JPH03128165A - Production of porous plug - Google Patents
Production of porous plugInfo
- Publication number
- JPH03128165A JPH03128165A JP1265448A JP26544889A JPH03128165A JP H03128165 A JPH03128165 A JP H03128165A JP 1265448 A JP1265448 A JP 1265448A JP 26544889 A JP26544889 A JP 26544889A JP H03128165 A JPH03128165 A JP H03128165A
- Authority
- JP
- Japan
- Prior art keywords
- porous plug
- raw material
- molten steel
- cao
- molding
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 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 5
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 239000011029 spinel Substances 0.000 claims abstract description 4
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 238000010304 firing Methods 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 13
- 239000010959 steel Substances 0.000 abstract description 13
- 230000035515 penetration Effects 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 238000004901 spalling Methods 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011230 binding agent Substances 0.000 abstract description 4
- 238000007664 blowing Methods 0.000 abstract description 4
- 239000011261 inert gas Substances 0.000 abstract description 4
- 239000011819 refractory material Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract 2
- 229910007941 ZrCaO3 Inorganic materials 0.000 abstract 1
- 239000013618 particulate matter Substances 0.000 abstract 1
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000029087 digestion Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、ポーラスプラグを製造する方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method of manufacturing a porous plug.
溶鋼成分温度の均一化、非金属介在物の浮上分離などを
目的として、溶鋼容器の底からに不活性ガスを吹き込む
ことが行われている。Inert gas is blown into the bottom of a molten steel container for the purpose of equalizing the temperature of molten steel components and floating and separating nonmetallic inclusions.
これに使用される耐火物製のポーラスプラグは、使用を
休止すると、ガス孔となる耐火物の気孔中に溶鋼が浸透
し、ガス吹き込みが再開出来なくなる。このため、酸素
洗浄で浸透部分の溶鋼を溶融除去しているが、酸素洗浄
は2000℃以上の高温を招き、ポーラスプラグ上端部
が著しく損傷される。If the refractory porous plug used for this is stopped, molten steel will penetrate into the pores of the refractory that serve as gas holes, making it impossible to resume gas injection. For this reason, the molten steel in the permeated portion is melted and removed by oxygen cleaning, but oxygen cleaning causes high temperatures of 2000° C. or higher, and the upper end of the porous plug is severely damaged.
そこで、炭素質原料を配合することで、酸素洗浄の際の
溶損あるいはスポーリングによる損傷を防止したポーラ
スプラグが提案されている(例えば、特開昭55−18
556号)。Therefore, porous plugs have been proposed that prevent damage due to erosion or spalling during oxygen cleaning by incorporating carbonaceous raw materials (for example, JP-A-55-18
No. 556).
しかし、炭素質原料の配合は通気性を低下するため、可
燃物の混入でガス孔を形成しているが、可燃物の使用は
ガス孔の径が大きくなり、溶鋼がより深く浸透する結果
となり、十分な解決策とはいえなかった。However, blending carbonaceous raw materials reduces air permeability, so gas pores are formed by mixing combustible materials, but using combustible materials increases the diameter of the gas pores, resulting in deeper penetration of molten steel. , it was not a sufficient solution.
本発明は、主たる鉱物組成がキュービックZrO,およ
びZrCaO1よりなり、化学組成としてCaO3〜4
0wt%、残部がZrO2を主材とする電融耐火原料(
以下、電融カルシウムジルコネート原料と称す)3〜2
5wt%、残部をアルミナ、マグネシア、スピネルから
選ばれる一種以上を主材とした配合物を成形後、焼成す
ることを特徴としたポーラスプラグの製造方法である。The main mineral composition of the present invention is cubic ZrO and ZrCaO1, and the chemical composition is CaO3-4.
0wt%, the balance being ZrO2 as the main material (
Hereinafter referred to as fused calcium zirconate raw material) 3-2
This is a method for producing a porous plug, which is characterized in that a compound containing 5 wt % and the balance mainly of one or more selected from alumina, magnesia, and spinel is molded and then fired.
