CN116730732A - Low-pollution long nozzle body material - Google Patents
Low-pollution long nozzle body material Download PDFInfo
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- CN116730732A CN116730732A CN202310874756.8A CN202310874756A CN116730732A CN 116730732 A CN116730732 A CN 116730732A CN 202310874756 A CN202310874756 A CN 202310874756A CN 116730732 A CN116730732 A CN 116730732A
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 65
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005011 phenolic resin Substances 0.000 claims abstract description 26
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 26
- 239000011029 spinel Substances 0.000 claims abstract description 23
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 23
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 9
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 7
- 239000010439 graphite Substances 0.000 claims abstract description 7
- 239000013590 bulk material Substances 0.000 claims abstract description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 21
- 239000001095 magnesium carbonate Substances 0.000 claims description 20
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 20
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 20
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 7
- 238000000713 high-energy ball milling Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000010431 corundum Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 abstract description 13
- 239000010959 steel Substances 0.000 abstract description 13
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000011819 refractory material Substances 0.000 abstract description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 15
- 238000005303 weighing Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000009749 continuous casting Methods 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
- 238000001035 drying Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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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- 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
- C04B35/44—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 aluminates
- C04B35/443—Magnesium aluminate spinel
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- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Abstract
The invention belongs to the technical field of refractory materials, and relates to a low-pollution long nozzle body material. The related raw material composition and mass percent of the low-pollution long nozzle body material are as follows: 20-40% of spinel hollow sphere, 10-20% of sintered magnesia-alumina spinel, 15-30% of composite powder, 2-5% of Carbores P, 15-25% of crystalline flake graphite and 3-5% of aluminum-magnesium alloy powder; the combination system of the low-pollution light-weight bulk material is phenolic resin powder, lithium carbonate and furfural; the addition amount of the phenolic resin powder is 6-10% of the total mass of the raw materials of the materials; the addition amount of the furfural is 120-140% of the weight of the phenolic resin powder; the lithium carbonate accounts for 2 to 4 percent of the mass of the phenolic resin powder. The invention avoids the pollution of silicon to molten steel, and reduces the heat loss when the molten steel flows through the long nozzle due to low heat conductivity coefficient.
Description
Technical Field
The invention belongs to the technical field of refractory materials, and mainly relates to a low-pollution long nozzle body material.
Background
In the continuous casting process, the long water gap is an important functional element, can well play a role in preventing secondary oxidation and slag rolling of molten steel, and has direct or indirect connection with the pollution of the molten steel of the tundish, for example, in order to ensure the stability of a flow field of the tundish and the quality of the molten steel, the long water gap immersion type casting becomes an important production measure of the continuous casting process; recently, the long nozzle is continuously upgraded in the aspects of material performance, preparation process, application operation and the like, and the development and application of the novel long nozzle, especially the horn-shaped long nozzle, well realize immersion type casting, and are beneficial to molten steel quality; however, compared with the original straight-tube long nozzle, the horn-shaped long nozzle has the advantages that the weight is obviously increased, the labor intensity is increased in the process of hoisting and carrying, and the operation is difficult.
The traditional long nozzle body material is introduced into fused quartz SiO 2 Although the weight can be reduced, the addition of a large amount causes cristobalite, and the performance of the nozzle material is deteriorated. Mullite is introduced to reduce the weight to a certain extent, but the mullite is desilicated at high temperature, and silicon diffuses into molten steel to pollute the molten steel. Therefore, the silica material is introduced into the lightweight long nozzle, so that the density can be reduced to achieve the purpose of weight reduction, but the molten steel is easy to be polluted.
Disclosure of Invention
The invention aims to provide a low-pollution long nozzle body material, which can realize the weight reduction of a long nozzle, reduce the introduction and use of siliceous materials, can not pollute molten steel in the use process, and is beneficial to the quality of molten steel.
The invention adopts the following technical scheme for accomplishing the purposes:
the low-pollution long nozzle body material comprises the following raw materials in percentage by mass: 20-40% of spinel hollow sphere, 10-20% of sintered magnesia-alumina spinel, 15-30% of composite powder, 2-5% of Carbores P, 15-25% of crystalline flake graphite and 3-5% of aluminum-magnesium alloy powder; the combination system of the low-pollution light-weight bulk material is phenolic resin powder, lithium carbonate and furfural; the addition amount of the phenolic resin powder is 6-10% of the total mass of the raw materials of the materials; the addition amount of the furfural is 120-140% of the mass of the phenolic resin powder; the lithium carbonate accounts for 2 to 4 percent of the mass of the phenolic resin powder.
