WO2021197002A1 - 防结瘤中间包透气上水口 - Google Patents

防结瘤中间包透气上水口 Download PDF

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WO2021197002A1
WO2021197002A1 PCT/CN2021/079874 CN2021079874W WO2021197002A1 WO 2021197002 A1 WO2021197002 A1 WO 2021197002A1 CN 2021079874 W CN2021079874 W CN 2021079874W WO 2021197002 A1 WO2021197002 A1 WO 2021197002A1
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Prior art keywords
upper nozzle
mgo
tundish
gas
tumor
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PCT/CN2021/079874
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English (en)
French (fr)
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甘菲芳
高华
陈兆平
蒋晓放
徐国栋
梅峰
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宝山钢铁股份有限公司
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Publication of WO2021197002A1 publication Critical patent/WO2021197002A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B22D41/52—Manufacturing or repairing thereof
    • B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B22D41/58—Pouring-nozzles with gas injecting means
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay

Definitions

  • the invention relates to the technical field of steelmaking and continuous casting, in particular to an anti-nodging tundish venting nozzle.
  • the tundish must not only stabilize the quality of the molten steel after the secondary treatment, but also promote the floating and separation of inclusions in the molten steel, uniform composition and temperature, improve the quality of molten steel and stabilize the casting operation.
  • the upper nozzle of the tundish is an important part in continuous casting production.
  • the bowl of the upper nozzle and the head of the stopper rod cooperate to control the flow of molten steel and affect the liquid level of the tundish.
  • the inner wall and bowl of the upper nozzle often have inclusions in the molten steel adhering to it, resulting in nodules or blockage of the upper nozzle, which seriously affects the quality of the cast steel and the casting billet.
  • the commonly used argon blowing and venting top nozzle is that the tundish venting top nozzle blows inert gas-argon into the molten steel.
  • the argon bubbles formed can accelerate the floating of inclusions and form a bubble film on the inner wall surface to prevent the inclusions from adhering. This slows down the reduction in the diameter of the inner hole of the upper nozzle and ensures the castability of molten steel.
  • Diffusion type upper nozzle is generally formed into a loose porous structure by using materials with higher porosity in the bowl of the upper nozzle.
  • the disadvantage is that the air permeability is unstable and the air permeability cannot be adjusted in time according to production needs.
  • Straight-through hole type tundish breathable upper nozzle usually includes a bowl, an outer body and an inner breather.
  • the inner breather is a cavity structure to form the inner cavity of the upper nozzle, and the inner cavity is connected with the bowl for molten steel to flow through.
  • a number of through holes are pre-embedded in the inner wall of the gas vent.
  • the straight through holes communicate with the argon blowing pipe through the air chamber slits arranged between the outer body and the inner gas vent.
  • the air-permeable upper nozzle material needs to have excellent air permeability (that is, no tumors, no clogging), thermal shock resistance and corrosion resistance of molten steel.
  • air permeability that is, no tumors, no clogging
  • thermal shock resistance and corrosion resistance of molten steel.
  • materials that can be used for the air-permeable upper nozzle of the tundish mainly Al 2 O 3 -SiO 2 of corundum and mullite, Al 2 O 3 -Cr 2 O 3 of chromium corundum, and Al 2 O 3 -C Al 2 O 3 -ZrO 2 -C, etc.
  • corundum mullite contains SiO 2 so that it has good thermal shock resistance, but it has poor corrosion resistance and is prone to nodules and clogging after melting.
  • Chromium corundum contains Al 2 O 3, which makes it have good corrosion resistance, high strength, and erosion resistance, but it has poor thermal shock resistance and is prone to cracks. It can also cause nodules on the inner wall.
  • Tundish ventilating nozzles can also be divided into two categories: carbon-containing and non-carbon.
  • the carbon content of carbon-containing nozzles is generally at least 18%.
  • the high carbon content results in lower strength, and is not resistant to erosion, oxidation and anti-caking.
  • the tumor performance is poor, and the carbon-free top nozzle is usually made of Al 2 O 3 -SiO 2 with an Al 2 O 3 content of 72 to 88% and a SiO 2 content of 5 to 25%, which will cause unstable air permeability , Disadvantages of low service life.
