CN112645731B - Lightweight spinel-corundum-carbon refractory material and preparation method thereof - Google Patents
Lightweight spinel-corundum-carbon refractory material and preparation method thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000011819 refractory material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 163
- 239000010431 corundum Substances 0.000 claims abstract description 163
- 239000000919 ceramic Substances 0.000 claims abstract description 142
- 239000002245 particle Substances 0.000 claims abstract description 100
- 239000000843 powder Substances 0.000 claims abstract description 90
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 239000011159 matrix material Substances 0.000 claims abstract description 38
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000005011 phenolic resin Substances 0.000 claims abstract description 36
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 36
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 36
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 19
- 238000003825 pressing Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000012216 screening Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 43
- 239000011148 porous material Substances 0.000 claims description 36
- 239000001095 magnesium carbonate Substances 0.000 claims description 27
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 27
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 27
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 27
- 229910052596 spinel Inorganic materials 0.000 claims description 27
- 239000011029 spinel Substances 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 6
- 239000002893 slag Substances 0.000 abstract description 22
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000035939 shock Effects 0.000 abstract description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 description 20
- 239000002041 carbon nanotube Substances 0.000 description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000004134 energy conservation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008646 thermal stress Effects 0.000 description 6
- 229910052566 spinel group Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- -1 so that the strength Substances 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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Abstract
The invention relates to a lightweight spinel-corundum-carbon refractory material and a preparation method thereof. The technical scheme is as follows: placing the porous spinel-corundum ceramic in a vacuum device, adding the modified solution, standing, crushing and screening. Taking the screened modified porous spinel-corundum ceramic particles I, modified porous spinel-corundum ceramic particles II and modified porous spinel-corundum ceramic particles III as aggregates, and taking the screened porous spinel-corundum ceramic fine powder, elemental silicon powder and crystalline flake graphite as substrates; firstly, uniformly mixing aggregate, adding modified liquid thermosetting phenolic resin, uniformly mixing, adding a matrix, and uniformly mixing; and (3) mechanically pressing and forming, performing heat treatment, preserving heat under the conditions of carbon burying and 1150-1250 ℃, and naturally cooling to obtain the lightweight spinel-corundum-carbon refractory material. The product prepared by the invention has low thermal conductivity, high strength, good thermal shock stability, excellent slag resistance and excellent oxidation resistance.
Description
Technical Field
The invention belongs to the technical field of spinel-corundum-carbon refractory materials. In particular to a lightweight spinel-corundum-carbon refractory material and a preparation method thereof.
Background
The spinel-corundum-carbon refractory material is a key device widely applied to a steel-making refining link, such as a water gap, a sliding plate and the like, and the performance of the spinel-corundum-carbon refractory material has important influence on the safe production, energy conservation, consumption reduction and molten steel purity of the steel-making industry. Therefore, researches on preparation technologies of spinel-corundum-carbon refractory materials are more, and the spinel-corundum-carbon refractory materials are mainly prepared from dense fused corundum, high-purity fused spinel and the like serving as main raw materials.
For example, the patent technology of 'a tundish low-carbon corundum spinel impact brick and a preparation method thereof' (CN103420683A) adopts alumina, white corundum, spinel, alumina micro powder, aluminum powder, titanium dioxide powder, crystalline flake graphite, nano carbon and fused magnesia as main raw materials to prepare the brick, and the technology adopts alumina and white corundum as compact aggregates, so that the heat conductivity coefficient of the product is higher; the interface compatibility of the compact aggregate and the matrix, particularly the non-oxide in the matrix is poor, so that the bonding strength of the aggregate/matrix interface is low; meanwhile, the spinel is difficult to distribute uniformly in the material, so that the strength of the obtained product is limited; meanwhile, neck connection is difficult to form among the compact aggregates, so that the product has poor thermal shock stability.
As for the literature technology (Weixian, et al, development and use of corundum-spinel-carbon unfired nozzle, refractory material, 2000, 34 (4): 217 + 219) the corundum-spinel-carbon unfired nozzle is prepared by taking the fused corundum sand and the high-purity fused spinel as main raw materials, and the technology also adopts the fused corundum sand, etc. as compact aggregate, and the problems of high heat conductivity coefficient, lower bonding strength of the aggregate/substrate interface and uneven distribution of the spinel in the material exist, so that the strength of the obtained product is limited; and the spinel is unevenly distributed in the material, so that the slag resistance and the oxidation resistance of the product are poor.
For another example, the patent technology of "a low-carbon corundum spinel brick for refined steel ladle and its preparation method" (CN101613207A) adopts the electric smelting corundum granules and fine powder, electric smelting magnesite granules and fine powder, electric smelting spinel fine powder and alpha-Al 2 O 3 The micro powder, the aluminum powder, the silicon powder and the like are used as raw materials, and the bonding agent, the superfine graphite and the titanium dioxide are added to prepare the paint. The aggregate adopted by the technology is fused corundum and fused magnesia, which are both compact aggregates, and the problems of high heat conductivity coefficient, low aggregate/matrix interface bonding strength and uneven distribution of spinel in the material also exist, so that the strength is limited.
In summary, the existing corundum-spinel-carbon refractory materials still have some technical defects: (1) the heat conductivity coefficient is increased by the compact raw materials, the heat loss of the molten steel is accelerated, and the energy conservation and emission reduction are not facilitated; (2) the compact aggregate and the matrix, particularly the aggregate and the non-oxide interface in the matrix have poor compatibility and are difficult to sinter, so that the strength and the thermal shock stability are limited; (3) the spinel phase is unevenly distributed in the material, so that the strength, slag resistance and oxidation resistance of the material are limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and aims to provide a preparation method of a lightweight spinel-corundum-carbon refractory material.
