A method for preparing a metal toughened silicon carbide-silicon nitride jointing material

Abstract

This invention relates to the field of refractory materials technology, and in particular to a method for preparing a metal-toughened silicon carbide-silicon nitride gunning compound. The method for preparing the metal-toughened silicon carbide-silicon nitride gunning compound is as follows: First, a modified phenolic resin composition is prepared; then, refractory aggregates, dispersants, additives, and composite carbon powder are dry-kneaded; finally, the modified phenolic resin composition is added, mixed, milled, extruded, and cut to obtain the finished metal-toughened silicon carbide-silicon nitride gunning compound. This invention uses a modified phenolic resin composition to replace the traditional binder, overcoming the shortcomings of traditional tar binders (high apparent porosity) and gunning compound (high apparent porosity), resulting in poor mechanical properties and volumetric stability, thus endowing it with excellent mechanical properties and volumetric stability.

Description

Technical Field

[0001] This invention relates to the field of refractory materials technology, and in particular to a method for preparing a metal-toughened silicon carbide-silicon nitride gunning clay material. Background Technology

[0002] Taphole clay is used to seal the taphole of a blast furnace. The molten iron produced by blast furnace smelting needs to flow from the taphole into the iron trough, then through the main trough and branch troughs into the ladle or torpedo ladle. After tapping the iron, the taphole of the blast furnace needs to be blocked with taphole clay. After the blast furnace smelts again, the taphole clay is opened up by a tapping machine to tap out the iron. This process is repeated. Therefore, taphole clay is a refractory material used to block the taphole during the blast furnace ironmaking process. It can quickly and accurately block the taphole after tapping the iron, allowing the blast furnace to enter the next smelting cycle. It is an important guarantee for the safety and smooth operation of the blast furnace.

[0003] With the rapid development of the steel industry, blast furnaces are gradually becoming larger, and the number of times slag and iron are tapped from blast furnaces is decreasing. This leads to an increase in the amount of slag and iron tapped per batch, which intensifies the erosion and corrosion of the taphole clay. Consequently, more stringent requirements are placed on the mechanical properties, volumetric stability, and erosion resistance of the taphole clay. Currently, taphole clay is mainly divided into hydrated taphole clay and anhydrous taphole clay. Due to its poor resistance to slag and iron erosion, low bulk density, slow heating rate, and the problem of the taphole turning red before sintering, hydrated taphole clay can no longer meet the performance requirements of large blast furnaces. Anhydrous taphole clay, due to its superior performance in all aspects, has gradually replaced hydrated taphole clay as the main refractory material.

[0004] Currently, the binders in anhydrous tapping mud are mostly composed of at least one of tar, anthracene oil, and coal tar pitch, resulting in high apparent porosity, poor mechanical properties and volume stability. Furthermore, they release carcinogenic substances such as benzo[a]pyrene during use, leading to poor environmental performance and affecting the health of operators. Summary of the Invention

[0005] To address the technical problems of high apparent porosity, poor mechanical properties, and poor volumetric stability in existing anhydrous tapping clay, this invention provides a method for preparing metal-toughened silicon carbide-silicon nitride tapping clay material. This method replaces at least one of the traditional binders—tar, anthracene oil, and coal tar pitch—with a modified phenolic resin composition, overcoming the shortcomings of traditional tar binders, such as high apparent porosity and poor mechanical properties, erosion resistance, and volumetric stability.

[0006] The present invention provides a method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material, which is achieved through the following technical solution:

[0007] A metal-toughened silicon carbide-silicon nitride gunning compound is made from the following raw materials in the indicated mass percentages: 44-52% refractory aggregate, 0.6-1.0% dispersant, 14-18% modified phenolic resin composition, 5-10% composite carbon powder, and the balance being additives; the additives are composed of additive A and additive B in a mass ratio of (2-9):1; additive A is at least one of silicon carbide, silicon nitride, and metallic silicon powder; additive B is a nano-metal cluster modified additive;

[0008] A method for preparing a metal-toughened silicon carbide-silicon nitride gunning compound is as follows: First, a modified phenolic resin composition is prepared. Then, refractory aggregates, dispersants, additives, and composite carbon powder are dry-kneaded. Finally, the modified phenolic resin composition is added, mixed, rolled, extruded, and cut to obtain the finished metal-toughened silicon carbide-silicon nitride gunning compound.

[0009] This invention replaces traditional binders with modified phenolic resin compositions, overcoming the shortcomings of traditional tar binders with high apparent porosity and high apparent porosity of gunning clay, resulting in poor mechanical properties and volume stability, and endowing them with good mechanical properties and volume stability.

[0010] Preferably, the modified phenolic resin composition is prepared as follows:

[0011] S1. A 40-60% solid content phenolic resin solution is formed in acetone solvent with a methyl phenolic resin solvent. C6-C12 saturated fatty acids and tetraisopropyl titanate are added to the methyl phenolic resin solution. The mass ratio of the C6-C12 saturated fatty acids to the methyl phenolic resin solvent is 1:(10-100), and the mass ratio of the tetraisopropyl titanate to the methyl phenolic resin solvent is 1:(100-400). The esterification reaction is carried out at 60-80℃ for 1-4 hours. Acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl methyl phenolic resin.

[0012] S2. Add 5-10 parts of partially blocked hydroxymethyl methyl phenolic resin from S1, 20-50 parts of linear phenolic resin, 5-10 parts of boron-modified phenolic resin, and 2-4 parts of curing agent to 40-80 parts of small molecule alcohol and mix evenly to obtain a modified phenolic resin composition.

[0013] The preparation method of the modified phenolic resin composition is relatively simple and facilitates large-scale production. Furthermore, the prepared modified phenolic resin composition overcomes the problems of traditional thermosetting phenolic resins, which have a rapid curing rate, resulting in insufficient plasticity of the taphole clay, leading to agglomeration, blockage of the taphole, and disruption of the normal taphole channel. By reacting C6-C12 saturated fatty acids with the hydroxymethyl groups in the thermosetting phenolic resin, the partially blocked hydroxymethyl methylated methylated phenolic resin controls the curing rate. Simultaneously, the modified phenolic resin composition, combined with linear phenolic resin, boron-modified phenolic resin, and a curing agent, improves the fluidity of the taphole clay under high-temperature conditions, enhancing its processing plasticity and thermal stability. In addition, the boron-modified phenolic resin forms a boron carbide protective layer under high temperatures, improving the mechanical strength and oxidation resistance of the taphole clay. Furthermore, boron, as a low-temperature sintering agent, can carbonize additives to form a carbon-bonded protective layer, thereby improving the sintering performance, mechanical strength, volume stability, and erosion resistance of the taphole clay.

