JPH0723253B2 - Refractory material - Google Patents

Refractory material

Info

Publication number
JPH0723253B2
JPH0723253B2 JP3708992A JP3708992A JPH0723253B2 JP H0723253 B2 JPH0723253 B2 JP H0723253B2 JP 3708992 A JP3708992 A JP 3708992A JP 3708992 A JP3708992 A JP 3708992A JP H0723253 B2 JPH0723253 B2 JP H0723253B2
Authority
JP
Japan
Prior art keywords
materials
alumina
cao
nozzle
refractory 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.)
Expired - Lifetime
Application number
JP3708992A
Other languages
Japanese (ja)
Other versions
JPH05201759A (en
Inventor
喜久雄 有賀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TYK Corp
Original Assignee
TYK Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TYK Corp filed Critical TYK Corp
Priority to JP3708992A priority Critical patent/JPH0723253B2/en
Publication of JPH05201759A publication Critical patent/JPH05201759A/en
Publication of JPH0723253B2 publication Critical patent/JPH0723253B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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  • Compositions Of Oxide Ceramics (AREA)
  • Casting Support Devices, Ladles, And Melt Control Thereby (AREA)

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】この発明は耐火物用材料に関する
もので、さらに詳しくはCaO,SiO2,B23の3
成分を必須成分とする高機能性を有し、製鋼用ノズルに
用いる電融耐火材料に関するものである。
BACKGROUND OF THE INVENTION This invention relates to refractory materials, more particularly CaO, 3 of SiO 2, B 2 O 3
TECHNICAL FIELD The present invention relates to an electromelting refractory material having high functionality with essential components used for a steelmaking nozzle.

【0002】[0002]

【従来の技術】従来の製鋼の連続鋳造時に用いられるノ
ズル用材として用いられる耐火物は、溶融石英材や、ア
ルミナおよびまたはアルミナ−シリカ系の高アルミナ材
料、ジルコニア材料,ジルコニア−カルシア材料の一者
もしくは二者以上または特殊な使用条件下では、マグネ
シアおよびまたはマグネシア−アルミナ系のスピネル材
等の酸化物耐火材料を主体とし、これに黒鉛質材,炭素
質材(カーボン材)炭化物材,窒化珪素材の一者若しく
は二者以上を配合して構成された耐火材料を用い混練成
形し焼成されたノズルが使用されている。
2. Description of the Related Art Refractory materials used as materials for nozzles used in continuous casting of conventional steelmaking are one of fused silica materials, alumina and / or alumina-silica high alumina materials, zirconia materials, and zirconia-calcia materials. Alternatively, under two or more or special use conditions, oxide refractory materials such as magnesia and / or magnesia-alumina spinel materials are mainly used, and graphite material, carbonaceous material (carbon material) carbide material, silicon nitride A nozzle is used in which a refractory material composed of one or two or more raw materials is kneaded, molded, and fired.