In order to achieve the purpose, the invention adopts the technical scheme that:
step 1, preparation of porous spinel-corundum ceramics
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 320-450 ℃ at the speed of 0.5-2.5 ℃/min, preserving the heat for 4-7 h, and naturally cooling to obtain the porous alumina powder with high porosity.
Step 1.2, mixing the porous alumina powder with high porosity and the light-burned magnesite micro powder according to the mass ratio of the porous alumina powder with high porosity to the light-burned magnesite micro powder of 100: 15-25 to obtain a mixture.
And step 1.3, performing mechanical pressing molding on the mixture under the condition of 150-180 MPa, drying the molded blank at the temperature of 110-150 ℃ for 12-24 h, then placing the dried blank in a high-temperature furnace, heating to 1650-1700 ℃ at the speed of 3-5 ℃/min, preserving heat for 3-6 h, and naturally cooling to obtain the porous spinel-corundum ceramic.
The porous spinel-corundum ceramic: the apparent porosity is 25-38%; the bulk density is 2.29-2.85 g/cm 3 (ii) a The average pore diameter is 600 nm-1.5 mu m, the pore diameter distribution is double peaks, the small pore peak is 500-700 nm, and the large pore peak is 1-2.5 mu m; the compressive strength is 65-145 MPa; the porous spinel-corundum ceramic takes corundum and spinel as main crystal phases.
Step 2, preparation of modified porous spinel-corundum ceramic particles
And 2.1, mixing the deionized water and the catalyst according to the mass ratio of the deionized water to the catalyst of 100: 1.5-5.5, and uniformly stirring to obtain a modified solution.
And 2.2, placing the porous spinel-corundum ceramic in a vacuum device according to the mass ratio of 100: 34-39 of the porous spinel-corundum ceramic to the modification solution, vacuumizing to 1.9-2.1 kPa, adding the modification solution, standing for 30-36 min, closing a vacuumizing system, and drying for 24-36 h at the temperature of 110-150 ℃ to obtain the modified porous spinel-corundum ceramic.
And 2.3, crushing and screening the modified porous spinel-corundum ceramic to respectively obtain modified porous spinel-corundum ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous spinel-corundum ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm, modified porous spinel-corundum ceramic particles III with the particle size of less than 1mm and more than or equal to 0.1mm and porous spinel-corundum ceramic fine powder with the particle size of less than 0.088 mm.
Step 3, preparation of lightweight spinel-corundum-carbon refractory material
And 3.1, mixing the liquid thermosetting phenolic resin and the catalyst according to the mass ratio of the liquid thermosetting phenolic resin to the catalyst of 100 to (5-10), and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
And 3.2, taking 15-20 wt% of the modified porous spinel-corundum ceramic particle I, 20-30 wt% of the modified porous spinel-corundum ceramic particle II and 15-20 wt% of the modified porous spinel-corundum ceramic particle III as aggregates, taking 25-35 wt% of porous spinel-corundum ceramic fine powder, 2-5 wt% of simple substance silicon powder and 4-10 wt% of flake graphite as substrates, and taking the sum of the aggregates and the substrates as raw materials.
Firstly, placing the aggregate into a stirrer, uniformly mixing, then adding modified liquid thermosetting phenolic resin accounting for 4-6 wt% of the raw materials, uniformly mixing, then adding the matrix, and uniformly mixing; the method comprises the steps of machine pressing and forming under the condition of 150-200 MPa, heat treatment for 15-36 hours at the temperature of 200-260 ℃, heat preservation for 3-10 hours at the temperature of 1150-1250 ℃ in a carbon burying mode, and natural cooling to obtain the lightweight spinel-corundum-carbon refractory material.
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 64-66 wt%.
The particle 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 or equal to 95 wt%.
The catalyst is ferric nitrate nonahydrate or cobalt nitrate hexahydrate, and the catalyst in the step 2.1 is the same as the catalyst in the step 3.1;
the ferric nitrate nonahydrateMiddle Fe (NO) 3 ) 3 ·9H 2 The content of O is more than 98wt percent, and Co (NO) in the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content is more than 98 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is more than or equal to 40 wt%.
The particle size of the elemental silicon powder is less than 45 mu m; the Si content of the elemental silicon powder is more than or equal to 98 wt%.
The grain size of the crystalline flake graphite is less than 74 mu m; the C content of the crystalline flake graphite is more than or equal to 97 wt%.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
(1) the modified porous spinel-corundum ceramic particles and the porous spinel-corundum fine powder prepared by the method can effectively reduce the heat conductivity coefficient of the product, slow down the heat loss of molten steel and contribute to energy conservation and emission reduction.
According to the invention, three kinds of modified porous spinel-corundum ceramic particles and porous spinel-corundum ceramic fine powder are adopted, porous alumina powder with high porosity is used as a raw material, and the microstructures of the modified porous spinel-corundum ceramic particles and the porous spinel-corundum ceramic fine powder are controlled through light-burned magnesite micro powder and high forming pressure to obtain a micro-nano porous structure, so that the internal pore diameters of the modified porous spinel-corundum ceramic particles and the porous spinel-corundum fine powder are small and uniformly distributed, the heat conductivity coefficient of a product is greatly reduced, the heat loss of molten steel is effectively slowed down, and the energy conservation and emission reduction are facilitated.
(2) According to the invention, the strength and the thermal shock stability of the product are greatly improved by utilizing the micro-nano porous structure and the silicon carbide whiskers and the carbon nano tubes which are specially distributed.
The surface of the aggregate and the matrix adopted by the invention has a large number of micro-nano pores, so that the contact area between the aggregate and the matrix can be increased, the material transmission between the aggregate and the matrix at high temperature is promoted, the interface compatibility between the aggregate and carbon is improved, the formation of a sawtooth occlusion-shaped interface between the aggregate and the matrix is promoted, the combination strength of the sawtooth occlusion-shaped interface formed between the aggregate and the matrix is improved, and the strength of a product is increased.
