JPH05254967A - Method for preventing deposition of al2o3 or the like on refractory - Google Patents
Method for preventing deposition of al2o3 or the like on refractoryInfo
- Publication number
- JPH05254967A JPH05254967A JP4086084A JP8608492A JPH05254967A JP H05254967 A JPH05254967 A JP H05254967A JP 4086084 A JP4086084 A JP 4086084A JP 8608492 A JP8608492 A JP 8608492A JP H05254967 A JPH05254967 A JP H05254967A
- Authority
- JP
- Japan
- Prior art keywords
- refractory
- nozzle
- al2o3
- sio2
- coating material
- 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.)
- Granted
Links
Landscapes
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は例えば溶鋼を収容処理す
る窯炉、取鍋、タンディッシュ、真空脱ガス装置、ノズ
ル、浸漬管等の溶鋼流通管、ストッパー等付帯設備に使
用される耐火物のAl2O3等付着防止処理方法に関する
ものである。BACKGROUND OF THE INVENTION The present invention relates to a refractory used for, for example, a furnace for accommodating and treating molten steel, a ladle, a tundish, a vacuum degassing device, a molten steel distribution pipe such as a nozzle and a dip pipe, and an auxiliary facility such as a stopper. The present invention relates to a method for preventing adhesion of Al 2 O 3, etc.
【0002】[0002]
【従来の技術】近年、例えば鋼の連続鋳造装置において
は、鋼材品質の厳格化と生産性向上の要求に伴い、連続
鋳造用耐火物、とりわけ浸漬ノズルの閉塞が大きな問題
となっている。従来広く使用されているAl2O3−C質
の浸漬ノズルには、使用中に内面あるいは吐出口付近に
多量のAl2O3が付着し、鋳造中止に追い込まれること
もめずらしくない。この問題を解決するために、従来か
ら多くの努力が払われてきた。しかし、この浸漬ノズル
の閉塞現象は解決されたとは言い難い。2. Description of the Related Art In recent years, for example, in a continuous casting apparatus for steel, a refractory for continuous casting, especially a block of a dipping nozzle, has become a serious problem with the demand for strict steel quality and improved productivity. It is not uncommon for a large amount of Al 2 O 3 to adhere to the inner surface or the vicinity of the discharge port during use of an Al 2 O 3 -C quality immersion nozzle that has been widely used in the past and to be forced to stop casting. Many efforts have been made in the past to solve this problem. However, it cannot be said that the blockage phenomenon of the immersion nozzle has been solved.
【0003】この問題を解決するために、最近CaZr
O3を含有した浸漬ノズル用耐火材が開発され(特開昭
57−71860号公報)、試用されるようになってき
た。このCaZrO3はAl2O3と反応して低融点物質
を生成する性質を有しており、この耐火材を浸漬ノズル
に用いた場合、CaZrO3は溶鋼中で生成するAl2O
3と反応して低融点物質を生成し、溶融し易くなるた
め、浸漬ノズル表面にAl2O3が付着・残留することは
なく、ノズル閉塞を防止することができる。To solve this problem, CaZr has recently been used.
A refractory material for an immersion nozzle containing O 3 has been developed (Japanese Patent Application Laid-Open No. 57-71860) and has come into trial use. This CaZrO 3 has the property of reacting with Al 2 O 3 to produce a low melting point substance, when using the refractory material immersion nozzle, Al 2 CaZrO 3 is produced in the molten steel O
Since it reacts with 3 to form a low-melting point substance, which easily melts, Al 2 O 3 does not adhere to or remains on the surface of the immersion nozzle, and nozzle clogging can be prevented.
【0004】[0004]
【発明が解決しようとする課題】しかし、CaZrO3
を含有したノズルを用いても、場合によっては期待通り
のノズル閉塞防止効果が十分に発現しない場合があり、
このノズル閉塞防止効果を安定的に発現させることが、
CaZrO3含有ノズル使用のための大きな技術的課題
になっている。[Problems to be Solved by the Invention] However, CaZrO 3
Even if using a nozzle containing, in some cases, the expected effect of preventing nozzle clogging may not be sufficiently expressed,
Stable expression of this nozzle blockage prevention effect,
It has become a major technical challenge for the use of nozzles containing CaZrO 3 .
