JPH09201659A - Bao-zro2-c nozzle for continuous casting - Google Patents
Bao-zro2-c nozzle for continuous castingInfo
- Publication number
- JPH09201659A JPH09201659A JP8032625A JP3262596A JPH09201659A JP H09201659 A JPH09201659 A JP H09201659A JP 8032625 A JP8032625 A JP 8032625A JP 3262596 A JP3262596 A JP 3262596A JP H09201659 A JPH09201659 A JP H09201659A
- Authority
- JP
- Japan
- Prior art keywords
- nozzle
- bao
- alumina
- molten steel
- refractory
- 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
- 238000009749 continuous casting Methods 0.000 title claims abstract description 11
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 28
- 239000010959 steel Substances 0.000 claims abstract description 28
- 239000011819 refractory material Substances 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003628 erosive effect Effects 0.000 abstract description 3
- 238000002844 melting Methods 0.000 description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 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 2
- 229910000655 Killed steel Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002436 steel type Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910018566 Al—Si—Mg Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019621 digestibility Nutrition 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は鋼を連続鋳造する際
に使用するロングノズルや浸漬ノズルなどの鋳造用ノズ
ルに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a casting nozzle such as a long nozzle or a dipping nozzle used when continuously casting steel.
【０００２】[0002]
【従来の技術】鋼の連続鋳造用ノズルは鍋−タンデッシ
ュ間、タンデッシュ−モ−ルド間の溶鋼の移送に際し、
溶鋼汚染や溶鋼流の乱れを防止し、長時間通湯しなけれ
ばならない役割をもっている。このためノズルには溶鋼
やスラグに対する耐溶損性、耐摩耗性に優れ、かつ熱衝
撃や溶鋼圧に耐える特性が要求される。さらに地金や溶
鋼中の介在物がノズル内壁に付着しないことも重要な特
性である。これらの特性を満たす耐火物として、Al2O3-
C質が広く使用され、またノズル外周のパウダ−ライン
部には耐食性の大きなZrO2-C質が使用されることが多
い。2. Description of the Related Art Nozzles for continuous casting of steel are used for transferring molten steel between a pan and a tundish and between a tundish and a mold.
It plays a role in preventing molten steel contamination and turbulence in molten steel flow, and requiring long-term hot water supply. For this reason, the nozzle is required to have excellent resistance to erosion and abrasion against molten steel and slag, and to be resistant to thermal shock and molten steel pressure. It is also an important characteristic that inclusions in the metal or molten steel do not adhere to the inner wall of the nozzle. As a refractory material that satisfies these characteristics, Al 2 O 3-
C quality is widely used, and ZrO 2 -C quality with high corrosion resistance is often used in the powder line around the nozzle.
【０００３】連続鋳造用ノズルの問題点の一つに鋼中介
在物（特にAl2O3）の付着に起因するノズル内孔部の閉
塞がある。特にアルミキルド鋼やアルミシリコンキルド
鋼の連続鋳造時には、溶鋼中の脱酸生成物であるアルミ
ナがノズルの内孔部、吐出孔の壁面に付着し、次第に成
長して遂にはノズル閉塞に至ることが多い。さらにこの
付着物が剥落して溶鋼中に取り込まれると、製品の劣化
を招くことになる。One of the problems of the continuous casting nozzle is clogging of the nozzle inner hole portion due to adhesion of inclusions in steel (particularly Al 2 O 3 ). In particular, during continuous casting of aluminum-killed steel or aluminum-silicon-killed steel, alumina, which is a deoxidation product in molten steel, adheres to the inner hole of the nozzle and the wall of the discharge hole, and gradually grows, eventually leading to nozzle blockage. Many. Furthermore, if the deposits fall off and are taken into the molten steel, the product will be degraded.
【０００４】ノズル閉塞の防止法として、ノズル内孔部
壁面にArなどの不活性ガスを吹き込み、Al2O3などの付
着を防止する方法も一般的に行われている。しかし、こ
の方法でも多連鋳工程ではアルミナが付着、成長しノズ
ル閉塞に至る場合もあり対策としては十分ではない。As a method for preventing the nozzle clogging, a method of blowing an inert gas such as Ar into the wall surface of the nozzle inner hole to prevent the adhesion of Al 2 O 3 or the like is generally used. However, even in this method, alumina may adhere and grow in the multiple casting step, leading to nozzle blockage, which is not sufficient as a countermeasure.