本発明により得られる耐火物は、電融カルシウムジルコ
ネート原料中のCaOが骨材成分からくるAl2O,と
反応し、次式のとおりカルシウムアルミネート(XCa
O・YAI□03)を生成する。In the refractory obtained by the present invention, CaO in the fused calcium zirconate raw material reacts with Al2O from the aggregate component, and calcium aluminate (XCa
O・YAI□03) is generated.
X CaO+ Y A lx Ox →X Ca0−Y
A lx 03このカルシウムアルミネートは12C
a0・7A120..3CaOA1.O。X CaO+ Y A lx Ox →X Ca0-Y
A lx 03 This calcium aluminate is 12C
a0・7A120. .. 3CaOA1. O.
などの低融点物質であることによって、ポーラスプラグ
稼動面の溶鋼浸透部の溶損によるガス孔閉塞防止ととも
に、応力緩和による耐スポーリング性に効果がある。By being a low melting point substance such as, it is effective in preventing gas pore clogging due to erosion of the molten steel penetration part on the working surface of the porous plug, as well as in spalling resistance due to stress relaxation.
また、本発明により得られる耐火物はポーラスプラグで
あることによって、耐火物組織中を通過させた不活性ガ
スを噴出させつつ使用される。この不活性ガスの存在で
、耐火物中のCaOと耐火物または溶鋼中の非金属介在
物中のAl2O,との反応が抑制され、カルシウムアル
ミネートの生成による溶損が徐々に進行し、必要以上の
溶損がないので、ポーラスプラグの耐食性を低下させる
こともない。Moreover, since the refractory obtained by the present invention is a porous plug, it can be used while blowing out the inert gas that has passed through the refractory structure. The presence of this inert gas suppresses the reaction between CaO in the refractory and Al2O in the refractory or nonmetallic inclusions in the molten steel, and erosion due to the formation of calcium aluminate gradually progresses, causing the necessary Since there is no melting loss as described above, the corrosion resistance of the porous plug is not reduced.
本発明で使用する電融カルシウムジルコネート原料は、
主たる鉱物組成がキュービックZrO□およびZrCa
O3よりなり、化学組成としてはCaO3〜40vt%
のものを使用する。化学組成としてのCaOが5vt%
未満では電融カルシウムジルコネート原料から十分なC
a0fflが析出せず、カルシウムアルミネートの生成
量が少なくなって浸透防止の効果が得られない、 Ca
O量が40%jt%を超えると遊離のCaO量が多くな
り、耐消化性に劣り、製造上の問題が生じるばかりでな
く、耐食性をも低下させる。The fused calcium zirconate raw material used in the present invention is
Main mineral composition is cubic ZrO□ and ZrCa
Composed of O3, chemical composition is CaO3~40vt%
Use the one. CaO as a chemical composition is 5vt%
If less than enough C is obtained from the fused calcium zirconate raw material
a0ffl does not precipitate, the amount of calcium aluminate produced is small, and the effect of preventing penetration cannot be obtained.Ca
When the amount of O exceeds 40%jt%, the amount of free CaO increases, resulting in poor digestion resistance, which not only causes manufacturing problems, but also reduces corrosion resistance.
この電融カルシウムジルコネート原料は、例えばZrO
,原料に内掛けでCaO原料を5〜40wt%添加した
ものを電融処理することで製造される。電融処理によっ
て、主たる鉱物組成がキュービックZrO,およびZr
CaO,の原料となる。粒度調整は、粉砕によって行う
。This fused calcium zirconate raw material is, for example, ZrO
It is produced by electromelting a raw material to which 5 to 40 wt% of CaO raw material is added. The main mineral composition is cubic ZrO and Zr by electromelting treatment.