【0005】[0005]
【課題を解決するための手段】本発明は、CaO成分を
5〜35重量%とZrO2成分を65〜95重量%を含
有する粒子50〜80重量%と、C10〜30重量%と
Si系材質5〜25%を含有する耐火物の表面にSiO
2、又はSiO2,Na2O,Al2O3,B2O3,Zr
O2,K2O,Li2O,BaO,SrO,CaO,Mg
O,ZnO,CdO,PbO,Bi2O3のうち1種、又
は2種以上の成分を配合してなる被覆材を、一層、また
は二層以上被覆させ、これを1200℃以上で60分以
上熱処理することを特徴とする耐火物のAl2O3等付着
防止処理方法である。According to the present invention, particles containing 5 to 35% by weight of CaO component and 65 to 95% by weight of ZrO 2 component, 50 to 80% by weight, C 10 to 30% by weight and Si-based particles. SiO on the surface of the refractory containing 5-25% of material
2 , or SiO 2 , Na 2 O, Al 2 O 3 , B 2 O 3 , Zr
O 2 , K 2 O, Li 2 O, BaO, SrO, CaO, Mg
One or two or more layers of a coating material containing one or more components selected from O, ZnO, CdO, PbO, and Bi 2 O 3 are coated, and this is coated at 1200 ° C. or more for 60 minutes or more. A method for preventing adhesion of refractory materials such as Al 2 O 3 is characterized by heat treatment.
【0006】本発明者等は、CaZrO3を含有ししか
も十分な閉塞防止効果が見られた使用後ノズルを解析し
た結果、表面にはCaZrO3が分解して生じたZrO2
と、ここから供給されたCaOと酸化防止材起源のSi
O2、さらに溶鋼起因のAl2O3からなるAl2O3−C
aO−SiO2系の低融点物質が検出された。この事実
から、CaZrO3を効果的にAl2O3と作用させ、ノ
ズル閉塞を防止するためには、ノズルとこれを被覆する
酸化防止材を使用開始前に熱処理し、予めCaZrO3
を酸化防止材に含まれる成分と反応させて分解させ、低
融点物質を生成させておくことが効果的であることを知
見した。本発明は、これらの知見に基づいてなされたも
のである。The present inventors analyzed a nozzle after use that contained CaZrO 3 and showed a sufficient blocking preventing effect, and as a result, ZrO 2 produced by decomposition of CaZrO 3 on the surface was produced.
And CaO supplied from this and Si originating from the antioxidant
O 2, Al 2 O 3 -C, further consisting of the molten steel caused by the Al 2 O 3
low melting point material aO--SiO 2 system is detected. From this fact, in order to cause CaZrO 3 to effectively act on Al 2 O 3 and prevent nozzle clogging, the nozzle and the antioxidant that covers the nozzle should be heat-treated before the start of use, and CaZrO 3 should be prepared beforehand.
It has been found that it is effective to react with the component contained in the antioxidant to decompose it and generate a low melting point substance. The present invention has been made based on these findings.
【0007】[0007]
【作用】例えばCaZrO3を含有したノズル表面にS
iO2を主成分とする被覆材を塗布し、1200℃以上
60分以上熱処理すると、ノズル表面に塗布された被覆
材中のSiO2はノズル材質中のCaZrO3と反応して
ノズル表面にZrO2とCaO−SiO2系の低融点物質
が生成する。この状態でノズルを使用する(溶鋼を流通
させる)と、ノズルの溶鋼接触面近傍は溶鋼の温度、即
ち1550℃程度となり、この温度では、前記CaO−
SiO2系低融点物質は、溶融状態になり、これに溶鋼
起源のAl2O3が溶け込み、この溶融物はAl2O3−C
aO−SiO2組成となる。この組成の物質はCaO−
SiO2系の場合よりもさらに低融点であり、ノズル表
面から容易に溶流するため、ノズル表面に付着・残留す
ることは少なく、その結果ノズルの閉塞を防止される。[Function] For example, S is formed on the nozzle surface containing CaZrO 3.