【０００５】ノズル材質にアルミナが付着しにくい材料
を採用することによって、付着防止をしようとする試み
も行われている。このような材質としてはZrO2-CaO-C系
材料がある。ZrO2-CaO-C質耐火物は、溶鋼中のアルミナ
と接触した際に、CaO-Al2O3系の低融物を生成し、これ
が適度に溶損されることによってアルミナの付着を防止
すると言われている。しかしこのZrO2-CaO-C質耐火物で
も鋼種や使用条件によっては、溶損が大きすぎたり、逆
に溶損が小さく長時間使用した場合にはアルミナ付着が
生ずるなど常に安定した使用状態が得られないと言う問
題があった。Attempts have been made to prevent adhesion by using a material to which alumina is unlikely to adhere as a nozzle material. As such a material, there is a ZrO 2 —CaO—C-based material. ZrO 2 -CaO-C refractory forms CaO-Al 2 O 3 low melt when it comes into contact with alumina in molten steel, and it prevents alumina from adhering due to moderate melting loss. It is said that. However, even with this ZrO 2 -CaO-C refractory, depending on the steel type and operating conditions, the melting loss is too large, and conversely, the melting loss is so small that alumina adhesion occurs when used for a long time, so that a stable usage condition is always present. There was a problem that I could not get it.
【０００６】[0006]
【本発明が解決しようとする課題】本発明の目的はアル
ミナが付着しにくい連続鋳造用ノズルを提供することに
ある。前述したようにアルミナが付着しにくい材料とし
ては、CaO系材料が有効である。しかしCaOは空気中の水
分と水和反応して体積膨張し遂には崩壊するという特性
（消化性）があるため、CaOの形では使用しにくいため
他の酸化物と複合させた形で用いられる。このような複
合酸化物としてはジルコン酸カルシウム（CaZrO3）が知
られている。SUMMARY OF THE INVENTION It is an object of the present invention to provide a continuous casting nozzle to which alumina does not easily adhere. As described above, a CaO-based material is effective as a material to which alumina does not easily adhere. However, since CaO has the property (digestibility) that it hydrates with water in the air to undergo volume expansion and eventually collapses, it is difficult to use in the form of CaO, so it is used in a form combined with other oxides. . Calcium zirconate (CaZrO 3 ) is known as such a complex oxide.
【０００７】しかしCaZrO3中のCaO成分の量は、理論組
成で僅かに31重量％にすぎない。またノズルにはCaZrO3
以外に炭素材料や酸化防止材などが添加されるため、ノ
ズル中のCaO含有量はさらに少なくなる。またCaOとAl2O
3とが反応して低融化するには少なくとも40重量％程度
のAl2O3量が必要となるため、反応としては必ずしも効
率よいものではなかった。この結果、CaZrO3-C質ノズル
では鋼種や使用条件によっては、CaOのアルミナ付着防
止効果が不十分となり、ノズル閉塞を引き起こすことも
あった。本発明はアルミナの難付着成分としてCaOに換
えBaOを採用することにより、アルミナ付着防止の機能
を高め、しかも適度な溶損を維持することで耐用性の向
上した連続鋳造用ノズルを提供することを目的とする。However, the amount of CaO component in CaZrO 3 is only 31% by weight in theoretical composition. In addition, the nozzle is made of CaZrO 3
Besides, since a carbon material and an antioxidant are added, the CaO content in the nozzle is further reduced. Also CaO and Al 2 O
At least about 40% by weight of Al 2 O 3 is necessary for the reaction with 3 to lower the melting point, so the reaction was not always efficient. As a result, in CaZrO 3 -C quality nozzles, CaO had insufficient effect of preventing alumina from adhering to alumina, depending on the type of steel and the operating conditions, which sometimes caused nozzle clogging. The present invention provides a continuous casting nozzle having improved durability by adopting BaO instead of CaO as a difficult-to-adhere component of alumina, thereby enhancing the function of preventing alumina adhesion and maintaining appropriate melting loss. With the goal.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、アルミナ