  • Part of the upper nozzle of the tundish will also be made of Al 2 O 3 -Cr 2 O 3 , the composition of Al 2 O 3 is 85-92%, and the composition of Cr 2 O 3 is 2-8%, although it improves the resistance to molten steel erosion and erosion
  • the performance solves the problem of rapid melting loss of the upper nozzle during use, but it is prone to nodules and blockages, which affects the qualification rate of argon blowing in continuous casting production. With the changes in steel-making process conditions and the continuous increase in the number of continuous casting furnaces, the existing water inlet can no longer meet the needs of steel mills' process and smelting steel types.
  • the purpose of the present invention is to provide an anti-tumor tundish air-permeable upper nozzle, the inner layer of the upper nozzle is made of Al 2 O 3 -MgO-C material, through the through-hole ventilation method, can effectively reduce the upper nozzle nodules And blockage.
  • the present invention is realized as follows:
  • An anti-tumor tundish breathable water inlet comprising a bowl, an outer body, an inner breather, a through hole, a gas chamber slit, and an air inlet argon blowing pipe.
  • the external argon gas passes through the inlet argon blowing pipe and the Chamber slits and through holes enter the inner cavity of the upper nozzle;
  • the bowl and the inner layer gas permeable body are made of Al 2 O 3 -MgO-C material, and its chemical composition is as follows by weight percentage: Al 2 O 3 : 60-74%, MgO: 18-32%, C: 6 ⁇ 10%, and the rest are trace impurities; the Al 2 O 3 -MgO-C material is additionally added with antioxidants and phenolic resin binders.
  • the raw material of the chemical component Al 2 O 3 is one or a combination of fused corundum, sintered corundum, alumina powder, and magnesia-aluminum spinel.
  • the raw material of the chemical component MgO is one or a combination of fused magnesia, sintered magnesia, and magnesia-aluminum spinel.
  • the raw material of the chemical component C is one or a combination of graphite, carbon black, pitch, resin, and silicon carbide.
  • the invention adopts a through-hole venting method, the upper nozzle bowl and the inner layer vent adopts Al 2 O 3 -MgO-C material, the main component is Al 2 O 3 : 60-74%, MgO: 18-32%, C : 6-10%, so that the material can form or maintain the phases of corundum (Al 2 O 3 ) and magnesia-aluminum spinel (Al 2 O 3 -MgO) during high-temperature applications.
  • Magnesium aluminum spinel (Al 2 O 3 -MgO) not only has excellent corrosion resistance, but also provides better thermal shock resistance than corundum (Al 2 O 3 ).
  • the combination of the two can ensure the corrosion resistance of the material ,
  • the anti-scouring performance of molten steel and thermal shock resistance meet the requirements of use, while controlling the appropriate carbon (C) content, so that the material is not easy to sinter during use, the air permeability is relatively stable, and it is not easy to be infiltrated by molten steel and molten slag, and thermal shock resistance Good performance, not easy to crack or break, and ensure strength and oxidation resistance.
  • corundum (Al 2 O 3 )-magnesium-aluminum spinel (Al 2 O 3 -MgO)-low-carbon material is also used in the upper nozzle bowl, which can significantly improve the anti-tumor and anti-tumor prevention of the upper nozzle of the tundish. Blocking performance.
  • the outer body of the water inlet is made of Al 2 O 3 -C material, which can not only control lower costs, but also ensure stable quality, and has excellent product cost performance.
  • the upper nozzle adopts a through-hole ventilation method, which is simple to manufacture and has a high yield, and the argon blowing gas flow is stable without hysteresis, which effectively guarantees the permeability and stability of the argon blowing.
  • the present invention has the following beneficial effects: the air-permeable upper nozzle of the tundish can provide excellent thermal shock resistance, erosion resistance, oxidation resistance, resistance to molten steel scouring performance, excellent overall performance, and can improve the ease of the upper nozzle.
  • the problem of nodulation and blockage, and the cost is reasonable, and the quality is stable.
  • Fig. 1 is a schematic diagram of the structure of the ventilating upper nozzle of the anti-tumor tundish according to the present invention.
  • an anti-tumor tundish air-permeable upper nozzle including a bowl 1, an outer body 2, an inner vent 3, a through hole 4, a gas chamber slit 5 and an air inlet argon blowing pipe 6, and an external argon
  • the gas enters the inner cavity of the upper nozzle through the gas inlet argon blowing pipe 6, the gas chamber slit 5 and the through hole 4 in sequence.