[0014] Preferably, in step S1, a phenolic resin solvent with a solid content of 40-60% is formed in acetone solvent. C6-C12 saturated fatty acids and tetraisopropyl titanate are added to the phenolic resin solution. The mass ratio of the C6-C12 saturated fatty acids to the phenolic resin solvent is 1:(40-50), and the mass ratio of the tetraisopropyl titanate to the phenolic resin solvent is 1:(200-250). The esterification reaction is carried out at 60-80°C for 3-4 hours. Acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl phenolic resin.

[0015] Preferably, in step S2, 8-10 parts of partially blocked hydroxymethyl methylated phenolic resin from step S1, 35 parts of linear phenolic resin, 8-10 parts of boron-modified phenolic resin, and 3-4 parts of curing agent are added to 45 parts of small molecule alcohol and mixed evenly to obtain a modified phenolic resin composition.

[0016] Preferably, the curing agent is one or more of hexamethylenetetramine, polyoxymethylene, melamine, and urea-formaldehyde, or the curing agent is at least one of hexamethylenetetramine, polyoxymethylene, melamine, and urea-formaldehyde combined with at least one of di(acetylacetone)titanate and di(ethyl acetoacetate)titanate.

[0017] The diisopropyl di(acetylacetone) titanate and / or diisopropyl di(acetoacetate) titanate contained in the curing agent of this invention can undergo cross-linking reaction with the hydroxyl groups in the modified phenolic resin composition under thermal action, which can improve the early mechanical strength and also make the refractory aggregate, additives and composite carbon powder dispersed uniformly in the modified phenolic resin composition, thereby improving the mechanical properties and erosion resistance of the slurry after high-temperature curing.

[0018] Preferably, the small molecule alcohol is one or more of methanol, ethanol, ethylene glycol, diethylene glycol, and glycerol.

[0019] Preferably, the refractory aggregate is at least one of white fused alumina and brown fused alumina; or the refractory aggregate is composed of white fused alumina and / or brown fused alumina combined with at least one of zirconium oxide and tetrapod zinc oxide.

[0020] Preferably, the nano-metal cluster modified additive includes an additive carrier and nano-metal clusters formed on the surface of the additive carrier by a sol-gel method and in-situ reaction, wherein the nano-metal clusters are at least one of nano-titanium clusters, nano-zirconium clusters, and nano-molybdenum clusters; and the additive carrier is at least one of silicon carbide, silicon nitride, and metallic silicon powder.

[0021] Preferably, the additive is composed of silicon carbide, silicon nitride, metallic silicon powder, nano-metal cluster modified silicon carbide, and nano-metal cluster modified silicon nitride in a mass ratio of 3:1:1:(0.3-0.4):(0.3-0.4).

[0022] The nano-metal clusters on the surface of the additive carrier have high activity. At high temperatures, they preferentially form high-melting-point metal oxides, metal carbides, and metal nitrides with oxygen, nitrogen, and coke. These can fill the gaps caused by thermal expansion of the taphole clay, improve the mechanical properties, volume stability, and erosion resistance of the taphole clay after high-temperature curing. At the same time, an appropriate amount of silicon nitride is needed to improve the opening performance and permeability of the taphole clay, so as to avoid the taphole clay's open performance being affected by its low apparent porosity.

[0023] Preferably, the dispersing agent is at least one selected from the following: triisostearate titanate isopropyl, di(dioctylphospho)titanate ethylene, di(dioctylpyrophospho)titanate ethylene, di(acetylacetone)titanate diisopropyl, and di(acetoacetate)titanate diisopropyl.

[0024] In this invention, titanate coupling agent is used as a dispersant, which can improve the dispersion uniformity of refractory aggregates, additives and composite carbon powder in the modified phenolic resin composition, thereby improving the mechanical properties, erosion resistance and volume stability of the gunning clay, and also improve the high temperature resistance of the gunning clay.

[0025] In summary, the present invention has the following advantages:

[0026] 1. The gun clay prepared in this invention has low apparent porosity, good mechanical properties and volume stability, overcoming the defects of high apparent porosity, poor mechanical properties, erosion resistance and volume stability caused by traditional tar binders.

[0027] 2. The preparation method of the present invention is relatively simple, easy to operate, and easy to achieve large-scale production.

[0028] 3. In this invention, the composition and ratio of additives are optimized to reduce the apparent porosity of the tapping clay while ensuring that the tapping clay has good opening performance, thereby improving the mechanical properties, volume stability and erosion resistance of the tapping clay. Detailed Implementation

[0029] To further understand the inventiveness and technical advancements of this invention, the preferred embodiments of this invention will be discussed in detail below with reference to examples and comparative examples.

[0030] Example: A metal-toughened silicon carbide-silicon nitride gunning compound is made from the following raw materials in the following mass percentages: 44-52% refractory aggregate, 0.6-1.0% dispersant, 14-18% modified phenolic resin composition, 5-10% composite carbon powder, and the balance being additives.

[0031] The refractory aggregate is at least one of white fused alumina and brown fused alumina; or the refractory aggregate is composed of white fused alumina and / or brown fused alumina combined with at least one of zirconium oxide and tetrapod zinc oxide.

[0032] The dispersing agent is at least one of the following: triisostearate titanate isopropyl, di(dioctylphosphoyl)titanate ethylene, di(dioctylpyrophosphoyl)titanate ethylene, di(acetylacetone)titanate diisopropyl, and di(acetoacetate)titanate diisopropyl.

[0033] The composite toner is composed of coke powder combined with at least one of carbon fiber powder, graphene, graphite, carbon nanotubes, and C60. Preferably, the composite toner is composed of coke powder and flake graphite.

[0034] The additive consists of additive A and additive B in a mass ratio of (2-9):1. Additive A is at least one of silicon carbide, silicon nitride, and metallic silicon powder. Additive B is a nano-metal cluster modified additive. The nano-metal cluster modified additive includes an additive carrier and nano-metal clusters formed on the surface of the additive carrier through a sol-gel method and in-situ reaction. The nano-metal clusters are at least one of titanium nanoclusters, zirconium nanoclusters, and molybdenum nanoclusters; the additive carrier is at least one of silicon carbide, silicon nitride, and metallic silicon powder.

