CN1060752C - Production method of refractory material for immersed sprue - Google Patents
Production method of refractory material for immersed sprue Download PDFInfo
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- CN1060752C CN1060752C CN97100785A CN97100785A CN1060752C CN 1060752 C CN1060752 C CN 1060752C CN 97100785 A CN97100785 A CN 97100785A CN 97100785 A CN97100785 A CN 97100785A CN 1060752 C CN1060752 C CN 1060752C
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- river
- mouth
- oxide
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- magnesium
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Abstract
The present invention relates to a method for preparing carbon composite refractory materials for an immersion nozzle used for continuous casting. An immersion nozzle is composed of a nozzle body and a composite layer for preventing clogging in the nozzle, wherein the composite layer for preventing clogging has the preparing method that after zirconite, silicon nitride, magnesia alumina spinel and sintering assistant are uniformly mixed, the raw materials are formed in an isostatic pressing mode; the raw materials are sintered into ceramic composite sand at 1500 to 1750 DEG C in a non-oxidizing atmosphere; after 25 to 45% of composite sand, 20 to 35% of stable zirconium oxide, 10 to 15% of natural scale graphite, 5 to 8% of phenolic resin and 5 to 10% of Alon are uniformly mixed and ground into mud, the mud is combined with the nozzle body; the composite layer can be obtained by isostatic pressing forming and sintering.
Description
The present invention relates to a kind of manufacture method of refractory materials, especially thin-walled, can prevent AL
2O
3The manufacture method of sedimentary submerged nozzle.
Immersion water gap for continuously casting is prevented Al
2O
3Deposition or obstruction are the stable inevitable requirements of continuous casting process, Al
2O
3The reason of stopping up is because the Al in the molten steel
2O
3Separate out or the mouth of a river in SiO
2, the Al reaction in SiC etc. and the molten steel and be deposited on result's (being nozzle clogging) of mouth of a river inwall, this obstruction all is the problem that does not solve fully to general continuous casting or sheet blank continuous casting, mainly contains following several solution in the prior art:
1. adopt the Puffer type multilayer structure, this is the anti-Al in the present mouth of a river
2O
3Deposit the most frequently used method, the gate structure complexity.For sheet blank continuous casting,, obviously can't adopt this structure because itself tube wall of the used thin-walled mouth of a river is very thin.
2. mouth of a river insulation, Al
2O
3Separating out is because liquid steel temperature descends, and the state that reaches capacity of the Al in the steel is given Al
2O
3Separate out the condition created, outer wall is wrapped ceramic fiber layer at the mouth of a river, to reduce molten steel thermosteresis in the submerged nozzle, helps anti-Al
2O
3Deposition.This is a kind of householder method eventually, and for sheet blank continuous casting, this measure is limited by thin-walled equally.
3. on the inwall material of the mouth of a river, improve, select for use and adhere to Al
2O
3Reaction forms the material of eutectic, and eutectic can be washed out by molten steel, can prevent Al
2O
3Stop up.The Japanese Patent spy opens clear 57-71860, and 62-288161, spy open flat 4-224061 has all proposed to introduce CaO in the material of the mouth of a river method, promptly select CaO-ZrO for use
2-C based material is to form Al
2O
3-CaO-ZrO
2Molten thing hangs down in system, reaches to prevent Al
2O
3Sedimentary purpose, CaO content height in this class technologic material, body is dissolved in the equal Yishui River of raw material and goods.Chinese patent CN1112909A discloses a kind of anti-Al
2O
3The mouth of a river material that deposition is stopped up is promptly at ZrO
2Add Calcium Fluoride (Fluorspan) in the-C material, this is to be that cost adopts the melting loss method to reach anti-Al with the partial sacrifice mouth of a river life-span
2O
3Sedimentary purpose for the not thick thin-walled mouth of a river of wall itself, obviously is not suitable for the melting loss method.
United States Patent (USP) 4804644 discloses a kind of " stupalith ", be by zircon, silicon nitride, aluminum oxide and sintering aid such as yttrium oxide or magnesium-aluminium spinel etc. through etc. static pressure, so 1500-1750 ℃ of following sintering obtains being uniform-distribution with ZrO in O '-Sialon matrix
2Stupalith, the anti-AL of this material
2O
3Deposition properties is good, but anti-erosion, anti-molten steel scouring ability are relatively poor, can not adapt to the processing requirement at the thin-walled mouth of a river.
The objective of the invention is to obtain a kind of manufacture method of refractory material for immersed sprue, this material and Al
2O
3Reactivity is poor, associativity is little, and stronger anti-molten steel scouring, aggressiveness are arranged again.
