CN112811917B - Whisker reinforced lightweight aluminum-carbon refractory material and preparation method thereof - Google Patents

Whisker reinforced lightweight aluminum-carbon refractory material and preparation method thereof Download PDF

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CN112811917B
CN112811917B CN202110025255.3A CN202110025255A CN112811917B CN 112811917 B CN112811917 B CN 112811917B CN 202110025255 A CN202110025255 A CN 202110025255A CN 112811917 B CN112811917 B CN 112811917B
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CN112811917A (en
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鄢文
陈哲
白晨
李亚伟
李远兵
李楠
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Wuhan University of Science and Engineering WUSE
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates

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Abstract

The invention relates to a whisker reinforced lightweight aluminum-carbon refractory material and a preparation method thereof. The technical scheme is as follows: taking 20-30 wt% of modified porous ceramic particles I and 25-35 wt% of modified porous ceramic particles II as aggregates, and taking 24-36 wt% of modified porous ceramic fine powder, 2-6 wt% of simple substance Si powder and 4-10 wt% of carbon powder as matrixes; firstly, placing the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-6 wt% of the sum of the aggregate and the matrix, mixing, then adding the matrix, uniformly stirring, carrying out mechanical compression molding, carrying out heat treatment at 180-310 ℃, finally carrying out heat preservation at 1100-1450 ℃ for 3-10 hours in a carbon burying environment, and naturally cooling to obtain the whisker reinforced lightweight aluminum-carbon refractory material. The prepared product has the characteristics of low heat conductivity coefficient, high strength, excellent thermal shock stability, and good slag resistance and oxidation resistance.

Description

Whisker reinforced lightweight aluminum-carbon refractory material and preparation method thereof
Technical Field
The invention belongs to the technical field of lightweight aluminum-carbon refractory materials. In particular to a whisker reinforced lightweight aluminum-carbon refractory material and a preparation method thereof.
Background
The aluminum-carbon refractory material has good high temperature resistance, erosion resistance, thermal shock resistance and other performances, and is widely applied to three key functional refractory devices of a slide plate brick of a slide gate nozzle system for continuous casting, an upper gate and a lower gate of a ladle, a tundish, a continuous casting piece and the like. When the aluminum-carbon refractory material is used, on one hand, due to the high heat conductivity coefficient of the aluminum-carbon refractory material, the heat of molten steel is dissipated and lost through a functional refractory device, such as a water gap and the like, so that the heat loss of the molten steel is accelerated, and more energy is consumed; on the other hand, the aluminum-carbon refractory material needs to bear the scouring wear of high-temperature molten steel for many times, so that the service life of the refractory material is reduced, the production efficiency is influenced, and even the damaged refractory material can pollute the molten steel when falling into the molten steel. Therefore, how to reduce the thermal conductivity of the aluminum-carbon refractory material and improve the mechanical property is an urgent problem to be solved in the technical field.
Currently, many studies on aluminum-carbonaceous refractory materials have been reported: for example, in the patent technology of 'a low-carbon aluminum-carbon refractory material with multi-dimensional enhancement and a preparation method thereof' (CN 201810592472.9), simple substance silicon powder, aluminum powder, activated alumina micro powder, corundum powder (the particle size is less than or equal to 8 mm), carbon and the like are taken as main raw materials to prepare the low-carbon aluminum-carbon refractory material; for example, in the literature technology (beam male, etc. influence of purified soil-like graphite on the microstructure and mechanical property of the aluminum-carbon material. Silicate science report 2014.42 (3): 357-365), plate-like corundum particles, silicon oxide micro powder, metal Al powder, simple substance Si powder, crystalline flake graphite and purified soil-like graphite are taken as main raw materials to prepare the aluminum-carbon refractory material; for another example, in the literature technology (Liu Tufu, etc., the influence of boron carbide addition on the microstructure and the performance of the low-carbon aluminum-carbon refractory material, silicate science reports, 2017.45 (9): 1340-1346), the low-carbon aluminum-carbon refractory material is prepared by taking tabular corundum and activated alumina micro powder as main raw materials, nano carbon black as a carbon source and boron carbide and simple substance Si powder as additives.
These techniques, while having well-known advantages, have the following problems: (1) The existing aluminum-carbon refractory material adopts compact corundum such as plate-shaped corundum, fused corundum and the like as aggregate, has high density, and causes the over-high heat conductivity coefficient of the obtained product together with high-heat-conductivity carbon in a matrix; (2) The surface of the compact corundum aggregate is smooth, and the compact corundum aggregate has poor interface compatibility with non-oxides in the matrix, so that the strength of the aggregate/matrix interface is low, the strength of the obtained product is low, and the improvement of the thermal shock stability, the slag resistance and the oxidation resistance of the product is limited; (3) Although the matrix part of the aluminum-carbon refractory material is reinforced to a certain extent by using whiskers and the like, the generated whiskers are mainly distributed in the matrix, the number of whisker bridges at the interface of the aggregate/matrix is small, the compatibility between the whiskers and the interface of the aggregate is poor, the reinforcement of the interface of the aggregate/matrix is limited, and the strength of the obtained product needs to be further improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a whisker reinforced lightweight alumina-carbon refractory material which has low heat conductivity, high strength, excellent thermal shock stability, excellent slag resistance and good oxidation resistance and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:
step 1, preparation of modified porous ceramic particles and modified porous ceramic fine powder
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 290-480 ℃ at the speed of 2-3.4 ℃/min, preserving the heat for 3-6 h, and naturally cooling to obtain the alumina powder with high porosity.
Step 1.2, placing the alumina powder with high porosity and the light-burned magnesite micro powder into a stirrer, adding the water, mixing, and stirring for 14-22 min to obtain a mixture, wherein the mass ratio of the alumina powder with high porosity to the light-burned magnesite micro powder to the water is 100: 1.4-2: 2-5.
