1000°C at a heating rate of 10°C / min, then heat it to 1450°C at a heating rate of 5°C / min, hold it at that temperature for 1 h, and cool it to 25°C with the furnace to obtain a refractory material with high thermal shock resistance.
[0025] Example 2: This embodiment describes a method for preparing a refractory material with high thermal shock resistance, including the following steps: Step S1: Add 7.5g boric acid, 7.5g melamine and 500mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Mix and stir at 85℃ for 3.5h, cool naturally to 25℃, let stand for 7h, filter, place the filter cake in a freeze dryer at -30℃, freeze dry for 1.5h, transfer to a high-temperature tube furnace under nitrogen atmosphere, heat treat at 1200℃ for 2.5h, cool naturally to 25℃, and obtain hexagonal boron nitride whiskers; Step S2: Add 125g of phenol and 130mL of 37% formaldehyde solution to a three-necked flask equipped with a stirrer and thermometer, mix and stir for 30min, add 24mL of tetraethyl orthosilicate, and continue stirring for 30min; add 8g of carbon black, 400mL of 98% concentrated sulfuric acid and 63% concentrated nitric acid in a volume ratio of 3:1 to a beaker and mix and stir for 30min, place in a constant temperature water bath at 90℃ for 3h, wash 3 times with deionized water, dry in a vacuum drying oven at 60℃ for 24h, add 30mL of anhydrous ethanol to a beaker and sonicate for 1h, add to the above three-necked flask, add 50mL of 1mol / L NaOH solution, heat to 90℃, react at a constant temperature for 2.5h, adjust the pH to 6 with 36% acetic acid solution, dehydrate under vacuum, add 20mL of ethylene glycol and mix and stir for 30min to obtain the binder; Step S3: Add 60g of ZrB2 powder with a particle size of 3μm, 15g of SiC powder with a particle size of 1μm, 10g of TaSi2 powder with a particle size of 2μm, 190mL of anhydrous ethanol and 2.5g of polyvinyl butyral to a ball mill jar, mix and ball mill for 18h to obtain coating slurry. Step S4: Weigh out the following components by weight: 13 parts α-Al2O3 micro powder, 3 parts TiO2 micro powder, 4 parts hexagonal boron nitride whiskers, 10 parts fused magnesia, 30 parts fused white corundum, 20 parts microporous sintered corundum, 6 parts magnesium aluminum spinel, 3 parts silicon powder, 2 parts aluminum powder, 4 parts flake graphite, 4 parts zircon, 1.5 parts Y2O3 powder, 6 parts additives, 7 parts anhydrous ethanol, 3 parts binder, and 7 parts coating slurry. The α-Al₂O₃ micro powder has a particle size of 3 μm, the TiO₂ micro powder has a particle size of 3 μm, the fused magnesia consists of fused magnesia particles with a particle size of 2 mm and fused magnesia fine powder with a particle size ≤74 μm, mixed in a mass ratio of 65 g: 28 g, the fused white corundum consists of fused white corundum aggregate with a particle size of 4 mm, fused white corundum aggregate with a particle size of 2 mm and fused white corundum fine powder with a particle size of 85 μm, mixed in a mass ratio of 13 g: 20 g: 20 g, and the microporous sintered corundum consists of microporous sintered corundum with a particle size of 4 mm. The mixture consists of microporous sintered corundum with a particle size of 2 mm and microporous sintered corundum with a particle size ≤ 1 mm, mixed in a mass ratio of 13g:20g:11g; magnesium aluminum spinel with a particle size of 70μm; silicon powder with a particle size ≤ 43μm; aluminum powder with a particle size ≤ 74μm; flake graphite with a particle size ≤ 74μm; zircon, consisting of zircon sand with a particle size < 125μm and zircon powder with a particle size ≤ 74μm, mixed in a mass ratio of 60g:40g; Y₂O₃ powder with a particle size ≤ 43μm; and additives consisting of MgAl₂O₃ and Ca. 12 Al 14 O 33 Alumina was obtained by ball milling and calcining a mixture of 43g:13g:28g. Step S5: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill and dry mix for 30 min to obtain aggregate; add hexagonal boron nitride whiskers to anhydrous ethanol and stir magnetically for 10 min, add binder and continue stirring for 1 h, add the above aggregate, mix and stir for 15 min, acclimate at 25℃ for 12 h, press under a 150MPa cold press, transfer to a drying oven and cure at 60℃, 120℃ and 180℃ for 12 h respectively, hold at 1600℃ for 3 h under argon atmosphere, and cool to 25℃ with the furnace to obtain refractory material; Step S6: Apply the coating slurry to the surface of the refractory material with a coating thickness of 140 μm, transfer it to an oven and dry it at 60°C for 12 h, place it in a high-temperature tube furnace, introduce argon gas, heat it to 900°C at a heating rate of 10°C / min, hold it at that temperature for 1.5 h, cool it to 700°C at a cooling rate of 5°C / min, cool it to 25°C with the furnace, place it in a vacuum sintering furnace for gaseous silicon infiltration treatment, introduce argon gas, heat it to 1000°C at a heating rate of 10°C / min, then heat it to 1500°C at a heating rate of 5°C / min, hold it at that temperature for 1.5 h, cool it to 25°C with the furnace, and obtain a refractory material with high thermal shock resistance.