[0035] A method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material is as follows:

[0036] First, prepare a modified phenolic resin composition:

[0037] S1.1. A 40-60% solid content phenolic resin solution is formed in acetone solvent with a methyl phenolic resin solvent. C6-C12 saturated fatty acids and tetraisopropyl titanate are added to the methyl phenolic resin solution. The mass ratio of the C6-C12 saturated fatty acids to the methyl phenolic resin solvent is 1:(10-100), and the mass ratio of the tetraisopropyl titanate to the methyl phenolic resin solvent is 1:(100-400). The esterification reaction is carried out at 60-80℃ for 1-4 hours. Acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl methyl phenolic resin.

[0038] S1.2. Add 5-10 parts of partially blocked hydroxymethyl methyl phenolic resin from S1, 20-50 parts of linear phenolic resin, 5-10 parts of boron-modified phenolic resin, and 2-4 parts of curing agent to 40-80 parts of small molecule alcohol and mix evenly to obtain a modified phenolic resin composition.

[0039] Small molecule alcohols are composed of one or more of methanol, ethanol, ethylene glycol, diethylene glycol, and glycerol;

[0040] The curing agent is one or more of hexamethylenetetramine, polyoxymethylene, melamine, and urea-formaldehyde, or the curing agent is at least one of hexamethylenetetramine, polyoxymethylene, melamine, and urea-formaldehyde combined with at least one of di(acetylacetone)titanate and di(ethyl acetoacetate)titanate.

[0041] The refractory aggregate, dispersant, additives, and composite carbon powder are then subjected to dry kneading.

[0042] Finally, after adding the modified phenolic resin composition and mixing, the mixture is ground, extruded, and cut to obtain the finished metal-toughened silicon carbide-silicon nitride gunning putty material.

[0043] Preparation Example 1: The preparation method of nano-titanium cluster modified silicon carbide is as follows: S1. Dissolve 20g of titanium oxysulfate (Maclean) in 1000mL of distilled water and stir magnetically at 200rpm / min for half an hour. Then add 50g of 800-mesh silicon carbide and stir magnetically at 200rpm / min for 15min. Then perform ultrasonic dispersion treatment for half an hour. The ultrasonic power is 40kHz and the ultrasonic frequency is 1000W. After ultrasonic dispersion treatment, filter to obtain solid powder. Place the obtained solid powder in a vacuum drying oven and dry at 20Pa and 120℃ for 8h. Solid powder was calcined in an atmosphere tube furnace at 20℃ / min for 2 hours to obtain anatase TiO2@silicon carbide powder. S2. The anatase TiO2@silicon carbide powder was placed in an atmosphere tube furnace and a hydrogen-argon mixture was introduced, with a hydrogen-argon volume ratio of 1:1. The reduction reaction was maintained at 650℃ for 4 hours. After the furnace was opened and allowed to cool naturally to room temperature, the powder was ball-milled at 60 rpm for 30 minutes. Finally, it was screened using an 800-mesh sieve to obtain ≤800-mesh nano-titanium cluster modified silicon carbide.

[0044] The difference between Preparation Example 2 and Preparation Example 1 is as follows: The preparation method of nano-titanium cluster modified silicon nitride is as follows: S1. Dissolve 20g of titanium oxysulfate in 1000mL of distilled water and stir magnetically at 200rpm / min for half an hour. Then add 50g of 800-mesh silicon nitride and stir magnetically at 200rpm / min for 15min. Then perform ultrasonic dispersion treatment for half an hour. The ultrasonic power is 40kHz and the ultrasonic frequency is 1000W. After ultrasonic dispersion treatment, filter to obtain solid powder. The obtained solid powder is placed in a vacuum drying oven and dried at 20Pa and 120℃ for 8h. Dry solid powder was transferred to an atmosphere tube furnace for calcination treatment. The temperature was increased to 550℃ at 20℃ / min under air atmosphere and calcined for 2 hours to obtain anatase TiO2@silicon carbide powder. S2. Anatase TiO2@silicon carbide powder was placed in an atmosphere tube furnace and a hydrogen-argon mixture was introduced. The volume ratio of hydrogen to argon in the hydrogen-argon mixture was 1:1. The reduction reaction was carried out at 650℃ for 4 hours. The furnace was opened and naturally cooled to room temperature. Then, it was ball-milled at 60 rpm for 30 min. Finally, it was screened with an 800-mesh sieve to obtain ≤800-mesh nano-titanium cluster modified silicon nitride.

[0045] The difference between Preparation Example 3 and Preparation Example 1 is as follows: The preparation method of nano-zirconium cluster modified silicon carbide is as follows: S1. Dissolve 26.8g of zirconium sulfate tetrahydrate (Wuhan Kanos Technology Co., Ltd.) in 1000mL of distilled water and stir magnetically at 200rpm / min for half an hour. Then add 50g of 800-mesh silicon carbide and stir magnetically at 200rpm / min for 15min. Add 5wt% ammonia water until Zr is completely precipitated, and continue stirring magnetically at 200rpm / min for 1 hour. After standing for 24h, filter to obtain solid powder. Place the obtained solid powder in a vacuum drying oven and dry at 2... The powder was dried at 0 Pa and 120℃ for 8 hours. The resulting dry solid powder was then transferred to an atmosphere tube furnace for calcination. The temperature was increased to 550℃ at 20℃ / min under air atmosphere for 2 hours to obtain ZrO2@silicon carbide powder. S2. Anatase ZrO2@silicon carbide powder was placed in an atmosphere tube furnace and a hydrogen-argon mixture was introduced. The volume ratio of hydrogen to argon in the hydrogen-argon mixture was 1:1. The reduction reaction was carried out at 650℃ for 4 hours. The furnace was then opened and allowed to cool naturally to room temperature. Subsequently, the powder was ball-milled at 60 rpm for 30 minutes. Finally, it was screened using an 800-mesh sieve to obtain ≤800-mesh nano-zirconium cluster modified silicon carbide.