The spinel hollow sphere is prepared by an electrofusion method, and has the volume density of 0.4-0.8 g/cm 3 The surface of the glass is pre-coated with a layer of PVA with the thickness of 3-5 mu m.
The surface of the sintered magnesia-alumina spinel is pre-coated with a layer of PVA with the thickness of 2-3 mu m.
The composite powder is aluminum hydroxide coated magnesite powder, and the composite powder of aluminum hydroxide and magnesite is prepared by a high-energy ball milling method to be used as a precursor, wherein the precursor is mainly characterized in that the aluminum hydroxide is coated with magnesite, wherein the aluminum hydroxide is less than 5 mu m, the magnesite is less than 0.088mm, and the ratio of the aluminum hydroxide to the magnesite is 3:1, the preparation method adopts a high-energy ball milling process to prepare, and aluminum hydroxide micropowder, magnesite powder and corundum grinding balls are added into a ball milling tank, wherein the mass ratio of the mixed powder to the grinding balls is 1:5-8; high-energy ball milling is carried out for 2 to 5 hours at the speed of 300 to 500 revolutions per minute to obtain composite powder of aluminum hydroxide coated magnesite powder; the preparation principle of the composite powder is as follows: under the high-energy mechanical acting force, the particle surface becomes more irregular under the physical impact of a grinding medium, a plurality of defect positions also exist on the particle surface, aluminum hydroxide micropowder is easy to adhere to the surface of ceramic particles due to the high specific surface area and high activation energy, meanwhile, aluminum powder in the mixture obtains energy due to the grinding and impact effects of grinding balls, when the energy is large enough, the surface of the powder can be activated, and at the moment, the aluminum hydroxide micropowder is adsorbed on the activation positions on the surface of the magnesite powder, and the obtained powder needs to pass through 0.2mm sieve holes.
The aluminum magnesium alloy powder comprises the following components: mg=3: 1 mass ratio, alloy powder is less than 0.088mm.
The specific preparation method of the invention comprises the following steps: mixing the materials in a high-speed mixer, drying the blank, controlling proper volatile matters, taking the blank as the blank of the part in the process of preparing the horn-shaped long nozzle, carrying out static pressure molding under 30-50 MPa, maintaining the pressure for 1-5 minutes, and curing the blank to obtain the heat treatment atmosphere of N 2 Heat treatment is carried out at 800-1000 ℃ and the temperature is kept for 1-3 hours.
The low-pollution long nozzle body material provided by the invention does not introduce siliceous materials, so that the pollution of silicon to molten steel is avoided; the technology reduces the heat conductivity coefficient of the long nozzle body material so as to reduce the heat loss when the steel liquid flows through the long nozzle; the coating technology is adopted to reduce the thermal expansion coefficient and the in-situ spinel reaction, so that the mechanical property and the thermal shock resistance of the material are improved, the coating technology has obvious innovation, and meanwhile, the application prospect is wide;
in the heat treatment process, a layer of PVA coated on the surfaces of spinel hollow spheres and sintering spinel fine particles volatilizes to leave gaps (stress generated by self-expansion can be relieved when thermal shock is received), so that the thermal shock resistance of the material can be improved.
In the heat treatment process, aluminum hydroxide can be formed into gamma-type aluminum oxide in the heat treatment process, and magnesite powder can be decomposed into magnesium oxide, so that more micropores can be formed in the matrix, the thermal expansion of the material can be reduced, and the thermal shock stability of the material can be improved; the structure of alumina coated magnesia is formed, and the magnesia has higher activity, but the alumina can inhibit the reaction between magnesia and external matters; particularly, under the field service condition, the spinel reaction generated by the composite powder can improve the mechanical property of the material, and meanwhile, the porous structure formed by the coating structure can relieve the volume effect generated by the spinel.
