Preparation method of metal toughened silicon carbide-silicon nitride stemming material

Abstract

The invention relates to the technical field of refractory materials, in particular to a preparation method of a metal toughened silicon carbide-silicon nitride stemming material. The preparation method of the metal toughened silicon carbide-silicon nitride stemming material comprises the following steps: firstly, preparing the modified phenolic resin composition, and then carrying out dry kneading treatment on the refractory aggregate, the dispersing aid, the additive and the composite carbon powder to obtain the metal toughened silicon carbide-silicon nitride stemming material. And finally, adding the modified phenolic resin composition, mixing, grinding, extruding and cutting to obtain a finished product of the metal toughened silicon carbide-silicon nitride stemming material. The modified phenolic resin composition is used for replacing a traditional binding agent, the defects that a traditional tar binding agent is high in apparent porosity and stemming is high in apparent porosity and poor in mechanical property and volume stability are overcome, and the modified phenolic resin composition is endowed with good mechanical property and volume stability.

Description

Technical Field

[0001] The present invention relates to the technical field of refractories, and particularly to a preparation method of a metal toughened silicon carbide - silicon nitride taphole clay material. Background Art

[0002] Taphole clay is used to plug the tapping hole of a blast furnace. The molten iron formed during the smelting in the blast furnace needs to flow out from the tapping hole into the trough, and then through the main trough and branch troughs into the ladle or torpedo ladle. After the tapping is completed, the tapping hole of the blast furnace needs to be blocked with taphole clay and wait for the next smelting completion in the blast furnace for tapping. After that, the taphole clay is penetrated with an opening machine for tapping, and this process repeats. Therefore, taphole clay is a refractory material used to block the tapping hole during the blast furnace ironmaking process. It can quickly and accurately block the tapping hole after tapping, enabling the blast furnace to enter the next smelting cycle, and is an important guarantee for the safe and smooth operation of the blast furnace.

[0003] With the rapid development of the steel industry, blast furnaces are gradually tending towards large - scale development. The number of slag and iron tapping times in blast furnaces is gradually decreasing, resulting in an increase in the single - time slag and iron output, which increases the erosion and scouring of taphole clay. As a result, more stringent requirements are put forward for the mechanical properties, volume stability properties, and erosion resistance properties of taphole clay. Currently, taphole clay is mainly divided into water - containing taphole clay and water - free taphole clay. Due to problems such as poor slag and iron erosion resistance, low bulk density, and slow heating rate of water - containing taphole clay (the un - sintered iron mouth turns red), it can no longer meet the requirements of large - scale blast furnaces for the properties of taphole clay. Water - free taphole clay has gradually replaced water - containing taphole clay as the main refractory material due to its excellent properties in various aspects.

[0004] Currently, the binders in water - free taphole clay mostly consist of at least one of tar, anthracene oil, and coal tar pitch, resulting in a relatively high apparent porosity of the prepared taphole clay, poor mechanical properties and volume stability properties, and the release of carcinogenic substances such as benzo[a]pyrene during use, with poor environmental protection performance and also affecting the health of operating workers. Summary of the Invention

[0005] In order to solve the technical problems of relatively high apparent porosity of the existing water - free taphole clay, and poor mechanical properties and volume stability properties, the present invention provides a preparation method of a metal toughened silicon carbide - silicon nitride taphole clay material, which replaces the traditional binder composed of at least one of tar, anthracene oil, and coal tar pitch with a modified phenolic resin composition, overcoming the defects of high apparent porosity, poor mechanical properties, erosion resistance properties, and volume stability properties brought by the traditional tar binder.

[0006] The preparation method of a metal toughened silicon carbide - silicon nitride taphole clay material provided by the present invention is achieved through the following technical solutions:

[0007] A metal toughened silicon carbide - silicon nitride gun clay material is made from raw materials in the following mass percentages: 44 - 52% refractory aggregate, 0.6 - 1.0% dispersing aid, 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] The preparation method of a metal toughened silicon carbide - silicon nitride gun clay material is as follows: First, prepare the modified phenolic resin composition, then perform dry kneading treatment on the refractory aggregate, dispersing aid, additives, and composite carbon powder, and finally add the modified phenolic resin composition, mix, roll, and extrude and cut to obtain the finished metal toughened silicon carbide - silicon nitride gun clay material.

[0009] The present invention replaces the traditional binder with a modified phenolic resin composition, overcomes the defects of high apparent porosity of the traditional tar binder and relatively high apparent porosity of the gun clay, as well as poor mechanical properties and volume stability, and endows it with good mechanical properties and volume stability.

[0010] Preferably, the preparation method of the modified phenolic resin composition is as follows:

[0011] S1. The resol phenolic resin solvent forms a resol phenolic resin solution with a solid content of 40 - 60% in an acetone solvent. Add C6 - C12 saturated fatty acid and tetra - isopropyl titanate to the resol phenolic resin solution. The mass ratio of the C6 - C12 saturated fatty acid to the resol phenolic resin solvent is 1:(10 - 100), and the mass ratio of the tetra - isopropyl titanate to the resol phenolic resin solvent is 1:(100 - 400). Heat up to 60 - 80 °C and carry out an esterification reaction for 1 - 4 h, and remove acetone and water by vacuum distillation to obtain a partially blocked hydroxymethyl resol phenolic resin.

[0012] S2. Add 5 - 10 parts of the partially blocked hydroxymethyl resol phenolic resin obtained in 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, mix evenly to obtain the modified phenolic resin composition.