  • the bowl 1 and the inner layer gas-permeable body 3 are made of Al 2 O 3 -MgO-C material, and their chemical components are as follows by weight percentage: Al 2 O 3 : 60-74%, MgO: 18-32%, C :6 ⁇ 10%, the rest are trace impurities, the composition phase is corundum (Al 2 O 3 )-magnesium aluminum spinel (Al 2 O 3 -MgO)-low carbon material, it is a low carbon type functional refractory material .
  • the melting point of Al 2 O 3 is 2050°C
  • the melting point of MgO is 2800°C
  • the melting point of magnesium aluminum spinel (Al 2 O 3 -MgO) is 2135°C, which makes the Al 2 O 3 -MgO-C material resistant to high temperature.
  • Good, to further improve the anti-nodulation effect mainly based on corundum (Al 2 O 3 ) and magnesium aluminum spinel (Al 2 O 3 -MgO) phases, which can ensure excellent corrosion resistance, molten steel erosion resistance and resistance Thermal shock performance.
  • carbon-containing materials are not easy to sinter during use, have good air permeability stability, are not easy to be infiltrated by molten steel and slag, can meet the requirements of anti-nodulation, and have good thermal shock resistance, and are not easy to crack or break. Too high carbon content will lead to material strength reduction, corrosion resistance, and poor oxidation resistance. Therefore , the carbon content of Al 2 O 3 -MgO-C materials is controlled at 6-10%, which can achieve a better performance balance. . In the technology of the present invention, Al 2 O 3 and MgO are the main components, so the content is relatively high.
  • the content of Al 2 O 3 needs to be relatively high, in the range of 60-74%.
  • the MgO content is 18-32%. If the MgO content is too high, there will be more MgO after the formation of magnesia-aluminum spinel, and the material contains more periclase mineral phase (MgO). Although the corrosion resistance is still good, the thermal shock resistance will decrease. Therefore, the composition of the present invention is reasonably controlled, each performance is balanced, and at the same time, the effects of anti-tumor and long life are achieved.
  • the raw material of the chemical component Al 2 O 3 can be selected from one or more of refractory materials such as fused corundum, sintered corundum, alumina powder, magnesia alumina spinel, etc.
  • the raw material of chemical component MgO can choose one or more combinations of refractory materials such as fused magnesia, sintered magnesia, magnesia aluminum spinel, and the raw material of chemical component C can choose graphite, carbon black, pitch,
  • One or more combinations of carbon-containing raw materials such as resins are compounded and added according to the weight percentage of the chemical components (Al 2 O 3 : 60-74%, MgO: 18-32%, C: 6-10%)
  • Appropriate amount of antioxidant and phenolic resin binder are compounded and added according to the weight percentage of the chemical components (Al 2 O 3 : 60-74%, MgO: 18-32%, C: 6-10%)
  • Appropriate amount of antioxidant and phenolic resin binder are compounded and added according to the weight percentage of the chemical components (Al 2 O 3 : 60-74%, MgO: 18-32%, C: 6-10%)
  • Appropriate amount of antioxidant and phenolic resin binder optionally, add 1 to
  • the outer body 2 is made of Al 2 O 3 -C material, which can maintain low cost and stable quality, and provide better product cost performance.
  • Table 1 lists the specific weight percentages (wt%) of the chemical components of Examples 1 to 5, and lists Comparative Examples 1 to 4, which are compared with the examples in terms of chemical composition and performance, as shown below Show:
  • the compressive strength test method is carried out according to GB/T 5072; the lower the corrosive index, the better the corrosion resistance.
  • the test method of the corrosive index is: make the material to be tested into a crucible sample, put the steel slag in the crucible, and test conditions It is 1550°C, 3h high temperature slag resistance. Cut the crucible open and measure the area eroded by the slag on the crucible section.
  • Corrosion index (%) area eroded by the crucible sample section/original section area of the crucible sample; the thermal shock resistance test method is carried out according to GB/T 30873; the effect of preventing nodules and blockage is observed by observing the bowl and inner layer of the upper nozzle Judging by the surface of the gas permeable body, a smooth surface without nodules has a good effect on preventing nodules and clogging, while a surface with uneven surface and adhesives has a poor effect on preventing nodules and clogging.