Step 1.3, performing mechanical pressing molding on the mixture under the condition of 100-180 MPa, and drying the molded blank at the temperature of 120-170 ℃ for 18-24 h; then the dried blank body is placed in a high temperature furnace, the temperature is raised to 1600-1740 ℃ at the speed of 4-6.5 ℃/min, the temperature is kept for 5-10 h, and the porous ceramic material taking corundum as the main crystal phase is obtained after natural cooling.
The porous ceramic material with corundum as a main crystal phase comprises the following components in percentage by weight: the apparent porosity is 21.2-38.1%; the volume density is 2.42 to 3.07g/cm 3 (ii) a The average pore diameter is 260nm to 1.9 mu m, the pore diameter distribution is double peaks, the small pore peak is 240 to 820nm, and the large pore peak is 1.2 to 2.4 mu m; the compressive strength is 82-210 MPa.
Step 1.4, placing the porous ceramic material taking corundum as a main crystal phase into a vacuum device according to the mass ratio of the porous ceramic material taking corundum as a main crystal phase to a modification solution of 100: 39-44, vacuumizing to 1.8-2.5 kPa, adding the modification solution, standing for 30-60 min, closing a vacuumizing system, and drying for 24-36 h at the temperature of 110-150 ℃ to obtain the modified porous ceramic material;
the preparation method of the modified solution comprises the following steps: mixing the deionized water and the catalyst according to the mass ratio of 100: 2.2-4, and uniformly stirring to obtain a modified solution.
And step 1.5, crushing and screening the modified porous ceramic material to respectively obtain modified porous ceramic particles I, modified porous ceramic particles II and modified porous ceramic fine powder.
The particle size of the modified porous ceramic particles I is smaller than 3mm and larger than or equal to 1.2mm, the particle size of the modified porous ceramic particles II is smaller than 1.2mm and larger than or equal to 0.5mm, and the particle size of the modified porous ceramic fine powder is smaller than 0.088mm.
Step 2, preparation of whisker reinforced lightweight aluminum-carbon refractory material
Taking 20-30 wt% of modified porous ceramic particles I and 25-35 wt% of modified porous ceramic particles II as aggregates, and taking 24-36 wt% of modified porous ceramic fine powder, 2-6 wt% of simple substance Si powder and 4-10 wt% of carbon powder as matrixes; firstly, placing the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-6 wt% of the sum of the aggregate and the matrix, mixing, then adding the matrix, uniformly stirring, then carrying out mechanical press molding under the condition of 100-210 MPa, carrying out heat treatment for 12-36 hours at the temperature of 180-310 ℃, finally carrying out heat preservation for 3-10 hours in a carbon-embedded environment at the temperature of 1100-1450 ℃, and naturally cooling to prepare the whisker reinforced lightweight aluminum-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate in a mass ratio of 100: 5-10, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
The particle size of the aluminum hydroxide fine powder is less than 44 mu m; al of the aluminum hydroxide fine powder 2 O 3 The content is 64 to 65wt percent.
The grain size of the light-burned magnesite micro powder is less than 2 mu m; the MgO content of the light-burned magnesite micro powder is more than 96wt%.
The catalyst is one or two of ferric nitrate nonahydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate 3 ) 3 ·9H 2 The content of O is more than 98wt percent, and the Co (NO) of the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content is more than 98wt%.
The particle size of the simple substance Si powder is less than 0.045mm; the Si content of the simple substance Si powder is more than 98wt%.
The carbon powder is one or two of crystalline flake graphite and microcrystalline graphite, and the particle size of the carbon powder is less than 0.074mm; wherein: the C content of the crystalline flake graphite is more than 97wt%, and the C content of the microcrystalline graphite is more than 97wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is more than 40 percent.
Ni (NO) of the nickel nitrate hexahydrate 3 ) 2 ·6H 2 The O content is more than 98wt%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
(1) The modified porous ceramic particles adopted by the invention introduce a micro-nano porous structure, so that the heat conductivity coefficient of the product is effectively reduced.
The invention adopts Al (OH) 3 The alumina powder with high porosity obtained by decomposition is used as a raw material, and the microstructure of the porous ceramic material is regulated by light-burned magnesite micropowder and high-pressure forming to prepare modified porous ceramic particles and modified porous ceramic fine powder which can be applied to higher temperature and have micro-nano pore diameter.
According to the invention, the modified porous ceramic particles are introduced with a micro-nano porous structure, and the modified porous ceramic particles are used as aggregate, so that the heat conductivity coefficient of the product can be effectively reduced, the heat loss is reduced, and the energy is saved.
(2) The invention adopts the micro-nano porous structure and the silicon carbide crystal whiskers and the carbon nano tubes which are specially distributed to be compounded and enhanced, thereby improving the strength and the thermal shock stability of the product.
Firstly, more micro-nano pores exist on the surface of the aggregate used by the invention, so that the contact area between the aggregate and the matrix can be increased, on one hand, the sintering process of the aggregate and the oxide in the matrix is accelerated, on the other hand, the interface compatibility of the aggregate and the non-oxide in the matrix is improved, the combination of the aggregate/matrix interface is tighter, a better sawtooth occlusion-shaped interface structure is formed, and the strength of the product is obviously improved.