[0013] The preparation method of the modified phenolic resin composition is relatively simple and convenient for large-scale production. Moreover, the prepared modified phenolic resin composition overcomes the problems of traditional thermosetting phenolic resin, such as relatively fast curing rate under heat, insufficient plasticity of the gun clay, easy caking of the gun clay, blockage of the clay gun, and damage to the normal tapping hole channel. By reacting C6-C12 saturated fatty acids with hydroxymethyl in the thermosetting phenolic resin, the prepared partially blocked hydroxymethyl novolac phenolic resin controls the heat curing rate. At the same time, it is combined with linear phenolic resin, boron-modified phenolic resin, and curing agent to form a modified phenolic resin composition, which is beneficial to improving the fluidity of the gun clay under high-temperature conditions and improving the processing plasticity and thermal stability of the gun clay. In addition, the boron-modified phenolic resin will form a boron carbide protective layer under the action of high heat temperature, improving the mechanical strength and antioxidant performance of the gun clay. And boron element, as a low-temperature sintering agent, can carbonize the additive to form a carbon-bonded protective layer, thereby improving the sintering performance, mechanical strength, volume stability performance, and erosion resistance of the gun clay.

[0014] Preferably, in S1, the novolac phenolic resin solvent forms a novolac phenolic resin solution with a solid content of 40-60% in acetone solvent. C6-C12 saturated fatty acid and tetra-isopropyl titanate are added to the novolac phenolic resin solution. The mass ratio of the C6-C12 saturated fatty acid to the novolac phenolic resin solvent is 1:(40-50), and the mass ratio of the tetra-isopropyl titanate to the novolac phenolic resin solvent is 1:(200-250). The temperature is raised to 60-80 °C for esterification reaction for 3-4 h, and acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl novolac phenolic resin.

[0015] Preferably, in S2, 8-10 parts of the partially blocked hydroxymethyl novolac phenolic resin in 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 the modified phenolic resin composition.

[0016] Preferably, the curing agent is composed of one or more of hexamethylenetetramine, paraformaldehyde, melamine, and urea formaldehyde, or the curing agent is composed of at least one of hexamethylenetetramine, paraformaldehyde, melamine, and urea formaldehyde in combination with at least one of diisopropyl bis(acetylacetonate) titanate and diisopropyl bis(ethylacetoacetate) titanate.

[0017] The diisopropyl bis(acetylacetonate) titanate and / or diisopropyl bis(ethylacetoacetate) titanate contained in the curing agent of the present invention can carry out cross-linking reaction with the hydroxyl groups in the modified phenolic resin composition under heat, which can improve the early mechanical strength and also make the dispersion uniformity of refractory aggregates, additives, and composite carbon powder in the modified phenolic resin composition, improving the mechanical properties and erosion resistance of the gun clay 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 in combination with at least one of zirconia 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 sol-gel method + 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 metal silicon powder.

[0021] Preferably, the additive is composed of silicon carbide, silicon nitride, metal 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 relatively high activity and preferentially form high melting point metal oxides, metal carbides, and metal nitrides with oxygen, nitrogen, and coke at high temperatures. They can fill the gaps generated by the thermal expansion of the gun clay, improving the mechanical properties, volume stability, and erosion resistance of the gun clay after high-temperature curing. At the same time, an appropriate amount of silicon nitride is needed to improve the opening and air permeability of the gun clay, avoiding the too low apparent porosity of the gun clay affecting its opening performance.

[0023] Preferably, the dispersion aid is at least one of isopropyl triisostearoyl titanate, ethyl bis(dioctylphosphoryl) titanite, ethyl bis(dioctylpyrophosphoryl) titanite, diisopropyl bis(acetylacetonate) titanate, and diisopropyl bis(ethyl acetoacetate) titanate.

[0024] In the present invention, a titanate coupling agent is used as the dispersion aid. On the one hand, it can improve the dispersion uniformity of the refractory aggregate, additive, and composite carbon powder in the modified phenolic resin composition, and further improve the mechanical properties, erosion resistance, and volume stability of the gun clay. On the other hand, it can improve the high-temperature resistance of the gun clay.

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

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

[0027] 2. The preparation method of the present invention is relatively simple, with low operation difficulty, and is convenient for large-scale production and manufacturing.

[0028] 3. In the present invention, the composition and proportion of the additives are optimized. On the premise of ensuring good opening performance of the gun clay, the apparent porosity of the gun clay is reduced, and the mechanical properties, volume stability and corrosion resistance of the gun clay are improved. Specific Embodiments

[0029] In order to further understand the creativity and technological progress of the present invention, the preferred implementation schemes of the present invention will be discussed in detail below in combination with examples and comparative examples.

[0030] Example: A metal toughened silicon carbide - silicon nitride gun clay material is made from raw materials in the following mass percentages: 44 - 52% refractory aggregate, 0.6 - 1.0% dispersion aid, 14 - 18% modified phenolic resin composition, 5 - 10% composite carbon powder, and the balance is 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 in combination with at least one of zirconia and tetrapod-like zinc oxide.

[0032] The dispersion aid is at least one of isopropyl triisostearoyl titanate, diethyl (dioctylphosphoryl) titanate, diethyl (dioctylpyrophosphoryl) titanate, diisopropyl (acetylacetonate) titanate, and diisopropyl (ethyl acetoacetate) titanate.

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

[0034] 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 metal 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 by the sol - gel method + 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 metal silicon powder.