  • the ratio of such chemical components makes the overall performance of the overall material Excellent performance, can improve the problem of nodulation and clogging of the air outlet of the tundish.
  • the chemical components of Examples 1 to 5 only contain trace amounts of SiO 2 impurities (SiO 2 impurity content ⁇ 0.4%) brought in by the raw materials.
  • antioxidants and phenolic resin binders are raw material additives, which are not within the calculation range of the weight percentage of chemical components.
  • Comparative Example 1 is an aluminum carbon material of Al 2 O 3 -SiO 2 -C.
  • the content of SiO 2 is relatively high, resulting in poor corrosion resistance, low compressive strength, and poor anti-nodging and blocking effect.
  • Comparative Example 2 is an Al 2 O 3 -ZrO 2 -C aluminum-zirconium carbonaceous material. Compared with Comparative Example 1, the corrosion resistance is improved, but the carbon content is higher, resulting in low oxidation resistance and compressive strength, reducing the material The service life is not conducive to anti-tumor and anti-clogging.
  • Comparative Example 3 is the commonly used Al 2 O 3 -SiO 2 corundum mullite material. The content of SiO 2 is high.
  • Comparative Example 4 is an Al 2 O 3 -Cr 2 O 3 chromium corundum carbon-free material, which has good corrosion resistance, but poor thermal shock performance, and is easy to crack during use, resulting in argon blowing and air leakage, and poor anti-nodulation and clogging effects.
  • the bowl and inner vent of the anti-tumor tundish air-permeable upper nozzle of the present invention adopt Al 2 O 3 -MgO-C quality materials, so that the upper nozzle has corrosion resistance, erosion resistance, thermal shock resistance, and oxidation resistance. It is better, not easy to build up, and has a long service life.
  • blowing argon to form bubbles and bubble film can prevent the water inlet from clogging or clogging.
