Ultrahigh-pulling-speed immersion type drain nozzle erosion-resistant material and preparation method thereof
阅读说明：本技术 一种超高拉速浸入式下水口耐侵蚀材料及其制备方法 (Ultrahigh-pulling-speed immersion type drain nozzle erosion-resistant material and preparation method thereof ) 是由 谭杜 彭灿锋 钟立明 骆忠文 周志勇 于 2020-11-24 设计创作，主要内容包括：本发明公开了一种超高拉速浸入式下水口耐侵蚀材料,属于连铸耐火材料技术领域。按重量份计算,包括以下成分：氧化锆颗粒40～60份；氧化锆细粉30～45份；氧化锆微粉5～15份；金属粉末添加剂3～8份；结合剂5～10份；氧化锆纤维2～4份。同时本发明还公开了上述超高拉速浸入式下水口耐侵蚀材料的制备方法。本发明通过在配料中添加氧化锆纤维材料,氧化锆纤维能在ZrO-2-C材料中,能有效形成网状结构,对材料的裂纹起到阻止作用,其稳定性优于传统的ZrO-2-C材料,同时除保证材料成品热震性能外,其自身在ZrO-2-C中,是无污染高耐侵蚀氧化锆材料,具有非常优异的耐侵蚀性能,与传统ZrO-2-C材料比热震性能提高,抗侵蚀效果明显。(The invention discloses an erosion-resistant material for an ultra-high pulling speed submerged nozzle, belonging to the technical field of continuous casting refractory materials. The coating comprises the following components in parts by weight: 40-60 parts of zirconia particles; 30-45 parts of zirconia fine powder; 5-15 parts of zirconia micro powder; 3-8 parts of a metal powder additive; 5-10 parts of a binding agent; 2-4 parts of zirconia fiber. Meanwhile, the invention also discloses a preparation method of the erosion-resistant material for the ultra-high-pulling-speed submerged nozzle. The invention adds zirconia fiber material in the mixture, and the zirconia fiber can be in ZrO 2 In the-C material, a net structure can be effectively formed, the crack of the material is prevented, and the stability of the material is superior to that of the traditional ZrO 2 -C material, which is self-ZrO in addition to guaranteeing the thermal shock property of the finished material 2 in-C, is pollution-free and highly resistantEroding zirconia material with excellent erosion resistance compared with conventional ZrO 2 The specific thermal shock performance of the-C material is improved, and the anti-corrosion effect is obvious.)
1. The erosion-resistant material for the ultra-high-pulling-speed submerged nozzle is characterized by comprising the following components in parts by weight: 40-60 parts of zirconia particles; 30-45 parts of zirconia fine powder; 5-15 parts of zirconia micro powder; 3-8 parts of a metal powder additive; 5-10 parts of a binding agent; 2-4 parts of zirconia fiber.
2. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 1, wherein: the zirconia particles are one or more of fused zirconia, fused stabilized zirconia or calcium yttrium composite stabilized zirconia.
3. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 2, wherein: the particle size distribution of the zirconia particles is as follows according to the parts by weight: 10-25 parts of 0.6-0.4 mm, 35-55 parts of 0.4-0.125 mm.
4. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 3, wherein: ZrO in the zirconia particles2≥94.0wt％。
5. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 1, wherein: the zirconia fine powder comprises the following components in parts by weight: 10-25 parts of 0.074-0.044 mm and 20-35 parts of 0.044-0.020 mm.
6. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 5, wherein: ZrO in the zirconia micropowder2Not less than 98.5 wt%, and the granularity of the zirconia micro powder is<3μm。
7. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 1, wherein: the bonding agent is phenolic resin, the particle size of the bonding agent is less than 150 meshes, the metal powder additive is a mixture of aluminum and silicon, and the content of Al and Si in the metal powder is more than 98%.
8. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 1, wherein: the zirconia fiber is formed by high-temperature treatment at the temperature of 1400-1800 ℃ for 2-4h, the compressive strength of the zirconia fiber is more than or equal to 80MPa, and the flexural strength of the zirconia fiber is 15-20 MPa.
9. The erosion-resistant material for an ultra-high pulling speed submerged entry nozzle of claim 9, wherein: ZrO in the zirconia fiber2>90wt％。
10. A method for preparing an erosion-resistant material for an ultra-high pulling speed submerged entry nozzle according to any one of claims 1 to 9, comprising the steps of: weighing zirconia particles, zirconia fine powder, zirconia micro powder, metal powder additive, bonding agent and zirconia fiber according to a proportion, mixing and granulating the raw materials, compounding the material on the outer wall of the slag line part of the water gap, pressing the mixture into a green body by isostatic pressing, and firing the green body at 800-1000 ℃ to obtain a finished product.