[0035] A preparation method of a metal toughened silicon carbide - silicon nitride gun clay material is as follows:

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

[0037] S1.1. The resol phenolic resin solvent forms a resol phenolic resin solution with a solid content of 40-60% in acetone solvent. Add C6-C12 saturated fatty acid and tetra-isopropyl titanate to the resol phenolic resin solution. The mass ratio of the C6-C12 saturated fatty acid to the resol phenolic resin solvent is 1:(10-100), and the mass ratio of the tetra-isopropyl titanate to the resol phenolic resin solvent is 1:(100-400). Heat up to 60-80 °C for esterification reaction for 1-4 h, and remove acetone and water by vacuum distillation to obtain a partial blocked hydroxymethyl resol phenolic resin.

[0038] S1.2. Add 5-10 parts of the partial blocked hydroxymethyl resol phenolic resin in 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. After mixing evenly, a modified phenolic resin composition can be obtained.

[0039] The small molecule alcohol is composed of one or more of methanol, ethanol, ethylene glycol, diethylene glycol, and glycerol.

[0040] The curing agent is composed of one or more of hexamethylenetetramine, paraformaldehyde, melamine, and urea formaldehyde, or the curing agent is composed of at least one of hexamethylenetetramine, paraformaldehyde, melamine, and urea formaldehyde in combination with at least one of diisopropyl bis(acetylacetonate) titanate and diisopropyl bis(ethyl acetoacetate) titanate.

[0041] Subsequently, perform dry kneading treatment on refractory aggregate, dispersion aid, additive, and composite carbon powder.

[0042] Finally, add the modified phenolic resin composition, mix, roll, extrude, and cut to obtain the finished product of metal toughened silicon carbide-silicon nitride gun mud material.

[0043] Preparation Example 1: The preparation method of nano titanium cluster modified silicon carbide is as follows: S1. Dissolve 20 g of titanium oxysulfate (Macklin) in 1000 mL of distilled water and stir magnetically at 200 rpm / min for half an hour. Then add 50 g of 800-mesh silicon carbide and stir magnetically at 200 rpm / min for 15 min. Then perform ultrasonic dispersion treatment for half an hour, with an ultrasonic power of 40 kHz and an ultrasonic frequency of 1000 W. After ultrasonic dispersion treatment, filter to obtain solid powder. Place the obtained solid powder in a vacuum drying oven and dry at 20 Pa and 120 °C for 8 h. Transfer the obtained dried solid powder to an atmosphere tube furnace for calcination treatment. Heat up to 550 °C at 20 °C / min in an air atmosphere and calcine for 2 hours to obtain anatase TiO2@silicon carbide powder; S2. Place the anatase TiO2@silicon carbide powder in an atmosphere tube furnace, introduce a hydrogen-argon mixed gas, and the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 1:1. Maintain the temperature at 650 °C for a reduction reaction for 4 hours. Open the furnace and cool naturally to room temperature. Then perform ball milling treatment at 60 rpm for 30 min. Finally, screen with an 800-mesh sieve to obtain nano titanium cluster modified silicon carbide with a particle size ≤ 800 mesh.

[0044] Preparation Example 2 is different from Preparation Example 1 in that: The preparation method of nano titanium cluster modified silicon nitride is as follows: S1. Dissolve 20 g of titanium oxysulfate in 1000 mL of distilled water and stir magnetically at 200 rpm / min for half an hour. Then add 50 g of 800-mesh silicon nitride and stir magnetically at 200 rpm / min for 15 min. Then perform ultrasonic dispersion treatment for half an hour, with an ultrasonic power of 40 kHz and an ultrasonic frequency of 1000 W. After ultrasonic dispersion treatment, filter to obtain solid powder. Place the obtained solid powder in a vacuum drying oven and dry at 20 Pa and 120 °C for 8 h. Transfer the obtained dried solid powder to an atmosphere tube furnace for calcination treatment. Heat up to 550 °C at 20 °C / min in an air atmosphere and calcine for 2 hours to obtain anatase TiO2@silicon carbide powder; S2. Place the anatase TiO2@silicon carbide powder in an atmosphere tube furnace, introduce a hydrogen-argon mixed gas, and the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 1:1. Maintain the temperature at 650 °C for a reduction reaction for 4 hours. Open the furnace and cool naturally to room temperature. Then perform ball milling treatment at 60 rpm for 30 min. Finally, screen with an 800-mesh sieve to obtain nano titanium cluster modified silicon nitride with a particle size ≤ 800 mesh.

[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 26.8 g of zirconium sulfate tetrahydrate (Wuhan Canos Technology Co., Ltd.) in 1000 mL of distilled water and stir magnetically at 200 rpm / min for half an hour. Then add 50 g of 800-mesh silicon carbide and stir magnetically at 200 rpm / min for 15 min. Add ammonia water with a concentration of 5 wt%, and continue to stir magnetically at 200 rpm / min for 1 hour until Zr is completely precipitated. After standing for 24 h, filter to obtain solid powder. The obtained solid powder is placed in a vacuum drying oven and dried at 20 Pa and 120 °C for 8 h. The obtained dried solid powder is transferred to an atmosphere tube furnace for calcination treatment, and calcined at 550 °C for 2 h at a heating rate of 20 °C / min in an air atmosphere to obtain ZrO2@silicon carbide powder; S2. The anatase ZrO2@silicon carbide powder is placed in an atmosphere tube furnace, and a hydrogen-argon mixed gas is introduced. The volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 1:1. The reduction reaction is carried out at 650 °C for 4 h, and the furnace is opened and cooled naturally to room temperature. Then, ball milling treatment is carried out at 60 rpm for 30 min, and finally screening is carried out with an 800-mesh sieve to obtain nano zirconium cluster modified silicon carbide with a particle size of ≤800 mesh.