The object of the present invention is achieved like this:
A kind of manufacture method of soaking people's formula mouth of a river refractory materials, be that anti-clogging plug composite bed two portions by mouth of a river body and inside, the mouth of a river are composited, the manufacture method of anti-clogging plug composite bed is: use zircon, silicon nitride, magnesium-aluminium spinel and sintering aid are raw material, mixing is after isostatic pressing, in 1500-1750 ℃ of Low fire ceramic complex sand in non-oxidizing atmosphere, with this complex sand fragmentation, sieve into the desired particle size specification, and by following composition (weight): complex sand: 25-45%, stable zirconium oxide: 20-35%, natural flake graphite: 10-25%, resol: 5-8%, A Long is Alon:5-10%, after mixing grinds mud, with this volume recombination of the mouth of a river, with sintering behind the hydrostatic pressing, promptly can be made into required submerged nozzle.
The material composition (weight) of making complex sand is: zircon: 35-55%, silicon nitride: 20-50%, magnesium-aluminium spinel: 1O-20%, sintering aid: 2-8%.
Sintering aid is the arbitrary combination of any or above additive in yttrium oxide, aluminum oxide, magnesium oxide, calcium oxide, the silicon oxide.
Below the present invention is further described.
The complex sand that the present invention makes is to be added sintering aids and done raw material by zircon, silicon nitride, magnesium-aluminium spinel, three kinds of materials, each components contents and acting as:
Zircon: 35-55% (weight percent, as follows) can improve the corrosion resistance of material, too highly then makes anti-Al
2O
3Deposition property variation, and when sintering, easily cause burning, low excessively when making sintering density low.
Following reaction, take place with zircon in silicon nitride: 20-50%:
Si
2N
2O and Al
2O
3Reaction obtains O '-Sialon, and the O ' that obtains-Sialon has anti-Al
2O
3Deposition with the characteristics of molten steel wettability difference, forms the liquid phase film at high temperature more than 1550-1600 ℃, makes Al
2O
3Adhere to difficulty.
Magnesium-aluminium spinel: 10-20%, the present invention also increase finely divided magnesium-aluminium spinel, and a part is as sintering aid, and another part can improve the corrosion resistance of material as independently being present in mutually in the matrix.
Sintering aid: 2-8% is the arbitrary combination of a kind of or above-mentioned additive in yttrium oxide, aluminum oxide, calcium oxide, the silicon oxide.
Top raw material blending is ground mud, through isostatic pressing, Low fire ceramic material in l500-1750 ℃ of following non-oxidizing atmosphere, it is a kind of and Al
2O
3Reactive little, poor with molten steel wettability, the stupalith that corrosion resistance is strong, its main phase composite is: O '-Sialon, magnesium-aluminium spinel, stabilizing zirconia and full-bodied glassy phase, through fragmentation, Ceramic Composite sand is made in screening, make the anti-clogging plug layer carbon composite of mouth of a river inwall with this complex sand and other raw material, its composition is (weight percent): complex sand: 30-50%, stabilizing zirconia: 20-40%, natural flake graphite: 10-25%, resol: 5-8%, Alon:5-10%, with above-mentioned raw materials after mixing grinds mud, with aluminium carbon, this volume recombination of the mouth of a river of zirconium carbon, through hydrostatic pressing and sintering, promptly can be made into submerged nozzle, the acting as of each component:
Complex sand: 25-45%, (weight percent, as follows) is owing to exist O '-Sialon, cubic zirconia ZrO in the complex sand
2With magnesium-aluminium spinel mutually, a kind of braiding structure of the interlaced formation of the needle-like crystal of O '-Sialon, ZrO
2, the magnesium-aluminium spinel particle then mainly is filled in the control crack of braiding structure and plays dispersion-strengthened action, so material has excellent mechanical property.Under the condition of high temperature, molten steel and complex sand surface form the full-bodied liquid phase film of one deck and hinder Al
2O
3Deposition, magnesium-aluminium spinel can improve the corrosion resistance of material mutually simultaneously.
Stable zirconium oxide: 20-35% forms cubic zirconia, improves the resistance to fouling of material, too high anti-Al
2O
3Deposition property variation is crossed low resistance to fouling and is descended.
Natural flake graphite: 10-25% improves the heat-shock resistance of material, anti-molten steel erosion.
Resol: 5-8%, the binding agent during press forming, low excessively, the pug wettability is poor, and blank strength is poor, and is too high, pug volatile content height, base substrate easily cracks.
A Long (Alon): 5-10%, high-temperature stability is good, replaceable part of O '-Sialon, improve material anti-erosion, thermal shock ability, low excessively, inoperative, too high, cost is too high.
Above-mentioned raw materials after mixing grinds mud, with this volume recombination of the mouth of a river of aluminium carbon, zirconium carbon material, is used hydrostatic pressing, promptly can be made into submerged nozzle behind the sintering.