Technical Field
The invention belongs to the technical field of continuous casting refractory materials, and mainly relates to an ultrahigh-pulling-speed immersion type drain nozzle erosion-resistant material and a preparation method thereof.
Background
In the continuous development process of the steel industry, the refractory material for the continuous casting tundish is rapidly developed, and powerful support is provided for the progress of the continuous casting process technology. The design scheme of the submerged nozzle used in the current continuous casting process is generally Al combined by resin2O3The slag line part of the material is mainly made of zirconium oxide, graphite and other materials, the zirconium carbon material is combined by resin, and additives such as SiC, Si, Al, B4C and the like are partially added to improve the oxidation resistance of the material and ensure that the requirements of a continuous casting process are met. However, with the accelerated smelting rhythm of the converter, the maximum drawing speed of the small square billet casting machine reaches 5.73m/min, and the subsequent ultrahigh drawing speed continuous casting production becomes an advanced continuous casting process or a normal state pursued by various steel plants. Under the condition of ultrahigh drawing speed production, in order to ensure the blank shell cooling effect and the rapid dissolution of the covering slag, maintain certain lubricity, prevent slag entrapment and other factors, the alkalinity of the covering slag needs to be increased, and the melting point is reduced along with the alkalinity; in order to prevent the overlarge fluctuation of the liquid level in the crystallizer under the condition of high pulling speed, the immersion depth of the water outlet can be adjusted only within the range of 10-20 mm, and meanwhile, in the actual production process, the influence of deformation of the bottom of a tundish and the like exists, so that the secondary slag line of the water outlet is not obvious, and the situation that the secondary slag line is almost close to one slag line is caused. This makes the use conditions of the slag line part (the joint of molten steel and casting powder) of the mating submerged nozzle more and more severe. While conventional ZrO2the-C material cannot meet the use requirement of the continuous casting process, and a common sewer nozzle manufacturer generally improves the content of zirconia to improve the erosion resistance of the slag line material, but the improvement of the zirconia greatly reduces the thermal shock performance, greatly increases the cracking hidden danger of the sewer nozzle, often cracks just on the sewer nozzle, the pouring cannot be normally carried out, and the use requirement of the continuous casting production on long service life cannot be met. If a manufacturer sets an anti-cracking layer on the inner wall of the lower nozzle, the effective wall thickness of the lower nozzle is thinned, and the service life is shortened.
Disclosure of Invention
The invention provides an ultra-high-pulling-speed submerged nozzle corrosion-resistant material and a preparation method thereof, and aims to solve the problems in the background art.
In order to achieve the technical purpose, the invention mainly adopts the following technical scheme:
an ultra-high pulling speed immersion type drain nozzle erosion-resistant material comprises the following components in parts by weight: 40-60 parts of zirconia particles; 30-45 parts of zirconia fine powder; 5-15 parts of zirconia micro powder; 3-8 parts of a metal powder additive; 5-10 parts of a binding agent; 2-4 parts of zirconia fiber.
Wherein, the zirconia particles are one or more of electric melting zirconia, electric melting stabilized zirconia or calcium yttrium composite stabilized zirconia.
Preferably, the zirconia particles have a particle size distribution of, by weight: 10-25 parts of 0.6-0.4 mm, 35-55 parts of 0.4-0.125 mm.
Further, ZrO in the zirconia particles2≥94.0wt％。
In the invention, the zirconia fine powder has the following grain size distribution by weight: 10-25 parts of 0.074-0.044 mm and 20-35 parts of 0.044-0.020 mm.
Further, ZrO in the fine zirconia powder2Not less than 98.5 wt%, and the granularity of the zirconia micro powder is<3μm。
In the invention, the binding agent is phenolic resin, the granularity of the binding agent is less than 150 meshes, the metal powder additive is a mixture of aluminum and silicon, and the content of Al and Si in the metal powder is more than 98%.
In the invention, the zirconia fiber is formed by high-temperature treatment at the temperature of 1400 ℃ and 1800 ℃ for 2-4h, the compressive strength of the zirconia fiber is more than or equal to 80MPa, and the flexural strength of the zirconia fiber is 15-20 MPa.