The lithium carbonate contained in the binding system can reduce the graphitization transition temperature of the phenolic resin and improve the graphitization degree, so that the oxidation resistance of the binding phase is improved, and simultaneously, the introduced high-temperature asphalt carbon P is carbonized at high temperature to form amorphous carbon, so that the thermal expansion coefficient of the material can be reduced, and the mechanical property of the material can be improved; the long water gap is usually recycled for 4-8 times, so that the mechanical property of the long water gap is reduced to a certain extent after each use, particularly the body part serving as a structural support is easy to crack or break.
Description of the embodiments
The invention will be described in detail with reference to specific examples:
examples
The mass ratio of the low-pollution long nozzle body material is as follows: 40 percent of electric melting spinel hollow sphere coated with PVA (< 1 mm); 10% (< 0.2 mm) of sintered magnesia alumina spinel coated with PVA; 20 percent of composite powder of magnesite powder coated by aluminum hydroxide micropowder (< 0.2 mm); carbores P2% (< 0.074 mm); 3 percent of aluminum magnesium alloy powder is less than 0.088 mm); flake graphite 25% (< 0.088 mm).
Firstly weighing solid raw materials according to the proportion, then weighing phenolic resin powder accounting for 12% of the total mass of the raw materials, lithium carbonate accounting for 4% of the total mass of the phenolic resin powder and furfural accounting for 14% of the total mass of the phenolic resin powder, mixing for 10min in a high-speed mixer, mixing for 5min again, drying the blank, pouring into a mould, forming in an isostatic press, maintaining the pressure at the maximum of 30MPa and 5 min. After demoulding, the blank is cured and then heat treated, wherein the atmosphere is N 2 Preserving heat for 3 hours at 800 ℃ to obtain the long nozzle.
Examples
The mass ratio of the low-pollution long nozzle body material is as follows: 30 percent (less than 1 mm) of electric melting spinel hollow sphere coated with PVA; 10% (< 0.2 mm) of sintered magnesia alumina spinel coated with PVA; 30 percent of aluminum hydroxide micropowder coated magnesite powder composite powder (less than 0.2 mm); carbores P5% (< 0.074 mm); aluminum magnesium alloy powder 5% < 0.088 mm); flake graphite 20% (< 0.088 mm).
Firstly weighing solid raw materials according to the proportion, then weighing phenolic resin powder accounting for 10 percent of the total mass of the raw materials, lithium carbonate accounting for 2 percent of the total mass of the phenolic resin powder and furfural accounting for 13 percent of the total mass of the phenolic resin powder, mixing for 10min in a high-speed mixer, mixing for 5min again, pouring the dried blank into a mould, forming in an isostatic press, maintaining the pressure at 40MPa at the maximum and 3 min. After demoulding, the blank is cured and then heat treated, wherein the atmosphere is N 2 Preserving heat for 2 hours at 900 ℃ to obtain the long nozzle.
Examples
The mass ratio of the low-pollution long nozzle body material is as follows: 38 percent (less than 1 mm) of electric melting spinel hollow sphere coated with PVA; 14% (< 0.2 mm) of sintered magnesia alumina spinel coated with PVA; 25 percent of composite powder of aluminum hydroxide micropowder coated magnesite powder (< 0.2 mm); carbores P4% (< 0.074 mm); aluminum magnesium alloy powder 4% < 0.088 mm); flake graphite 25% (< 0.088 mm).
Firstly weighing solid raw materials according to the proportion, then weighing phenolic resin powder accounting for 8 percent of the total mass of the raw materials, lithium carbonate accounting for 3 percent of the total mass of the phenolic resin powder and furfural accounting for 12 percent of the total mass of the phenolic resin powder, mixing for 10min in a high-speed mixer, mixing for 5min again, pouring the dried blank into a mould, forming in an isostatic press, maintaining the pressure at 50MPa at the maximum and 1 min. After demoulding, the blank is cured and then heat treated, wherein the atmosphere is N 2 Preserving heat for 1 hour at 1000 ℃ to obtain the long nozzle.
Examples
The mass ratio of the low-pollution long nozzle body material is as follows: 40 percent of electric melting spinel hollow sphere coated with PVA (< 1 mm); 18% (< 0.2 mm) of sintered magnesia alumina spinel coated with PVA; 15 percent of aluminum hydroxide micropowder coated magnesite powder composite powder (less than 0.2 mm); carbores P3% (< 0.074 mm); aluminum magnesium alloy powder 4% < 0.088 mm); flake graphite 20% (< 0.088 mm).