Secondly, the modified porous spinel-corundum ceramic particles and the porous spinel-corundum ceramic fine powder are internally adhered with a catalyst, so that sites are provided for the formation and growth of the silicon carbide whiskers and the carbon nano tubes in the modified porous spinel-corundum ceramic fine powder, the silicon carbide whiskers and the carbon nano tubes are distributed in the matrix, the silicon carbide whiskers and the carbon nano tubes are also distributed in the aggregate and the interface of the aggregate/matrix, a meshed-interwoven composite reinforced interface structure is formed, and the specially distributed silicon carbide whiskers and the carbon nano tubes further reinforce the meshed-shaped interface of the microparticles and the sawteeth, so that the combination of the interface is tighter, and the strength of the product is further increased.
The aggregate and the matrix adopted by the invention both contain the spinels with uniform distribution and small grain size, so that the product can be reinforced and toughened, and the spinels with uniform distribution can effectively improve the high-temperature strength of the product.
When the product is damaged by thermal stress, on one hand, the silicon carbide whiskers and the carbon nano tubes in a meshed-interwoven shape have higher toughness and can block crack propagation; on the other hand, the micro-nano holes, the silicon carbide whiskers and the carbon nano tubes in the product can absorb thermal stress and prevent the accumulation of strain energy. The composite structure of the micro-nano hole coupled silicon carbide whisker and the carbon nano tube strengthens the thermal shock stability of the product and effectively prevents the damage of thermal stress to the product.
(3) According to the invention, the slag resistance and the oxidation resistance of the product are improved by utilizing the micro-nano holes, the silicon carbide whiskers and the carbon nano tubes which are specially distributed and the spinel which is uniformly distributed.
Firstly, air holes in the product are micro-nano in size, and silicon carbide whiskers and carbon nano tubes which are not wet to molten slag are arranged in the air holes, so that the composite structure effectively prevents the molten slag and air from permeating; even if the silicon carbide whiskers in the air holes are oxidized by air, the oxidation product SiO 2 Will react with Al 2 O 3 Mullite with volume expansion is formed in situ to block pores and prevent oxygen from further permeating, and the smaller the pore diameter of the pores is, the more difficult the permeation of air, slag and the like is. Meanwhile, the aggregate and the matrix interface in the product are combined more tightly, so that the penetration of slag or oxygen along the aggregate/matrix interface is prevented more effectively, and the resistance of the product is improvedSlag properties and oxidation resistance.
Secondly, the aggregate and the matrix prepared by the method contain the aluminum-rich spinel which is uniformly distributed, and the slag resistance of the product can be effectively improved. Because the dissolution rate of the aluminum-rich spinel in the ladle slag is far lower than that of corundum, and the aluminum-rich spinel has strong absorption capacity to FeO and MnO, the slag resistance of the product can be more effectively improved by uniformly distributed spinel.
The lightweight spinel-corundum-carbon refractory material prepared by the invention is detected as follows: the apparent porosity is 23-30%; the bulk density is 2.43-2.68 g/cm 3 (ii) a The breaking strength is 23-36 MPa.
Therefore, the lightweight spinel-corundum-carbon refractory material prepared by the invention has the advantages of low heat conductivity coefficient, high strength, good thermal shock stability, excellent slag resistance and excellent oxidation resistance.
Detailed Description
A lightweight spinel-corundum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of porous spinel-corundum ceramics
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 320-450 ℃ at the speed of 0.5-2.5 ℃/min, preserving the heat for 4-7 h, and naturally cooling to obtain the porous alumina powder with high porosity.
Step 1.2, mixing the porous alumina powder with high porosity and the light-burned magnesite micro powder according to the mass ratio of the porous alumina powder with high porosity to the light-burned magnesite micro powder of 100: 15-25 to obtain a mixture.
And step 1.3, performing mechanical pressing molding on the mixture under the condition of 150-180 MPa, drying the molded blank at the temperature of 110-150 ℃ for 12-24 h, then placing the dried blank in a high-temperature furnace, heating to 1650-1700 ℃ at the speed of 3-5 ℃/min, preserving heat for 3-6 h, and naturally cooling to obtain the porous spinel-corundum ceramic.
The porous spinel-corundum ceramic: the apparent porosity is 25-38%; the bulk density is 2.29-2.85 g/cm 3 (ii) a The average pore diameter is 600 nm-1.5 mu m, and the pore diameterThe distribution is double peaks, the small pore peak is 500-700 nm, and the large pore peak is 1-2.5 μm; the compressive strength is 65-145 MPa; the porous spinel-corundum ceramic takes corundum and spinel as main crystal phases.
Step 2, preparation of modified porous spinel-corundum ceramic particles
And 2.1, mixing the deionized water and the catalyst according to the mass ratio of the deionized water to the catalyst of 100: 1.5-5.5, and uniformly stirring to obtain a modified solution.
And 2.2, placing the porous spinel-corundum ceramic in a vacuum device according to the mass ratio of the porous spinel-corundum ceramic to the modified solution of 100 to (34-39), vacuumizing to 1.9-2.1 kPa, adding the modified solution, standing for 30-36 min, closing a vacuumizing system, and drying for 24-36 h at the temperature of 110-150 ℃ to obtain the modified porous spinel-corundum ceramic.
And 2.3, crushing and screening the modified porous spinel-corundum ceramic to obtain modified porous spinel-corundum ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous spinel-corundum ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm, modified porous spinel-corundum ceramic particles III with the particle size of less than 1mm and more than or equal to 0.1mm and porous spinel-corundum ceramic fine powder with the particle size of less than 0.088 mm.