Secondly, the invention utilizes the in-situ formation of the silicon carbide whiskers and the carbon nano tubes which are specially distributed to strengthen the aggregate/matrix sawtooth occlusion interface. The aggregate used in the invention has a large number of micro-nano pores in the interior and on the surface, and the pore structure is in a through shape and is adhered with the catalyst. When the temperature is kept at 1100-1450 ℃ under the condition of carbon burying, gases such as SiO, CO and the like generated in the matrix by reaction can be diffused to the surface and the interior of the aggregate, and a large amount of silicon carbide whiskers are generated in situ on the surface and the interior of the aggregate by a gas-liquid-solid reaction mechanism under the action of a catalyst. Therefore, the silicon carbide whiskers are distributed not only among the matrix fine powder, but also in the aggregate and on the aggregate/matrix sawtooth occlusion interface structure, the number of whisker bridges at the interface is obviously increased, the occlusion-interweaving silicon carbide whisker reinforced interface structure is formed, the bonding at the interface is tighter, and the strength of the product is improved. Meanwhile, after the modified liquid thermosetting phenolic resin is subjected to catalytic cracking, carbon nanotubes can be generated in pores on the surface layer of the aggregate, in the matrix and at the interface of the aggregate/matrix in situ, and the carbon nanotubes and silicon carbide whiskers at the interface generate a synergistic composite reinforcing effect, so that the strength of the product is further improved.
Thirdly, when the product obtained by the invention is under the action of thermal stress, on one hand, the meshed-interwoven silicon carbide crystal whisker reinforced interface structure can prevent the crack from expanding along the aggregate/matrix interface, and the crack expansion resistance is increased; on the other hand, the silicon carbide crystal whisker and the carbon nano tube which are generated in situ in the aggregate and the micro-nano-scale pore structure in the aggregate can disperse thermal stress, thus being beneficial to the deflection of cracks and effectively relieving the damage of the thermal stress to products, and creating favorable conditions for improving the thermal shock stability of the products.
(3) The special pore structure and the silicon carbide whiskers distributed specially lead the product to have good slag resistance and oxidation resistance.
Firstly, the smaller the pore diameter is, the more difficult the slag permeation is, and the pore diameter of the pores in the aggregate used by the invention is micro-nano-scale, thereby effectively blocking the permeation of the slag. Secondly, on one hand, the silicon carbide whiskers in the occlusion-interweaving state enhance the interface structure to enable the interface to be combined more tightly; on the other hand, oxygen reacts with SiC and Al at the aggregate/matrix interface at high temperatures 2 O 3 Mullite is generated by the reaction, which is beneficial to blocking the gap at the interface and further improving the binding property at the interface. The better interface structure hinders the penetration and diffusion of slag and oxygen along the interface, so that the slag resistance and the oxidation resistance of the product are obviously improved. Meanwhile, the silicon carbide whiskers in the aggregate and on the surface have poor wettability with the slag, and the reaction with the slag at high temperature can increase the SiO content in the permeated slag 2 Content, increase the viscosity of the infiltration slag, which not only hinders the further erosion and infiltration of the slag, but also reduces the chance of carbon oxidation inside the product.
The whisker reinforced lightweight aluminum-carbon refractory material prepared by the invention is detected as follows: the apparent porosity is 20.2-28.6%; the volume density is 2.54-2.72 g/cm 3 (ii) a The breaking strength is 26-34 MPa.
Therefore, the whisker reinforced lightweight aluminum-carbon refractory material prepared by the invention has the characteristics of low thermal conductivity coefficient, high strength, excellent thermal shock stability, excellent slag resistance and good oxidation resistance, and is suitable for parts such as a sliding gate system for continuous casting, a tundish and three continuous casting parts.
Detailed Description
The invention is further described with reference to specific embodiments, but without limiting its scope.
A whisker reinforced lightweight aluminum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of modified porous ceramic particles and modified porous ceramic fine powder
Step 1.1, placing the aluminum hydroxide fine powder in a high-temperature furnace, heating to 290-480 ℃ at the speed of 2-3.4 ℃/min, preserving the heat for 3-6 h, and naturally cooling to obtain the alumina powder with high porosity.
Step 1.2, placing the alumina powder with high porosity and the light-burned magnesite micro powder into a stirrer, adding the water, mixing, and stirring for 14-22 min to obtain a mixture, wherein the mass ratio of the alumina powder with high porosity to the light-burned magnesite micro powder to the water is 100: 1.4-2: 2-5.
Step 1.3, performing mechanical pressing molding on the mixture under the condition of 100-180 MPa, and drying the molded blank at the temperature of 120-170 ℃ for 18-24 h; then the dried blank body is placed in a high temperature furnace, the temperature is raised to 1600-1740 ℃ at the speed of 4-6.5 ℃/min, the temperature is kept for 5-10 h, and the porous ceramic material taking corundum as the main crystal phase is obtained after natural cooling.
The porous ceramic material taking corundum as a main crystal phase: the apparent porosity is 21.2-38.1%; the volume density is 2.42 to 3.07g/cm 3 (ii) a The average pore diameter is 260 nm-1.9 μm, the pore diameter distribution is double peaks, the small pore peak is 240-820 nm, and the large pore peak is 1.2-2.4 μm; the compressive strength is 82-210 MPa.
Step 1.4, placing the porous ceramic material taking corundum as a main crystal phase into a vacuum device according to the mass ratio of the porous ceramic material taking corundum as a main crystal phase to a modification solution of 100: 39-44, vacuumizing to 1.8-2.5 kPa, adding the modification solution, standing for 30-60 min, closing a vacuumizing system, and drying for 24-36 h at the temperature of 110-150 ℃ to obtain the modified porous ceramic material;
the preparation method of the modified solution comprises the following steps: mixing the deionized water and the catalyst according to the mass ratio of 100: 2.2-4, and uniformly stirring to obtain a modified solution.
And step 1.5, crushing and screening the modified porous ceramic material to respectively obtain modified porous ceramic particles I, modified porous ceramic particles II and modified porous ceramic fine powder.
The particle size of the modified porous ceramic particle I is smaller than 3mm and larger than or equal to 1.2mm, the particle size of the modified porous ceramic particle II is smaller than 1.2mm and larger than or equal to 0.5mm, and the particle size of the modified porous ceramic fine powder is smaller than 0.088mm.