[0026] Example 3: This embodiment describes a method for preparing a refractory material with high thermal shock resistance, including the following steps: Step S1: Add 10g boric acid, 10g melamine and 500mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Mix and stir at 85℃ for 4h, cool naturally to 25℃, let stand for 8h, filter, place the filter cake in a freeze dryer at -30℃, freeze dry for 2h, transfer to a high temperature tube furnace under nitrogen atmosphere, heat treat at 1400℃ for 4h, cool naturally to 25℃, and obtain hexagonal boron nitride whiskers; Step S2: Add 150g of phenol and 150mL of 37% formaldehyde solution to a three-necked flask equipped with a stirrer and thermometer, mix and stir for 30min, add 42mL of tetraethyl orthosilicate, and continue stirring for 30min; add 16g of carbon black, 400mL of 98% concentrated sulfuric acid and 68% concentrated nitric acid in a volume ratio of 3:1 to a beaker and mix and stir for 30min, place in a constant temperature water bath at 90℃ for 3h, wash 3 times with deionized water, dry in a vacuum drying oven at 60℃ for 24h, add 30mL of anhydrous ethanol to a beaker and sonicate for 1h, add to the above three-necked flask, add 50mL of 1mol / L NaOH solution, heat to 90℃, react at a constant temperature for 3h, adjust the pH to 6.5 with 36% acetic acid solution, dehydrate under vacuum, add 20mL of ethylene glycol and mix and stir for 30min to obtain the binder; Step S3: Add 70g of ZrB2 powder with a particle size of 5μm, 20g of SiC powder with a particle size of 2μm, 15g of TaSi2 powder with a particle size of 3μm, 240mL of anhydrous ethanol and 3g of polyvinyl butyral to a ball mill jar, mix and ball mill for 24h to obtain coating slurry. Step S4: Weigh out the following components by weight: 15 parts α-Al2O3 micro powder, 4 parts TiO2 micro powder, 5 parts hexagonal boron nitride whiskers, 12 parts fused magnesia, 35 parts fused white corundum, 25 parts microporous sintered corundum, 8 parts magnesium aluminum spinel, 4 parts silicon powder, 3 parts aluminum powder, 5 parts flake graphite, 6 parts zircon, 2 parts Y2O3 powder, 8 parts additives, 10 parts anhydrous ethanol, 4 parts binder, and 10 parts coating slurry. The α-Al₂O₃ micro powder has a particle size of 5 μm, the TiO₂ micro powder has a particle size of 5 μm, the fused magnesia consists of fused magnesia particles with a particle size of 3 mm and fused magnesia fine powder with a particle size ≤74 μm, mixed in a mass ratio of 65 g: 29 g, the fused white corundum consists of fused white corundum aggregate with a particle size of 5 mm, fused white corundum aggregate with a particle size of 3 mm and fused white corundum fine powder with a particle size of 100 μm, mixed in a mass ratio of 13 g: 30 g: 25 g, and the microporous sintered corundum consists of microporous sintered corundum with a particle size of 5 mm. The mixture consists of microporous sintered corundum with a particle size of 3mm and microporous sintered corundum with a particle size ≤1mm, mixed in a mass ratio of 13g:30g:11g; magnesium aluminum spinel with a particle size of 100μm; silicon powder with a particle size ≤43μm; aluminum powder with a particle size ≤74μm; flake graphite with a particle size ≤74μm; zircon sand with a particle size <125μm and zircon powder with a particle size ≤74μm, mixed in a mass ratio of 60g:40g; Y2O3 powder with a particle size ≤43μm; and additives consisting of MgAl2O3 and Ca. 12 Al 14 O 33 Alumina is obtained by ball milling and calcining a mixture of 45g:15g:32g. Step S5: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill and dry mix for 30 min to