[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 26.8 g of zirconium sulfate tetrahydrate (Wuhan Canos Technology Co., Ltd.) in 1000 mL of distilled water and stir magnetically at 200 rpm / min for half an hour. Then add 50 g of 800-mesh silicon nitride and stir magnetically at 200 rpm / min for 15 min. Add ammonia water with a concentration of 5 wt%, and continue to stir magnetically at 200 rpm / min for 1 hour until Zr is completely precipitated. After standing for 24 h, filter to obtain solid powder. The obtained solid powder is placed in a vacuum drying oven and dried at 20 Pa and 120 °C for 8 h. The obtained dried solid powder is transferred to an atmosphere tube furnace for calcination treatment, and calcined at 550 °C for 2 h to obtain ZrO2@silicon carbide powder; S2. The anatase ZrO2@silicon carbide powder is placed in an atmosphere tube furnace, and a hydrogen-argon mixed gas is introduced. The volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 1:1. The reduction reaction is carried out at 650 °C for 4 h, and the furnace is opened and cooled naturally to room temperature. Then, ball milling treatment is carried out at 60 rpm for 30 min, and finally screening is carried out with an 800-mesh sieve to obtain nano zirconium cluster modified silicon nitride with a particle size of ≤800 mesh.

[0047] Example 1: A metal toughened silicon carbide - silicon nitride ramming paste material is made from raw materials with the following mass 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 screened by a 325 - mesh sieve, 0.8% isopropyl triisostearoyl titanate, 16% modified phenolic resin composition, 3.0% coke powder with a mesh size of 60, 2.0% coke powder with a mesh size of 325, 1.6% natural flake graphite with a mesh size of 325, 0.6% ultra - fine natural flake graphite, and 26.0% additive.

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

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

[0050] The white fused alumina with a particle size of 1 - 3 mm, white fused alumina with a particle size of 0 - 1 mm, and white fused alumina screened by a 325 - mesh sieve are all provided by Henan Shengxing Environmental Protection Materials Co., Ltd. The isopropyl triisostearoyl titanate is provided by Nanjing Aocheng Chemical Co., Ltd. The 60 - mesh coke powder and 325 - mesh coke powder are both provided by Lingshou County Henglin Mineral Products Co., Ltd. The 325 - mesh natural flake graphite and 4000 - mesh ultra - fine natural flake graphite are provided by Qingdao Tianfeng Graphite Co., Ltd.

[0051] The preparation method of a metal toughened silicon carbide - silicon nitride ramming paste material is as follows:

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

[0053] S1.1. A phenolic phase resin (Shandong Chengtai Chemical Co., Ltd., solid phase A one-step amine-free thermosetting phenolic resin) solvent is added to an acetone solvent to form a phenolic phase 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) are added to the phenolic phase resin solution. The mass ratio of lauric acid to the phenolic phase resin solvent is 1:50, and the mass ratio of tetraisopropyl titanate to the phenolic phase resin solvent is 1:250. The temperature is raised to 70°C for esterification reaction for 4 hours, and the acetone and water are removed by distillation under reduced pressure to obtain a phenolic phase resin with partially blocked hydroxymethyl groups;

[0054] S1.2. To 45 parts of ethylene glycol, 8 parts of partially blocked hydroxymethyl-containing phenolic resin in S1, 35 parts of linear phenolic resin 2123 (effective ingredient content 99%, 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), 1 part of diisopropyl di(acetylacetonate) titanate (HY-1801, Hangzhou Jessica Chemical Co., Ltd.) were added, heated to 40 ° C and magnetically stirred for 15 min, then cooled to 20 ° C and ultrasonically dispersed with an ultrasonic mixer JH1000W-20 for 10 min, with an ultrasonic frequency of 20 kHz and an ultrasonic power of 1000 W to obtain a modified phenolic resin composition;

[0055] Subsequently, 20 parts by weight of white corundum with a particle size of 1-3 mm, 25 parts by weight of white corundum with a particle size of 0-1 mm, 5 parts by weight of white corundum sieved through a 325-mesh sieve, 0.8 parts by weight of isopropyl titanate 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 treatment for 30 minutes;

[0056] Finally, 16 parts by weight of the modified phenolic resin composition prepared in S1.2 above are added into the vacuum kneader. The kneaded material is kneaded by dry kneading for 5 minutes. The kneaded material is transferred to a planetary wheel mixer and mixed and ground for 1 hour to obtain a mixed material. The mixed material is transferred to an automatic cutting and packaging gun mud machine for extrusion and cutting. The finished metal toughened silicon carbide-silicon nitride gun mud material can be obtained by packaging.

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

[0058] S1.1. The resol resin solvent forms a resol resin solution with a solid content of 50% in acetone solvent. Lauric acid and tetra-isopropyl titanate are added to the resol resin solution. The mass ratio of lauric acid to the resol resin solvent is 1:80, and the mass ratio of tetra-isopropyl titanate to the resol resin solvent is 1:250. The temperature is raised to 70 °C for an esterification reaction for 4 h, and acetone and water are removed by vacuum distillation to obtain a partial blocked hydroxymethyl resol resin.