When a coating material containing iO 2 as a main component is applied and heat treatment is performed at 1200 ° C. or more for 60 minutes or more, SiO 2 in the coating material applied to the nozzle surface reacts with CaZrO 3 in the nozzle material and ZrO 2 is applied to the nozzle surface. And a CaO—SiO 2 -based low melting point substance is generated. When the nozzle is used (the molten steel is circulated) in this state, the temperature of the molten steel in the vicinity of the molten steel contact surface is about 1550 ° C., and at this temperature, the CaO-
SiO 2 based low-melting material becomes molten, this penetration is Al 2 O 3 of the molten steel origin, the melt is Al 2 O 3 -C
the aO-SiO 2 composition. The substance of this composition is CaO-
Since it has a lower melting point than that of the SiO 2 type and easily melts from the nozzle surface, it rarely adheres to and remains on the nozzle surface, and as a result, clogging of the nozzle is prevented.
【0008】ちなみに、従来のように上記の処理を行わ
ない場合、CaZrO3が高温下で酸化防止材起源のS
iO2及び溶鋼起源のAl2O3と直接反応することにな
る。この場合は事前に低融点物質が生成していないの
で、反応が起こり難く、従って低融点物質の生成が円滑
に行われない。このためAl2O3が付着しやすく、ノズ
ルの閉塞が起こりやすい。By the way, if the above treatment is not carried out as in the conventional case, CaZrO 3 is S derived from an antioxidant at high temperature.
It will directly react with iO 2 and Al 2 O 3 derived from molten steel. In this case, since the low-melting point substance has not been generated in advance, the reaction is unlikely to occur, so that the low-melting point substance is not smoothly generated. For this reason, Al 2 O 3 is likely to adhere, and the nozzle is likely to be clogged.
【0009】本発明が効果を発揮するためのノズル母材
としては以下のようなものが例示できる。即ち、CaO
を5〜35重量%とZrO2を65〜95重量%含有す
るCaZrO3と、SiO2,Al2O3,MgO,ZrO
2、等の酸化物、BN,SiC,B4C,Si3N4,Zr
B2,TiC,TiN,AlN等の非酸化物、あるいは
Si,Ti,Mg,Ca等の金属と、黒鉛等の炭素材、
及び若干のバインダー等の添加物と混練し成形した後
に、必要に応じて熱処理を加えることで得られる母材で
ある。The following can be exemplified as the nozzle base material for the effect of the present invention. That is, CaO
And 5 to 35 wt% and CaZrO 3 containing ZrO 2 65 to 95 wt%, SiO 2, Al 2 O 3, MgO, ZrO
2 , oxides such as BN, SiC, B 4 C, Si 3 N 4 , Zr
Non-oxides such as B 2 , TiC, TiN and AlN, or metals such as Si, Ti, Mg and Ca, and carbon materials such as graphite,
And a base material obtained by kneading and molding with a slight amount of an additive such as a binder and then heat-treating as necessary.
【0010】一方、この母材表面を被覆する被覆材とし
ては表1の組成のようなものが例示でき、これをドブ漬
け、ハケ塗り、スプレー塗布などの方法で、0.2mm
程度の厚さで表面を均一に付着させておく。熱処理の方
法として、被覆剤で被覆されたノズルを熱処理炉で処理
する方法、あるいは被覆されたノズルを連続鋳造設備に
装着し、ノズル予熱装置で熱することによる熱処理方法
等が例示できる。熱処理温度としては、CaZrO3と
SiO2を反応させるために、1200℃以上が必要で
あり、処理時間は60分以上必要である。On the other hand, as a coating material for coating the surface of the base material, the one having the composition shown in Table 1 can be exemplified, and the coating material is dipped, brushed, sprayed, etc.
The surface is attached uniformly with a certain thickness. Examples of the heat treatment method include a method in which a nozzle coated with a coating agent is treated in a heat treatment furnace, or a heat treatment method in which the coated nozzle is mounted in a continuous casting facility and heated by a nozzle preheating device. The heat treatment temperature needs to be 1200 ° C. or higher in order to react CaZrO 3 and SiO 2 , and the treatment time needs to be 60 minutes or longer.