obtain aggregate; add hexagonal boron nitride whiskers to anhydrous ethanol and stir magnetically for 10 min, add binder and continue stirring for 1 h, add the above aggregate, mix and stir for 15 min, acclimate at 25℃ for 12 h, press under a 150MPa cold press, transfer to a drying oven and cure at 60℃, 120℃ and 180℃ for 12 h respectively, hold at 1650℃ for 4 h under argon atmosphere, and cool to 25℃ with the furnace to obtain refractory material; Step S6: Apply the coating slurry to the surface of the refractory material with a coating thickness of 200 μm, transfer it to an oven and dry it at 60°C for 12 h, place it in a high-temperature tube furnace, introduce argon gas, heat it to 1000°C at a heating rate of 10°C / min, hold it at that temperature for 2 h, cool it to 700°C at a cooling rate of 5°C / min, cool it to 25°C with the furnace, place it in a vacuum sintering furnace for gaseous silicon infiltration treatment, introduce argon gas, heat it to 1000°C at a heating rate of 10°C / min, then heat it to 1550°C at a heating rate of 5°C / min, hold it at that temperature for 2 h, and cool it to 25°C with the furnace to obtain a refractory material with high thermal shock resistance.
[0027] Comparative Example 1: This comparative example illustrates a method for preparing a highly thermally shock resistant refractory material, comprising the following steps: Step S1: Weigh out the following components by weight: 13 parts α-Al2O3 micro powder, 3 parts TiO2 micro powder, 10 parts fused magnesia, 30 parts fused white corundum, 20 parts microporous sintered corundum, 6 parts magnesium aluminum spinel, 3 parts silicon powder, 2 parts aluminum powder, 4 parts flake graphite, 4 parts zircon, 1.5 parts Y2O3 powder, 3 parts phenolic resin, and 7 parts anhydrous ethanol. The α-Al₂O₃ micro powder has a particle size of 3 μm, the TiO₂ micro powder has a particle size of 3 μm, the fused magnesia consists of fused magnesia particles with a particle size of 2 mm and fused magnesia fine powder with a particle size ≤74 μm, mixed in a mass ratio of 65 g: 28 g, the fused white corundum consists of fused white corundum aggregate with a particle size of 4 mm, fused white corundum aggregate with a particle size of 2 mm and fused white corundum fine powder with a particle size of 85 μm, mixed in a mass ratio of 13 g: 20 g: 20 g, and the microporous sintered corundum consists of microporous sintered corundum with a particle size of 4 mm. The mixture consists of microporous sintered corundum with a particle size of 2 mm and microporous sintered corundum with a particle size ≤ 1 mm, mixed in a mass ratio of 13g:20g:11g; magnesium aluminum spinel with a particle size of 70μm; silicon powder with a particle size ≤ 43μm; aluminum powder with a particle size ≤ 74μm; flake graphite with a particle size ≤ 74μm; zircon, consisting of zircon sand with a particle size < 125μm and zircon powder with a particle size ≤ 74μm, mixed in a mass ratio of 60g:40g; Y₂O₃ powder with a particle size ≤ 43μm; and additives consisting of MgAl₂O₃ and Ca. 12 Al 14 O 33 Alumina was obtained by ball milling and calcining a mixture of 43g:13g:28g. Step S2: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill and dry mix for 30 min. Add phenolic resin and mix for 15 min. Cure the mixture at 25°C for 12 h. Press the mixture under a 150 MPa cold press. Transfer the mixture to a drying oven and cure it at 60°C, 120°C and 180°C for 12 h respectively. Hold the mixture at 1600°C for 3 h under an argon atmosphere. Cool the mixture to 25°C with the furnace to obtain a refractory material with high thermal shock resistance.