Step 2, preparation of whisker reinforced lightweight aluminum-carbon refractory material
Taking 20-30 wt% of modified porous ceramic particles I and 25-35 wt% of modified porous ceramic particles II as aggregates, and taking 24-36 wt% of modified porous ceramic fine powder, 2-6 wt% of simple substance Si powder and 4-10 wt% of carbon powder as matrixes; firstly, placing the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-6 wt% of the sum of the aggregate and the matrix, mixing, then adding the matrix, uniformly stirring, then carrying out mechanical press molding under the condition of 100-210 MPa, carrying out heat treatment for 12-36 hours at the temperature of 180-310 ℃, finally carrying out heat preservation for 3-10 hours in a carbon-buried environment at the temperature of 1100-1450 ℃, and naturally cooling to prepare the whisker reinforced lightweight aluminum-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate in a mass ratio of 100: 5-10, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
Al of the aluminum hydroxide fine powder 2 O 3 The content is 64 to 65wt percent.
The MgO content of the light-burned magnesite micro powder is more than 96wt%.
The catalyst is one or two of ferric nitrate nonahydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate 3 ) 3 ·9H 2 The content of O is more than 98wt percent, and the Co (NO) of the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content is more than 98wt%.
The Si content of the simple substance Si powder is more than 98wt%.
The carbon powder is one or two of crystalline flake graphite and microcrystalline graphite; wherein: the C content of the crystalline flake graphite is more than 97wt%, and the C content of the microcrystalline graphite is more than 97wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is more than 40 percent.
Ni (NO) of the nickel nitrate hexahydrate 3 ) 2 ·6H 2 Content of O＞98wt％。
In this embodiment:
the particle size of the aluminum hydroxide fine powder is less than 44 mu m;
the grain size of the light-burned magnesite micro powder is less than 2 mu m;
the particle size of the simple substance Si powder is less than 0.045mm;
the grain size of the carbon powder is less than 0.074mm;
the detailed description is omitted in the embodiments.
Example 1
A whisker reinforced lightweight aluminum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of modified porous ceramic particles and modified porous ceramic fine powder
Step 1.1, placing the aluminum hydroxide fine powder in a high-temperature furnace, heating to 290 ℃ at the speed of 2.6 ℃/min, preserving heat for 4h, and naturally cooling to obtain the alumina powder with high porosity.
Step 1.2, placing the alumina powder with high porosity and the light-burned magnesite micro powder into a stirrer according to the mass ratio of the alumina powder with high porosity to the light-burned magnesite micro powder to water of 100: 1.4: 3, adding the water into the stirrer for mixing, and stirring for 18min to obtain a mixture.
1.3, mechanically pressing and molding the mixture under the condition of 150MPa, and drying the molded blank at 140 ℃ for 20 hours; and then placing the dried blank body in a high-temperature furnace, heating to 1600 ℃ at the speed of 6.5 ℃/min, preserving the temperature for 7h, and naturally cooling to obtain the porous ceramic material taking corundum as a main crystal phase.
The porous ceramic material taking corundum as a main crystal phase: the apparent porosity was 37.7%; the bulk density is 2.45g/cm 3 (ii) a The average pore diameter is 1.7 mu m, the pore diameter distribution is double peaks, the small pore peak is 760nm, and the large pore peak is 2.3 mu m; the compressive strength was 89MPa.
Step 1.4, placing the porous ceramic material taking corundum as a main crystal phase in a vacuum device according to the mass ratio of the porous ceramic material taking corundum as a main crystal phase to a modification solution of 100: 41, vacuumizing to 2kPa, adding the modification solution, standing for 30min, closing a vacuumizing system, and drying for 32h at 120 ℃ to obtain the modified porous ceramic material;
the preparation method of the modified solution comprises the following steps: mixing the deionized water and the catalyst according to the mass ratio of 100: 2.8, and uniformly stirring to obtain a modified solution.
And step 1.5, crushing and screening the modified porous ceramic material to respectively obtain modified porous ceramic particles I, modified porous ceramic particles II and modified porous ceramic fine powder.
The particle size of the modified porous ceramic particles I is smaller than 3mm and larger than or equal to 1.2mm, the particle size of the modified porous ceramic particles II is smaller than 1.2mm and larger than or equal to 0.5mm, and the particle size of the modified porous ceramic fine powder is smaller than 0.088mm.
Step 2, preparation of whisker reinforced lightweight aluminum-carbon refractory material
Taking 30wt% of modified porous ceramic particles I and 26.3wt% of modified porous ceramic particles II as aggregates, and taking 31.7wt% of modified porous ceramic fine powder, 2wt% of simple substance Si powder and 10wt% of carbon powder as matrixes; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2wt% of the sum of the aggregate and the matrix, mixing, adding the matrix, uniformly stirring, carrying out mechanical press molding under the condition of 100MPa, carrying out heat treatment at 180 ℃ for 36 hours, carrying out heat preservation at 1240 ℃ in a carbon-embedded environment for 4.5 hours, and naturally cooling to obtain the whisker reinforced lightweight aluminum-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of 100: 6, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
In this embodiment:
al of the aluminum hydroxide fine powder 2 O 3 The content was 64.3wt%.
The MgO content of the light-burned magnesite micro powder is 96.4wt%.
The catalyst is ferric nitrate nonahydrate; fe (NO) of the iron nitrate nonahydrate 3 ) 3 ·9H 2 The O content was 98.5wt%.
The Si content of the simple substance Si powder is 98.4wt%.
The carbon powder is a mixture of crystalline flake graphite and microcrystalline graphite; wherein: the content of C in the crystalline flake graphite is 97.4wt%, and the content of C in the microcrystalline graphite is 97.3wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 42%.