が付着し難い材料について検討した結果、難付着成分と
してBaOを含むBaZrO3に着目した。すなわちBaZrO3中のB
aO成分は、高温下において溶鋼中のAl2O3と反応して低
融点成分を生成させるが、CaOの場合よりもAl2O3が少量
でも容易に低融点成分を生成させるため、ノズル壁への
アルミナ付着を効率よく防止できるものと予測した。さ
らにBaZrO3の熱膨張率はCaZrO3に比較して小さく、熱応
力を受けにくいためノズル用材質として最適と思われ
た。Means for Solving the Problems As a result of studying a material on which alumina is difficult to adhere, the present inventors have focused on BaZrO 3 containing BaO as a difficult-to-adhere component. That is, B in BaZrO 3
The aO component reacts with Al 2 O 3 in molten steel at high temperature to form a low-melting point component, but even if a small amount of Al 2 O 3 produces a low-melting point component as compared with CaO, the aO component easily forms a low-melting point component. It was predicted that the adhesion of alumina to aluminum could be efficiently prevented. Furthermore, the thermal expansion coefficient of BaZrO 3 is smaller than that of CaZrO 3 , and it is less likely to be subjected to thermal stress, so it was considered to be the most suitable material for nozzles.
【０００９】発明者らはこれらの知見に基づき、ノズル
材質としてBaZrO3を含有するBaO-ZrO2系耐火材料を用
い、これに適量の炭素質材料を組み合わせたところ、ノ
ズル壁へのアルミナ付着を効果的に防止できるととも
に、ノズル壁の溶損速度を小さく維持できることを見い
出し本発明を完成させたものである。Based on these findings, the inventors used a BaO-ZrO 2 -based refractory material containing BaZrO 3 as a nozzle material and combined it with an appropriate amount of carbonaceous material. The present invention has been completed by finding that it can be effectively prevented, and that the melting rate of the nozzle wall can be kept small.
【００１０】すなわち本発明の連続鋳造用ノズルは、Ba
Oを10〜56重量％含有するBaO-ZrO2系耐火材料を40〜90
重量％および炭素質材料10〜40重量％を含有し、残部が
他の耐火材料からなる耐火物を少なくとも溶鋼に接触す
る部位に配設したことを特徴とするものである。That is, the continuous casting nozzle of the present invention is
O and the BaO-ZrO 2 refractory material containing 10-56 wt% 40 to 90
A refractory material containing 10% by weight of carbonaceous material and 10 to 40% by weight of carbonaceous material, the remainder being made of another refractory material, is disposed at least at a portion in contact with molten steel.
【００１１】[0011]
【発明の実施の形態】本発明で使用するBaO-ZrO2系耐火
材料は、BaOを10〜56重量％含有し、鉱物組成がBaZrO3
単一または残部が安定化されたZrO2からなる電融体また
は焼結体である。BaOが10重量％未満ではアルミナ付着
防止の効果が不十分になるとともに、ZrO2の増加により
耐熱衝撃性が低下するようになる。逆にBaOが56重量％
を越えると、遊離のBaOが生成することにより耐消化性
が著しく低下し、耐火材料としての取り扱いが困難にな
るため好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION The BaO-ZrO 2 refractory material used in the present invention contains 10 to 56% by weight of BaO and has a mineral composition of BaZrO 3
It is an electric melt or a sintered body made of ZrO 2 which is single or the rest is stabilized. When BaO is less than 10% by weight, the effect of preventing the adhesion of alumina becomes insufficient, and the thermal shock resistance decreases due to the increase of ZrO 2 . On the contrary, BaO is 56% by weight
When it exceeds the above range, free BaO is generated, so that the digestion resistance is remarkably lowered and it becomes difficult to handle as a refractory material, which is not preferable.