[0028] Comparative Example 2: This comparative example illustrates a method for preparing a highly thermally shock resistant refractory material, comprising the following steps: Step S1: Add 125g of phenol and 130mL of 37% formaldehyde solution to a three-necked flask equipped with a stirrer and thermometer, mix and stir for 30min, add 24mL of tetraethyl orthosilicate, and continue stirring for 30min; add 8g of carbon black, 400mL of 98% concentrated sulfuric acid and 63% concentrated nitric acid in a volume ratio of 3:1 to a beaker and mix and stir for 30min, place in a constant temperature water bath at 90℃ for 3h, wash 3 times with deionized water, dry in a vacuum drying oven at 60℃ for 24h, add 30mL of anhydrous ethanol to a beaker and sonicate for 1h, add to the above three-necked flask, add 50mL of 1mol / L NaOH solution, heat to 90℃, react at a constant temperature for 2.5h, adjust the pH to 6 with 36% acetic acid solution, dehydrate under vacuum, add 20mL of ethylene glycol and mix and stir for 30min to obtain the binder; Step S2: Add 60g of ZrB2 powder with a particle size of 3μm, 15g of SiC powder with a particle size of 1μm, 10g of TaSi2 powder with a particle size of 2μm, 190mL of anhydrous ethanol and 2.5g of polyvinyl butyral to a ball mill jar, mix and ball mill for 18h to obtain coating slurry. Step S3: Weigh out the following components by weight: 13 parts α-Al2O3 micro powder, 3 parts TiO2 micro powder, 10 parts fused magnesia, 30 parts fused white corundum, 20 parts microporous sintered corundum, 6 parts magnesium aluminum spinel, 3 parts silicon powder, 2 parts aluminum powder, 4 parts flake graphite, 4 parts zircon, 1.5 parts Y2O3 powder, 6 parts additives, 7 parts anhydrous ethanol, 3 parts binder, and 7 parts coating slurry. The α-Al₂O₃ micro powder has a particle size of 3 μm, the TiO₂ micro powder has a particle size of 3 μm, the fused magnesia consists of fused magnesia particles with a particle size of 2 mm and fused magnesia fine powder with a particle size ≤74 μm, mixed in a mass ratio of 65 g: 28 g, the fused white corundum consists of fused white corundum aggregate with a particle size of 4 mm, fused white corundum aggregate with a particle size of 2 mm and fused white corundum fine powder with a particle size of 85 μm, mixed in a mass ratio of 13 g: 20 g: 20 g, and the microporous sintered corundum consists of microporous sintered corundum with a particle size of 4 mm. The mixture consists of microporous sintered corundum with a particle size of 2 mm and microporous sintered corundum with a particle size ≤ 1 mm, mixed in a mass ratio of 13g:20g:11g; magnesium aluminum spinel with a particle size of 70μm; silicon powder with a particle size ≤ 43μm; aluminum powder with a particle size ≤ 74μm; flake graphite with a particle size ≤ 74μm; zircon, consisting of zircon sand with a particle size < 125μm and zircon powder with a particle size ≤ 74μm, mixed in a mass ratio of 60g:40g; Y₂O₃ powder with a particle size ≤ 43μm; and additives consisting of MgAl₂O₃ and Ca. 12 Al 14 O 33Alumina was obtained by ball milling and calcining a mixture of 43g:13g:28g. Step S5: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill and dry mix for 30 min. Add binder and continue stirring for 1 h. Curing is carried out at 25℃ for 12 h. Pressing is carried out under a 150MPa cold press. Transfer to a drying oven and curing is carried out at 60℃, 120℃ and 180℃ for 12 h respectively. Under an argon atmosphere, the temperature is held at 1600℃ for 3 h. Cooling is carried out with the furnace to 25℃ to obtain the refractory material. Step S6: Apply the coating slurry to the surface of the refractory material with a coating thickness of 140 μm, transfer it to an oven and dry it at 60°C for 12 h, place it in a high-temperature tube furnace, introduce argon gas, heat it to 900°C at a heating rate of 10°C / min, hold it at that temperature for 1.5 h, cool it to 700°C at a cooling rate of 5°C / min, cool it to 25°C with the furnace, place it in a vacuum sintering furnace for gaseous silicon infiltration treatment, introduce argon gas, heat it to 1000°C at a heating rate of 10°C / min, then heat it to 1500°C at a heating rate of 5°C / min, hold it at that temperature for 1.5 h, cool it to 25°C with the furnace, and obtain a refractory material with high thermal shock resistance.