It becomes the raw material for CaO. Particle size adjustment is performed by grinding.
ffl融カルシウムジルコネート原料の配合割合は、3
wt%未満では浸透防止の効果がなく、2ht%を超
えると耐食性が低下する。配合物中、電融カルシウムジ
ルコネート原料の残部は、焼結および/または電融のア
ルミナ、マグネシア、スピネルから選ばれる一種以上を
主材とする。必要により、さらに炭化物、窒化物、炭素
、酸化クロム、粘土、シリカ、ガラス、金属粉などを適
量添加してもよい。The blending ratio of ffl-fused calcium zirconate raw materials is 3
If it is less than wt%, there is no effect of preventing penetration, and if it exceeds 2ht%, corrosion resistance will decrease. In the formulation, the remainder of the fused calcium zirconate raw material is based on one or more selected from sintered and/or fused alumina, magnesia, and spinel. If necessary, appropriate amounts of carbides, nitrides, carbon, chromium oxide, clay, silica, glass, metal powder, etc. may be added.
本発明は、以上の各原料の組合せからなる配合物を成形
後、焼成して、ポーラスプラグを製造する。底形には、
耐火物用バインダーとして知られている無機物、有機物
あるいは有機無機複合物を適量添加して混線後、フリク
ションプレス、オイルプレスなどで加圧する。焼成は1
000〜1800℃が好ましい。In the present invention, a porous plug is manufactured by molding and firing a mixture made of a combination of the above-mentioned raw materials. The bottom shape is
After adding an appropriate amount of an inorganic substance, an organic substance, or an organic-inorganic composite known as a binder for refractories and mixing, the mixture is pressurized using a friction press, an oil press, or the like. Firing is 1
000-1800°C is preferred.
こうして得られる耐火物にガス吹き込み機能をもたせる
ためには、゛従来のポーラスプラグの製造方法と同様、
例えば耐火原料の粒度調整、配合物に焼失性空隙形成材
を混入するなどにより、耐火物組織を気孔率15〜30
%程度の高通気性材質にする。In order to provide the refractory obtained in this way with a gas blowing function, it is necessary to
For example, by adjusting the particle size of the refractory raw material or mixing a burnable pore-forming material into the compound, the refractory structure can be adjusted to a porosity of 15 to 30.
% of material with high air permeability.
なお、本発明より得られるポーラスプラグは、耐火物部
分全体を同材質にしたもの、あるいは同材質の外周を緻
密質耐火物にしたものなど、その構造は限定されるもの
ではない。Note that the structure of the porous plug obtained by the present invention is not limited, such as one in which the entire refractory portion is made of the same material, or one in which the outer periphery of the same material is made of dense refractory material.
以下、本発明実施例とその比較例を示す。 Examples of the present invention and comparative examples thereof are shown below.
第1表は、各側で使用した主な原料の化学組成を示す。Table 1 shows the chemical composition of the main raw materials used on each side.
電融カルシウムジルコネート原料について、CaOが5
vt%未満のものを使用すると浸透防止の効果がなく、
40wt%を超えると。Regarding the fused calcium zirconate raw material, CaO is 5
If less than vt% is used, there will be no penetration prevention effect,
If it exceeds 40wt%.
耐消化性に劣るので、ここではCaOが本発明の限定範
囲内のものを二種類あげた。Since they are inferior in digestion resistance, two types with CaO within the limited range of the present invention are listed here.
第2表は、本発明実施例あるいは比較例で使用した配合
組成と試験結果を示したものである。各側は、いずれも
第2表に示す配合物をミキサーで混練し、フリクション
プレスにてポーラスプラグ形状に成形後、1600℃×
4時間で焼成した。Table 2 shows the formulation compositions and test results used in the Examples and Comparative Examples of the present invention. Each side was prepared by kneading the compounds shown in Table 2 with a mixer, forming them into a porous plug shape with a friction press, and heating them at 1600°C.
It was baked in 4 hours.
前記の混純において実施例10は、配合物全体に結合剤
として液状フェノール樹脂を外掛け2wt%添加した。In Example 10, liquid phenol resin was added as a binder to the entire blend in an amount of 2 wt%.
その他の実施例・比較例は、いずれも配合物全体に結合
剤としてリグニンスルホン酸カルシウム1wt%および
水2wt%を添加した。In all other Examples and Comparative Examples, 1 wt % of calcium lignin sulfonate and 2 wt % of water were added as a binder to the entire formulation.
その他の例では、配合物全体に外掛けで液状フェノール
樹脂を2wt%添加した。In other examples, 2 wt% liquid phenolic resin was added to the entire formulation.