【００１２】本発明で用いる耐火材料として、このBaO-
ZrO2系耐火材料を単独で使用できるのはもちろんのこ
と、使用条件や鋼種によっては他の耐火材料を併用する
ことも可能である。併用できる耐火材料としてはジルコ
ニア、ジルコン酸カルシウム、ジルコン、マグネシア、
アルミナ、スピネル、溶融シリカなどがある。アルミナ
付着防止の効果を十分に発現させるためには、BaO-ZrO2
系耐火材料を40重量％以上使用する。この量が40重量％
未満では、効果が十分に得られず、また90重量％を越え
ると耐食性や耐熱衝撃性が低下するため好ましくない。
この耐火材料の調製法の一例として、BaO源に主に炭酸
バリウムをまたZrO2源にバデライトや電融の未安定また
は安定化ジルコニアを用い、これらを所定の割合に調合
した原料配合物を電気溶融するか、または1600℃以上の
温度で焼成する。この原料を粒度調整して使用する。As a refractory material used in the present invention, this BaO-
Not only can the ZrO 2 -based refractory material be used alone, but other refractory materials can also be used in combination depending on the operating conditions and steel type. Refractory materials that can be used in combination include zirconia, calcium zirconate, zircon, magnesia,
Alumina, spinel, fused silica and the like. In order to fully develop the effect of preventing adhesion of alumina, BaO-ZrO 2
Use at least 40% by weight of refractory materials. This amount is 40% by weight
If it is less than the above range, the effect is not sufficiently obtained, and if it exceeds 90% by weight, the corrosion resistance and the thermal shock resistance are deteriorated, which is not preferable.
As an example of the method for preparing this refractory material, barium carbonate is mainly used as the BaO source, and baderite or electrostable unstabilized or stabilized zirconia is used as the ZrO 2 source. Melt or bake at temperatures above 1600 ° C. This raw material is used after adjusting the particle size.
【００１３】炭素質材料は、耐熱衝撃性と耐食性を付与
するために添加されるもので、鱗状黒鉛、土状黒鉛、人
造黒鉛、カ−ボンブラック、石油コ−クス、炭素繊維、
メソフェ−ズカ−ボンなどを用いることができるが、特
性的に見て天然の鱗状黒鉛が最適といえる。炭素材料の
量が10重量％未満では耐食性や耐熱衝撃性が不十分とな
り、逆に40重量％を越えると組織劣化が進行しやすくな
り耐摩耗性が低下するため好ましくない。このため炭素
材料は10〜40重量％の範囲で使用する。Carbonaceous materials are added to impart heat shock resistance and corrosion resistance, and include scaly graphite, earthy graphite, artificial graphite, carbon black, petroleum coke, carbon fiber,
Mesophase carbon and the like can be used, but natural scaly graphite can be said to be optimal in view of characteristics. If the amount of the carbon material is less than 10% by weight, the corrosion resistance and thermal shock resistance will be insufficient, while if it exceeds 40% by weight, the deterioration of the structure will be apt to proceed and the abrasion resistance will be deteriorated. Therefore, the carbon material is used in the range of 10-40% by weight.
【００１４】また本発明では、炭素質材料の酸化防止や
熱間強度を向上させるために酸化防止材を添加すること
もできる。このような材料として金属や合金などの金属
材料および炭化物、窒化物、ホウ化物などの非酸化物系
材料の中から１種または２種以上を用いることができ
る。例えば金属材料としてはAl,Siなどの金属やAl-Si,A
l-Mg,Al-Si-Mgなどの合金を、また非酸化物系材料とし
てはB4C,SiC,TiC,WC,BN,AlN,Si3N4,ZrCなどを使用す
る。酸化防止材は微粒状または粉末状のものを耐火材料
100重量部に対し、0.1〜10重量部の範囲で用いる。この
量が0.1重量部未満の場合は、酸化防止や熱間強度発現
の効果が得られず、また10重量部を越えると耐熱衝撃性
や耐溶損性が低下することになる。Further, in the present invention, an antioxidant may be added in order to prevent oxidation of the carbonaceous material and improve the hot strength. As such a material, one kind or two or more kinds can be used from metal materials such as metals and alloys and non-oxide materials such as carbides, nitrides and borides. For example, metal materials such as Al, Si and Al-Si, A
Alloys such as l-Mg and Al-Si-Mg are used, and B 4 C, SiC, TiC, WC, BN, AlN, Si 3 N 4 and ZrC are used as non-oxide materials. Anti-oxidant is fine-grained or powdered refractory material
It is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight. If this amount is less than 0.1 part by weight, the effect of preventing oxidation and development of hot strength cannot be obtained, and if it exceeds 10 parts by weight, thermal shock resistance and erosion resistance deteriorate.