[0029] Comparative Example 3: This comparative example illustrates a method for preparing a highly thermally shock resistant refractory material, comprising the following steps: Step S1: Add 7.5g boric acid, 7.5g melamine and 500mL deionized water to a three-necked flask equipped with a stirrer and thermometer. Mix and stir at 85℃ for 3.5h, cool naturally to 25℃, let stand for 7h, filter, place the filter cake in a freeze dryer at -30℃, freeze dry for 1.5h, transfer to a high-temperature tube furnace under nitrogen atmosphere, heat treat at 1200℃ for 2.5h, cool naturally to 25℃, and obtain hexagonal boron nitride whiskers; Step S2: Add 60g of ZrB2 powder with a particle size of 3μm, 15g of SiC powder with a particle size of 1μm, 10g of TaSi2 powder with a particle size of 2μm, 190mL of anhydrous ethanol and 2.5g of polyvinyl butyral to a ball mill jar, mix and ball mill for 18h to obtain coating slurry. Step S3: Weigh out the following components by weight: 13 parts α-Al2O3 micro powder, 3 parts TiO2 micro powder, 4 parts hexagonal boron nitride whiskers, 10 parts fused magnesia, 30 parts fused white corundum, 20 parts microporous sintered corundum, 6 parts magnesium aluminum spinel, 3 parts silicon powder, 2 parts aluminum powder, 4 parts flake graphite, 4 parts zircon, 1.5 parts Y2O3 powder, 6 parts additives, 7 parts anhydrous ethanol, 3 parts phenolic resin, and 7 parts coating slurry. The α-Al₂O₃ micro powder has a particle size of 3 μm, the TiO₂ micro powder has a particle size of 3 μm, the fused magnesia consists of fused magnesia particles with a particle size of 2 mm and fused magnesia fine powder with a particle size ≤74 μm, mixed in a mass ratio of 65 g: 28 g, the fused white corundum consists of fused white corundum aggregate with a particle size of 4 mm, fused white corundum aggregate with a particle size of 2 mm and fused white corundum fine powder with a particle size of 85 μm, mixed in a mass ratio of 13 g: 20 g: 20 g, and the microporous sintered corundum consists of microporous sintered corundum with a particle size of 4 mm. The mixture consists of microporous sintered corundum with a particle size of 2 mm and microporous sintered corundum with a particle size ≤ 1 mm, mixed in a mass ratio of 13g:20g:11g; magnesium aluminum spinel with a particle size of 70μm; silicon powder with a particle size ≤ 43μm; aluminum powder with a particle size ≤ 74μm; flake graphite with a particle size ≤ 74μm; zircon, consisting of zircon sand with a particle size < 125μm and zircon powder with a particle size ≤ 74μm, mixed in a mass ratio of 60g:40g; Y₂O₃ powder with a particle size ≤ 43μm; and additives consisting of MgAl₂O₃ and Ca. 12 Al 14 O 33 Alumina was obtained by ball milling and calcining a mixture of 43g:13g:28g. Step S4: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill and dry mix for 30 min to obtain aggregate; add hexagonal boron nitride whiskers to anhydrous ethanol and stir magnetically for 10 min, add phenolic resin and continue stirring for 1 h, add the above aggregate, mix and stir for 15 min, acclimate at 25℃ for 12 h, press under a 150MPa cold press, transfer to a drying oven and cure at 60℃, 120℃ and 180℃ for 12 h respectively, hold at 1600℃ for 3 h under argon atmosphere, and cool to 25℃ with the furnace to obtain refractory material; Step S6: Apply the coating slurry to the surface of the refractory material with a coating thickness of 140 μm, transfer it to an oven and dry it at 60°C for 12 h, place it in a high-temperature tube furnace, introduce argon gas, heat it to 900°C at a heating rate of 10°C / min, hold it at that temperature for 1.5 h, cool it to 700°C at a cooling rate of 5°C / min, cool it to 25°C with the furnace, place it in a vacuum sintering furnace for gaseous silicon infiltration treatment, introduce argon gas, heat it to 1000°C at a heating rate of 10°C / min, then heat it to 1500°C at a heating rate of 5°C / min, hold it at that temperature for 1.5 h, cool it to 25°C with the furnace, and obtain a refractory material with high thermal shock resistance.