【0011】[0011]
【表1】 [Table 1]
【0012】本発明に用いるCaO成分を5〜35重量
%含有するカルシウムジルコネート系クリンカーの配合
量の設定範囲については、50重量%未満では、耐食性
に劣ることになり、また80重量%をこえると耐スポー
ル性に劣る結果となる。このため50〜80重量%の範
囲が望ましい。またカルシウムジルコネート系クリンカ
ーのCaO含有量については5重量%未満では付着防止
に効果がなく35重量%をこえるとZrO2含有量が少
なく耐食性に劣る結果となるため5〜35重量%の範囲
が望ましい。Regarding the set range of the amount of calcium zirconate clinker containing CaO component used in the present invention in an amount of 5 to 35% by weight, if the amount is less than 50% by weight, the corrosion resistance will be poor, and it will exceed 80% by weight. And, the result is inferior spall resistance. Therefore, the range of 50 to 80% by weight is desirable. Regarding the CaO content of the calcium zirconate-based clinker, if it is less than 5% by weight, there is no effect in preventing adhesion, and if it exceeds 35% by weight, the ZrO 2 content is small and the corrosion resistance is poor. desirable.
【0013】炭素材の配合量の設定範囲については、1
0重量%未満では耐スポール性に対し効果が薄く、30
重量%をこえると耐食性が低下するために10〜30重
量%の範囲が望ましい。Regarding the setting range of the blending amount of the carbonaceous material, 1
If it is less than 0% by weight, the effect on spall resistance is small and
If it exceeds 10% by weight, the corrosion resistance decreases, so that the range of 10 to 30% by weight is desirable.
【0014】Si系材質としては金属Si,SiC,S
iO2,Si3N4,ZrSiO4が挙げられ、炭素材の酸
化防止並びに骨材の焼結材として添加するものである。
配合量の設定範囲については、5重量%以下では効果が
薄く、25重量%以上では逆に耐食性に劣る結果となる
ため5〜25重量%の範囲が望ましい。Metals such as Si, SiC, and S are used as the Si-based material.
Examples include iO 2 , Si 3 N 4 and ZrSiO 4, which are added as an antioxidant for carbon materials and as a sintering material for aggregates.
Regarding the setting range of the blending amount, if the amount is 5% by weight or less, the effect is small, and if it is 25% by weight or more, the corrosion resistance is deteriorated.
【0015】[0015]
【実施例】本発明による方法で処理した連続鋳造用浸漬
ノズルを、2ストランド型連続鋳造設備に適用し、効果
を確認した。使用したノズルの材質を表2に示す。EXAMPLE The immersion nozzle for continuous casting treated by the method according to the present invention was applied to a two-strand type continuous casting facility to confirm the effect. Table 2 shows the nozzle materials used.
【0016】[0016]
【表2】 [Table 2]
【0017】CaZrO3を含有したノズルである。こ
れを表1に示す組成、すなわち、SiO2の下層とSi
O2を主体としNa2O,Al2O3,B2O3,ZrO2を
含有する上層の2層による被覆材で被覆した。この被覆
材は、酸化防止機能と、低融点物質生成機能を有するも
のである。このようにして得られたノズルを2本用意
し、両ストランドに装着し、1ストランド側は予熱バー
ナーで800℃まで加熱し、60分間保持した。2スト
ランド側は1200℃まで加熱し、60分間保持し、そ
の後ただちに連続鋳造に供した。鋳造鋼種は、低炭アル
ミキルド鋼であった。この結果、1ストランド側では浸
漬ノズルが鋳造途中に閉塞し、鋳造を断念した。A nozzle containing CaZrO 3 . This has the composition shown in Table 1, that is, the lower layer of SiO 2 and Si.
It was coated with a coating material consisting of two layers of an upper layer containing O 2 as a main component and containing Na 2 O, Al 2 O 3 , B 2 O 3 and ZrO 2 . This coating material has an antioxidant function and a low melting point substance generating function. Two nozzles thus obtained were prepared, mounted on both strands, and one strand side was heated to 800 ° C. with a preheating burner and held for 60 minutes. The 2 strand side was heated to 1200 ° C., held for 60 minutes, and then immediately subjected to continuous casting. The casting grade was low carbon aluminized steel. As a result, the dipping nozzle was clogged during casting on the 1st strand side, and casting was abandoned.