【００１５】本発明のノズルの製造に際しては、所定の
割合に調合した原料配合物にピッチやフェノ−ル樹脂の
ような液状の結合剤を加えて混練した後、ラバ−プレス
などでノズル形状に成形し、非酸化雰囲気下800℃以上
の温度で焼成する。本発明では、少なくともノズル内壁
の溶鋼流接触面の2mm以上の厚み部分に本発明で規定す
る材質の耐火物を配設した構造とする。したがって本発
明で規定する材質だけでノズル全体を構成することもも
ちろん可能であるが、例えば母体をAl2O3-C質とし、パ
ウダ−ラインにZrO2-C質を配し、溶鋼流接触面の2mm以
上の厚み部分を本発明材質によって構成させることもで
きる。またアルミナ付着防止の効果を損なわない程度で
あれば、既知の焼結剤、ファイバ−類を添加しても良い
し、焼成後はタ−ル、ピッチ、フェノ−ル樹脂などで含
浸処理を行うこともできる。In manufacturing the nozzle of the present invention, a liquid binder such as pitch or phenol resin is added to a raw material mixture prepared in a predetermined ratio and kneaded, and then the nozzle shape is formed by a rubber press or the like. Form and fire at a temperature of 800 ° C or higher in a non-oxidizing atmosphere. The present invention has a structure in which a refractory material of the material specified in the present invention is disposed at least in a portion of the inner wall of the nozzle where the molten steel flow contact surface has a thickness of 2 mm or more. Therefore, it is of course possible to form the entire nozzle only with the materials specified in the present invention, but for example, the matrix is made of Al 2 O 3 -C material, the powder line is made of ZrO 2 -C material, and the molten steel flow contact is performed. The thickness of 2 mm or more of the surface can be made of the material of the present invention. Known sintering agents and fibers may be added as long as the effect of preventing adhesion of alumina is not impaired. After firing, impregnation treatment is performed with tar, pitch, phenol resin or the like. You can also
【００１６】本発明で使用するBaO-ZrO2系耐火材料中に
多量に含まれるBaOは、溶鋼流とノズルとの界面におい
て溶鋼中のAl2O3と反応し3BaO・Al2O3などの低融点化合
物を生成し、溶鋼中に浮上することにより、ノズル壁へ
のアルミナ付着を防止する。BaOはCaOに比較してより少
ないAl2O3量で容易に低融点化合物を生成し、反応は効
率よく行われるため、特に優れた付着防止効果が発揮さ
れる。さらに炭素質材料や酸化防止材の相乗効果によっ
て耐熱衝撃性、耐食性、耐摩耗性が付与される結果、連
続鋳造用ノズルの閉塞を防止し、耐用性を著しく向上さ
せることができ、多連続鋳造に対しても十分対応できる
ものとした。A large amount of BaO contained in the BaO-ZrO 2 -based refractory material used in the present invention reacts with Al 2 O 3 in the molten steel at the interface between the molten steel flow and the nozzle, so that 3BaO.Al 2 O 3 etc. A low melting point compound is generated and floats in molten steel to prevent alumina from adhering to the nozzle wall. BaO easily produces a low-melting point compound with a smaller amount of Al 2 O 3 than CaO, and the reaction is efficiently performed, so that a particularly excellent anti-adhesion effect is exhibited. Furthermore, as a result of the thermal shock resistance, corrosion resistance, and wear resistance being imparted by the synergistic effect of carbonaceous materials and antioxidants, it is possible to prevent clogging of the continuous casting nozzle and significantly improve its durability. It is possible to deal with
【００１７】[0017]
【実施例】以下、本発明の実施例について説明する。実
施例で使用したBaO-ZrO2系耐火材料の作製に際しては、
BaO原料として炭酸バリウムを、ZrO2原料として電融のC
aO安定型ジルコニアを用いた。耐火材料１および２は、
BaO／ZrO2比をそれぞれ30／70、55／45（いずれも重量
比）とした原料配合物の成形体を1600℃で5時間焼成
後、0.5mm以下に粒度調整したものである。これらの鉱
物組成は、耐火材料１がBaZrO3と立方晶のZrO2で耐火材
料２がBaZrO3であった。Embodiments of the present invention will be described below. In producing the BaO-ZrO 2 refractory material used in the examples,
Barium carbonate as the BaO raw material and electrofused C as the ZrO 2 raw material
AO stable zirconia was used. Refractory materials 1 and 2 are
A molded body of a raw material mixture having a BaO / ZrO 2 ratio of 30/70 and 55/45 (both are weight ratios) was fired at 1600 ° C. for 5 hours and then the particle size was adjusted to 0.5 mm or less. In these mineral compositions, the refractory material 1 was BaZrO 3 and cubic ZrO 2 , and the refractory material 2 was BaZrO 3 .
