CN102335730B - Silicone-free submersed nozzle and manufacturing method thereof - Google Patents
Silicone-free submersed nozzle and manufacturing method thereof Download PDFInfo
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- CN102335730B CN102335730B CN 201010236300 CN201010236300A CN102335730B CN 102335730 B CN102335730 B CN 102335730B CN 201010236300 CN201010236300 CN 201010236300 CN 201010236300 A CN201010236300 A CN 201010236300A CN 102335730 B CN102335730 B CN 102335730B
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- submersed nozzle
- slag line
- line section
- silicon
- aluminium titanates
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Abstract
The invention relates to a silicone-free submersed nozzle and a manufacturing method thereof. The silicone-free submersed nozzle comprises a body and a slag line segment, wherein the body comprises the following components in percentage by weight: 15-35% of crystalline flake graphite, 35-55% of white corundum and 20-50% of alumina titanate, and theslag line segment comprises the following components in weight percentage: 15-25% of crystalline flake graphite, 40-75% of zirconium oxide and 0-40% of alumina titanate. According to the invention, under the condition that the thermal shock resistance and the service life of the product can not be influenced, the generation of nodulation can be relieved or prevented by the mode of preventing the generation of SiO, and the nozzle is prevented from being blocked.
Description
Technical field
The present invention relates to a kind of mouth of a river material and manufacture method, especially relate to no silicon submersed nozzle and the manufacture method thereof of the tundish that in continuous casting steel machine is produced, uses.
Background technology
Submersed nozzle is one of functional refractory of most critical during continuous casting of iron and steel is produced, and its result of use directly influences stability and the billet quality that continuous casting is produced.Submersed nozzle is between tundish and crystallizer; it is the only way that molten steel enters crystallizer; play a part water conservancy diversion and protection molten steel; prevent that molten steel from contacting the possibility that oxidation takes place again with airborne oxygen; simultaneously by gate structure reasonable in design; can prevent from producing unreasonable flow field when molten steel from entering crystallizer, influence the quality of steel.
At present, the used material of submersed nozzle mainly is Al
2O
3-C matter.Its batching mainly is fused white corundum, flaky graphite, bond and additive etc.
Aluminium carbon submersed nozzle produces the dross clogging through regular meeting in the casting process except the machinery damage and deteriorating.Particularly when cast aluminum killed steel, Al in the Chang Yingang liquid
zO
3Be attached to mouth of a river inwall and stop up Deng field trash, thereby influence working continuously of continuous casting.Owing to stick to the field trash of submersed nozzle inner surface, may come off in casting cycle simultaneously, fall in the molten steel, cause the nonmetal inclusion in the continuous casting billet, and influence the quality of continuous casting steel billet, seriously be these slag inclusion things base shell generation bleed-out accidents of can being nipped.In addition, the dross of submersed nozzle inwall also can cause the bias current of molten steel in mold, and this influences the quality of strand equally, and the abnormality processing after bias current makes the matter worse especially to the incidence of strand slag inclusion, the formation that is mingled with and accident.
Research work to Mechanism of clogging in submerged entry nozzle has been carried out more than 20 year, concludes and gets up to mainly contain following several viewpoint: (1) reaction formation mechanism; (2) evaporation one cohesion causes physical deposition.According to the research to nozzle blocking mechanism, taked much way targetedly, mainly take preventive measures from process for making angle and submersed nozzle two aspects.
Reduce deoxidation product fusing point from process for making angle: A.; B. molten steel cleans.From the submersed nozzle angle: a kind of is that structure is anti-blocking, and principle is to change molten steel in the fluidised form of inside, the mouth of a river, reduces eddy current, thereby eliminates dross; Another kind is that material is anti-blocking, namely in the mouth of a river, add additive or in the mouth of a river the anti-blocking material liner of compound one deck, reduce or eliminate deposition, because of the material difference, anti-blocking mechanism is also different.The improvement of mouth of a river material is the main direction that solves the nozzle blocking problem.Main two classes of dividing add additive and improve mouth of a river material and the new mouth of a river material of exploitation.