  • the inclusions in the molten steel are accompanied by argon.
  • the bubbles float up to clean the molten steel, which not only improves the service life of the nozzle, but also ensures the number of continuous casting and continuous casting furnaces and the qualification rate of argon blowing.

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Abstract

一种防结瘤中间包透气上水口，包括碗部(1)、外层本体(2)、内层透气体(3)、直通孔(4)、气室狭缝(5)和进气吹氩管(6)，外部氩气依次经进气吹氩管、气室狭缝和直通孔进入到所述上水口的内腔中；所述碗部和内层透气体为Al2O3-MgO-C质材料，其化学组分按重量百分比为：Al2O3：60～74％、MgO：18～32％、C：6～10％，其余为微量杂质；所述Al2O3-MgO-C质材料还外加有抗氧化剂和酚醛树脂结合剂。该中间包透气上水口能提供优良的抗热震性、抗侵蚀性、抗氧化性、抗钢水冲刷性能，综合性能优异，能改善上水口容易结瘤和堵塞的问题，且成本合理、质量稳定。

Description

防结瘤中间包透气上水口 技术领域
本发明涉及炼钢连铸技术领域，特别涉及一种防结瘤中间包透气上水口。
背景技术
中间包作为连铸系统中的重要环节，既要稳定二次处理后钢水的质量，又要促进钢水中夹杂物上浮分离，均匀成分和温度，改善钢水质量和稳定浇铸操作。中间包上水口是连铸生产中的重要部件，上水口碗部与塞棒棒头配合控制钢水的流量，影响中间包的液面。但在连铸生产过程中上水口内壁及碗部经常会有钢水中的夹杂物粘附在其上，造成上水口结瘤或堵塞，严重影响浇钢及铸坯质量。
现在普遍采用的吹氩透气上水口，即中间包透气上水口往钢水中吹入惰性气体-氩气，形成的氩气泡能加速夹杂物上浮，并在内壁表面形成气泡膜阻止夹杂物粘附，从而减缓上水口内孔直径缩小，保证钢水可浇性。透气的方式有弥散式和直通孔式。弥散式上水口一般是在上水口的碗部使用气孔率较高的材质来成型为疏松多孔结构，缺点是透气性能不稳定、透气量无法根据生产需要及时调节等。直通孔式中间包透气上水口通常包括碗部、外层本体和内层透气体，内层透气体为空腔结构形成上水口的内腔，内腔与碗部连通供钢水流过，并在内层透气体壁内预埋多个直通孔，直通孔经过设置在外层本体和内层透气体之间的气室狭缝与进气吹氩管连通，优点是透气性能好且透气量可调节。
因此，透气上水口材质需要具备优良的透气性(即不结瘤、不堵塞)，耐热冲击性和耐钢水侵蚀性。目前，中间包透气上水口可以采用的材质种类很多，主要有刚玉莫来石的Al 2O 3-SiO 2质、铬刚玉的Al 2O 3-Cr 2O 3质、Al 2O 3-C质、Al 2O 3-ZrO 2-C质等，其中，刚玉莫来石因含有SiO 2使得热震性很好，但抗侵蚀性较差，熔损后容易结瘤和堵塞，而刚玉及铬刚玉因含有Al 2O 3使得抗侵蚀性好、强度高、耐冲刷，但热震性较差，容易出现裂纹，在内壁上也会造成结瘤。中间包透气上水口也可以分为含碳和不含碳两大类，含碳上水口的C含量一般至少为18％，含碳量高导致强度较低，不耐冲刷，抗氧化和防结瘤性能都较差，而不含碳上水口则通常为 Al 2O 3-SiO 2材质，Al 2O 3成分为72～88％，SiO 2成分为5～25％，会造成透气性能不稳定、使用寿命低的弊端。部分中间包上水口也会采用Al 2O 3-Cr 2O 3材质，Al 2O 3成分为85-～92％，Cr 2O 3成分为2～8％，虽提高了抗钢水冲刷和侵蚀性能，解决了上水口在使用过程中熔损快的问题，但容易发生结瘤和堵塞，影响了连铸生产的吹氩合格率。随着炼钢工艺条件的变化，连铸炉数的不断提高，现有的上水口已不能适应钢厂工艺和冶炼钢种变化的需要。
发明内容
本发明的目的在于提供一种防结瘤中间包透气上水口，该上水口的内层透气体为Al 2O 3-MgO-C质材料，通过直通孔透气方式，可有效减轻上水口结瘤和堵塞。
本发明是这样实现的：
一种防结瘤中间包透气上水口，包括碗部、外层本体、内层透气体、直通孔、气室狭缝和进气吹氩管，外部氩气依次经进气吹氩管、气室狭缝和直通孔进入到所述上水口的内腔中；