[0030] The high thermal shock resistant refractory materials prepared in Examples 1-3 and Comparative Examples 1-3 were tested for thermal shock resistance using the water quenching method according to GB / T 30873-2014 "Test Method for Thermal Shock Resistance of Refractory Materials". The test results are as follows: Figure 1 As shown: Comparing the thermal shock refractory materials prepared in Examples 1-3 with those in Comparative Examples 1-3: In Example 1, the amount of hexagonal boron nitride whiskers was insufficient, resulting in a less dense whisker bridging network and insufficient toughening effect; Example 2 had the optimal amount, forming an effective network that fully realized crack deflection, bridging, and pull-out; Example 3 had an excessive amount, which may lead to agglomeration, becoming stress concentration points and impairing strength and uniformity; In Example 1, the binder was insufficient, resulting in a relatively weak carbon network with insufficient high-temperature bonding strength and toughness support; In Examples 2-3, the binder was sufficient, forming a more continuous and stable carbon network, providing better high-temperature strength and oxidation protection; The coating in Example 1 was thin, with limited protective ability; The coating in Example 2 had a moderate thickness and good protection and toughness; The coating in Example 3 was the thickest, making it prone to cracking or peeling due to internal forces during preparation and thermal shock; Comparing Example 2 with Comparative Example 1 shows that: In Example 2, the hexagonal boron nitride whiskers, through Bridging, pull-out, and deflection of cracks dissipate energy; the binder provides excellent high-temperature bonding strength and toughness; the protective coating isolates oxygen and erosion, protecting the matrix. These three elements work synergistically to improve thermal shock resistance. In Comparative Example 1, the absence of hexagonal boron nitride whiskers to prevent cracking indicates a lack of toughening mechanism. The low carbon residue of ordinary phenolic resin results in a poor-quality carbon network, insufficient bonding strength at high temperatures, and direct exposure of the matrix to a high-temperature oxidizing environment leads to rapid performance degradation. Comparing Example 2 with Comparative Example 2 reveals that while Comparative Example 2 utilizes a binder and protective coating to provide a robust matrix and external protection, it lacks the core toughening component of hexagonal boron nitride whiskers. Under thermal stress, cracks can easily penetrate the matrix, resulting in brittle fracture. Comparing Example 2 with Comparative Example 3 reveals that Comparative Example 2 uses ordinary phenolic resin, which cannot form a strong chemical bond with matrix particles or a strong interface with hexagonal boron nitride whiskers, leading to easy pull-out of the whiskers rather than bridging.
[0031] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0032] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in this application, they should all fall within the protection scope of the present invention.
Claims
1. A refractory material with high thermal shock resistance, characterized in that, Includes the following components by weight: 10-15 parts α-Al2O3 micro powder, 2-4 parts TiO2 micro powder, 3-5 parts hexagonal boron nitride whiskers, 8-12 parts fused magnesia, 25-35 parts fused white corundum, 15-25 parts microporous sintered corundum, 5-8 parts magnesium aluminum spinel, 2-4 parts silicon powder, 1-3 parts aluminum powder, 3-5 parts flake graphite, 3-6 parts zircon, 1-2 parts Y2O3 powder, 4-8 parts additives, 2-4 parts binder, and 5-10 parts coating slurry; The hexagonal boron nitride whiskers are prepared by the following steps: Boric acid, melamine, and deionized water were mixed and stirred, allowed to cool naturally, allowed to stand, filtered, and the filter cake was placed in a freeze dryer for freeze drying. The cake was then transferred to a high-temperature tube furnace under a nitrogen atmosphere for heat treatment and allowed to cool naturally to obtain hexagonal boron nitride whiskers.
2. The high thermal shock resistant refractory material according to claim 1, characterized in that, The ratio of boric acid, melamine, and deionized water is 5-10g: 5-10g: 500mL.
3. The high thermal shock resistant refractory material according to claim 1, characterized in that, The α-Al₂O₃ micro powder has a particle size of 1-5 μm; the TiO₂ micro powder has a particle size of 1-5 μm; the silicon powder has a particle size ≤43 μm; the aluminum powder has a particle size ≤74 μm; the flake graphite has a particle size ≤74 μm; the magnesium aluminum spinel has a particle size of 45-100 μm; the Y₂O₃ powder has a particle size ≤43 μm; the fused magnesia is a mixture of fused magnesia particles with a particle size of 1-3 mm and fused magnesia fine powder with a particle size ≤74 μm at a mass ratio of 65 g: 27-29 g; the fused white corundum is a mixture of fused white corundum aggregate with a particle size of 3-5 mm, fused white corundum aggregate with a particle size of 1-3 mm, and fused white corundum fine powder with a particle size of 75-100 μm at a mass ratio of 13 g: 10-30 g: 15-25 g.