Step 3, preparation of lightweight spinel-corundum-carbon refractory material
And 3.1, mixing the liquid thermosetting phenolic resin and the catalyst according to the mass ratio of the liquid thermosetting phenolic resin to the catalyst of 100 to (5-10), and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
And 3.2, taking 15-20 wt% of the modified porous spinel-corundum ceramic particle I, 20-30 wt% of the modified porous spinel-corundum ceramic particle II and 15-20 wt% of the modified porous spinel-corundum ceramic particle III as aggregates, taking 25-35 wt% of porous spinel-corundum ceramic fine powder, 2-5 wt% of simple substance silicon powder and 4-10 wt% of flake graphite as substrates, and taking the sum of the aggregates and the substrates as raw materials.
Firstly, placing the aggregate into a stirrer, uniformly mixing, then adding modified liquid thermosetting phenolic resin accounting for 4-6 wt% of the raw materials, uniformly mixing, then adding the matrix, and uniformly mixing; the method comprises the steps of machine pressing and forming under the condition of 150-200 MPa, heat treatment for 15-36 hours at the temperature of 200-260 ℃, heat preservation for 3-10 hours at the temperature of 1150-1250 ℃ in a carbon burying mode, and natural cooling to obtain the lightweight spinel-corundum-carbon refractory material.
Al of the aluminum hydroxide fine powder 2 O 3 The content is 64-66 wt%.
The MgO content of the light-burned magnesite micro powder is more than or equal to 95 wt%.
The catalyst is ferric nitrate nonahydrate or cobalt nitrate hexahydrate.
Fe (NO) in the ferric nitrate nonahydrate 3 ) 3 ·9H 2 The content of O is more than 98wt percent, and Co (NO) in the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content is more than 98 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is more than or equal to 40 wt%.
The Si content of the elemental silicon powder is more than or equal to 98 wt%.
The C content of the crystalline flake graphite is more than or equal to 97 wt%.
In this embodiment:
the particle size of the aluminum hydroxide fine powder is less than 44 mu m;
the particle size of the light-burned magnesite micro powder is less than 2 mu m;
the catalyst in step 2.1 is the same as the catalyst in step 3.1;
the particle size of the elemental silicon powder is less than 45 mu m;
the grain size of the crystalline flake graphite is less than 74 mu m.
The details in the embodiments are not repeated.
Example 1
A lightweight spinel-corundum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of porous spinel-corundum ceramics
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 320 ℃ at the speed of 1.3 ℃/min, preserving heat for 5 hours, and naturally cooling to obtain the porous aluminum oxide powder with high porosity.
Step 1.2, mixing the porous alumina powder with high porosity and the light-burned magnesite micro powder uniformly according to the mass ratio of the porous alumina powder with high porosity to the light-burned magnesite micro powder of 100: 15 to obtain a mixture.
And step 1.3, performing mechanical pressing molding on the mixture under the condition of 150MPa, drying the molded blank for 24 hours at the temperature of 150 ℃, then placing the dried blank in a high-temperature furnace, heating to 1650 ℃ at the speed of 4.3 ℃/min, preserving heat for 3 hours, and naturally cooling to obtain the porous spinel-corundum ceramic.
The porous spinel-corundum ceramic: the apparent porosity is 38%; the bulk density is 2.29g/cm 3 (ii) a The average pore diameter is 1.5 mu m, the pore diameter distribution is bimodal, the small pore peak is 700nm, and the large pore peak is 2.5 mu m; the compressive strength is 65 MPa; the porous spinel-corundum ceramic takes corundum and spinel as main crystal phases.
Step 2, preparation of modified porous spinel-corundum ceramic particles
And 2.1, mixing the deionized water and the catalyst according to the mass ratio of the deionized water to the catalyst of 100: 2.5, and uniformly stirring to obtain a modified solution.
And 2.2, putting the porous spinel-corundum ceramic into a vacuum device according to the mass ratio of the porous spinel-corundum ceramic to the modified solution of 100: 34, vacuumizing to 1.9kPa, adding the modified solution, standing for 34min, closing a vacuumizing system, and drying for 33h at the temperature of 110 ℃ to obtain the modified porous spinel-corundum ceramic.
And 2.3, crushing and screening the modified porous spinel-corundum ceramic to respectively obtain modified porous spinel-corundum ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous spinel-corundum ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm, modified porous spinel-corundum ceramic particles III with the particle size of less than 1mm and more than or equal to 0.1mm and porous spinel-corundum ceramic fine powder with the particle size of less than 0.088 mm.
Step 3, preparation of lightweight spinel-corundum-carbon refractory material
And 3.1, mixing the liquid thermosetting phenolic resin and the catalyst according to the mass ratio of the liquid thermosetting phenolic resin to the catalyst of 100: 10, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
And 3.2, taking 15.2 wt% of the modified porous spinel-corundum ceramic particle I, 27.2 wt% of the modified porous spinel-corundum ceramic particle II and 17.3 wt% of the modified porous spinel-corundum ceramic particle III as aggregates, taking 29.9 wt% of porous spinel-corundum ceramic fine powder, 3.7 wt% of simple substance silicon powder and 6.7 wt% of flake graphite as substrates, and taking the sum of the aggregates and the substrates as raw materials.
Firstly, placing the aggregate in a stirrer, uniformly mixing, then adding modified liquid thermosetting phenolic resin accounting for 4.1 wt% of the raw materials, uniformly mixing, then adding the matrix, and uniformly mixing; mechanically pressing and molding under 188MPa, performing heat treatment at 240 ℃ for 22 hours, then preserving heat for 4 hours under the conditions of carbon burying and 1150 ℃, and naturally cooling to obtain the lightweight spinel-corundum-carbon refractory material.
Al of the aluminum hydroxide fine powder 2 O 3 The content was 64.2 wt%.
The MgO content of the light-burned magnesite micro powder is 95.2 wt%.
The catalyst is ferric nitrate nonahydrate; fe (NO) in the ferric nitrate nonahydrate 3 ) 3 ·9H 2 The O content was 98.2 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 40.6 wt%.