Further, ZrO in the zirconia fiber2>90wt％。
The invention also provides a preparation method of the erosion-resistant material for the ultra-high pulling speed submerged nozzle, which comprises the following steps: weighing zirconia particles, zirconia fine powder, zirconia micro powder, metal powder additive, bonding agent and zirconia fiber according to a proportion, mixing and granulating the raw materials, compounding the material on the outer wall of the slag line part of the water gap, pressing the mixture into a green body by isostatic pressing, and firing the green body at 800-1000 ℃ to obtain a finished product.
Compared with the prior art, the invention has the following beneficial effects:
1. adding zirconia fiber material into the mixture, the zirconia fiber can be in ZrO2In the-C material, a net structure can be effectively formed, the crack of the material is prevented, and the stability of the material is superior to that of the traditional ZrO2-C material, even if the zirconia content is increased, the cracking problem is relieved, and besides guaranteeing the thermal shock performance of the finished material, the material is self-ZrO2among-C, is a pollution-free high-corrosion-resistance zirconia material with very excellent corrosion resistance compared with the traditional ZrO2The specific thermal shock performance of the-C material is improved, and the anti-corrosion effect is obvious;
2. the service life of the submerged nozzle is prolonged, the frequency of replacing the submerged nozzle in the continuous casting production process is effectively solved, and the yield of casting blanks is improved;
3. the service life of the submerged nozzle is prolonged, and the labor intensity of post staff for replacing the submerged nozzle and the occurrence probability of production cutoff accidents in the replacement process are reduced;
4. the service life of the submerged nozzle is prolonged, the erosion of refractory materials is further reduced, the inclusion in molten steel is reduced, and the quality of the molten steel is improved.
Detailed Description
The principles and features of this invention are described below in conjunction with specific embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
Example 1 ultra high pulling speed immersion type drain nozzle erosion-resistant Material 1
The erosion-resistant material for the ultra-high-pulling-speed submerged nozzle in the embodiment comprises the following components in parts by weight: 40 parts of zirconia particles; 30 parts of zirconia fine powder; 5 parts of zirconia micro powder; 3 parts of a metal powder additive; 5 parts of a binding agent; and 2 parts of zirconia fiber.
Wherein, the zirconia particles are one or more of electric melting zirconia, electric melting stabilized zirconia or calcium yttrium composite stabilized zirconia. Zirconium oxideThe particle size distribution of the particles is as follows: 0.6mm 10 parts, 0.4mm 35 parts, and ZrO in zirconia grains2≥94.0wt％。
Wherein, the grain size composition of the zirconia fine powder is as follows according to the parts by weight: 10 parts of 0.074mm, 20 parts of 0.044mm and 5 parts of zirconia micro powder, wherein ZrO in the zirconia micro powder2Not less than 98.5 wt%, and the granularity of the zirconia micro powder is<3μm。
The bonding agent is phenolic resin, the particle size of the bonding agent is less than 150 meshes, the metal powder additive is a mixture of aluminum and silicon, and the content of Al and Si in the metal powder is more than 98%.
The zirconia fiber is formed by high-temperature treatment at 1400 ℃ for 2h, the compressive strength of the zirconia fiber is more than or equal to 80MPa, and the breaking strength reaches 15 MPa.
ZrO in zirconia fiber2>90wt％。
The preparation method of the erosion-resistant material 1 for the ultra-high-pulling-speed submerged nozzle comprises the following steps:
weighing 40 parts of zirconia particles, 30 parts of zirconia fine powder, 5 parts of zirconia micro powder, 3 parts of metal powder additive, 5 parts of binding agent and 2 parts of zirconia fiber according to a proportion, mixing the raw materials, granulating, compounding the granulated material on the outer wall of a water gap slag line part, pressing the granulated material into a green body by isostatic pressing, and firing the green body at 800-1000 ℃ to obtain a finished product.
Example 2 ultra high pulling speed immersion type drain nozzle erosion resistant Material 2
The erosion-resistant material for the ultra-high-pulling-speed submerged nozzle in the embodiment comprises the following components in parts by weight: 50 parts of zirconia particles; 37 parts of zirconia fine powder; 10 parts of zirconia micro powder; 6 parts of a metal powder additive; 7 parts of a binding agent; 3 parts of zirconia fiber.
Wherein, the zirconia particles are one or more of electric melting zirconia, electric melting stabilized zirconia or calcium yttrium composite stabilized zirconia. The size grading of the zirconia particles is as follows: 17 parts of 0.5mm, 45 parts of 0.25mm, and ZrO in the zirconia particles2≥94.0wt％。
Wherein, the grain size composition of the zirconia fine powder is as follows according to the parts by weight: 17 parts of 0.059mm, 27 parts of 0.032mm and zirconium oxide10 parts of micro powder, and ZrO in the zirconia micro powder2Not less than 98.5 wt%, and the granularity of the zirconia micro powder is<3μm。
The bonding agent is phenolic resin, the particle size of the bonding agent is less than 150 meshes, the metal powder additive is a mixture of aluminum and silicon, and the content of Al and Si in the metal powder is more than 98%.