所述碗部和内层透气体为Al 2O 3-MgO-C质材料，其化学组分按重量百分比为：Al 2O 3：60～74％、MgO：18～32％、C：6～10％，其余为微量杂质；所述Al 2O 3-MgO-C质材料还外加有抗氧化剂和酚醛树脂结合剂。
所述化学组分Al 2O 3的原料为电熔刚玉、烧结刚玉、氧化铝微粉、镁铝尖晶石中的一种或几种组合。
所述化学组分MgO的原料为电熔镁砂、烧结镁砂、镁铝尖晶石中的一种或几种组合。
所述化学组分C的原料为石墨、炭黑、沥青、树脂、碳化硅中的一种或几种组合。
本发明采用直通孔透气方式，上水口碗部和内层透气体采用Al 2O 3-MgO-C质材料，主成分为Al 2O 3：60～74％、MgO：18～32％、C：6～10％，这样可以使材料在高温应用过程中形成或保持刚玉(Al 2O 3)和镁铝尖晶石(Al 2O 3-MgO)的物相。镁铝尖晶石(Al 2O 3-MgO)不仅抗侵蚀性能出色，而且相较于刚玉(Al 2O 3)能提供更好的抗热震性，两者结合能保证材料的抗侵蚀性能、抗钢水冲刷性能和抗热震性能满足使用要求，同时控制合适的碳(C)含量，使材料在使用过程中不易烧结，透气稳定性比较好，不易被钢水、熔渣浸润，抗热震性能好，不易开裂或断 裂，并且保证强度和抗氧化性能。尤其是在上水口碗部也采用了刚玉(Al 2O 3)-镁铝尖晶石(Al 2O 3-MgO)-低碳材料，能明显提升中间包透气上水口的防结瘤、防堵塞性能。上水口的外层本体采用Al 2O 3-C材质，既能控制较低的成本，又能保证稳定的质量，具备优良的产品性价比。另外，该上水口为直通孔透气方式，制作简单、成品率高，且吹氩气流稳定、没有滞后性，有效保证了吹氩的通透性和稳定性。
本发明与现有技术相比，具有如下有益效果：中间包透气上水口能提供优良的抗热震性、抗侵蚀性、抗氧化性、抗钢水冲刷性能，综合性能优异，能改善上水口容易结瘤和堵塞的问题，且成本合理、质量稳定。
附图说明
图1为本发明防结瘤中间包透气上水口的结构示意图。
附图标记：
1.碗部；2.外层本体；3.内层透气体；4.直通孔；5.气室狭缝；6.进气吹氩管。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明。
参见图1，一种防结瘤中间包透气上水口，包括碗部1、外层本体2、内层透气体3、直通孔4、气室狭缝5和进气吹氩管6，外部氩气依次经进气吹氩管6、气室狭缝5和直通孔4进入到所述上水口的内腔中。
所述碗部1和内层透气体3为Al 2O 3-MgO-C质材料，其化学组分按重量百分比为：Al 2O 3：60～74％、MgO：18～32％、C：6～10％，其余为微量杂质，组成物相为刚玉(Al 2O 3)-镁铝尖晶石(Al 2O 3-MgO)-低碳材料，是一种低碳型功能耐火材料。其中，Al 2O 3熔点为2050℃，MgO熔点为2800℃，镁铝尖晶石(Al 2O 3-MgO)的熔点为2135℃，使得Al 2O 3-MgO-C质材料耐高温性能良好，进一步提高防结瘤效果，以刚玉(Al 2O 3)和镁铝尖晶石(Al 2O 3-MgO)物相为主，能保证优异的抗侵蚀性能、抗钢水冲刷性能和抗热震性能。同时，含碳材料在使用过程中不易烧结，透气稳定性也比较好，不易被钢水、熔渣浸润，能满足防结瘤要求，还具备良好的抗热震性，不易开裂或断裂，但如果碳含量太高则会导致材料强度降低、不耐侵蚀、抗氧化性能较差，因此Al 2O 3-MgO-C质材料的碳含量控制在6～10％， 能达到较好的性能平衡点。本发明技术中Al 2O 3、MgO为主成分，所以含量较高。为了应用过程中形成或保持上水口材料的镁铝尖晶石物相，需要Al 2O 3含量比较高，在60～74％范围内。相应地MgO含量为18～32％。如果MgO含量太高则形成镁铝尖晶石后过剩较多的MgO，材料中含方镁石矿物相(MgO)多，虽然抗侵蚀仍然较好，但抗热震性能会下降。因此本发明成分控制合理，均衡各个使用性能，同时达到防结瘤与长寿命效果。
所述Al 2O 3-MgO-C质材料中，化学组分Al 2O 3的原料可选择电熔刚玉、烧结刚玉、氧化铝微粉、镁铝尖晶石等耐火材料的一种或多种组合，化学组分MgO的原料可选择电熔镁砂、烧结镁砂、镁铝尖晶石等耐火材料的一种或多种组合，化学组分C的原料可选择石墨、炭黑、沥青、树脂等含碳原料的一种或多种组合，按化学组分的重量百分比(Al 2O 3：60～74％、MgO：18～32％、C：6～10％)进行配料，并添加适量抗氧化剂和酚醛树脂结合剂，可选的，相对于100重量份的Al 2O 3-MgO-C质材料外加入1～2重量份的抗氧化剂(例如B 4C、Al或Mg，可以是其中的一种或二种)和3～4重量份的酚醛树脂结合剂，配料混合均匀后放入成型模具内一体化、一次性等静压成型。所述外层本体2为Al 2O 3-C质材料，能保持较低的成本和稳定的质量，提供较好的产品性价比。