Ni (NO) of the nickel nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.1wt%.
The whisker reinforced lightweight aluminum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 28.4%; the bulk density is 2.55g/cm 3 (ii) a The breaking strength is 26MPa.
Example 2
A whisker reinforced lightweight aluminum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of modified porous ceramic particles and modified porous ceramic fine powder
Step 1.1, placing the aluminum hydroxide fine powder in a high-temperature furnace, heating to 380 ℃ at the speed of 2 ℃/min, preserving heat for 3.5 hours, and naturally cooling to obtain the alumina powder with high porosity.
Step 1.2, according to the mass ratio of the alumina powder with high porosity to the light-burned magnesite micro powder to water being 100: 1.6: 2, firstly placing the alumina powder with high porosity and the light-burned magnesite micro powder in a stirrer, adding the water for mixing, and stirring for 14min to obtain a mixture.
Step 1.3, performing mechanical pressing molding on the mixture under the condition of 180MPa, and drying the molded blank at 150 ℃ for 18h; and then placing the dried blank body in a high-temperature furnace, heating to 1740 ℃ at the speed of 4.9 ℃/min, preserving the temperature for 8 hours, and naturally cooling to obtain the porous ceramic material taking corundum as a main crystal phase.
The porous ceramic material taking corundum as a main crystal phase: apparent porosityIs 21.3 percent; the bulk density is 3.05g/cm 3 (ii) a The average pore diameter is 270nm, the pore diameter distribution is double peaks, the small pore peak is 260nm, and the large pore peak is 1.4 μm; the compressive strength was 205MPa.
Step 1.4, placing the porous ceramic material taking corundum as a main crystal phase in a vacuum device according to the mass ratio of the porous ceramic material taking corundum as a main crystal phase to a modification solution of 100: 42, vacuumizing to 1.8kPa, adding the modification solution, standing for 50min, closing a vacuumizing system, and drying for 24h at 140 ℃ to obtain the modified porous ceramic material;
the preparation method of the modified solution comprises the following steps: and mixing the deionized water and the catalyst according to the mass ratio of 100: 3.4, and uniformly stirring to obtain a modified solution.
And step 1.5, crushing and screening the modified porous ceramic material to respectively obtain modified porous ceramic particles I, modified porous ceramic particles II and modified porous ceramic fine powder.
The particle size of the modified porous ceramic particle I is smaller than 3mm and larger than or equal to 1.2mm, the particle size of the modified porous ceramic particle II is smaller than 1.2mm and larger than or equal to 0.5mm, and the particle size of the modified porous ceramic fine powder is smaller than 0.088mm.
Step 2, preparation of whisker reinforced lightweight aluminum-carbon refractory material
27wt% of modified porous ceramic particles I and 31wt% of modified porous ceramic particles II are used as aggregates, and 33.5wt% of modified porous ceramic fine powder, 4.5wt% of simple substance Si powder and 4wt% of carbon powder are used as substrates; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 4.5wt% of the sum of the aggregate and the matrix, mixing, adding the matrix, uniformly stirring, carrying out mechanical press molding under the condition of 210MPa, carrying out heat treatment for 32 hours at the temperature of 280 ℃, carrying out heat preservation for 10 hours in a carbon-embedded environment at the temperature of 1310 ℃, and naturally cooling to prepare the whisker reinforced lightweight aluminum-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of 100: 8, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
In this embodiment:
al of the aluminum hydroxide fine powder 2 O 3 The content was 64.7% by weight.
The MgO content of the light-burned magnesite micro powder is 96.2wt%.
The catalyst is a mixture of ferric nitrate nonahydrate and cobalt nitrate hexahydrate; wherein: fe (NO) of the iron nitrate nonahydrate 3 ) 3 ·9H 2 The content of O is 98.6wt%, and the Co (NO) of the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.5wt%.
The Si content of the simple substance Si powder is 98.7wt%.
The carbon powder is microcrystalline graphite; the content of C in the microcrystalline graphite is 97.6wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 44%.
Ni (NO) of the nickel nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.6wt%.
The whisker reinforced lightweight aluminum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 20.6%; the bulk density is 2.7g/cm 3 (ii) a The breaking strength is 32MPa.
Example 3
A whisker reinforced lightweight aluminum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of modified porous ceramic particles and modified porous ceramic fine powder
Step 1.1, placing the aluminum hydroxide fine powder in a high-temperature furnace, heating to 480 ℃ at the speed of 3 ℃/min, preserving heat for 3 hours, and naturally cooling to obtain the alumina powder with high porosity.
Step 1.2, placing the alumina powder with high porosity and the light-burned magnesite micro powder into a stirrer according to the mass ratio of the alumina powder with high porosity to the light-burned magnesite micro powder to water of 100: 2: 4, adding the water into the stirrer for mixing, and stirring for 22min to obtain a mixture.
1.3, mechanically pressing the mixture under the condition of 120MPa, and drying a formed blank at the temperature of 120 ℃ for 24 hours; and then placing the dried blank body in a high-temperature furnace, heating to 1700 ℃ at the speed of 4 ℃/min, preserving the heat for 10h, and naturally cooling to obtain the porous ceramic material taking corundum as a main crystal phase.
The porous ceramic material with corundum as a main crystal phase comprises the following components in percentage by weight: the apparent porosity is 25.1%; the bulk density is 2.78g/cm 3 (ii) a The average pore diameter is 760nm, the pore diameter distribution is double peaks, the small pore peak is 550nm, and the large pore peak is 1.7 μm; the compressive strength was 167MPa.