The zirconia fiber is formed by high-temperature treatment at 1600 ℃ for 3h, the compressive strength of the zirconia fiber is more than or equal to 80MPa, and the breaking strength reaches 18 MPa.
ZrO in zirconia fiber2>90wt％。
The preparation method of the erosion-resistant material 2 for the ultra-high-pulling-speed submerged nozzle comprises the following steps:
weighing 50 parts of zirconia particles, 37 parts of zirconia fine powder, 10 parts of zirconia micro powder, 6 parts of metal powder additive, 7 parts of binding agent and 3 parts of zirconia fiber according to a proportion, mixing the raw materials, granulating, compounding the granulated material on the outer wall of a water gap slag line part, pressing the granulated material into a green body by isostatic pressing, and firing the green body at 800-1000 ℃ to obtain a finished product.
Example 3 ultra high pulling speed immersion type drain nozzle erosion resistant Material 3
The erosion-resistant material for the ultra-high-pulling-speed submerged nozzle in the embodiment comprises the following components in parts by weight: 60 parts of zirconia particles; 45 parts of zirconium oxide fine powder; 15 parts of zirconia micro powder; 8 parts of a metal powder additive; 10 parts of a binding agent; 4 parts of zirconia fiber.
Wherein, the zirconia particles are one or more of electric melting zirconia, electric melting stabilized zirconia or calcium yttrium composite stabilized zirconia. The size grading of the zirconia particles is as follows: 25 parts of 0.4mm, 55 parts of 0.0125mm and ZrO in the zirconia particles2≥94.0wt％。
Wherein, the grain size distribution of the zirconia fine powder is as follows according to the weight portion: 25 parts of 0.044mm, 35 parts of 0.020mm and 15 parts of zirconia micro powder, wherein ZrO in the zirconia micro powder2Not less than 98.5 wt%, and the granularity of the zirconia micro powder is<3μm。
The bonding agent is phenolic resin, the particle size of the bonding agent is less than 150 meshes, the metal powder additive is a mixture of aluminum and silicon, and the content of Al and Si in the metal powder is more than 98%.
The zirconia fiber is formed by high-temperature treatment at 1400 ℃ for 4 hours, the compressive strength of the zirconia fiber is more than or equal to 80MPa, and the breaking strength reaches 20 MPa.
ZrO in zirconia fiber2>90wt％。
The preparation method of the erosion-resistant material 3 for the ultra-high-pulling-speed submerged nozzle comprises the following steps:
weighing 60 parts of zirconia particles, 45 parts of zirconia fine powder, 15 parts of zirconia micro powder, 8 parts of metal powder additive, 10 parts of binding agent and 4 parts of zirconia fiber according to a proportion, mixing the raw materials, granulating, compounding the granulated material on the outer wall of a water gap slag line part, pressing the granulated material into a green body by isostatic pressing, and firing the green body at 800-1000 ℃ to obtain a finished product.
Comparative example 1
The erosion-resistant material of the ultra-high-pulling-speed submerged entry nozzle prepared in the embodiments 1 to 3 of the invention and the traditional ZrO2The results of the erosion-resistant material performance tests are shown in Table 1, in comparison with the-C material.
Name (R)
Specification (mm)
Example 1
Example 2
Example 3
Conventional ZrO2-C material
Specific gravity of
cm3/g
3.95
3.97
4.01
3.75
Apparent porosity
％
16.1
15.9
15.6
16.4
Compressive strength
MPa
29
31
33
31.2
Flexural strength
MPa
16
17
18
26
Time of use
h
12
14
15
7.5
Erosion Rate
mm/h
1.2
1.0
0.9
1.8
From the results in Table 1, it is clear that when a zirconia fiber material is added to the blend, the zirconia fiber can be in ZrO2In the-C material, a net structure can be effectively formed, the crack of the material is prevented, and the stability of the material is superior to that of the traditional ZrO2-C material, which is self-ZrO in addition to guaranteeing the thermal shock property of the finished material2among-C, is a pollution-free high-corrosion-resistance zirconia material with very excellent corrosion resistance compared with the traditional ZrO2The specific thermal shock performance of the-C material is improved, and the anti-corrosion effect is obvious;
the above embodiments are illustrative embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents and are included in the scope of the present invention.