The Si content of the elemental silicon powder is 98.6 wt%.
The C content of the flake graphite is 97.3 wt%.
The lightweight spinel-corundum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 29.8%; the bulk density is 2.46g/cm 3 (ii) a The breaking strength is 23.2 MPa.
Example 2
A lightweight spinel-corundum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of porous spinel-corundum ceramics
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 360 ℃ at the speed of 0.5 ℃/min, preserving heat for 6 hours, and naturally cooling to obtain the porous aluminum oxide powder with high porosity.
Step 1.2, mixing materials according to the mass ratio of the porous alumina powder with high porosity to the light-burned magnesite micro powder of 100: 18, and uniformly mixing the porous alumina powder with high porosity and the light-burned magnesite micro powder to obtain a mixture.
And step 1.3, performing machine pressing molding on the mixture under the condition of 160MPa, drying the molded blank for 21 hours at the temperature of 110 ℃, then placing the dried blank in a high-temperature furnace, heating to 1660 ℃ at the speed of 3.7 ℃/min, preserving heat for 5 hours, and naturally cooling to obtain the porous spinel-corundum ceramic.
The porous spinel-corundum ceramic: the apparent porosity is 32%; the bulk density is 2.5g/cm 3 (ii) a The average pore diameter is 880nm, the pore diameter distribution is double peaks, the small pore peak is 650nm, and the large pore peak is 2 μm; the compressive strength is 97 MPa; the porous spinel-corundum ceramic takes corundum and spinel as main crystal phases.
Step 2, preparation of modified porous spinel-corundum ceramic particles
And 2.1, mixing the deionized water and the catalyst according to the mass ratio of the deionized water to the catalyst of 100: 5.5, and uniformly stirring to obtain a modified solution.
And 2.2, placing the porous spinel-corundum ceramic in a vacuum device according to the mass ratio of 100: 35.5 of the porous spinel-corundum ceramic to the modified solution, vacuumizing to 2kPa, adding the modified solution, standing for 30min, closing a vacuumizing system, and drying for 29h at 120 ℃ to obtain the modified porous spinel-corundum ceramic.
And 2.3, crushing and screening the modified porous spinel-corundum ceramic to obtain modified porous spinel-corundum ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous spinel-corundum ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm, modified porous spinel-corundum ceramic particles III with the particle size of less than 1mm and more than or equal to 0.1mm and porous spinel-corundum ceramic fine powder with the particle size of less than 0.088 mm.
Step 3, preparation of lightweight spinel-corundum-carbon refractory material
And 3.1, mixing the liquid thermosetting phenolic resin and the catalyst according to the mass ratio of the liquid thermosetting phenolic resin to the catalyst of 100: 5, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
And 3.2, taking 16.1 wt% of the modified porous spinel-corundum ceramic particle I, 30wt% of the modified porous spinel-corundum ceramic particle II and 19.8 wt% of the modified porous spinel-corundum ceramic particle III as aggregates, taking 25 wt% of porous spinel-corundum ceramic fine powder, 4.9 wt% of simple substance silicon powder and 4.2 wt% of crystalline flake graphite as substrates, and taking the sum of the aggregates and the substrates as raw materials.
Firstly, placing the aggregate in a stirrer, uniformly mixing, then adding modified liquid thermosetting phenolic resin accounting for 5.4 wt% of the raw materials, uniformly mixing, then adding the matrix, and uniformly mixing; and (3) performing mechanical pressing forming under the condition of 165MPa, performing heat treatment for 15 hours at the temperature of 260 ℃, then performing heat preservation for 6 hours under the conditions of carbon burying and 1185 ℃, and naturally cooling to obtain the lightweight spinel-corundum-carbon refractory material.
Al of the aluminum hydroxide fine powder 2 O 3 The content was 65.1 wt%.
The MgO content of the light-burned magnesite micro powder is 95.7 wt%.
The catalyst is cobalt nitrate hexahydrate; co (NO) in the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.2 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 40.4 wt%.
The Si content of the elemental silicon powder is 98.3 wt%.
The C content of the flake graphite is 97.1 wt%.
The lightweight spinel-corundum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 27.9%; the bulk density is 2.53g/cm 3 (ii) a The breaking strength was 26.7 MPa.
Example 3
A lightweight spinel-corundum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of porous spinel-corundum ceramics
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 450 ℃ at the speed of 2 ℃/min, preserving heat for 4 hours, and naturally cooling to obtain the porous aluminum oxide powder with high porosity.
Step 1.2, mixing the porous alumina powder with high porosity and the light-burned magnesite micro powder uniformly according to the mass ratio of the porous alumina powder with high porosity to the light-burned magnesite micro powder of 100: 22 to obtain a mixture.
And step 1.3, performing mechanical pressing molding on the mixture under the condition of 170MPa, drying the molded blank at 125 ℃ for 17 hours, then placing the dried blank in a high-temperature furnace, heating to 1680 ℃ at the speed of 3 ℃/min, preserving heat for 4 hours, and naturally cooling to obtain the porous spinel-corundum ceramic.
The porous spinel-corundum ceramic: the apparent porosity is 28%; the bulk density is 2.7g/cm 3 (ii) a The average pore diameter is 670nm, the pore diameter distribution is double peaks, the small pore peak is 620nm, and the large pore peak is 1.3 μm; the compressive strength is 127 MPa; the porous spinel-corundum ceramic takes corundum and spinel as main crystal phases.
Step 2, preparation of modified porous spinel-corundum ceramic particles
And 2.1, mixing the deionized water and the catalyst according to the mass ratio of the deionized water to the catalyst of 100: 3.8, and uniformly stirring to obtain a modified solution.