表1列出了实施例1～5的化学组分的具体重量百分比(wt％)，并列出了比较例1～4，与实施例在化学组分和性能表现上作了对比，如下所示：
Figure PCTCN2021079874-appb-000001
耐压强度测试方法按GB/T 5072进行；侵蚀性指数越低抗侵蚀性能越好，侵蚀性指数的测试方法为：将待测材料做成坩埚试样，将钢渣放入坩埚内，试验条件为1550℃，3h高温烧后抗渣。将坩埚切开，测量出坩埚截面上被渣侵蚀掉的面积。侵蚀性指数(％)＝坩埚试样截面侵蚀掉的面积/坩埚试样原始截面面积；抗热震性测试方法按GB/T 30873进行；防结瘤堵塞效果通过观察上水口碗部和内层透气体的表面来判定，表层光滑、无结瘤物则防结瘤堵塞效果好，表层凹凸、含粘结物则防结瘤堵塞效果较差。
从表1可以看出，实施例1～5的化学组分的重量百分比数值范围为：Al 2O 3：60～74％、MgO：18～32％、C：6～10％，以刚玉(Al 2O 3)和镁铝尖晶石(Al 2O 3-MgO)物相为主，能提供优异的抗侵蚀和抗钢水冲刷性能和抗热震性能，进而保证Al 2O 3-MgO-C质材料的防结瘤堵塞效果，同时合适的碳含量能保证材料的防结瘤、抗热震、高耐压强度和抗氧化性能，这样的化学组分的配比使得整体材料的综合性能表现优异，能改善中间包透气上水口的结瘤、堵塞的问题。实施例1～5的化学组分中仅包含由原料带入的微量SiO 2杂质(SiO 2杂质含量≤0.4％)。另外，抗氧化剂和酚醛树脂结合剂为原料添加剂，不在化学组分的重量百分比计算范围内。
比较例1为Al 2O 3-SiO 2-C的铝碳质材料，SiO 2含量较高，导致抗侵蚀性能较差，耐压强度较低，防结瘤堵塞效果较差。比较例2为Al 2O 3-ZrO 2-C的铝锆碳质材料，抗侵蚀性能相较于比较例1提高，但碳含量较高，导致抗氧化性和耐压强度不高，减少材料使用寿命，不利于防结瘤、防堵塞。比较例3为常用的Al 2O 3-SiO 2的刚玉莫来石材料，SiO 2含量较高，使用过程中容易烧结，降低透气性，同时抗侵蚀性差、抗热震性较差，导致结瘤堵塞现象常有发生。比较例4为Al 2O 3-Cr 2O 3的铬刚玉无碳材料，抗侵蚀性好，但是热震性能较差，使用中容易开裂，导致吹氩漏气，防结瘤堵塞效果差。
本发明防结瘤中间包透气上水口的碗部和内层透气体采用Al 2O 3-MgO-C质材料，使得上水口的抗侵蚀性能、抗冲刷性能、抗热震性能、抗氧化性能较好，不易结瘤，使用寿命长，并结合在内层透气体中设置直通孔的透气方式，吹氩形成气泡和气泡膜能防止上水口结瘤或堵塞，钢水中的夹杂物随氩气气泡上浮从而洁净钢水，不仅提高了上水口的使用寿命，而且能保证连铸连浇炉数和吹氩合格率。
以上仅为本发明的较佳实施例而已，并非用于限定本发明的保护范围，因此，凡在本发明的精神和原则之内所作的任何修改、等同替换、改进等，均应包含在 本发明的保护范围之内。

Claims (4)

  1. 一种防结瘤中间包透气上水口，包括碗部(1)、外层本体(2)、内层透气体(3)、直通孔(4)、气室狭缝(5)和进气吹氩管(6)，外部氩气依次经进气吹氩管(6)、气室狭缝(5)和直通孔(4)进入到所述上水口的内腔中；
    其特征在于：所述碗部(1)和内层透气体(3)为Al 2O 3-MgO-C质材料，其化学组分按重量百分比为：Al 2O 3：60～74％、MgO：18～32％、C：6～10％，其余为微量杂质；所述Al 2O 3-MgO-C质材料还外加有抗氧化剂和酚醛树脂结合剂。
  2. 根据权利要求1所述的防结瘤中间包透气上水口，其特征在于：所述化学组分Al 2O 3的原料为电熔刚玉、烧结刚玉、氧化铝微粉、镁铝尖晶石中的一种或几种组合。
  3. 根据权利要求1所述的防结瘤中间包透气上水口，其特征在于：所述化学组分MgO的原料为电熔镁砂、烧结镁砂、镁铝尖晶石中的一种或几种组合。
  4. 根据权利要求1所述的防结瘤中间包透气上水口，其特征在于：所述化学组分C的原料为石墨、炭黑、沥青、树脂中的一种或几种组合。
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