[0059] S1.2. Add 5 parts of the partial blocked hydroxymethyl resol resin in 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 bis(acetylacetonate) titanate HY-1801 to 45 parts of ethylene glycol. After raising the temperature to 40 °C and stirring magnetically for 15 min, cool down to 20 °C and perform ultrasonic dispersion treatment for 10 min using an ultrasonic mixing stirrer JH1000W-20. The ultrasonic frequency is 20 kHz and the ultrasonic power is 1000 W to obtain the modified phenolic resin composition.

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

[0061] S1.1. The resol resin solvent forms a resol resin solution with a solid content of 50% in acetone solvent. Lauric acid and tetra-isopropyl titanate are added to the resol resin solution. The mass ratio of lauric acid to the resol resin solvent is 1:50, and the mass ratio of tetra-isopropyl titanate to the resol resin solvent is 1:250. The temperature is raised to 70 °C for an esterification reaction for 4 h, and acetone and water are removed by vacuum distillation to obtain a partial blocked hydroxymethyl resol resin.

[0062] S1.2. Add 8 parts of the partial blocked hydroxymethyl resol resin in 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. After raising the temperature to 40 °C and stirring magnetically for 15 min, cool down to 20 °C and perform ultrasonic dispersion treatment for 10 min using an ultrasonic mixing stirrer JH1000W-20. The ultrasonic frequency is 20 kHz and the ultrasonic power is 1000 W to obtain the modified phenolic resin composition.

[0063] Example 4 is different from Example 1 in that the metal toughened silicon carbide - silicon nitride ramming paste material is made of raw materials with the following mass 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, 0.5% isopropyl triisostearoyl titanate, 0.3% diisopropyl bis(acetylacetonate) titanate, 16% modified phenolic resin composition, 3.0% coke powder with a mesh size of 60, 2.0% coke powder with a mesh size of 325, 1.6% natural flake graphite with a mesh size of 325, 0.6% ultra - fine natural flake graphite, and 26.0% additive.

[0064] Example 5 is different from Example 4 in that the metal toughened silicon carbide - silicon nitride ramming paste material is made of raw materials with the following mass percentages: 20% white fused alumina with a particle size of 1 - 3 mm, 23% white fused alumina with a particle size of 0 - 1 mm, 2% zirconia (Shandong Desheng New Materials Co., Ltd.) with a mesh size of 325, 5% white fused alumina sieved through a 325 - mesh sieve, 0.5% isopropyl triisostearoyl titanate, 0.3% diisopropyl bis(acetylacetonate) titanate, 16% modified phenolic resin composition, 3.0% coke powder with a mesh size of 60, 2.0% coke powder with a mesh size of 325, 1.6% natural flake graphite with a mesh size of 325, 0.6% ultra - fine natural flake graphite, and 26.0% additive.

[0065] Example 6 is different from Example 4 in that the metal toughened silicon carbide - silicon nitride ramming paste material is made of raw materials with the following mass percentages: 20% white fused alumina with a particle size of 1 - 3 mm, 24% white fused alumina with a particle size of 0 - 1 mm, 5% white fused alumina sieved through a 325 - mesh sieve, 1% tetrapod - shaped zinc oxide whisker T - ZnO (XD - Z1X05, diameter 0.5 - 5 microns, length 10 - 50 microns, Qinghe County Chaotai Metal Materials Co., Ltd.), 0.5% isopropyl triisostearoyl titanate, 0.3% diisopropyl bis(acetylacetonate) titanate, 16% modified phenolic resin composition, 3.0% coke powder with a mesh size of 60, 2.0% coke powder with a mesh size of 325, 1.6% natural flake graphite with a mesh size of 325, 0.6% ultra - fine natural flake graphite, and 26.0% additive.

[0066] Example 7 is different from Example 4 in that the metal toughened silicon carbide-silicon nitride ramming material is made of raw materials with the following mass percentages: 20% of white fused alumina with a particle size of 1-3 mm, 23% of white fused alumina with a particle size of 0-1 mm, 5% of white fused alumina screened by a 325-mesh sieve, 1.5% of zirconia with a mesh size of 325, 0.5% of four-legged zinc oxide whisker XD-Z1X05, 0.5% of triisostearoyl titanate isopropyl ester, 0.3% of diisopropyl bis(acetylacetonate) titanate, 16% of modified phenolic resin composition, 3.0% of 60-mesh coke powder, 2.0% of 325-mesh coke powder, 1.6% of 325-mesh natural flake graphite, 0.6% of ultrafine natural flake graphite, and 26.0% of additives.

[0067] Example 8 is different from Example 7 in that the metal toughened silicon carbide-silicon nitride ramming material is made of raw materials with the following mass percentages: 20% of white fused alumina with a particle size of 1-3 mm, 23% of white fused alumina with a particle size of 0-1 mm, 5% of white fused alumina screened by a 325-mesh sieve, 1.5% of zirconia with a mesh size of 325, 0.5% of four-legged zinc oxide whisker XD-Z1X05, 0.5% of triisostearoyl titanate isopropyl ester, 0.3% of diisopropyl bis(acetylacetonate) titanate, 16% of modified phenolic resin composition, 4.32% of 60-mesh coke powder, 2.88% of 325-mesh coke powder, and 26.0% of additives.