[0046] The difference between Preparation Example 4 and Preparation Example 1 is as follows: The preparation method of nano-zirconium cluster modified silicon nitride is as follows: S1. Dissolve 26.8g of zirconium sulfate tetrahydrate (Wuhan Kanos Technology Co., Ltd.) in 1000mL of distilled water and stir magnetically at 200rpm / min for half an hour. Then add 50g of 800-mesh silicon nitride and stir magnetically at 200rpm / min for 15min. Add 5wt% ammonia water until Zr is completely precipitated, and continue stirring magnetically at 200rpm / min for 1 hour. After standing for 24h, filter to obtain solid powder. Place the obtained solid powder in a vacuum drying oven and dry at 2... The solid powder was dried at 0 Pa and 120℃ for 8 hours. The resulting dry solid powder was then transferred to an atmosphere tube furnace for calcination. The temperature was increased to 550℃ at 20℃ / min under air atmosphere for 2 hours to obtain ZrO2@silicon carbide powder. S2. Anatase ZrO2@silicon carbide powder was placed in an atmosphere tube furnace and a hydrogen-argon mixture was introduced. The volume ratio of hydrogen to argon in the hydrogen-argon mixture was 1:1. The reduction reaction was carried out at 650℃ for 4 hours. The furnace was then opened and allowed to cool naturally to room temperature. Subsequently, the powder was ball-milled at 60 rpm for 30 minutes. Finally, it was screened using an 800-mesh sieve to obtain ≤800-mesh nano-zirconium cluster modified silicon nitride.

[0047] Example 1: A metal-toughened silicon carbide-silicon nitride gunning compound is made from the following raw materials in the following weight percentages: 20% white fused alumina with a particle size of 1-3 mm, 25% white fused alumina with a particle size of 0-1 mm, 5% white fused alumina sieved through a 325-mesh sieve, 0.8% isopropyl triisostearate titanate, 16% modified phenolic resin composition, 3.0% 60-mesh coke powder, 2.0% 325-mesh coke powder, 1.6% 325-mesh natural flake graphite, 0.6% ultrafine natural flake graphite, and 26.0% additives.

[0048] The additive consists of silicon carbide, silicon nitride, metallic silicon powder, and nano-titanium cluster modified silicon carbide from Preparation Example 1 in a mass ratio of 3:1:1:0.6. The silicon carbide is composed of 325-mesh silicon carbide and 2000-mesh silicon carbide in a mass ratio of 9:1, the silicon nitride is composed of 325-mesh silicon nitride and 2000-mesh silicon nitride in a mass ratio of 9:1, and the metallic silicon powder is composed of 325-mesh metallic silicon powder and 2000-mesh metallic silicon powder in a mass ratio of 9:1.

[0049] 325-mesh silicon carbide, 800-mesh silicon carbide, and 2000-mesh silicon carbide are supplied by Qinghe County Chaotai Metal Materials Co., Ltd. 325-mesh silicon nitride, 800-mesh silicon nitride, and 2000-mesh silicon nitride are also supplied by Qinghe County Chaotai Metal Materials Co., Ltd. 325-mesh metallic silicon powder and 2000-mesh metallic silicon powder are also supplied by Qinghe County Chaotai Metal Materials Co., Ltd.

[0050] White fused alumina with particle sizes of 1-3mm, 0-1mm, and sieved through a 325-mesh sieve were all supplied by Henan Shengxing Environmental Protection Materials Co., Ltd. Triisostearate titanate isopropyl triisostearate was supplied by Nanjing Aocheng Chemical Co., Ltd. 60-mesh and 325-mesh coke powders were both supplied by Lingshou County Henglin Mineral Products Co., Ltd. 325-mesh natural flake graphite and 4000-mesh ultrafine natural flake graphite were supplied by Qingdao Tianfeng Graphite Co., Ltd.

[0051] A method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material is as follows:

[0052] First, a modified phenolic resin composition is prepared. The preparation method of the modified phenolic resin composition is as follows:

[0053] S1.1. A solid-phase phenolic resin (Shandong Chengtian Chemical Co., Ltd., solid-phase one-step amine-free thermosetting phenolic resin) was solventized in acetone to form a solid-phase phenolic resin solution with a solid content of 50%. Lauric acid (CAS No.: 143-07-7, purity 99%, Guangzhou Zouyang Chemical Co., Ltd.) and tetraisopropyl titanate (CAS No.: 546-68-9, purity 95%, Aladdin) were added to the solid-phase phenolic resin solution. The mass ratio of lauric acid to solid-phase phenolic resin solvent was 1:50, and the mass ratio of tetraisopropyl titanate to solid-phase phenolic resin solvent was 1:250. The esterification reaction was carried out at 70℃ for 4 hours. Acetone and water were removed by vacuum distillation to obtain partially blocked hydroxymethyl solid-phase phenolic resin.

[0054] S1.2. Add 8 parts of partially blocked hydroxymethyl methyl phenolic resin from S1, 35 parts of linear phenolic resin 2123 (99% effective ingredient content, Jinan Dahui Chemical Technology Co., Ltd.), 8 parts of boron-modified phenolic resin TY03 (Jining Fangyu Chemical Co., Ltd.), 3 parts of hexamethylenetetramine (CAS No.: 100-97-0, purity ≥99.5%, Merck Chemicals), and 1 part of diisopropyl di(acetylacetone) titanate (HY-1801, Hangzhou Jessica Chemical Co., Ltd.) to 45 parts of ethylene glycol. Heat to 40℃ and stir magnetically for 15 min. Then cool to 20℃ and use an ultrasonic mixer JH1000W-20 to perform ultrasonic dispersion treatment for 10 min, with an ultrasonic frequency of 20kHz and an ultrasonic power of 1000W to obtain the modified phenolic resin composition.

[0055] Subsequently, 20 parts by weight of white fused alumina with a particle size of 1-3 mm, 25 parts by weight of white fused alumina with a particle size of 0-1 mm, 5 parts by weight of white fused alumina sieved through a 325-mesh sieve, 0.8 parts by weight of triisostearate titanate isopropyl triisostearate, 5 parts by weight of coke powder, 2.2 parts by weight of flake graphite, and 26 parts by weight of additives were put into a vacuum kneader for dry kneading for 30 minutes.

[0056] Finally, 16 parts by weight of the modified phenolic resin composition prepared in S1.2 above are added to the vacuum kneader. After 5 minutes of dry kneading, the kneaded material is transferred to a planetary roller mill for 1 hour of mixing and milling to obtain a mixed material. The mixed material is then transferred to an automatic cutting and packaging clay machine for extrusion cutting and packaging to obtain the finished metal-toughened silicon carbide-silicon nitride clay material.