【００１８】試料の作製は表１に示す配合割合に基づい
て実施した。最初にこれらの配合物に結合剤としてフェ
ノ−ル樹脂を添加して混練後、ラバ−プレスを用いて試
料形状に成形した。次にこの成形体をアルゴン雰囲気下
1000℃で5時間焼成して供試体とした。表１には評価結
果も示している。なお評価方法は下記に示す方法に従い
実施した。The samples were prepared based on the blending ratio shown in Table 1. First, a phenol resin was added to these blends as a binder and kneaded, and then molded into a sample shape by using a rubber press. Next, this molded body is placed in an argon atmosphere.
The sample was fired at 1000 ° C for 5 hours. Table 1 also shows the evaluation results. The evaluation method was carried out according to the method shown below.
【００１９】[0019]
【表１】[Table 1]
【００２０】比較例についても実施例と同様に試料作製
を行い、評価試験を実施した。配合割合、特性および評
価結果を表２に示す。Also in the comparative example, a sample was prepared in the same manner as in the example, and an evaluation test was conducted. Table 2 shows the blending ratio, characteristics and evaluation results.
【００２１】[0021]
【表２】[Table 2]
【００２２】本発明の実施例は、いずれもアルミナの付
着量が少ない結果を示している。これに対して比較例
は、比較例１、２を除きアルミナ付着量が実施例よりも
多くノズル閉塞を起こしやすい傾向を示していた。比較
例１、２は、アルミナ付着の点では優れているものの、
それぞれ耐スポ−リング性や耐損耗性に問題があり耐用
性に劣ることが予測された。The examples of the present invention all show results in which the adhered amount of alumina is small. On the other hand, in Comparative Examples, except for Comparative Examples 1 and 2, the adhered amount of alumina was larger than that in Examples, and the nozzle clogging was likely to occur. Although Comparative Examples 1 and 2 are excellent in terms of alumina adhesion,
It was predicted that each had a problem in sponging resistance and wear resistance and was inferior in durability.
【００２３】次に実施例１組成の浸漬ノズルおよび比較
例４のアルミナ−黒鉛質浸漬ノズルをそれぞれ250トン容
量のタンデイッシュに設置して鋳造を行い、300分鋳造
後におけるノズル内壁への非金属介在物の付着状況を調
べたところ、本発明の浸漬ノズルにはほとんど付着が認
められなかったのに対し、アルミナ−黒鉛質浸漬ノズル
は非金属介在物の付着量が多く、ノズル閉塞を起こしや
すい状態であった。Next, the immersion nozzle having the composition of Example 1 and the alumina-graphite immersion nozzle of Comparative Example 4 were respectively installed in a tundish having a capacity of 250 tons and casting was performed, and after casting for 300 minutes, the non-metal on the inner wall of the nozzle was cast. When the adhesion state of inclusions was examined, almost no adhesion was observed in the immersion nozzle of the present invention, whereas in the alumina-graphite immersion nozzle, the amount of non-metallic inclusions was large and nozzle clogging was likely to occur. It was in a state.