【0003】これら連続鋳造方式の取鍋、タンディッシ
ュ等に用いられるロングノズルや浸漬ノズルは、当初は
溶融シリカ材で製造された材質のものが使用されていた
が、品質の安定性、鋳造の高能率化、鋳造コスト、鋳片
の歩留りの向上が進められるに至り、連続鋳造も多連鋳
化が指向されることとなり、溶融シリカ材では溶損が大
きくノズル孔の拡大や、ノズルが破損するなどの問題が
生じ多連続鋳造操業が出来なくなり、これに対処するた
めに溶融石英質材、アルミナ質材アルミナ−シリカ系の
高アルミナ材,ジルコニア質材,ジルコニア−カルシア
質材等の各種酸化物耐火材料の一者若しくは二者以上
や、特殊な使用条件ではマグネシア質材およびまたはア
ルミナ−マグネシア系のスピネル質材料を主体とし、こ
れに黒鉛質材,カーボン質材の一者若しくは二者と必要
に応じては炭化物材,窒化物材の一者若しくは二者以上
を配合し製造されたノズルに移行して多連続鋳造操業に
対処し効果をあげてきているが、その反面、ノズル孔内
壁にアルミニウムを主体とする酸化物,(非金属介在
物)が付着堆積して円滑な鋳造作業が出来ないこと、ま
たノズル孔内壁に付着堆積した非金属介在物が剥落し、
混入することにより大きな砂キズの原因となる等、操業
上及び品質上等に大きな問題が生じてきている。
The long nozzles and dipping nozzles used for these continuous casting ladle, tundish, etc. were initially made of a fused silica material, but the stability of quality and casting High efficiency, casting cost, and improved yield of slabs have been promoted, and continuous casting is also aimed at multi-casting, and fused silica material has large melting loss and nozzle hole expansion and nozzle damage. However, in order to deal with this problem, fused silica materials, alumina materials, alumina-silica-based high alumina materials, zirconia materials, zirconia-calcia materials, etc. One or more refractory materials, and under special use conditions, magnesia materials and / or alumina-magnesia spinel materials are mainly used. One or two of the carbonaceous materials and, if necessary, one or more of the carbide material and the nitride material are mixed to produce a nozzle, which is effective in dealing with the multi-continuous casting operation. On the other hand, on the other hand, the oxide mainly composed of aluminum and (non-metallic inclusions) adhere and deposit on the inner wall of the nozzle hole, which prevents smooth casting work, and the non-metallic inclusion that adheres and deposits on the inner wall of the nozzle hole. Things have fallen off,
A major problem in terms of operation and quality has arisen, such as being a cause of large sand scratches when mixed.

【0004】この問題を解決するため、前述種々の耐火
材の組合せやノズルの構造上多層構成とするとか、また
ノズル内壁より不活性ガスを吹き込みガスシール効果に
より内面保護をすることにより付着,堆積を防止するな
ど種々な対策がこうじられているが、いまだ充分な効果
を修める迄には至っていないのが現状でこの改善が強く
求められている。
In order to solve this problem, the above-mentioned various refractory materials are combined and the nozzle has a multi-layer structure in terms of the structure of the nozzle, and an inert gas is blown from the inner wall of the nozzle to protect the inner surface by the gas sealing effect. Although various measures have been taken to prevent this, there is a strong demand for this improvement under the present circumstances because it has not yet been able to achieve sufficient effects.

【0005】[0005]

【発明が解決しようとする課題】上記に鑑み、耐熱性、
耐食性を保ち、且つ溶湯中に介在するアルミニウム酸化
物を主体とする非金属介在物の付着、堆積を防止し得る
特殊な機能を有する耐火材料を提供することを技術的課
題とするものである。
In view of the above, heat resistance,
It is a technical object to provide a refractory material which has a special function of keeping corrosion resistance and preventing adhesion and deposition of non-metallic inclusions mainly composed of aluminum oxide present in the molten metal.

【0006】[0006]

【課題を解決するための手段】この発明は溶湯中の非金
属介在物の主成分であるアルミニウム酸化物のノズル内
壁への付着堆積を防ぎ、操業上、品質上の改善を計るも
のである。
The present invention is intended to prevent adhesion and deposition of aluminum oxide, which is the main component of non-metallic inclusions in a molten metal, on the inner wall of a nozzle, and to improve operation and quality.