[0057] The difference between Example 2 and Example 1 is that the modified phenolic resin composition is prepared as follows:

[0058] S1.1. A 50% solid content phenolic resin solution is formed in acetone solvent with a methyl phenolic resin solvent. Lauric acid and tetraisopropyl titanate are added to the methyl phenolic resin solution. The mass ratio of lauric acid to methyl phenolic resin solvent is 1:80, and the mass ratio of tetraisopropyl titanate to methyl phenolic resin solvent is 1:250. The esterification reaction is carried out at 70°C for 4 hours. Acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl methyl phenolic resin.

[0059] S1.2. Add 5 parts of partially blocked hydroxymethyl methylated phenolic resin from S1, 41 parts of linear phenolic resin 2123, 5 parts of boron-modified phenolic resin TY03, 3 parts of hexamethylenetetramine, and 1 part of diisopropyl di(acetylacetone)titanate HY-1801 to 45 parts of ethylene glycol. Heat to 40°C and stir magnetically for 15 minutes. Then cool to 20°C and perform ultrasonic dispersion treatment using an ultrasonic mixer JH1000W-20 for 10 minutes. The ultrasonic frequency is 20kHz and the ultrasonic power is 1000W to obtain the modified phenolic resin composition.

[0060] The difference between Example 3 and Example 1 is that the modified phenolic resin composition is prepared as follows:

[0061] S1.1. A 50% solid content phenolic resin solution is formed in acetone solvent with a methyl phenolic resin solvent. Lauric acid and tetraisopropyl titanate are added to the methyl phenolic resin solution. The mass ratio of lauric acid to methyl phenolic resin solvent is 1:50, and the mass ratio of tetraisopropyl titanate to methyl phenolic resin solvent is 1:250. The esterification reaction is carried out at 70°C for 4 hours. Acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl methyl phenolic resin.

[0062] S1.2. Add 8 parts of partially blocked hydroxymethyl methyl phenolic resin from S1, 35 parts of linear phenolic resin 2123, 10 parts of boron-modified phenolic resin TY03, and 4 parts of hexamethylenetetramine to 45 parts of ethylene glycol. Heat to 40°C and stir magnetically for 15 minutes. Then cool to 20°C and perform ultrasonic dispersion treatment using an ultrasonic mixer JH1000W-20 for 10 minutes. The ultrasonic frequency is 20kHz and the ultrasonic power is 1000W to obtain the modified phenolic resin composition.

[0063] The difference between Example 4 and Example 1 is that the metal-toughened silicon carbide-silicon nitride gunning paste material is made from the following raw materials in the following mass percentages: 20% white corundum with a particle size of 1-3 mm, 25% white corundum with a particle size of 0-1 mm, 5% white corundum sieved through a 325-mesh sieve, 0.5% triisostearate titanate isopropyl triisostearate, 0.3% diisopropyl di(acetylacetone) titanate, 16% modified phenolic resin composition, 3.0% 60-mesh coke powder, 2.0% 325-mesh coke powder, 1.6% 325-mesh natural flake graphite, 0.6% ultrafine natural flake graphite, and 26.0% additives.

[0064] The difference between Example 5 and Example 4 is that the metal-toughened silicon carbide-silicon nitride gunning paste material is made from the following raw materials in the following mass percentages: 20% white corundum with a particle size of 1-3 mm, 23% white corundum with a particle size of 0-1 mm, 2% 325-mesh zirconium oxide (Shandong Desheng New Material Co., Ltd.), 5% white corundum sieved through a 325-mesh sieve, 0.5% triisostearate titanate isopropyl titanate, 0.3% di(acetylacetone) titanate diisopropyl, 16% modified phenolic resin composition, 3.0% 60-mesh coke powder, 2.0% 325-mesh coke powder, 1.6% 325-mesh natural flake graphite, 0.6% ultrafine natural flake graphite, and 26.0% additives.

[0065] The difference between Example 6 and Example 4 is that the metal-toughened silicon carbide-silicon nitride gunning paste material is made from the following raw materials in the following mass percentages: 20% white corundum with a particle size of 1-3 mm, 24% white corundum with a particle size of 0-1 mm, 5% white corundum sieved through a 325-mesh sieve, 1% tetrapod zinc oxide whiskers T-ZnO (XD-Z1X05, diameter 0.5-5 micrometers, length 10-50 micrometers, Qinghe County Chaotai Metal Materials Co., Ltd.), 0.5% triisostearate titanate isopropyl triisostearate, 0.3% di(acetylacetone) titanate diisopropyl triisostearate, 16% modified phenolic resin composition, 3.0% 60-mesh coke powder, 2.0% 325-mesh coke powder, 1.6% 325-mesh natural flake graphite, 0.6% ultrafine natural flake graphite, and 26.0% additives.

[0066] The difference between Example 7 and Example 4 is that the metal-toughened silicon carbide-silicon nitride gunning paste material is made from the following raw materials in the following mass percentages: 20% white corundum with a particle size of 1-3 mm, 23% white corundum with a particle size of 0-1 mm, 5% white corundum sieved through a 325-mesh sieve, 1.5% 325-mesh zirconium oxide, 0.5% tetrapod zinc oxide whiskers XD-Z1X05, 0.5% triisostearate titanate isopropyl titanate, 0.3% di(acetylacetone) titanate diisopropyl, 16% modified phenolic resin composition, 3.0% 60-mesh coke powder, 2.0% 325-mesh coke powder, 1.6% 325-mesh natural flake graphite, 0.6% ultrafine natural flake graphite, and 26.0% additives.

[0067] The difference between Example 8 and Example 7 is that the metal-toughened silicon carbide-silicon nitride gunning paste material is made from the following raw materials in the following mass percentages: 20% white corundum with a particle size of 1-3 mm, 23% white corundum with a particle size of 0-1 mm, 5% white corundum sieved through a 325-mesh sieve, 1.5% 325-mesh zirconium oxide, 0.5% tetrapod zinc oxide whiskers XD-Z1X05, 0.5% triisostearate titanate isopropyl titanate, 0.3% di(acetylacetone) titanate diisopropyl, 16% modified phenolic resin composition, 4.32% 60-mesh coke powder, 2.88% 325-mesh coke powder, and 26.0% additives.