Submersed nozzle Al
2O
3The one of the main reasons of stopping up is the existence because of carbon in the material of the mouth of a river, with SiO wherein
2Reduction reaction takes place, reduzate SiO and CO further with molten steel in the Al reaction and generate Al
2O
3, stick to the Al that is exposed to mouth of a river internal face
2O
3On the aggregate, cause mouth of a river inwall Al
2O
3Deposition.Therefore realize that it is to solve one of main method of nozzle blocking that submersed nozzle does not have silication.
Summary of the invention
The object of the present invention is to provide a kind of no silicon submersed nozzle and manufacture method thereof, do not influencing the product thermal shock resistance, anti-erosion, under antiscour and the condition than the long life, by adding with carborundum and vitreous silica component in the alternative traditional submersed nozzle material of the material of aluminum titanate of bond modification, the material of aluminum titanate that adds by modification after, eliminated the low defective of material of aluminum titanate sintered body intensity, and vitreous silica and carborundum replaced in the material, effectively prevent from producing the generation of SiO and CO in the casting process, and then reduced the further oxidation of AL in itself and the molten steel and Al in generating
2O
3Thereby slow down or stop the generation of dross, prevent nozzle blocking, to promote the stable raising of continuous casting production and quality; The improvement of slag line section material consider that this position is subject in cast that covering slag corrodes and the basis of the characteristic of oxidation and zirconia use cost on; proportioning is carried out in actual demand according to the scene, and the meaning of its material introducing aluminium titanates also is oxidation and the Al for preventing slag lining
2O
3Generation and adopt aluminium titanates to substitute carborundum and vitreous silica, to improve casting quality.
For achieving the above object technical scheme of the present invention:
In order to prevent the generation of SiO, do not introduce material, as for improving the thermal shock resistance performance of submersed nozzle, often introduce 5～15% fused quartz powders, for slowing down graphite oxidation, often introduce carborundum and replace part graphite.The aluminium titanates that the present invention then introduces low-expansion coefficient, highly heatproof and shockproof replaces vitreous silica and carborundum, under the condition that does not influence product thermal shock resistance and service life, by preventing that mode that SiO generates from slowing down or stoping the generation of dross, prevent nozzle blocking.
Particularly, no silicon submersed nozzle of the present invention, it comprises body and slag line section; Wherein, body material weight percentages of components is: crystalline flake graphite 15～35%, white fused alumina 35～55%, aluminium titanates 20～50%; Slag line section material weight percentages of components is: crystalline flake graphite 15～25%, zirconia 40～75%, aluminium titanates 0～40%.
Further, described aluminium titanates component percentage composition is: Al
2O
340～50%, TiO
250～60%, add stabilizing agent; Wherein, the stabilizing agent that adds is MgO 1～4% or MgO 1～4% and CeO
21～3% or F
2O
33～8% or zirconia 0.5～2% or MgO and CeO
2And F
2O
3With the mixture 2～6% of zirconia, by weight percentage.
Aluminium titanates component described above and stabilizing agent close in advance by high temperature earlier, and pre-synthesis temperature is 1450～1700 ℃.
Above-mentioned additive interpolation content is the relative amount outside the raw material total amount 100%.
Aluminium titanates, it is pseudobrookite structural group compound, belongs to rhombic system, its crystal thermal coefficient of expansion in different directions is significantly different, therefore after burning till cooling, because internal stress is excessive, produces a large amount of micro-cracks in inside.In the aluminium titanates crystal structure, each aluminium ion and titanium ion are formed octahedral six oxygen atoms and surround and be positioned at octahedral center, these (TiO
6) or (AlO
6) on a axle, b direction of principal axis, link to each other with common edge.On the c direction of principal axis, three octahedral summits couple together and form continuous chain, and each chain infinitely extends in the space, cross link mutually, form the space network structure, this shows lower thermal coefficient of expansion in macroscopic view, but simultaneously the intensity of sintered body is reduced greatly.Usually need introduce additive and improve performance alumina titanate ceramics performance in host material, the additive that aluminium titanates modification is at present used has Li
2O, B
2O, Cr
2O
3, La
2O
3, CeO
2, SiC, Si
3N
4, SiO
2, MgO, F
2O
3, ZrO
2And FeTiO
3+ Fe
2O
3Deng.