4. The high thermal shock resistant refractory material according to claim 1, characterized in that, The microporous sintered corundum is a mixture of microporous sintered corundum with a particle size of 3-5 mm, microporous sintered corundum with a particle size of 1-3 mm, and microporous sintered corundum with a particle size of ≤1 mm in a mass ratio of 13g:10-30g:11g.
5. The high thermal shock resistant refractory material according to claim 1, characterized in that, The zircon is a mixture of zircon sand with a particle size <125μm and zircon powder with a particle size ≤74μm in a mass ratio of 60g:40g.
6. The high thermal shock resistant refractory material according to claim 1, characterized in that, The additive consists of MgAl2O3 and Ca. 12 Al 14 O 33 Al2O3 was obtained by ball milling and calcining a mixture of 40-45g:10-15g:24-32g.
7. A high thermal shock refractory material according to claim 1, characterized in that, The coating slurry is prepared by ball milling ZrB2 powder with a particle size of 1-5 μm, SiC powder with a particle size of 0.5-2 μm, TaSi2 powder with a particle size of 1-3 μm, anhydrous ethanol, and polyvinyl butyral in a ratio of 50-70 g: 10-20 g: 5-15 g: 140-240 mL: 2-3 g in a ball mill jar.
8. A high thermal shock refractory material according to claim 1, characterized in that, The binder is prepared by the following steps: Phenol and formaldehyde solutions were added to a three-necked flask and mixed and stirred. Tetraethyl orthosilicate was added and stirring continued. Carbon black and mixed acids were mixed and stirred, and then placed in a constant temperature water bath for heat preservation. The mixture was washed, dried, and added to a beaker with anhydrous ethanol. The mixture was then ultrasonically vibrated and added to the three-necked flask. NaOH solution was added, and the mixture was heated and reacted at a constant temperature. The pH was adjusted with acetic acid solution, and the mixture was dehydrated under vacuum. Ethylene glycol was added and stirred to obtain the binder.
9. A high thermal shock refractory material according to claim 8, characterized in that, The ratio of phenol, formaldehyde solution, tetraethyl orthosilicate, carbon black, mixed acid, anhydrous ethanol, NaOH solution, and ethylene glycol is 100-150g: 110-150mL: 6-42mL: 3-16g: 400mL: 30mL: 50mL: 20mL; the formaldehyde solution has a mass fraction of 37%; the mixed acid is a mixture of 98% concentrated sulfuric acid and 58-68% concentrated nitric acid at a volume ratio of 3:1; the NaOH solution has a molar concentration of 1mol / L; and the acetic acid solution has a mass fraction of 36%.
10. A method for preparing a high thermal shock resistant refractory material as described in any one of claims 1-9, characterized in that, Includes the following steps: Step 1: Weigh out the following components by weight: 10-15 parts α-Al2O3 micro powder, 2-4 parts TiO2 micro powder, 3-5 parts hexagonal boron nitride whiskers, 8-12 parts fused magnesia, 25-35 parts fused white corundum, 15-25 parts microporous sintered corundum, 5-8 parts magnesium aluminum spinel, 2-4 parts silicon powder, 1-3 parts aluminum powder, 3-5 parts flake graphite, 3-6 parts zircon, 1-2 parts Y2O3 powder, 4-8 parts additives, 5-10 parts anhydrous ethanol, 2-4 parts binder, and 5-10 parts coating slurry. Step 2: Add α-Al2O3 micro powder, TiO2 micro powder, fused magnesia, fused white corundum, microporous sintered corundum, magnesium aluminum spinel, silicon powder, aluminum powder, flake graphite, zircon, Y2O3 powder and additives to a ball mill for dry mixing to obtain aggregate; add hexagonal boron nitride whiskers to anhydrous ethanol and stir magnetically, add binder and continue stirring, add the above aggregate, mix and stir, trap the material, press under a cold press, transfer to a drying oven for curing, keep warm under an argon atmosphere, and cool with the furnace to obtain refractory material; Step 3: Apply the coating slurry to the surface of the refractory material, transfer it to an oven to dry, place it in a high-temperature tube furnace for sintering, cool it with the furnace, and then place it in a vacuum sintering furnace for gaseous silicon infiltration treatment, cooling it with the furnace to obtain a refractory material with high thermal shock resistance.