[0068] The difference between Example 9 and Example 7 is that the metal-toughened silicon carbide-silicon nitride gunning paste material is made from the following raw materials in the following mass percentages: 20% white corundum with a particle size of 1-3 mm, 23% white corundum with a particle size of 0-1 mm, 5% white corundum sieved through a 325-mesh sieve, 1.5% 325-mesh zirconium oxide, 0.5% tetrapod zinc oxide whiskers XD-Z1X05, 0.5% triisostearate titanate isopropyl titanate, 0.3% di(acetylacetone) titanate diisopropyl, 16% modified phenolic resin composition, 3% 60-mesh coke powder, 2% 325-mesh coke powder, 2% 325-mesh natural flake graphite, 0.2% industrial graphene (layers <100, purity >98.0%, particle size <20 μm, Hunan Fenghua Materials Development Co., Ltd.), and 26.0% additives.

[0069] The difference between Example 10 and Example 1 is that the additive is composed of silicon carbide, silicon nitride, metallic silicon powder, nano-titanium cluster modified silicon carbide in Preparation Example 1, and nano-titanium cluster modified silicon nitride in Preparation Example 2 in a mass ratio of 3:1:1:0.3:0.3.

[0070] The difference between Example 11 and Example 1 is that the additive is composed of silicon carbide, silicon nitride, metallic silicon powder, nano-titanium cluster modified silicon carbide in Preparation Example 1, and nano-titanium cluster modified silicon nitride in Preparation Example 2 in a mass ratio of 3:1:1:0.2:0.2.

[0071] The difference between Example 12 and Example 1 is that the additive is composed of silicon carbide, silicon nitride, metallic silicon powder, nano-titanium cluster modified silicon carbide in Preparation Example 1, and nano-titanium cluster modified silicon nitride in Preparation Example 2 in a mass ratio of 3:1:1:0.4:0.4.

[0072] The difference between Example 13 and Example 1 is that the additive is composed of silicon carbide, silicon nitride, metallic silicon powder, nano-titanium cluster modified silicon carbide in Preparation Example 1, and nano-titanium cluster modified silicon nitride in Preparation Example 2 in a mass ratio of 3:1:1:0.5:0.5.

[0073] The difference between Example 14 and Example 1 is that the additive is composed of nano-titanium cluster modified silicon carbide in Preparation Example 1, nano-titanium cluster modified silicon nitride in Preparation Example 2, and metallic silicon powder in a mass ratio of 3:1:1.

[0074] The difference between Example 15 and Example 1 is that the additive is composed of silicon carbide, silicon nitride, metallic silicon powder, nano-zirconium cluster modified silicon carbide in Preparation Example 3, and nano-zirconium cluster modified silicon nitride in Preparation Example 4 in a mass ratio of 3:1:1:0.3:0.3.

[0075] The difference between Comparative Example 1 and Example 1 is that the modified phenolic resin composition was replaced with a mixed binder, which consisted of 70# asphalt and a 55% solids-content methyl phenolic resin solution in a 1:1 mass ratio. The 55% solids-content methyl phenolic resin was prepared as follows: 50 parts of methyl phenolic resin and 5 parts of hexamethylenetetramine were dissolved in 45 parts of ethylene glycol to form a 55% solids-content methyl phenolic resin solution.

[0076] The difference between Comparative Example 2 and Example 1 is that the modified phenolic resin composition is prepared as follows: 50 parts of linear phenolic resin 2123, 4 parts of hexamethylenetetramine, and 1 part of diisopropyl di(acetylacetone)titanate HY-1801 are added to 45 parts of ethylene glycol. The mixture is heated to 40°C and magnetically stirred for 15 minutes. Then, it is cooled to 20°C and ultrasonically dispersed for 10 minutes using an ultrasonic mixer JH1000W-20 at a frequency of 20kHz and a power of 1000W to obtain the modified phenolic resin composition.

[0077] The difference between Comparative Example 3 and Example 1 is as follows: The modified phenolic resin composition is prepared as follows: 40 parts of linear phenolic resin 2123, 10 parts of boron-modified phenolic resin TY03, 4 parts of hexamethylenetetramine, and 1 part of diisopropyl di(acetylacetone)titanate HY-1801 are added to 45 parts of ethylene glycol. The mixture is heated to 40°C and magnetically stirred for 15 minutes. Then, it is cooled to 20°C and ultrasonically dispersed for 10 minutes using an ultrasonic mixer JH1000W-20 at an ultrasonic frequency of 20kHz and an ultrasonic power of 1000W to obtain the modified phenolic resin composition.

[0078] The difference between Comparative Example 4 and Example 1 is as follows: The modified phenolic resin composition is prepared as follows: 8 parts of methyl phenolic resin, 40 parts of linear phenolic resin 2123, 8 parts of boron-modified phenolic resin TY03, 4 parts of hexamethylenetetramine, and 1 part of diisopropyl di(acetylacetone)titanate HY-1801 are added to 45 parts of ethylene glycol. The mixture is heated to 40°C and magnetically stirred for 15 minutes. Then, it is cooled to 20°C and ultrasonically dispersed for 10 minutes using an ultrasonic mixer JH1000W-20 at a frequency of 20kHz and a power of 1000W to obtain the modified phenolic resin composition.

[0079] The difference between Comparative Example 5 and Example 1 is that the modified phenolic resin composition is prepared as follows:

[0080] S1.1. A solid-phase phenolic resin (Shandong Chengtian Chemical Co., Ltd., solid-phase one-step amine-free thermosetting phenolic resin) was solventized in acetone to form a solid-content phenolic resin solution of 50%. Lauric acid and tetraisopropyl titanate were added to the phenolic resin solution. The mass ratio of lauric acid to the phenolic resin solvent was 1:50, and the mass ratio of tetraisopropyl titanate to the phenolic resin solvent was 1:250. The esterification reaction was carried out at 70°C for 4 hours. Acetone and water were removed by vacuum distillation to obtain a partially blocked hydroxymethyl phenolic resin.