試験方法は次のとおりである。耐食性、耐浸透性および
耐スポーリング性は、300を取鍋用ポーラスプラグと
して使用し、測定した。The test method is as follows. Corrosion resistance, penetration resistance, and spalling resistance were measured using 300 as a porous plug for a ladle.
見掛気孔率・・・J I S −R2205に準じて測
定。Apparent porosity: Measured according to JIS-R2205.
通気率 ・・・常温空気を用いて測定。Air permeability...Measured using room temperature air.
単位は、cc、cn /(a#)(sec)・(水柱a
n)。Units are cc, cn/(a#)(sec)・(water column a
n).
耐食性
・・・比較例1の溶損寸法を100とした指数で示した
。数値が小さいものが耐食性に優れている。Corrosion resistance: Shown as an index with the erosion damage dimension of Comparative Example 1 set as 100. The smaller the number, the better the corrosion resistance.
耐浸透性
・・・溶鋼浸透寸法を測定し、比較例1での浸透寸法を
100とした指数で示した。数値が小さいものが耐浸透
性に優れている。Penetration resistance: The penetration dimension of molten steel was measured and expressed as an index with the penetration dimension of Comparative Example 1 as 100. The smaller the value, the better the penetration resistance.
耐スポーリング性
・・・ポーラスプラグのキレツの発生状況(キレツの発
生本数・大きさ)を、比
較例1の場合を基準にして、下記の3
段階に判定した。Spalling resistance: The occurrence of cracks in the porous plug (number and size of cracks) was evaluated in the following three grades based on Comparative Example 1.
○
;耐スポーリング佳人
Δ
同等
×
小
(効果)
以上に述べたとおり、本発明によって得られるポーラス
プラグは、溶鋼浸透防止、耐食性および耐スポーリング
性を兼ね備えている。したがって、このポーラスプラグ
は、その耐用寿命を格段に向上させることができる。○; Good spalling resistance Δ Same × Small (Effect) As described above, the porous plug obtained by the present invention has molten steel penetration prevention, corrosion resistance, and spalling resistance. Therefore, this porous plug can significantly improve its service life.
Claims (1)
CaO_3よりなり、化学組成として、CaO5〜40
wt%、残部がZrO_2を主材とする電融耐火原料3
〜25wt%、残部をアルミナ、マグネシア、スピネル
から選ばれる一種以上を主材とした配合物を成形後、焼
成することを特徴としたポーラスプラグの製造方法。Main mineral composition is cubic ZrO_2 and Zr
Consisting of CaO_3, chemical composition: CaO5-40
Electric melt refractory raw material 3 whose main material is wt% and the balance is ZrO_2
A method for producing a porous plug, which comprises molding and firing a compound containing ~25 wt% and the remainder being one or more selected from alumina, magnesia, and spinel.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1265448A JPH03128165A (en) | 1989-10-11 | 1989-10-11 | Production of porous plug |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1265448A JPH03128165A (en) | 1989-10-11 | 1989-10-11 | Production of porous plug |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03128165A true JPH03128165A (en) | 1991-05-31 |
Family
ID=17417299
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1265448A Pending JPH03128165A (en) | 1989-10-11 | 1989-10-11 | Production of porous plug |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03128165A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1243361A1 (en) * | 2001-03-19 | 2002-09-25 | Vesuvius Crucible Company | Apparatus for injecting gas into molten metal |
KR100643838B1 (en) * | 2005-05-02 | 2006-11-10 | 조선내화 주식회사 | bubbling plug for gas purging |
-
1989
- 1989-10-11 JP JP1265448A patent/JPH03128165A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1243361A1 (en) * | 2001-03-19 | 2002-09-25 | Vesuvius Crucible Company | Apparatus for injecting gas into molten metal |
WO2002074470A1 (en) * | 2001-03-19 | 2002-09-26 | Vesuvius Crucible Company | Refractory plug or brick for injecting gas into molten metal |
KR100643838B1 (en) * | 2005-05-02 | 2006-11-10 | 조선내화 주식회사 | bubbling plug for gas purging |
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