[0068] Example 9 is different from Example 7 in that the metal toughened silicon carbide-silicon nitride ramming material is made of raw materials with the following mass percentages: 20% of white fused alumina with a particle size of 1-3 mm, 23% of white fused alumina with a particle size of 0-1 mm, 5% of white fused alumina screened by a 325-mesh sieve, 1.5% of zirconia with a mesh size of 325, 0.5% of four-legged zinc oxide whisker XD-Z1X05, 0.5% of triisostearoyl titanate isopropyl ester, 0.3% of diisopropyl bis(acetylacetonate) titanate, 16% of modified phenolic resin composition, 3% of 60-mesh coke powder, 2% of 325-mesh coke powder, 2% of 325-mesh natural flake graphite, 0.2% of industrial graphene (number of layers < 100, purity > 98.0%, particle size < 20 um, Hunan Fenghua Material Development Co., Ltd.), and 26.0% of additives.

[0069] Example 10 is different from Example 1 in that the additives are composed of silicon carbide, silicon nitride, metal 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] Example 11 is different from Example 1 in that the additive is composed of silicon carbide, silicon nitride, 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] Example 12 is different from Example 1 in that the additive is composed of silicon carbide, silicon nitride, 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] Example 13 is different from Example 1 in that the additive is composed of silicon carbide, silicon nitride, 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] Example 14 is different from Example 1 in 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 silicon powder in a mass ratio of 3:1:1.

[0074] Example 15 is different from Example 1 in that the additive is composed of silicon carbide, silicon nitride, 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] Comparative Example 1 is different from Example 1 in that the modified phenolic resin composition is replaced with a mixed binder, and the mixed binder is composed of 70# asphalt and a resol resin solution with a solid content of 55% in a mass ratio of 1:1. The preparation method of the resol resin with a solid content of 55% is as follows: 50 parts of resol resin and 5 parts of hexamethylenetetramine are dissolved in 45 parts of ethylene glycol to form a resol resin solution with a solid content of 55%.

[0076] Comparative Example 2 is different from Example 1 in that the preparation method of the modified phenolic resin composition is as follows: 50 parts of linear phenolic resin 2123, 4 parts of hexamethylenetetramine, and 1 part of diisopropyl titanate bis(acetylacetonate) HY-1801 are added to 45 parts of ethylene glycol, heated to 40°C and magnetically stirred for 15 min, then cooled to 20°C and ultrasonically dispersed for 10 min using an ultrasonic mixing stirrer JH1000W-20, with an ultrasonic frequency of 20 kHz and an ultrasonic power of 1000 W, to obtain the modified phenolic resin composition.

[0077] The difference between Comparative Example 3 and Example 1 lies in that the preparation method of the modified phenolic resin composition is as follows: Add 40 parts of linear phenolic resin 2123, 10 parts of boron-modified phenolic resin TY03, 4 parts of hexamethylenetetramine, and 1 part of diisopropyl bis(acetylacetonate) titanate HY-1801 to 45 parts of ethylene glycol. After heating to 40 °C and magnetically stirring for 15 min, cool to 20 °C and perform ultrasonic dispersion treatment for 10 min using an ultrasonic mixing stirrer JH1000W-20. The ultrasonic frequency is 20 kHz and the ultrasonic power is 1000 W, then the modified phenolic resin composition can be obtained.

[0078] The difference between Comparative Example 4 and Example 1 lies in that the preparation method of the modified phenolic resin composition is as follows: Add 8 parts of novolac 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 bis(acetylacetonate) titanate HY-1801 to 45 parts of ethylene glycol. After heating to 40 °C and magnetically stirring for 15 min, cool to 20 °C and perform ultrasonic dispersion treatment for 10 min using an ultrasonic mixing stirrer JH1000W-20. The ultrasonic frequency is 20 kHz and the ultrasonic power is 1000 W, then the modified phenolic resin composition can be obtained.

[0079] The difference between Comparative Example 5 and Example 1 lies in that the preparation method of the modified phenolic resin composition is as follows:

[0080] S1.1. Novolac phenolic resin (Shandong Chengtai Chemical Co., Ltd., solid novolac one-step type amine-free thermosetting phenolic resin) is dissolved in acetone solvent to form a novolac phenolic resin solution with a solid content of 50%. Add lauric acid and tetraisopropyl titanate to the novolac phenolic resin solution. The mass ratio of lauric acid to novolac phenolic resin solvent is 1:50, and the mass ratio of tetraisopropyl titanate to novolac phenolic resin solvent is 1:250. Heat to 70 °C and carry out an esterification reaction for 4 h, and remove acetone and water by vacuum distillation to obtain a partially blocked hydroxymethyl novolac phenolic resin;

[0081] S1.2. Add 8 parts of the partially blocked hydroxymethyl novolac phenolic resin in S1, 43 parts of linear phenolic resin 2123, 3 parts of hexamethylenetetramine, and 1 part of diisopropyl bis(acetylacetonate) titanate to 45 parts of ethylene glycol. After heating to 40 °C and magnetically stirring for 15 min, cool to 20 °C and perform ultrasonic dispersion treatment for 10 min using an ultrasonic mixing stirrer JH1000W-20. The ultrasonic frequency is 20 kHz and the ultrasonic power is 1000 W, then the modified phenolic resin composition can be obtained.

[0082] The difference between Comparative Example 6 and Example 1 lies in that the preparation method of the modified phenolic resin composition is as follows:

[0083] S1.1. The phenol-formaldehyde resin in the alpha stage (Shandong Chengtai Chemical Co., Ltd., solid alpha-stage one-step amine-free thermosetting phenol-formaldehyde resin) is dissolved in acetone solvent to form a phenol-formaldehyde resin solution with a solid content of 50%. Lauric acid and tetra-isopropyl titanate are added to the phenol-formaldehyde resin solution. The mass ratio of lauric acid to the phenol-formaldehyde resin solvent is 1:50, and the mass ratio of tetra-isopropyl titanate to the phenol-formaldehyde resin solvent is 1:250. The temperature is raised to 70 °C for an esterification reaction for 4 h, and acetone and water are removed by vacuum distillation to obtain a partially blocked hydroxymethyl phenol-formaldehyde resin in the alpha stage.