[0081] S1.2. Add 8 parts of partially blocked hydroxymethyl methyl phenolic resin from S1, 43 parts of linear phenolic resin 2123, 3 parts of hexamethylenetetramine, and 1 part of diisopropyl di(acetylacetone)titanate to 45 parts of ethylene glycol. Heat to 40°C and stir magnetically for 15 minutes. Then cool to 20°C and perform ultrasonic dispersion treatment using an ultrasonic mixer JH1000W-20 for 10 minutes. The ultrasonic frequency is 20kHz and the ultrasonic power is 1000W to obtain the modified phenolic resin composition.

[0082] The difference between Comparative Example 6 and Example 1 is that the modified phenolic resin composition is prepared as follows:

[0083] S1.1. A solid-phase phenolic resin (Shandong Chengtian Chemical Co., Ltd., solid-phase one-step amine-free thermosetting phenolic resin) was solventized in acetone to form a solid-content phenolic resin solution of 50%. Lauric acid and tetraisopropyl titanate were added to the phenolic resin solution. The mass ratio of lauric acid to the phenolic resin solvent was 1:50, and the mass ratio of tetraisopropyl titanate to the phenolic resin solvent was 1:250. The esterification reaction was carried out at 70°C for 4 hours. Acetone and water were removed by vacuum distillation to obtain a partially blocked hydroxymethyl phenolic resin.

[0084] S1.2. Add 18 parts of partially blocked hydroxymethyl methylated phenolic resin from S1, 25 parts of linear phenolic resin 2123, 8 parts of boron-modified phenolic resin TY03, 3 parts of hexamethylenetetramine, and 1 part of diisopropyl di(acetylacetone)titanate HY-1801 to 45 parts of ethylene glycol. Heat to 40°C and stir magnetically for 15 minutes. Then cool to 20°C and perform ultrasonic dispersion treatment using an ultrasonic mixer JH1000W-20 for 10 minutes. The ultrasonic frequency is 20kHz and the ultrasonic power is 1000W to obtain the modified phenolic resin composition.

[0085] The difference between Comparative Example 7 and Example 1 is that the metal-toughened silicon carbide-silicon nitride gunning paste material is made from the following raw materials in the following mass percentages: 20% white corundum with a particle size of 1-3 mm, 25.8% white corundum with a particle size of 0-1 mm, 5% white corundum sieved through a 325-mesh sieve, 16% modified phenolic resin composition, 3.0% 60-mesh coke powder, 2.0% 325-mesh coke powder, 1.6% 325-mesh natural flake graphite, 0.6% ultrafine natural flake graphite, and 26.0% additives.

[0086] The difference between Comparative Example 8 and Example 1 is that the additive is composed of silicon carbide, silicon nitride, and metallic silicon powder in a mass ratio of 3:1:1.

[0087] Preparation of the clay sample: The clay was rolled into a cylindrical shape at 80 kN. The resulting cylindrical clay was preheated at 450℃ for 5 h and then subjected to carbon heat treatment at 1450℃ for 3 h. The clay sample was obtained by cooling to room temperature.

[0088] Performance testing of clay samples: 1. The linear shrinkage rate of the clay was tested according to national standard GB / T 5988-2007. 2. The bulk density and apparent porosity of the clay were tested according to GB / T 2997-2000. 3. The flexural strength of the clay was tested according to GB / T 5072-2008. 4. The compressive strength of the clay was tested according to GB / T3007-2004. 5. The slag resistance of the clay was tested according to Method 2 of GB / T 8931-2007 "Test Method for Slag Resistance of Refractory Materials" (5. Method 2 - Static Sample Immersion and Aeration Method). The slag erosion rate R of the sample was expressed as a mass fraction (%): R = 100(W-W1) / W, where: W is the mass of the sample before the test (g); W1 is the mass of the sample after the test (g). Test results were rounded to two decimal places according to GB / T8170. 6. The Mascher value of the blasting clay was determined using a GDP-500 blasting clay analyzer.

[0089] Table 1: Properties of the taphole clay materials in Examples 1-15 and Comparative Examples 1-7

[0090]

[0091]

[0092] As can be seen from Example 1 and Comparative Example 1, and Table 1, the modified phenolic resin composition prepared in this invention can reduce the apparent porosity of the tapping clay and improve its flexural strength, compressive strength, volume stability and erosion resistance.

[0093] Based on Examples 1 and Comparative Examples 2-5, and referring to Table 1, it can be seen that the erosion resistance (slag erosion rate R < 0.5) of the phenolic resin composition prepared with boron-modified phenolic resin TY03 is relatively good. In contrast, the erosion resistance (slag erosion rate R < 0.5) of the phenolic resin composition prepared with partially blocked hydroxymethyl methyl phenolic resin is relatively low, and exhibits relatively good flexural strength, compressive strength, volume stability, and erosion resistance.

[0094] Based on Example 1 and Comparative Example 1, and in conjunction with Table 6, it can be seen that the content of partially blocked hydroxymethyl methyl methyl phenolic resin in the modified phenolic resin composition needs to be controlled. Excessive partially blocked hydroxymethyl methyl methyl phenolic resin will also lead to an increase in apparent porosity, and the flexural strength, compressive strength, volume stability, and erosion resistance of the clay will show a downward trend. Therefore, the content of partially blocked hydroxymethyl methyl methyl phenolic resin in the modified phenolic resin composition of 5-10 parts is relatively suitable.

[0095] As can be seen from Examples 1-3 and Comparative Example 1 and Table 7, the addition of titanate coupling agent as a dispersant in the potting clay formulation can improve the flexural strength, compressive strength and erosion resistance of the potting clay.

[0096] Combining Examples 1 and 3 with Table 1, it can be seen that the addition of 1 part of diisopropyl di(acetylacetone)titanate HY-1801 to the modified phenolic resin composition is beneficial to the uniform dispersion of refractory aggregates, additives and composite carbon powder, and improves the flexural strength, compressive strength and volume stability of the refractory clay.

[0097] As can be seen from Examples 1 and 4 and Table 1, the diisopropyl di(acetylacetone)titanate in the modified phenolic resin composition can react with the hydroxyl groups in the phenolic resin to improve the overall crosslinking density of the mortar, thereby improving the flexural strength, compressive strength, erosion resistance and volume stability of the mortar.

[0098] As can be seen from Examples 4 and 5-7 and Table 1, doping refractory aggregate with appropriate amounts of zirconium oxide and / or tetrapod zinc oxide whiskers can improve the flexural strength, compressive strength, erosion resistance and volume stability of the refractory clay, and the improvement on the erosion resistance of the refractory clay is more significant.