The aluminum titanate ceramic material of modification preparation have high melt point, lower thermal coefficient of expansion (under RT-1000 ℃ of condition, α＜2.0 * 10
-6/ ℃), and have good thermal shock resistance: Δ Tc＞1000 ℃, thermal conductivity factor is little, has very big application potential under higher temperature and cold and hot frequent exchange condition.Have in addition and many metals (particularly non-ferrous metal) liquation and the nonwettable characteristic of glass melts, can stand washing away for a long time and corroding of high temperature metal solution and do not produce peeling phenomenon.
The preparation method of no silicon submersed nozzle of the present invention, it comprises the steps:
1) submersed nozzle comprises body and slag line section, and wherein, body material weight percentages of components is: crystalline flake graphite 15～35%, white fused alumina 35～55%, aluminium titanates 20～50%; Slag line material weight percentages of components is: crystalline flake graphite 15～25%, zirconia 40～75%, aluminium titanates 0～40%;
2) body material and slag line material are evenly mixed respectively, add 10% phenolic resin binder in the above-mentioned component toward wherein adding, use comminutor with the raw material granulation, the oven dry of granulation material drying bed, make it to satisfy the moulding requirement, body material granulation material and slag line material granulation material are added mould respectively, use the compression moulding under 80～150MPa pressure of static pressure machine;
3) shaped article is fired under reducing atmosphere or oxygen-free environment with 1200～1300 ℃ in shuttle kiln, burns till product through machined into, and product surface applies inoxidzable coating again, namely makes submersed nozzle after the oven dry.
Further, described reducing atmosphere or oxygen-free environment are mode under carbon burial sintering or vacuum-sintering or the inert gas.
Described inoxidzable coating is enamel.
Beneficial effect of the present invention
Compare with the product of prior art, the present invention is owing to adopt aluminium titanates to replace vitreous silica and carborundum, make product realize no silication, both guaranteed the due mechanical strength of submersed nozzle, high thermal shock stability and anti-erosion, scour resistance, the generation that also can prevent SiO and CO in actual use slow down or stop the further oxidation of AL in SiO and the molten steel to generate Al
2O
3, and stick to mouth of a river inwall, form dross, reach and prevent nozzle blocking, guarantee the purpose that the mouth of a river is inner bright and clean, thereby effectively prevented the bias current that causes because of nozzle clogging and the various abnormality processing that therefore take place, ensure the stability that continuous casting is produced, thereby improve the quality of strand.
The specific embodiment
The present invention will be further described below in conjunction with embodiment.
The present invention does not have silicon submersed nozzle embodiment composition referring to table 1.
The preparation method of no silicon submersed nozzle of the present invention, it comprises the steps: body material and slag line material are evenly mixed respectively, add 10% phenolic resin binder in the above-mentioned component toward wherein adding, use comminutor with the raw material granulation, the oven dry of granulation material drying bed, make it to satisfy the moulding requirement, body material granulation material and slag line material granulation material are added mould respectively, use the compression moulding under 80～150MPa pressure of static pressure machine; Shaped article is fired under reducing atmosphere or oxygen-free environment with 1200～1300 ℃ in shuttle kiln, burns till product through machined into, and product surface applies inoxidzable coating again, namely makes submersed nozzle after the oven dry.
Table 1 unit: percentage by weight
Claims (4)
1. do not have the silicon submersed nozzle, it is characterized in that: comprise body and slag line section; Wherein, body material weight percentages of components is: crystalline flake graphite 15～35%, white fused alumina 35～55%, aluminium titanates 20～50%; Slag line section material weight percentages of components is: crystalline flake graphite 15～25%, zirconia 40～75%, aluminium titanates 0～40%; Described aluminium titanates component percentage composition is: Al
2O
340～50%, TiO
250～60%, add stabilizing agent; Adding stabilizing agent is MgO 1～4% or MgO 1～4% and CeO
21～3% or zirconia 0.5～2%, by weight percentage.