[0084] S1.2. Add 18 parts of the partially blocked hydroxymethyl phenol-formaldehyde resin in S1, 25 parts of linear phenol-formaldehyde resin 2123, 8 parts of boron-modified phenol-formaldehyde resin TY03, 3 parts of hexamethylenetetramine, and 1 part of diisopropyl bis(acetylacetonate) titanate HY-1801 to 45 parts of ethylene glycol. After raising the temperature to 40 °C and magnetic stirring for 15 min, cool it to 20 °C and perform ultrasonic dispersion treatment for 10 min using an ultrasonic mixing stirrer JH1000W-20. The ultrasonic frequency is 20 kHz and the ultrasonic power is 1000 W, then the modified phenol-formaldehyde resin composition can be obtained.

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

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

[0087] Preparation of the ramming mix specimen: Roll it into a cylindrical shape under 80 kN. Preheat the obtained cylindrical ramming mix at 450 °C for 5 h and then perform carbon-buried heat treatment at 1450 °C for 3 h, and cool it to room temperature to obtain the ramming mix specimen.

[0088] Performance detection test of the gun clay sample: 1. The linear change rate of the clay material is detected in accordance with the national standard GB / T 5988-2007. 2. The bulk density and apparent porosity indexes of the clay material are detected according to GB / T 2997-2000. 3. The flexural strength index of the clay material is detected according to GB / T 5072-2008. 4. The compressive strength of the clay material is detected according to GB / T 3007-2004. 5. The slag resistance of the clay material is determined in accordance with Method 2 - Static sample immersion slag aeration method in GB / T 8931-2007 "Test Method for Slag Resistance of Refractory Materials". The slag erosion rate R of the sample is expressed as a mass fraction (%). R = 100(W - W1) / W, where: W is the mass of the sample before the test, in grams (g); W1 is the mass of the sample after the test, in grams (g). The test results are rounded to 2 decimal places according to GB / T 8170. 6. The Marshak value of the gun clay is measured with a GDP-500 type gun clay detector.

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

[0090]

[0091]

[0092] Combining Example 1 and Comparative Example 1 and referring to Table 1, it can be seen that by using the self-made modified phenolic resin composition in the present invention, the apparent porosity of the gun clay can be reduced, and the flexural strength, compressive strength, volume stability and erosion resistance of the gun clay can be improved.

[0093] Combining Example 1 and Comparative Examples 2-5 and referring to Table 1, it can be seen that the gun clay prepared from the modified phenolic resin composition containing boron-modified phenolic resin TY03 has good erosion resistance (slag erosion rate R < 0.5). The gun clay prepared from the modified phenolic resin composition containing partially blocked hydroxymethyl novolac resin has a relatively low apparent porosity, and relatively good flexural strength, compressive strength, volume stability and erosion resistance.

[0094] Combining Example 1 and Comparative Example 1 and referring to Table 6, it can be seen that by regulating the content requirement of the partially blocked hydroxymethyl novolac resin in the modified phenolic resin composition, too much partially blocked hydroxymethyl novolac resin will also cause an increase in apparent porosity, and the flexural strength, compressive strength, volume stability and erosion resistance of the gun clay show a downward trend. Therefore, the content of the partially blocked hydroxymethyl novolac resin in the modified phenolic resin composition is relatively suitable at 5-10 parts.

[0095] Combining Examples 1-3 and Comparative Example 1 and referring to Table 7, it can be seen that by adding titanate coupling agent as a dispersion aid to the gun clay formula, the flexural strength, compressive strength and erosion resistance of the gun clay can be improved.

[0096] Combined with Example 1 and Example 3 and with reference to Table 1, it can be seen that the addition of 1 part of diisopropyl bis(acetylacetonate) titanate HY-1801 in the modified phenolic resin composition is conducive to the uniform dispersion of refractory aggregates, additives and composite carbon powder, and improves the flexural strength, compressive strength and volume stability of the gun clay.

[0097] Combined with Example 1 and Example 4 and with reference to Table 1, it can be seen that diisopropyl bis(acetylacetonate) 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 gun clay, and further improve the flexural strength, compressive strength, erosion resistance and volume stability of the gun clay.

[0098] Combined with Example 4 and Examples 5-7 and with reference to Table 1, it can be seen that doping an appropriate amount of zirconia and / or tetrapod-like zinc oxide whiskers in the refractory aggregate can improve the flexural strength, compressive strength, erosion resistance and volume stability of the gun clay, and the improvement of the erosion resistance of the gun clay is more obvious.

[0099] Combined with Example 4 and Examples 8-9 and with reference to Table 1, it can be seen that doping an appropriate amount of natural graphite in the composite carbon powder will slightly increase the Martens hardness value of the gun clay, but can improve the flexural strength and compressive strength of the gun clay. When an appropriate amount of natural graphite and industrial graphene are doped in the composite carbon powder, although the improvement of the flexural strength and compressive strength of the gun clay is relatively better, the increase range of the Martens hardness value of the gun clay is relatively obvious and the cost is relatively high.