Step 1.4, placing the porous ceramic material taking corundum as a main crystal phase in a vacuum device according to the mass ratio of the porous ceramic material taking corundum as a main crystal phase to a modification solution of 100: 39, vacuumizing to 2.5kPa, adding the modification solution, standing for 40min, closing a vacuumizing system, and drying for 30h at 110 ℃ to obtain the modified porous ceramic material;
the preparation method of the modified solution comprises the following steps: and mixing the deionized water and the catalyst according to the mass ratio of 100: 4 of the deionized water to the catalyst, and uniformly stirring to obtain a modified solution.
And step 1.5, crushing and screening the modified porous ceramic material to respectively obtain modified porous ceramic particles I, modified porous ceramic particles II and modified porous ceramic fine powder.
The particle size of the modified porous ceramic particles I is smaller than 3mm and larger than or equal to 1.2mm, the particle size of the modified porous ceramic particles II is smaller than 1.2mm and larger than or equal to 0.5mm, and the particle size of the modified porous ceramic fine powder is smaller than 0.088mm.
Step 2, preparation of whisker reinforced lightweight aluminum-carbon refractory material
22wt% of modified porous ceramic particles I and 35wt% of modified porous ceramic particles II are used as aggregates, and 30.2wt% of modified porous ceramic fine powder, 6wt% of simple substance Si powder and 6.8wt% of carbon powder are used as matrixes; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 6wt% of the sum of the aggregate and the matrix, mixing, adding the matrix, uniformly stirring, performing mechanical compression molding under the condition of 180MPa, performing heat treatment at 310 ℃ for 12 hours, finally performing heat preservation at 1450 ℃ in a carbon-embedded environment for 7 hours, and naturally cooling to prepare the whisker reinforced lightweight aluminum-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of 100: 5, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
In this embodiment:
al of the aluminum hydroxide fine powder 2 O 3 The content was 64wt%.
The MgO content of the light-burned magnesite micro powder is 96.6wt%.
The catalyst is cobalt nitrate hexahydrate; co (NO) of the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.8wt%.
The Si content of the simple substance Si powder is 99wt%.
The carbon powder is crystalline flake graphite; the C content of the flake graphite is 97.2wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 46%.
Ni (NO) of the nickel nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.9wt%.
The whisker reinforced lightweight aluminum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 22.5%; the bulk density is 2.66g/cm 3 (ii) a The breaking strength is 29MPa.
Example 4
A whisker reinforced lightweight aluminum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of modified porous ceramic particles and modified porous ceramic fine powder
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 410 ℃ at the speed of 3.4 ℃/min, preserving heat for 6 hours, and naturally cooling to obtain the alumina powder with high porosity.
Step 1.2, placing the alumina powder with high porosity and the light-burned magnesite micro powder into a stirrer according to the mass ratio of the alumina powder with high porosity to the light-burned magnesite micro powder to water of 100: 1.8: 5, adding the water into the stirrer for mixing, and stirring for 18min to obtain a mixture.
1.3, mechanically pressing and molding the mixture under the condition of 100MPa, and drying a molded blank at the temperature of 170 ℃ for 22 hours; and then placing the dried blank body in a high-temperature furnace, heating to 1650 ℃ at the speed of 6 ℃/min, preserving the temperature for 5h, and naturally cooling to obtain the porous ceramic material taking corundum as a main crystal phase.
The porous ceramic material with corundum as a main crystal phase comprises the following components in percentage by weight: the apparent porosity is 28.6%; the bulk density is 2.57g/cm 3 (ii) a The average pore diameter is 990nm, the pore diameter distribution is double peaks, the small pore peak is 480nm, and the large pore peak is 1.9 μm; the compressive strength was 121MPa.
Step 1.4, placing the porous ceramic material taking corundum as a main crystal phase in a vacuum device according to the mass ratio of the porous ceramic material taking corundum as a main crystal phase to a modification solution of 100: 44, vacuumizing to 2.2kPa, adding the modification solution, standing for 60min, closing a vacuumizing system, and drying for 36h at 150 ℃ to obtain the modified porous ceramic material;
the preparation method of the modified solution comprises the following steps: and mixing the deionized water and the catalyst according to the mass ratio of 100: 2.2, and uniformly stirring to obtain a modified solution.
And step 1.5, crushing and screening the modified porous ceramic material to respectively obtain modified porous ceramic particles I, modified porous ceramic particles II and modified porous ceramic fine powder.
The particle size of the modified porous ceramic particles I is smaller than 3mm and larger than or equal to 1.2mm, the particle size of the modified porous ceramic particles II is smaller than 1.2mm and larger than or equal to 0.5mm, and the particle size of the modified porous ceramic fine powder is smaller than 0.088mm.
Step 2, preparation of whisker reinforced lightweight aluminum-carbon refractory material
26.2wt% of modified porous ceramic particles I and 33.8wt% of modified porous ceramic particles II are used as aggregates, and 27wt% of modified porous ceramic fine powder, 5.1wt% of simple substance Si powder and 7.9wt% of carbon powder are used as matrixes; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 5wt% of the sum of the aggregate and the matrix, mixing, adding the matrix, uniformly stirring, performing mechanical compression molding under the condition of 140MPa, performing heat treatment at 230 ℃ for 24 hours, finally performing heat preservation in a carbon-embedded environment at 1100 ℃ for 3 hours, and naturally cooling to prepare the whisker reinforced lightweight aluminum-carbon refractory material.
The preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: mixing the liquid thermosetting phenolic resin and the nickel nitrate hexahydrate according to the mass ratio of 100: 10, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
In this embodiment:
al of the aluminum hydroxide fine powder 2 O 3 The content was 65wt%.
The MgO content of the light-burned magnesite micro powder is 96.8wt%.
The catalyst is ferric nitrate nonahydrate; fe (NO) of the iron nitrate nonahydrate 3 ) 3 ·9H 2 The O content was 98.2wt%.
The Si content of the simple substance Si powder is 98.1wt%.
The carbon powder is crystalline flake graphite; the C content of the crystalline flake graphite is 97.8wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 48%.