2. do not have the manufacture method of silicon submersed nozzle, it comprises the steps:
1) submersed nozzle comprises body and slag line section, and wherein, body material weight percentages of components is: crystalline flake graphite 15～35%, white fused alumina 35～55%, aluminium titanates 20～50%; Slag line section material weight percentages of components is: crystalline flake graphite 15～25%, zirconia 40～75%, aluminium titanates 0～40%;
2) body material and slag line section material are evenly mixed respectively, add 6%～10% phenolic resin binder respectively in body material component and the slag line section material component, use comminutor with the raw material granulation, the oven dry of granulation material drying bed, make it to satisfy the moulding requirement, body material granulation material and slag line material granulation material are added mould respectively, use the compression moulding under 80～150MPa pressure of static pressure machine;
3) shaped article is fired under 1200～1300 ℃ of reducing atmospheres or oxygen-free environment in shuttle kiln, burns till product through machined into, and product surface applies inoxidzable coating again, namely makes no silicon submersed nozzle after the oven dry.
3. the manufacture method of no silicon submersed nozzle as claimed in claim 2, it is characterized in that: described reducing atmosphere or oxygen-free environment are mode under carbon burial sintering or vacuum-sintering or the inert gas.
4. the manufacture method of no silicon submersed nozzle as claimed in claim 2, it is characterized in that: described inoxidzable coating is enamel.
Priority Applications (1)
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|---|---|---|---|
| CN 201010236300 CN102335730B (en) | 2010-07-26 | 2010-07-26 | Silicone-free submersed nozzle and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010236300 CN102335730B (en) | 2010-07-26 | 2010-07-26 | Silicone-free submersed nozzle and manufacturing method thereof |
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| CN102335730B true CN102335730B (en) | 2013-07-17 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104289706B (en) * | 2014-09-29 | 2017-02-15 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Submersed water gap applied to electromagnetic stirring process |
| CN108971476B (en) * | 2018-07-13 | 2020-05-22 | 西峡县西保冶金材料有限公司 | Anti-blocking composite zirconium core built-in submerged nozzle for special steel and preparation process thereof |
| CN108975925B (en) * | 2018-08-09 | 2021-02-02 | 山东银山耐火材料有限公司 | Preparation method of ladle refractory air brick |
| CN112778001A (en) * | 2019-11-04 | 2021-05-11 | 江苏高鑫高温新材料科技有限公司 | Submersed nozzle and preparation method thereof |
| CN111889664B (en) * | 2020-07-29 | 2021-08-17 | 辽宁科大东方巨业高级陶瓷有限公司 | Self-sealing submerged nozzle and manufacturing method thereof |
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| CN1515372A (en) * | 2003-01-07 | 2004-07-28 | 武汉科技大学 | Preparation method of Al2O3-MgO-ZrO2 ladle air plug |
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| JP2543684B2 (en) * | 1986-10-18 | 1996-10-16 | 日本坩堝株式会社 | Highly corrosion-resistant immersion nozzle with two-layer structure |
| JP3344929B2 (en) * | 1997-07-22 | 2002-11-18 | 東芝セラミックス株式会社 | Nozzle for continuous casting |
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| CN1429673A (en) * | 2002-01-14 | 2003-07-16 | 鞍山市胜威高温陶瓷制造有限公司 | Non-preheating aluminium carbon zirconium mass immersion type sprue |
| CN1515372A (en) * | 2003-01-07 | 2004-07-28 | 武汉科技大学 | Preparation method of Al2O3-MgO-ZrO2 ladle air plug |
Non-Patent Citations (4)
| Title |
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| JP昭63-101059A 1988.05.06 |
| JP特开平11-33685A 1999.02.09 |
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