Introduce embodiments of the invention below in conjunction with effect.
Use following raw materials according: zircon, silicon nitride, magnesium-aluminium spinel, wherein the composition of magnesium-aluminium spinel is (weight percent): MgO:30%, Al
2O
3: 67%, SiO
2: 2.0%, CaO:0.5%, Fe
2O
3: 0.5%, the chemical constitution such as the table 1 of raw material show.
All raw materials all are milled to below the 7 μ m, and concrete ratio such as table 2 show, place ceramic ball mill respectively in required ratio, are grinding medium with alumina balls, add alcohol wet mixing half hour, and raw material is mixed, and be dry then, to grind the back standby.
Mixed raw material is placed the axle pressure in advance compression moulding of punching block with 30MPa earlier, and then the pressure with 200MPa carries out isostatic cool pressing on cold isostatic press.In resistance furnace; 1600 ℃ of following sintering of argon shield 3 hours; obtain Ceramic Composite sand; with this complex sand fragmentation, sieve into required granularity; with following ingredients: complex sand: stabilizing zirconia 30%: natural flake graphite 40%: resol 17%: Alon:8% 5%; concrete composition of anti-clogging plug composite bed such as the table 4 of making inside, the mouth of a river behind the mixing stone roller mud show; with alumina-carbon material this volume recombination of the mouth of a river after the 250-300MPa cold isostatic compaction was made submerged nozzle in 24 hours in 1150-1200 ℃ of sintering.The anti-clogging plug composite bed is carried out anti-Al
2O
3Deposition test, result such as table 5 show.Test conditions: 1600 ℃ of induction furnaces, 1 hour, the upper strata was a covering slag, and the bottom is a molten steel, and the molten steel chemical ingredients is (a calm steel): C:0.15, Si＜0.03, Mn:0.4, P:0.008, S:0.012, Al:0.051.
EDAX results shows: material of the present invention and O '-ZrO
2There is Al hardly in-C material hot side
2O
3, illustrate that the Al in the molten steel fails to be deposited on material surface.Compared with prior art, increased the strong magnesium-aluminium spinel of anti-erosion power in the material of the present invention, made a magnesium-aluminium spinel part as sintering aid, a part is as independently existing mutually, and therefore, the resistance to fouling of material of the present invention is than O '-ZrO
2-C material is strong.This material promptly has anti-preferably Al
2O
3Deposition properties has anti-preferably molten steel erosion, scouring capability again.
Table 1
| Raw material | N | Si | Free Si | ZrO 2 | Al 2O 3 | SiO 2 | Fe 2O 3 | TiO 2 | R 2O | CaO | MgO |
| Si 3N 4 | 38．07 | 57．11 | 1．7 | ||||||||
| ZrSiO 4 | 64．68 | ＜0．10 | 33．60 | 0．12 | 0．06 | 0．072 | 0．012 | ||||
| Al 2O 3 | 98．78 | 0．08 | Trace | 0．04 | ／ | ／ | |||||
| SiO 2 | 0．40 | 98．19 | 0．04 | 0．06 | 0．23 | 0．18 | 0．09 |
Table 2
Table 3
Table 4
Table 5
| Material of the present invention | CaO-ZrO 2-C material | O′-ZrO 2-C material | |
| Anti-Al 2O 3Deposition index | 1．8 | 2．0 | 1．8 |
| The anti-slagging of retractory (mm) | 0．020 | 0．020 | 0．048 |
| Anti-molten steel erosion (mm/min) | 0．015 | 0．015 | 0．021 |
Claims (1)
1. the manufacture method of a refractory material for immersed sprue, be that anti-clogging plug composite bed two portions by mouth of a river body and inside, the mouth of a river are composited, it is characterized in that: the manufacture method of anti-clogging plug layer is: the raw material of using following ingredients (weight): zircon: 35-55%, silicon nitride: 20-50%, magnesium-aluminium spinel: 10-20%, the sintering aid yttrium oxide, aluminum oxide, magnesium oxide, calcium oxide, the arbitrary combination of any in the silicon oxide or above additive: 2-8%, isostatic pressing behind mixing, in 1500-1750 ℃ of Low fire ceramic complex sand in non-oxidizing atmosphere, with this complex sand fragmentation, sieve into the desired particle size specification, and by following composition (weight): complex sand: 25-45%, stable zirconium oxide: 20-35%, natural flake graphite: 10-25%, resol: 5-8%, A Long are Alon:5-10%, after mixing grinds mud, with this volume recombination of the mouth of a river, with behind the hydrostatic pressing at 1150-1200 ℃ of sintering, promptly can be made into required submerged nozzle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100785A CN1060752C (en) | 1997-02-27 | 1997-02-27 | Production method of refractory material for immersed sprue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100785A CN1060752C (en) | 1997-02-27 | 1997-02-27 | Production method of refractory material for immersed sprue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1176236A CN1176236A (en) | 1998-03-18 |