Ni (NO) of the nickel nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.3wt%.
The whisker reinforced lightweight aluminum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 24.2%; the bulk density is 2.61g/cm 3 (ii) a The flexural strength was 27MPa.
Compared with the prior art, the specific implementation mode has the following positive effects:
(1) The modified porous ceramic particles adopted by the specific embodiment introduce a micro-nano porous structure, so that the heat conductivity coefficient of the product is effectively reduced.
The present embodiment uses Al (OH) 3 The alumina powder with high porosity obtained by decomposition is used as a raw material, and the light-burned magnesite micropowder and high-pressure forming are utilized to regulate and control the microstructure of the porous ceramic material, so that modified porous ceramic particles and modified porous ceramic fine powder which can be applied to higher temperature and have micro-nano apertures are prepared.
The modified porous ceramic particles adopted by the specific embodiment introduce a micro-nano porous structure, and the modified porous ceramic particles are used as aggregates, so that the heat conductivity coefficient of a product can be effectively reduced, heat loss is reduced, and energy is saved.
(2) According to the specific embodiment, the micro-nano porous structure, the silicon carbide whiskers and the carbon nano tubes which are specially distributed are compounded and enhanced, so that the strength and the thermal shock stability of the product are improved.
Firstly, more micro-nano pores exist on the surface of the aggregate used in the embodiment, so that the contact area between the aggregate and the matrix can be increased, the sintering process of the aggregate and the oxide in the matrix is accelerated, the interface compatibility of the aggregate and the non-oxide in the matrix is improved, the combination of the aggregate/matrix interface is tighter, a better sawtooth occlusion-shaped interface structure is formed, and the strength of a product is obviously improved.
Secondly, in the embodiment, the silicon carbide whiskers and the carbon nanotubes which are specially distributed are formed in situ, so that the sawtooth occlusion-shaped interface of the aggregate/matrix is enhanced. The aggregate used in the embodiment has a large number of micro-nano-scale pores in the interior and on the surface, and the pore structure is in a through shape and is attached with the catalyst. When the temperature is kept at 1100-1450 ℃ under the condition of carbon burying, gases such as SiO, CO and the like generated in the matrix by reaction can be diffused to the surface and the interior of the aggregate, and a large amount of silicon carbide whiskers are generated in situ on the surface and the interior of the aggregate by a gas-liquid-solid reaction mechanism under the action of a catalyst. Therefore, the silicon carbide whiskers are distributed not only among the matrix fine powder, but also in the aggregate and on the aggregate/matrix sawtooth occlusion interface structure, the number of whisker bridges at the interface is obviously increased, the occlusion-interweaving silicon carbide whisker reinforced interface structure is formed, the bonding at the interface is tighter, and the strength of the product is improved. Meanwhile, after the modified liquid thermosetting phenolic resin is subjected to catalytic cracking, carbon nanotubes can be generated in the pores on the surface layer of the aggregate, in the matrix and at the interface of the aggregate/matrix in situ, and the carbon nanotubes and silicon carbide whiskers at the interface generate a synergistic composite reinforcing effect, so that the strength of the product is further improved.
Thirdly, when the product obtained by the embodiment is subjected to the action of thermal stress, on one hand, the meshed-interwoven silicon carbide whisker reinforced interface structure can prevent cracks from expanding along an aggregate/matrix interface and increase the crack expansion resistance; on the other hand, the silicon carbide crystal whisker and the carbon nano tube which are generated in situ in the aggregate and the micro-nano-scale pore structure in the aggregate can disperse thermal stress, thus being beneficial to the deflection of cracks and effectively relieving the damage of the thermal stress to products, and creating favorable conditions for improving the thermal shock stability of the products.
(3) The special pore structure and the silicon carbide whiskers distributed specially in the embodiment enable the product to have good slag resistance and oxidation resistance.
First, the smaller the pore size, the more difficult the penetration of the slag, and the pore size of the pores in the aggregate used in the present embodiment is in the micro-nanometer range, which effectively hinders the penetration of the slag. Secondly, on one hand, the silicon carbide whiskers in the occlusion-interweaving state enhance the interface structure to enable the interface to be combined more tightly; on the other hand, oxygen reacts with SiC and Al at the aggregate/matrix interface at high temperatures 2 O 3 Mullite is generated by the reaction, which is beneficial to blocking the gaps at the interface and further improving the binding property at the interface. The better interface structure hinders the penetration and diffusion of slag and oxygen along the interface, and the slag resistance and the oxidation resistance of the product are obviously improved. Meanwhile, the silicon carbide whiskers in the aggregate and on the surface have poor wettability with the slag, and the reaction with the slag at high temperature can increase the SiO content in the permeated slag 2 Content, increase the viscosity of the infiltration slag, which not only hinders the further erosion and infiltration of the slag, but also reduces the chance of carbon oxidation inside the product.
The crystal whisker prepared by the embodimentThe detection shows that the strong and light aluminum-carbon refractory material comprises the following components: the apparent porosity is 20.2-28.6%; the volume density is 2.54-2.72 g/cm 3 (ii) a The breaking strength is 26-34 MPa.
Therefore, the whisker reinforced lightweight aluminum-carbon refractory material prepared by the embodiment has the characteristics of low thermal conductivity, high strength, excellent thermal shock stability, excellent slag resistance and good oxidation resistance, and is suitable for parts such as a sliding gate system for continuous casting, a tundish and three continuous casting parts.