And 2.2, placing the porous spinel-corundum ceramic in a vacuum device according to the mass ratio of 100: 37 of the porous spinel-corundum ceramic to the modified solution, vacuumizing to 2kPa, adding the modified solution, standing for 36min, closing a vacuumizing system, and drying for 24h at 135 ℃ to obtain the modified porous spinel-corundum ceramic.
And 2.3, crushing and screening the modified porous spinel-corundum ceramic to obtain modified porous spinel-corundum ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous spinel-corundum ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm, modified porous spinel-corundum ceramic particles III with the particle size of less than 1mm and more than or equal to 0.1mm and porous spinel-corundum ceramic fine powder with the particle size of less than 0.088 mm.
Step 3, preparation of lightweight spinel-corundum-carbon refractory material
And 3.1, mixing the liquid thermosetting phenolic resin and the catalyst according to the mass ratio of the liquid thermosetting phenolic resin to the catalyst of 100: 7, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
And 3.2, taking 17.5 wt% of the modified porous spinel-corundum ceramic particle I, 23 wt% of the modified porous spinel-corundum ceramic particle II and 15.2 wt% of the modified porous spinel-corundum ceramic particle III as aggregates, taking 31.5 wt% of the porous spinel-corundum ceramic fine powder, 3 wt% of simple substance silicon powder and 9.8 wt% of crystalline flake graphite as substrates, and taking the sum of the aggregates and the substrates as raw materials.
Firstly, placing the aggregate in a stirrer, uniformly mixing, then adding modified liquid thermosetting phenolic resin accounting for 6wt% of the raw materials, uniformly mixing, then adding the matrix, and uniformly mixing; performing mechanical pressing under the condition of 150MPa, performing heat treatment at 225 ℃ for 29 hours, then performing heat preservation under the conditions of carbon burying and 1250 ℃ for 10 hours, and naturally cooling to obtain the lightweight spinel-corundum-carbon refractory material.
Al of the aluminum hydroxide fine powder 2 O 3 The content was 64.8 wt%.
The MgO content of the light-burned magnesite micro powder is 95.4 wt%.
The catalyst is ferric nitrate nonahydrate; in the ferric nitrate nonahydrateFe(NO 3 ) 3 ·9H 2 The O content was 98.1 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 40.2 wt%.
The Si content of the elemental silicon powder is 98.5 wt%.
The C content of the crystalline flake graphite is 97.5 wt%.
The lightweight spinel-corundum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 25.2%; the bulk density is 2.58g/cm 3 (ii) a The breaking strength is 32.5 MPa.
Example 4
A lightweight spinel-corundum-carbon refractory material and a preparation method thereof. The preparation method of the embodiment comprises the following steps:
step 1, preparation of porous spinel-corundum ceramics
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 400 ℃ at the speed of 2.5 ℃/min, preserving heat for 7 hours, and naturally cooling to obtain the porous aluminum oxide powder with high porosity.
Step 1.2, mixing the porous alumina powder with high porosity and the light-burned magnesite micro powder uniformly according to the mass ratio of the porous alumina powder with high porosity to the light-burned magnesite micro powder of 100: 25 to obtain a mixture.
And step 1.3, performing mechanical pressing molding on the mixture under the condition of 180MPa, drying the molded blank at 140 ℃ for 12 hours, then placing the dried blank in a high-temperature furnace, heating to 1700 ℃ at the speed of 5 ℃/min, preserving heat for 6 hours, and naturally cooling to obtain the porous spinel-corundum ceramic.
The porous spinel-corundum ceramic: the apparent porosity is 25%; the bulk density is 2.85g/cm 3 (ii) a The average pore diameter is 600nm, the pore diameter distribution is double peaks, the small pore peak is 500nm, and the large pore peak is 1 μm; the compressive strength is 145 MPa; the porous spinel-corundum ceramic takes corundum and spinel as main crystal phases.
Step 2, preparation of modified porous spinel-corundum ceramic particles
And 2.1, mixing the deionized water and the catalyst according to the mass ratio of the deionized water to the catalyst of 100: 1.5, and uniformly stirring to obtain a modified solution.
And 2.2, putting the porous spinel-corundum ceramic into a vacuum device according to the mass ratio of the porous spinel-corundum ceramic to the modified solution of 100: 39, vacuumizing to 2.1kPa, adding the modified solution, standing for 32min, closing a vacuumizing system, and drying for 36h at 150 ℃ to obtain the modified porous spinel-corundum ceramic.
And 2.3, crushing and screening the modified porous spinel-corundum ceramic to respectively obtain modified porous spinel-corundum ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous spinel-corundum ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm, modified porous spinel-corundum ceramic particles III with the particle size of less than 1mm and more than or equal to 0.1mm and porous spinel-corundum ceramic fine powder with the particle size of less than 0.088 mm.
Step 3, preparation of lightweight spinel-corundum-carbon refractory material
And 3.1, mixing the liquid thermosetting phenolic resin and the catalyst according to the mass ratio of the liquid thermosetting phenolic resin to the catalyst of 100: 8, and uniformly stirring to obtain the modified liquid thermosetting phenolic resin.
And 3.2, taking 19.9 wt% of the modified porous spinel-corundum ceramic particle I, 20wt% of the modified porous spinel-corundum ceramic particle II and 15.8 wt% of the modified porous spinel-corundum ceramic particle III as aggregate, taking 35wt% of the porous spinel-corundum ceramic fine powder, 2.1 wt% of simple substance silicon powder and 7.2 wt% of crystalline flake graphite as matrix, and taking the sum of the aggregate and the matrix as raw materials.
Firstly, placing the aggregate in a stirrer, uniformly mixing, then adding modified liquid thermosetting phenolic resin accounting for 4.8 wt% of the raw materials, uniformly mixing, then adding the matrix, and uniformly mixing; mechanically pressing and molding under the condition of 200MPa, then carrying out heat treatment for 36 hours at the temperature of 200 ℃, then carrying out heat preservation for 3 hours under the conditions of carbon burying and 1215 ℃, and naturally cooling to obtain the lightweight spinel-corundum-carbon refractory material.