| CN1060752C true CN1060752C (en) | 2001-01-17 |
Family
ID=5165319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97100785A Expired - Fee Related CN1060752C (en) | 1997-02-27 | 1997-02-27 | Production method of refractory material for immersed sprue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060752C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100457321C (en) * | 2007-04-30 | 2009-02-04 | 山东中齐耐火材料有限公司 | Non-fabric heat-proof coating material for continuous casting nozzle |
| EP2169311A1 (en) | 2008-09-29 | 2010-03-31 | Siemens Aktiengesellschaft | Material mixture for producing a fire-retardant material, fire-retardant moulding body and method for its manufacture |
| CN102294470B (en) * | 2011-08-23 | 2013-08-28 | 湖州永联耐火材料有限公司 | Anti-blocking type long water gap bowl part |
| CN102838360B (en) * | 2012-09-12 | 2014-12-24 | 首钢总公司 | Composite fireproof material and preparation method thereof |
| CN102962445B (en) * | 2012-11-22 | 2015-06-10 | 河南省西保冶材集团有限公司 | Baking-free long water gap for large-plate-blank continuous casing low-carbon and low-silicon steel and preparation process of baking-free long water gap |
| CN105903666B (en) * | 2016-04-28 | 2018-03-06 | 安徽瑞联节能科技有限公司 | A kind of anti-clogging processing method for the gun barrel that discharges |
| CN105921390B (en) * | 2016-04-28 | 2018-03-06 | 安徽瑞联节能科技有限公司 | A kind of manufacture method of anti-clogging discharging gun barrel |
| CN109400121B (en) * | 2018-12-29 | 2022-02-11 | 河南新拓耐火材料有限公司 | Unfired and non-soaked magnesium-aluminum sliding plate for ladle sliding gate and preparation method thereof |
| CN110156462A (en) * | 2019-05-31 | 2019-08-23 | 鞍山市和丰耐火材料有限公司 | The smelting stainless steel submersed nozzle and its production method of resistant to corrosion long-life |
| CN110903086A (en) * | 2019-12-10 | 2020-03-24 | 中钢集团洛阳耐火材料研究院有限公司 | High-performance magnesium-stabilized zirconia raw material |
| CN113087539B (en) * | 2021-05-18 | 2022-06-21 | 江苏泰瑞耐火有限公司 | Refractory material for zirconia composite metering nozzle and application thereof |
| CN113277861B (en) * | 2021-05-18 | 2022-06-21 | 江苏泰瑞耐火有限公司 | Refractory material for submerged nozzle and application 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5771860A (en) * | 1980-10-24 | 1982-05-04 | Kurosaki Refractories Co | Cao-containing graphitic casting nozzle |
| JPS62288161A (en) * | 1986-06-05 | 1987-12-15 | 黒崎窯業株式会社 | Manufacture of dipping nozzle containing zro2-cao for continuous casting |
| JPH04224061A (en) * | 1990-12-27 | 1992-08-13 | Kurosaki Refract Co Ltd | Refractory for continuous casting |
| CN1112909A (en) * | 1995-03-13 | 1995-12-06 | 无锡市南方耐火材料厂 | Refractory for continuous casting and immersion type riser |
-
1997
- 1997-02-27 CN CN97100785A patent/CN1060752C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5771860A (en) * | 1980-10-24 | 1982-05-04 | Kurosaki Refractories Co | Cao-containing graphitic casting nozzle |
| JPS62288161A (en) * | 1986-06-05 | 1987-12-15 | 黒崎窯業株式会社 | Manufacture of dipping nozzle containing zro2-cao for continuous casting |
| JPH04224061A (en) * | 1990-12-27 | 1992-08-13 | Kurosaki Refract Co Ltd | Refractory for continuous casting |
| CN1112909A (en) * | 1995-03-13 | 1995-12-06 | 无锡市南方耐火材料厂 | Refractory for continuous casting and immersion type riser |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1176236A (en) | 1998-03-18 |
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Owner name: BAOSHAN IRON & STEEL CO., LTD.; WUHAN UNIVERSITY O Free format text: FORMER NAME OR ADDRESS: SHANGHAI BAO STEEL GROUP IRON AND STEEL CO LTD; WUHAN UNIVERSITY OF SCIENCEAND TECHNOLOGY Owner name: SHANGHAI BAO STEEL GROUP IRON AND STEEL CO LTD; WU Free format text: FORMER NAME OR ADDRESS: BAOSHAN STEEL GROUP IRON AND STEEL CO LTD; WUHAN METALLURGY TECHNOLOGY UNIVERSITY |
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Granted publication date: 20010117 Termination date: 20140227 |