【００２４】評価方法 1) 見掛け気孔率、カサ比重：ＪＩＳ−Ｒ２２０５ 2) 損耗量（mm） ：30×30×170mmに切り出し
た試験片を高周波炉で溶解した1600℃の溶鋼中に2時間
浸漬し、その損耗量を測定して求めた。 3) 耐スポ−リング性 ：40×40×170mm形状の試験
片を高周波炉で溶解した1600℃の溶鋼中に3分間浸漬し
た後,20分間空冷するサイクルを10回繰り返し、そのき
れつの発生状況を観察した。 4) アルミナ付着率 ：高周波炉で溶解した1600
℃の溶鋼中にアルミニウムを添加し、その中に30×30×
150mm形状の試片を2時間浸漬し溶鋼から析出したアルミ
ナの付着状況を観察した。Evaluation method 1) Apparent porosity, bulk specific gravity: JIS-R2205 2) Abrasion amount (mm): A test piece cut into 30 × 30 × 170 mm was immersed in molten steel at 1600 ° C. for 2 hours, which was melted in a high frequency furnace. Then, the amount of wear was measured and obtained. 3) Spooling resistance: A test piece of 40 × 40 × 170 mm shape was dipped in molten steel at 1600 ° C for 3 minutes in a high-frequency furnace and then air-cooled for 20 minutes, which was repeated 10 times. Was observed. 4) Alumina adhesion rate: 1600 melted in a high frequency furnace
Add aluminum to the molten steel at ℃, 30 × 30 × in it
A 150 mm test piece was immersed for 2 hours and the adhesion state of alumina precipitated from molten steel was observed.
【００２５】[0025]
【発明の効果】本発明で規定するBaO-ZrO2系耐火材料と
炭素質材料を含有する耐火物を連続鋳造用ノズルの溶鋼
流接触部に配設することにより、アルミナなどの非金属
介在物の付着を効率よく防止するとともに、適度の溶損
速度を維持させることができる。この結果、多連鋳での
使用においても、ノズル閉塞を起こすこともなく、優れ
た耐用性を発揮させることができる。The refractory material containing the BaO-ZrO 2 -based refractory material and the carbonaceous material defined in the present invention is disposed at the molten steel flow contact portion of the continuous casting nozzle to allow non-metallic inclusions such as alumina. It is possible to efficiently prevent the adherence of and to maintain an appropriate dissolution rate. As a result, even when used in multiple casting, excellent durability can be exhibited without causing nozzle clogging.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
Claims (1)
耐火材料40〜90重量％および炭素質材料10〜40重量％を
含有し、残部がその他の耐火材料からなる耐火物を少な
くとも溶鋼に接触する部位に配設したことを特徴とする
連続鋳造用ノズル。1. A refractory material containing 40 to 90% by weight of BaO-ZrO 2 -based refractory material containing 10 to 56% by weight of BaO and 10 to 40% by weight of carbonaceous material, with the balance being other refractory material. A continuous casting nozzle, characterized in that it is arranged at least at a portion in contact with molten steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8032625A JPH09201659A (en) | 1996-01-25 | 1996-01-25 | Bao-zro2-c nozzle for continuous casting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8032625A JPH09201659A (en) | 1996-01-25 | 1996-01-25 | Bao-zro2-c nozzle for continuous casting |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09201659A true JPH09201659A (en) | 1997-08-05 |
Family
ID=12364043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8032625A Pending JPH09201659A (en) | 1996-01-25 | 1996-01-25 | Bao-zro2-c nozzle for continuous casting |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09201659A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403374A (en) * | 2022-08-25 | 2022-11-29 | 淄博龙程耐火材料有限公司 | Plug rod capable of preventing flocculation and blocking and processing technology thereof |
-
1996
- 1996-01-25 JP JP8032625A patent/JPH09201659A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403374A (en) * | 2022-08-25 | 2022-11-29 | 淄博龙程耐火材料有限公司 | Plug rod capable of preventing flocculation and blocking and processing technology thereof |
| CN115403374B (en) * | 2022-08-25 | 2023-04-07 | 淄博龙程耐火材料有限公司 | Plug rod capable of preventing flocculation and blocking and processing technology thereof |
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