【0018】これに対して本発明による方法で処理した
2ストランド側では閉塞は起こらなかった。なお、以上
は、本発明を連続鋳造用ノズルに適用することを主体に
述べたが、本発明は、他のノズル、あるいは前記した他
の用途の耐火物に適用しても同様の効果を奏するもので
ある。On the other hand, no clogging occurred on the side of the two strands treated by the method of the present invention. In addition, although the present invention has been mainly described above applied to the nozzle for continuous casting, the present invention has the same effect even when applied to other nozzles or refractories for other applications described above. It is a thing.
【0019】[0019]
【発明の効果】以上のように、本発明によれば、CaZ
rO3を含有する例えば鋼の連続鋳造用ノズルのAl2O
3等付着による閉塞を非常に効果的にかつ安定的に防止
することができ、鉄鋼の生産性向上に大きく寄与するこ
とができる。As described above, according to the present invention, CaZ
Al 2 O containing nozzles for continuous casting of eg steel containing rO 3
It is possible to very effectively and stably prevent the blockage due to the adhesion of 3 etc., which can greatly contribute to the improvement of the productivity of steel.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 水越 大二郎 千葉県君津市君津1番地 新日本製鐵株式 会社君津製鐵所内 (72)発明者 荻林 成章 千葉県君津市君津1番地 新日本製鐵株式 会社君津製鐵所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Daijiro Mizukoshi 1 Kimitsu, Kimitsu-shi, Chiba Nippon Steel Co., Ltd. Kimitsu Steel Co., Ltd. Stock Company Kimitsu Works
Claims (1)
成分を65〜95重量%を含有する粒子50〜80重量
%と、C10〜30重量%とSi系材質5〜25%を含
有する耐火物の表面にSiO2、又はSiO2,Na
2O,Al2O3,B2O3,ZrO2,K2O,Li2O,B
aO,SrO,CaO,MgO,ZnO,CdO,Pb
O,Bi2O3のうち1種、又は2種以上の成分を配合し
てなる被覆材を、一層、または二層以上被覆させ、これ
を1200℃以上で60分以上熱処理することを特徴と
する耐火物のAl2O3等付着防止処理方法。1. A CaO component of 5 to 35% by weight and ZrO 2
SiO 2 component and particles 50 to 80% by weight containing 65 to 95 wt%, the surface of the refractory containing C10~30 wt% and Si-based material 5-25%, or SiO 2, Na
2 O, Al 2 O 3 , B 2 O 3 , ZrO 2 , K 2 O, Li 2 O, B
aO, SrO, CaO, MgO, ZnO, CdO, Pb
One or two or more components of O and Bi 2 O 3 mixed together are coated to form one layer or two or more layers, which are heat-treated at 1200 ° C. or more for 60 minutes or more. Method for preventing adhesion of Al 2 O 3 etc. to refractories.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4086084A JP2954419B2 (en) | 1992-03-10 | 1992-03-10 | Method for preventing adhesion of refractory to Al2O3 etc. |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4086084A JP2954419B2 (en) | 1992-03-10 | 1992-03-10 | Method for preventing adhesion of refractory to Al2O3 etc. |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05254967A true JPH05254967A (en) | 1993-10-05 |
JP2954419B2 JP2954419B2 (en) | 1999-09-27 |
Family
ID=13876844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4086084A Expired - Lifetime JP2954419B2 (en) | 1992-03-10 | 1992-03-10 | Method for preventing adhesion of refractory to Al2O3 etc. |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2954419B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2216308A1 (en) * | 2009-01-26 | 2010-08-11 | General Electric Company | Treated Refractory Material and Methods of Making |
KR20200054418A (en) * | 2018-11-09 | 2020-05-20 | (주)포스코케미칼 | Reusable magnesia-carbon refractories |
-
1992
- 1992-03-10 JP JP4086084A patent/JP2954419B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2216308A1 (en) * | 2009-01-26 | 2010-08-11 | General Electric Company | Treated Refractory Material and Methods of Making |
KR20200054418A (en) * | 2018-11-09 | 2020-05-20 | (주)포스코케미칼 | Reusable magnesia-carbon refractories |
Also Published As
Publication number | Publication date |
---|---|
JP2954419B2 (en) | 1999-09-27 |
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