[0100] Combined with Example 1 and Examples 10-15 and Comparative Example 8 and with reference to Table 1, it can be seen that in Example 14, 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 metal silicon powder in a mass ratio of 3:1:1. The comprehensive performance of the prepared gun clay is the best, but its production cost is also the highest. In Comparative Example 8, a nano-metal cluster modified additive is added. The flexural strength, compressive strength and erosion resistance of the prepared gun clay are relatively poor. In Examples 1, 10-13 and 15, an appropriate amount of nano-metal cluster modified additive is selected in the additive. The flexural strength, compressive strength and erosion resistance (slag erosion rate R < 0.5) of the prepared gun clay are relatively good and the overall production cost is reduced. The incorporation amount of the nano-metal cluster modified additive controlled at 10-15% is relatively good.

[0101] In summary, the gun clay prepared in the present invention has a low apparent porosity, good flexural strength, compressive strength, volume stability and erosion resistance (slag erosion rate R < 0.5), and overcomes the defects of high apparent porosity, poor mechanical properties, erosion resistance and volume stability brought by traditional tar binders.

[0102] It should be noted that: This specific embodiment is only an explanatory illustration of the technical solution of the present invention, and it is not a limitation of the present invention. After reading this specification, those skilled in the art can make modifications that do not contribute creatively to this embodiment as needed, but as long as it is within the scope of the claims of the present invention, it is protected by the patent law.

Claims

1. A preparation method of a metal toughened silicon carbide - silicon nitride ramming paste material, characterized in that: The metal toughened silicon carbide - silicon nitride ramming material is made from raw materials with the following mass percentages: 44 - 52% refractory aggregate, 0.6 - 1.0% dispersing aid, 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 ramming material is as follows: first prepare the modified phenolic resin composition, then conduct dry kneading treatment on the refractory aggregate, dispersing aid, additives, and composite carbon powder, and finally add the modified phenolic resin composition, mix, roll, and extrude and cut to obtain the finished metal toughened silicon carbide - silicon nitride ramming material.

2. The preparation method of a metal toughened silicon carbide - silicon nitride ramming material according to claim 1, characterized in that: The preparation method of the said modified phenolic resin composition is as follows: S1. The resol resin solvent forms a resol resin solution with a solid content of 40 - 60% in an acetone solvent. Add C6 - C12 saturated fatty acid and tetra - isopropyl titanate to the resol resin solution. The mass ratio of the C6 - C12 saturated fatty acid to the resol resin solvent is 1:(10 - 100), and the mass ratio of the tetra - isopropyl titanate to the resol resin solvent is 1:(100 - 400). Raise the temperature to 60 - 80 °C for esterification reaction for 1 - 4 h, and remove acetone and water by vacuum distillation to obtain a partially blocked hydroxymethyl resol resin. S2. Add 5 - 10 parts of the partially blocked hydroxymethyl resol resin obtained in 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, mix evenly to obtain the modified phenolic resin composition.

3. The preparation method of a metal toughened silicon carbide - silicon nitride gun clay material according to claim 2, characterized in that: S1. The resol resin solvent forms a resol resin solution with a solid content of 40 - 60% in an acetone solvent. Add C6 - C12 saturated fatty acid and tetra - isopropyl titanate to the resol resin solution. The mass ratio of the C6 - C12 saturated fatty acid to the resol resin solvent is 1:(40 - 50), and the mass ratio of the tetra - isopropyl titanate to the resol resin solvent is 1:(200 - 250). Raise the temperature to 60 - 80 °C for esterification reaction for 3 - 4 h, and remove acetone and water by vacuum distillation to obtain a partially blocked hydroxymethyl resol resin.

4. The preparation method of a metal toughened silicon carbide - silicon nitride ramming material according to claim 2, characterized in that: S2. Add 8 - 10 parts of the partially blocked hydroxymethyl resol resin obtained in 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, mix evenly to obtain the modified phenolic resin composition.

5. The preparation method of a metal toughened silicon carbide - silicon nitride ramming paste material according to claim 2, characterized in that: The curing agent is composed of one or more of hexamethylenetetramine, paraformaldehyde, melamine, and urea - formaldehyde, or the curing agent is composed of at least one of hexamethylenetetramine, paraformaldehyde, melamine, and urea - formaldehyde in combination with at least one of di - isopropyl bis(acetylacetonate)titanium and di - isopropyl bis(ethyl acetoacetate)titanium.

6. The preparation method of a metal toughened silicon carbide - silicon nitride ramming paste material according to claim 2, characterized in that: The small molecule alcohol is composed of one or more of methanol, ethanol, ethylene glycol, diethylene glycol, and glycerol.

7. The preparation method of a metal toughened silicon carbide - silicon nitride ramming 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 in combination with at least one of zirconia and tetrapod-like zinc oxide.

8. The preparation method of a metal toughened silicon carbide - silicon nitride ramming material according to claim 1, characterized in that: The nano metal cluster modified additive includes an additive carrier and nano metal clusters formed on the surface of the additive carrier by the sol-gel method + 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 metal silicon powder.

9. The preparation method of a metal toughened silicon carbide - silicon nitride ramming paste material according to claim 8, characterized in that: The additive is composed of silicon carbide, silicon nitride, metal 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).

10. The preparation method of a metal toughened silicon carbide - silicon nitride ramming material according to claim 1, characterized in that: The dispersion aid is at least one of isopropyl triisostearoyl titanate, diethyl (dioctylphosphoryl) titanite, diethyl (dioctylpyrophosphoryl) titanite, diisopropyl bis(acetylacetonato) titanate, and diisopropyl bis(ethylacetoacetato) titanate.

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