Al of the aluminum hydroxide fine powder 2 O 3 The content was 65.8 wt%.
The MgO content of the light-burned magnesite micro powder is 95.5 wt%.
The catalyst is cobalt nitrate hexahydrate; co (NO) in the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content was 98.2 wt%.
The carbon residue rate of the liquid thermosetting phenolic resin is 40.7 wt%.
The Si content of the elemental silicon powder is 98.2 wt%.
The C content of the flake graphite is 97.3 wt%.
The lightweight spinel-corundum-carbon refractory material prepared in the embodiment is detected as follows: the apparent porosity is 23.1%; the bulk density is 2.66g/cm 3 (ii) a The breaking strength was 35.7 MPa.
Compared with the prior art, the specific implementation mode has the following positive effects:
(1) the modified porous spinel-corundum ceramic particles and the porous spinel-corundum fine powder are prepared by the specific embodiment, so that the heat conductivity coefficient of the product can be effectively reduced, the heat loss of molten steel is reduced, and the energy conservation and emission reduction are facilitated.
The three modified porous spinel-corundum ceramic particles and the porous spinel-corundum ceramic fine powder adopted by the specific embodiment are all prepared by taking porous alumina powder with high porosity as a raw material, and controlling the microstructures of the modified porous spinel-corundum ceramic particles and the porous spinel-corundum ceramic fine powder through light-burned magnesite micro powder and high forming pressure to obtain a micro-nano porous structure, so that the internal pore diameters of the modified porous spinel-corundum ceramic particles and the porous spinel-corundum fine powder are small and uniformly distributed, the heat conductivity coefficient of a product is greatly reduced, the heat loss of molten steel is effectively slowed down, and energy conservation and emission reduction are facilitated.
(2) According to the specific embodiment, the strength and the thermal shock stability of the product are greatly improved by utilizing the micro-nano porous structure and the silicon carbide whiskers and the carbon nano tubes which are specially distributed.
The surface of the aggregate and the matrix adopted by the embodiment has a large number of micro-nano pores, so that the contact area between the aggregate and the matrix can be increased, the material transmission between the aggregate and the matrix at high temperature is promoted, the interface compatibility between the aggregate and carbon is improved, the formation of a sawtooth occlusion-shaped interface between the aggregate and the matrix is promoted, the combination strength of the sawtooth occlusion-shaped interface formed between the aggregate and the matrix is improved, and the strength of a product is increased.
Secondly, the modified porous spinel-corundum ceramic particles and the porous spinel-corundum ceramic fine powder adopted by the specific embodiment are internally adhered with a catalyst, so that sites are provided for the formation and growth of the silicon carbide whiskers and the carbon nanotubes in the silicon carbide ceramic fine powder, the silicon carbide whiskers and the carbon nanotubes are distributed in the matrix, the silicon carbide whiskers and the carbon nanotubes are also distributed in the aggregate and the interface of the aggregate/matrix, a meshing-interweaved composite enhanced interface structure is formed, and the specially distributed silicon carbide whiskers and the carbon nanotubes further enhance the meshing-shaped interface of the microparticles and the sawteeth, so that the interface is bonded more tightly, and the strength of the product is further increased.
The aggregate and the matrix adopted by the embodiment both contain spinels with uniform distribution and small grain size, so that the product can be reinforced and toughened, and the spinels with uniform distribution can effectively improve the high-temperature strength of the product.
When the product of the specific embodiment is damaged by thermal stress, on one hand, the silicon carbide whiskers and the carbon nano tubes in the occlusion-interweaving state have higher toughness and can block crack propagation; on the other hand, the micro-nano holes, the silicon carbide whiskers and the carbon nano tubes in the product can absorb thermal stress and prevent the accumulation of strain energy. The composite structure of the micro-nano hole coupled silicon carbide whisker and the carbon nano tube strengthens the thermal shock stability of the product and effectively prevents the damage of thermal stress to the product.
(3) According to the specific embodiment, the slag resistance and the oxidation resistance of the product are improved by utilizing the micro-nano holes, the silicon carbide whiskers and the carbon nano tubes which are specially distributed and the spinels which are uniformly distributed.
Firstly, the air holes in the product of the embodiment are in micro-nano size, and the silicon carbide whiskers and the carbon nano tubes which are not wet to the slag are arranged in the air holes, so that the composite structure effectively prevents the slag and the air from permeating; even in the air holeWhen the silicon carbide crystal whisker is oxidized by air, the oxidation product SiO 2 Will react with Al 2 O 3 Mullite with volume expansion is formed in situ to block air holes and prevent oxygen from further permeating, and the smaller the pore diameter of the air holes is, the more difficult the permeation of air, slag and the like is. Meanwhile, the aggregate and the matrix interface in the product of the embodiment are combined more tightly, thereby more effectively preventing slag or oxygen from permeating along the aggregate/matrix interface and improving the slag resistance and the oxidation resistance of the product.
Secondly, the aggregate and the matrix prepared by the embodiment contain the aluminum-rich spinel which is uniformly distributed, and the slag resistance of the product can be effectively improved. Because the dissolution rate of the aluminum-rich spinel in the ladle slag is far lower than that of corundum, and the aluminum-rich spinel has strong absorption capacity to FeO and MnO, the slag resistance of the product can be more effectively improved by uniformly distributed spinel.
The lightweight spinel-corundum-carbon refractory material prepared by the specific embodiment is detected as follows: the apparent porosity is 23-30%; the bulk density is 2.43-2.68 g/cm 3 (ii) a The breaking strength is 23-36 MPa.
Therefore, the lightweight spinel-corundum-carbon refractory material prepared by the specific embodiment has the advantages of low thermal conductivity, high strength, good thermal shock stability, excellent slag resistance and excellent oxidation resistance.