Claims (9)

1. A preparation method of a whisker reinforced lightweight aluminum-carbon refractory material is characterized by comprising the following steps:
step 1, preparation of modified porous ceramic particles and modified porous ceramic fine powder
Step 1.1, placing the aluminum hydroxide fine powder in a high-temperature furnace, heating to 290-480 ℃ at the speed of 2-3.4 ℃/min, preserving the heat for 3-6 h, and naturally cooling to obtain aluminum oxide powder with high porosity;
step 1.2, putting the alumina powder with high porosity and the light-burned magnesite micro powder into a stirrer, adding the water into the stirrer to mix, and stirring for 14 to 22min to obtain a mixture, wherein the mass ratio of the alumina powder with high porosity to the light-burned magnesite micro powder to the water is 100: 1.4 to 2: 2 to 5;
step 1.3, performing machine pressing molding on the mixture under the conditions of 100 to 180MPa, and drying the molded blank at the temperature of 120 to 170 ℃ for 18 to 24h; then placing the dried blank in a high-temperature furnace, heating to 1600-1740 ℃ at the speed of 4-6.5 ℃/min, preserving the heat for 5-10h, and naturally cooling to obtain a porous ceramic material with corundum as a main crystal phase;
the porous ceramic material taking corundum as a main crystal phase: the apparent porosity is 21.2 to 38.1 percent; the volume density is 2.42 to 3.07g/cm 3 (ii) a The average pore diameter is 260nm to 1.9 mu m, the pore diameter distribution is bimodal, the small pore peak is 240 to 820nm, and the large pore peak is 1.2 to 2.4 mu m; the compressive strength is 82 to 210MPa;
step 1.4, placing the porous ceramic material taking corundum as a main crystal phase into a vacuum device according to the mass ratio of the porous ceramic material taking corundum as a main crystal phase to a modified solution of 100: 39-44, vacuumizing to 1.8-2.5 kPa, adding the modified solution, standing for 30-60min, closing a vacuumizing system, and drying at 110-150 ℃ for 24-36h to obtain the modified porous ceramic material;
the preparation method of the modified solution comprises the following steps: mixing deionized water and a catalyst according to the mass ratio of 100: 2.2 to 4, and uniformly stirring to obtain a modified solution;
step 1.5, crushing and screening the modified porous ceramic material to respectively obtain modified porous ceramic particles I, modified porous ceramic particles II and modified porous ceramic fine powder;
the particle size of the modified porous ceramic particles I is less than 3mm and more than or equal to 1.2mm, the particle size of the modified porous ceramic particles II is less than 1.2mm and more than or equal to 0.5mm, and the particle size of the modified porous ceramic fine powder is less than 0.088mm;
step 2, preparation of whisker reinforced lightweight aluminum-carbon refractory material
Taking 20-30wt% of modified porous ceramic particles I and 25-35wt% of modified porous ceramic particles II as aggregates, and taking 24-36wt% of modified porous ceramic fine powder, 2-6 wt% of simple substance Si powder and 4-10wt% of carbon powder as substrates; putting the aggregate into a stirrer, adding modified liquid thermosetting phenolic resin accounting for 2-6 wt% of the sum of the aggregate and the matrix, mixing, adding the matrix, stirring uniformly, performing mechanical compression molding under the conditions of 100-210MPa, performing heat treatment for 12-36 hours under the conditions of 180-310 ℃, performing heat preservation for 3-10 hours under the conditions of 1100-1450 ℃, and naturally cooling to prepare the whisker reinforced lightweight aluminum carbonaceous refractory;
the preparation method of the modified liquid thermosetting phenolic resin comprises the following steps: mixing liquid thermosetting phenolic resin and nickel nitrate hexahydrate in a mass ratio of 100: 5-10, and uniformly stirring to obtain modified liquid thermosetting phenolic resin;
the catalyst is one or two of ferric nitrate nonahydrate and cobalt nitrate hexahydrate.
2. The method of making a whisker reinforced lightweight alumino-carbonaceous refractory according to claim 1, wherein the particle size of the fine aluminum hydroxide powder is < 44 μm; al of the aluminum hydroxide fine powder 2 O 3 The content is 64 to 65wt%.
3. The method of making a whisker reinforced lightweight alumino-carbon refractory according to claim 1, wherein the particle size of the lightly calcined magnesite micropowder is < 2 μm; the MgO content of the light-burned magnesite micro powder is more than 96wt%.
4. The method of preparing whisker reinforced lightweight aluminum-carbon refractory of claim 1, wherein the Fe (NO) of the iron nitrate nonahydrate 3 ) 3 •9H 2 The content of O is more than 98wt percent, and the Co (NO) of the cobalt nitrate hexahydrate 3 ) 2 •6H 2 The O content is more than 98wt%.
5. The method of preparing a whisker-reinforced lightweight aluminum-carbon refractory according to claim 1, wherein the elemental Si powder has a particle size of < 0.045mm; the Si content of the simple substance Si powder is more than 98wt%.
6. The method for preparing the whisker reinforced lightweight aluminum-carbon refractory material according to claim 1, wherein the carbon powder is one or two of crystalline flake graphite and microcrystalline graphite, and the particle size of the carbon powder is less than 0.074mm; wherein: the C content of the crystalline flake graphite is more than 97wt%, and the C content of the microcrystalline graphite is more than 97wt%.
7. The method of preparing a whisker-reinforced lightweight alumino-carbonaceous refractory according to claim 1, wherein the liquid thermosetting phenolic resin has a carbon residue ratio of > 40%.
8. The method of making a whisker reinforced lightweight alumino-carbonaceous refractory according to claim 1, wherein the Ni (NO) of nickel nitrate hexahydrate 3 ) 2 •6H 2 The O content is more than 98wt%.
9. A whisker-reinforced lightweight aluminocarbonaceous refractory, characterized in that the whisker-reinforced lightweight aluminocarbonaceous refractory is a whisker-reinforced lightweight aluminocarbonaceous refractory prepared by the method for preparing a whisker-reinforced lightweight aluminocarbonaceous refractory according to any one of claims 1 to 8.
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