[0099] Combining Examples 4 and 8-9 with Table 1, it can be seen that while doping the composite toner with an appropriate amount of natural graphite slightly increases the Massia value of the clay, it improves the flexural strength and compressive strength of the clay. While doping the composite toner with appropriate amounts of natural graphite and industrial graphene improves the flexural strength and compressive strength of the clay more effectively, the increase in the Massia value is more significant, and the cost is higher.

[0100] Combining Examples 1 and 10-15 with Comparative Example 8 and referring to Table 1, it can be seen that the additive in Example 14, composed of nano-titanium cluster modified silicon carbide from Preparation Example 1, nano-titanium cluster modified silicon nitride from Preparation Example 2, and metallic silicon powder in a mass ratio of 3:1:1, produces the best overall performance in the prepared gunning clay, but its production cost is also the highest. Comparative Example 8 did not use nano-metal cluster modified additives, resulting in relatively poor flexural strength, compressive strength, and erosion resistance in the prepared gunning clay. Examples 1, 10-13, and 15, by selecting appropriate amounts of nano-metal cluster modified additives in the additives, produced gunning clays with relatively good flexural strength, compressive strength, and erosion resistance (slag erosion rate R < 0.5), while also reducing the overall production cost. Controlling the amount of nano-metal cluster modified additives to 10-15% is relatively optimal.

[0101] In summary, the gunning clay prepared in this invention has low apparent porosity, good flexural strength, compressive strength, volumetric stability and erosion resistance (slag erosion rate R < 0.5), overcoming the defects of high apparent porosity, poor mechanical properties, erosion resistance and volumetric stability caused by traditional tar binders.

[0102] It should be noted that this specific embodiment is merely an explanation of the technical solution of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material, characterized in that: The metal-toughened silicon carbide-silicon nitride gunning compound is made from the following raw materials in the following mass percentages: 44-52% refractory aggregate, 0.6-1.0% dispersant, 14-18% modified phenolic resin composition, 5-10% composite carbon powder, and the balance being additives; the additives are composed of additive A and additive B in a mass ratio of (2-9):1; additive A is at least one of silicon carbide, silicon nitride, and metallic silicon powder; additive B is a nano-metal cluster modified additive; the preparation method of the metal-toughened silicon carbide-silicon nitride gunning compound is as follows: first, a modified phenolic resin composition is prepared; then, the refractory aggregate, dispersant, additives, and composite carbon powder are dry-kneaded; finally, the modified phenolic resin composition is added, mixed, rolled, extruded, and cut to obtain the finished metal-toughened silicon carbide-silicon nitride gunning compound; The modified phenolic resin composition is prepared as follows: S1. A 40-60% solid content phenolic resin solution is formed in acetone solvent using a methyl phenolic resin solvent. C6-C12 saturated fatty acids and tetraisopropyl titanate are added to the methyl phenolic resin solution, wherein the mass ratio of the C6-C12 saturated fatty acids to the methyl phenolic resin solvent is 1:(10-100), and the mass ratio of the tetraisopropyl titanate to the methyl phenolic resin solvent is 1:(100-400). The esterification reaction is carried out at 60-80℃ for 1-4 hours. Acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl methyl phenolic resin. S2. Add 5-10 parts of partially blocked hydroxymethyl methyl phenolic resin from S1, 20-50 parts of linear phenolic resin, 5-10 parts of boron-modified phenolic resin, and 2-4 parts of curing agent to 40-80 parts of small molecule alcohol and mix evenly to obtain a modified phenolic resin composition. The nano-metal cluster modified additive includes an additive carrier and nano-metal clusters formed on the surface of the additive carrier by a sol-gel method and in-situ reaction. The nano-metal clusters are at least one of nano-titanium clusters, nano-zirconium clusters, and nano-molybdenum clusters. The additive carrier is at least one of silicon carbide, silicon nitride, and metallic silicon powder.

2. The method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material according to claim 1, characterized in that: The S1. A methyl phenolic resin solvent is used to form a methyl phenolic resin solution with a solid content of 40-60% in acetone solvent. C6-C12 saturated fatty acids and tetraisopropyl titanate are added to the methyl phenolic resin solution. The mass ratio of the C6-C12 saturated fatty acids to the methyl phenolic resin solvent is 1:(40-50), and the mass ratio of the tetraisopropyl titanate to the methyl phenolic resin solvent is 1:(200-250). The esterification reaction is carried out at 60-80℃ for 3-4 hours. Acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl methyl phenolic resin.

3. The method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material according to claim 1, characterized in that: S2. Add 8-10 parts of partially blocked hydroxymethyl methyl phenolic resin from S1, 35 parts of linear phenolic resin, 8-10 parts of boron-modified phenolic resin, and 3-4 parts of curing agent to 45 parts of small molecule alcohol and mix evenly to obtain a modified phenolic resin composition.

4. The method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material according to claim 1, characterized in that: The curing agent is one or more of hexamethylenetetramine, polyoxymethylene, melamine, and urea-formaldehyde, or the curing agent is at least one of hexamethylenetetramine, polyoxymethylene, melamine, and urea-formaldehyde combined with at least one of di(acetylacetone)titanate and di(acetoacetate)titanate.

5. The method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material according to claim 1, characterized in that: The small molecule alcohol is one or more of methanol, ethanol, ethylene glycol, diethylene glycol, and glycerol.

6. The method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material according to claim 1, characterized in that: The refractory aggregate is at least one of white fused alumina and brown fused alumina; or the refractory aggregate is composed of white fused alumina and / or brown fused alumina combined with at least one of zirconium oxide and tetrapod zinc oxide.

7. The method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material according to claim 1, characterized in that: The additive is composed of silicon carbide, silicon nitride, metallic silicon powder, nano-metal cluster modified silicon carbide, and nano-metal cluster modified silicon nitride in a mass ratio of 3:1:1:(0.3-0.4):(0.3-0.4).

8. The method for preparing a metal-toughened silicon carbide-silicon nitride gunning paste material according to claim 1, characterized in that: The dispersing agent is at least one of the following: triisostearate titanate isopropyl, di(dioctylphospho)titanate ethylene, di(dioctylpyrophospho)titanate ethylene, di(acetylacetone)titanate diisopropyl, and di(acetoacetate)titanate diisopropyl.

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