Claims (7)
1. A preparation method of a lightweight spinel-corundum-carbon refractory material is characterized by comprising the following steps:
step 1, preparation of porous spinel-corundum ceramics
Step 1.1, placing the fine aluminum hydroxide powder in a high-temperature furnace, heating to 320-450 ℃ at the speed of 0.5-2.5 ℃/min, preserving the heat for 4-7 h, and naturally cooling to obtain porous alumina powder with high porosity;
step 1.2, mixing the porous alumina powder with high porosity and the light-burned magnesite micro powder according to the mass ratio of the porous alumina powder with high porosity to the light-burned magnesite micro powder of 100: 15-25 to obtain a mixture;
step 1.3, performing mechanical pressing molding on the mixture under the condition of 150-180 MPa, drying the molded blank at 110-150 ℃ for 12-24 h, then placing the dried blank in a high-temperature furnace, heating to 1650-1700 ℃ at the speed of 3-5 ℃/min, preserving heat for 3-6 h, and naturally cooling to obtain porous spinel-corundum ceramic;
the porous spinel-corundum ceramic: an apparent porosity of 25 to 38% and a bulk density of 2.29 to 2.85g/cm 3 The average pore diameter is 600 nm-1.5 mu m, the pore diameter distribution is double peaks, the small pore peak is 500-700 nm, the large pore peak is 1-2.5 mu m, and the compressive strength is 65-145 MPa; the porous spinel-corundum ceramic takes corundum and spinel as main crystal phases;
step 2, preparation of modified porous spinel-corundum ceramic particles
Step 2.1, mixing deionized water and a catalyst according to the mass ratio of the deionized water to the catalyst of 100: 1.5-5.5, and uniformly stirring to obtain a modified solution;
step 2.2, placing the porous spinel-corundum ceramic in a vacuum device according to the mass ratio of the porous spinel-corundum ceramic to the modified solution of 100 to (34-39), vacuumizing to 1.9-2.1 kPa, adding the modified solution, standing for 30-36 min, closing a vacuumizing system, and drying for 24-36 h at the temperature of 110-150 ℃ to obtain the modified porous spinel-corundum ceramic;
step 2.3, crushing and screening the modified porous spinel-corundum ceramics to respectively obtain modified porous spinel-corundum ceramic particles I with the particle size of less than 5mm and more than or equal to 3mm, modified porous spinel-corundum ceramic particles II with the particle size of less than 3mm and more than or equal to 1mm, modified porous spinel-corundum ceramic particles III with the particle size of less than 1mm and more than or equal to 0.1mm and modified porous spinel-corundum ceramic fine powder with the particle size of less than 0.088 mm;
step 3, preparation of lightweight spinel-corundum-carbon refractory material
3.1, mixing the liquid thermosetting phenolic resin and the catalyst according to the mass ratio of the liquid thermosetting phenolic resin to the catalyst of 100 to (5-10), and uniformly stirring to obtain modified liquid thermosetting phenolic resin;
step 3.2, taking 15-20 wt% of the modified porous spinel-corundum ceramic particles I, 20-30 wt% of the modified porous spinel-corundum ceramic particles II and 15-20 wt% of the modified porous spinel-corundum ceramic particles III as aggregates, taking 25-35 wt% of the modified porous spinel-corundum ceramic fine powder, 2-5 wt% of elemental silicon powder and 4-10 wt% of flake graphite as substrates, and taking the sum of the aggregates and the substrates as raw materials;
putting the aggregate into a stirrer, uniformly mixing, adding modified liquid thermosetting phenolic resin accounting for 4-6 wt% of the raw materials, uniformly mixing, adding the matrix, and uniformly mixing; performing mechanical pressing forming under the condition of 150-200 MPa, performing heat treatment for 15-36 hours at the temperature of 200-260 ℃, then performing heat preservation for 3-10 hours under the conditions of carbon burying and 1150-1250 ℃, and naturally cooling to obtain the lightweight spinel-corundum-carbon refractory material;
the catalyst is ferric nitrate nonahydrate or cobalt nitrate hexahydrate, and the catalyst in the step 2.1 is the same as the catalyst in the step 3.1; fe (NO) in the ferric nitrate nonahydrate 3 ) 3 ·9H 2 The content of O is more than 98wt percent, and Co (NO) in the cobalt nitrate hexahydrate 3 ) 2 ·6H 2 The O content is more than 98 wt%.
2. The method of producing a lightweight spinel-corundum-carbon refractory according to claim 1, wherein the particle size of said fine aluminum hydroxide powder is less than 44 μm; al of the aluminum hydroxide fine powder 2 O 3 The content is 64-66 wt%.
3. The method of preparing a lightweight spinel-corundum-carbon refractory according to claim 1, wherein the particle size of the light-burned magnesite micropowder is < 2 μm; the MgO content of the light-burned magnesite micro powder is more than or equal to 95 wt%.
4. The method for preparing a lightweight spinel-corundum-carbon refractory according to claim 1, wherein the liquid thermosetting phenolic resin has a carbon residue ratio of not less than 40 wt%.
5. The method for preparing the lightweight spinel-corundum-carbon refractory according to claim 1, wherein the particle size of the elemental silicon powder is less than 45 μm; the Si content of the elemental silicon powder is more than or equal to 98 wt%.
6. The method of preparing a lightweight spinel-corundum-carbon refractory according to claim 1, characterized in that the particle size of said crystalline flake graphite is < 74 μm; the C content of the crystalline flake graphite is more than or equal to 97 wt%.
7. A lightweight spinel-corundum-carbon refractory, characterized in that the lightweight spinel-corundum-carbon refractory is prepared by the method for preparing a lightweight spinel-corundum-carbon refractory according to any one of claims 1 to 6.
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