Firstly weighing solid raw materials according to the proportion, then weighing phenolic resin powder accounting for 11% of the total mass of the raw materials, lithium carbonate accounting for 2.5% of the total mass of the phenolic resin powder and furfural accounting for 13% of the total mass of the phenolic resin powder, firstly weighing the solid raw materials according to the proportion, then weighing phenolic resin powder accounting for +11% of the total mass of the raw materials, mixing for 10min in a high-speed mixer, mixing for 5min again, pouring the dried blank into a die, forming in an isostatic press, maintaining the pressure at 45MPa and separating seeds. After demoulding, the blank is cured and then heat treated, wherein the atmosphere is N 2 Preserving heat for 1 hour at 950 ℃ to obtain the long nozzle.
The performance of the material is compared with that of the existing conventional long nozzle body material, and the material is shown in table 2.
TABLE 2 comparison of the Material Properties of the inventive nozzle body with the conventional nozzle body
。
Claims (5)
1. A low pollution long mouth of a river body material, characterized by: the low-pollution light body material comprises the following raw materials in percentage by mass: 20-40% of spinel hollow sphere, 10-20% of sintered magnesia-alumina spinel, 15-30% of composite powder, 2-5% of Carbores P, 15-25% of crystalline flake graphite and 3-5% of aluminum-magnesium alloy powder; the combination system of the low-pollution light-weight bulk material is phenolic resin powder, lithium carbonate and furfural; the addition amount of the phenolic resin powder is 6-10% of the total mass of the raw materials of the materials; the addition amount of the furfural is 120-140% of the mass of the phenolic resin powder; the lithium carbonate accounts for 2 to 4 percent of the mass of the phenolic resin powder.
2. A low pollution long nozzle body material as claimed in claim 1, wherein: the spinel hollow sphere is prepared by an electrofusion method, and has the volume density of 0.4-0.8 g/cm 3 The surface of the glass is pre-coated with a layer of PVA with the thickness of 3-5 mu m.
3. A low pollution long nozzle body material as claimed in claim 1, wherein: the surface of the sintered magnesia-alumina spinel is pre-coated with a layer of PVA with the thickness of 2-3 mu m.
4. A low pollution long nozzle body material as claimed in claim 1, wherein: the composite powder is aluminum hydroxide coated magnesite powder, and the composite powder of aluminum hydroxide and magnesite is prepared by a high-energy ball milling method to be used as a precursor, wherein the precursor is mainly characterized in that the aluminum hydroxide is coated with magnesite, wherein the aluminum hydroxide is less than 5 mu m, the magnesite is less than 0.088mm, and the ratio of the aluminum hydroxide to the magnesite is 3:1, the preparation method adopts a high-energy ball milling process to prepare, and aluminum hydroxide micropowder, magnesite powder and corundum grinding balls are added into a ball milling tank, wherein the mass ratio of the mixed powder to the grinding balls is 1:5-8; and ball milling for 2-5 hours at the speed of 300-500 rpm to obtain the composite powder of the aluminum hydroxide coated magnesite powder.
5. A low pollution long nozzle body material as claimed in claim 1, wherein: the aluminum magnesium alloy powder comprises the following components: mg=3: 1 mass ratio, alloy powder is less than 0.088mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310874756.8A CN116730732A (en) | 2023-07-17 | 2023-07-17 | Low-pollution long nozzle body material |
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| CN202310874756.8A CN116730732A (en) | 2023-07-17 | 2023-07-17 | Low-pollution long nozzle body material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117226083A (en) * | 2023-11-14 | 2023-12-15 | 山西昊业新材料开发有限公司 | Long nozzle for continuous casting and preparation method thereof |
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- 2023-07-17 CN CN202310874756.8A patent/CN116730732A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117226083A (en) * | 2023-11-14 | 2023-12-15 | 山西昊业新材料开发有限公司 | Long nozzle for continuous casting and preparation method thereof |
| CN117226083B (en) * | 2023-11-14 | 2024-01-26 | 山西昊业新材料开发有限公司 | Long nozzle for continuous casting and preparation method thereof |
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