【0007】本発明はノズル内壁に付着堆積する主な成
分アルミナとの間で高い活性度を有し、化学反応を起こ
すことにより低溶融物を生成し流出せしめることに着目
し、種々研究を重ねた結果、CaOを主成分とする耐火
材料が最も有効であることを見い出した。更にCaOを
主成分とする耐火材料の中でもより反応性を高め付着防
止効果の高い材料とするには付着物の主成分でアルミナ
との関係上、CaOとSiO2のモル比が2:1〜3:
2とし、これに結晶安定化材としてB23を1%〜5%
添加し、この3者を必須成分となし、3者の合量が95
%以上で構成してなる電気溶融耐火材を開発した。本耐
火材は耐熱性および受熱,冷却等による熱変化に対して
も結晶の安定度が高く熱変化に対して安定し粉化等の現
象も生じない。(γ2CaOSiO2の生成がない)上
アルミナを主成分とする非金属介在物との間で高い反応
性を有する素材であり、これを提供するものである。
The present invention focuses on the fact that it has a high activity with alumina, which is the main component that adheres to and deposits on the inner wall of the nozzle, and that a low-melting substance is generated and flows out by causing a chemical reaction, and various studies have been repeated. As a result, they found that the refractory material containing CaO as the main component was the most effective. Further, in order to make the material having higher reactivity and higher anti-adhesion effect among the refractory materials containing CaO as the main component, the molar ratio of CaO to SiO 2 is 2: 1 to 1 because of the main component of the deposit and alumina. 3:
2 and 1% to 5% of B 2 O 3 as a crystal stabilizer.
Add these three components as essential ingredients and the total amount of the three components is 95
We have developed an electro-melting refractory material composed of more than 100%. This refractory material has high heat resistance and high crystal stability even with changes in heat due to heat reception, cooling, etc. and is stable against changes in heat and does not cause phenomena such as pulverization. It is a material having a high reactivity with non-metallic inclusions containing alumina as a main component (no generation of γ2CaOSiO 2 ), and provides this.

【0008】次に限定理由について記述する。 CaO,SiO2の比(モル比で2:1〜3:2) 〈a〉3:2以下であると耐熱性を大きく損なうことに
より溶損が非常に大きくなる。 〈b〉2:1以上となると耐熱性が高くなり、CaOを
多く含有するもアルミナを主成分とする非金属介在物と
の間での反応性が小さくなる。 B23の含有量(1%〜5%) 〈a〉1%以下では素材の結晶の安定度を充分保つこと
が出来ない。(2CaOSiO2→γ2CaOSiO2
結晶転移防止効果が不完全となるため粉化現象を生ず
る。) 〈b〉5%以上となると耐熱性に問題を生ずる。
Next, the reason for limitation will be described. The ratio of CaO and SiO 2 (molar ratio 2: 1 to 3: 2) <a> When the ratio is 3: 2 or less, the heat resistance is greatly impaired and the melting loss becomes very large. <B> When the ratio is 2: 1 or more, the heat resistance becomes high, and the reactivity with non-metallic inclusions containing alumina as a main component becomes small although CaO is contained in a large amount. If the content of B 2 O 3 (1% to 5%) <a> 1% or less, the crystal stability of the material cannot be sufficiently maintained. (Powdering phenomenon occurs due to the incomplete crystal transition preventing effect of 2CaOSiO 2 → γ2CaOSiO 2. ) <B> If it is 5% or more, heat resistance becomes a problem.

【0009】[0009]

【実施例】表1に示した原料を用い、表2に実施例、本
発明範囲内及び本発明範囲外の比較例を示す。
EXAMPLES Using the raw materials shown in Table 1, Table 2 shows Examples, Comparative Examples within the scope of the present invention and outside the scope of the present invention.

【0010】[0010]

【表1】 [Table 1]

【0011】表1に記した原料をそれぞれ単体で74μ
以下に粉砕し配合(石灰はCaO量で換算して配合す
る。なお石灰材料は水酸化石灰,または炭酸石灰等いず
れでも良い)を行い、ミキサーにて混合混練してブリケ
ットマシンで6×6×8mmに造粒した後、乾燥し、そ
の後三相電気炉を用い溶融し、炉を傾動させて取鍋に移
送して取鍋内で冷却して製造する。この溶融物から耐熱
試験は30×30×30mmの試験片を切り出し、耐水和
試験材は粉砕して3〜2mmの試料を調整をし、又加熱冷
却を行うことによる結晶の安定性、砿物組成の変化も同
試料を用いて行う。 機能性試験は溶融材料を粉砕して
3〜1mm 45%,1.0〜0.1mm 15%,0.1mm
以下 40%に樹脂を5%添加しウエットパンにて混
合,混練を行い、1000kg/cm2の圧力で成形し、最高
温度1450℃のトンネル窯にて焼成をほどこし評価試
験用試料を製造する。評価試験結果は表2に記述する。
Each of the raw materials shown in Table 1 is 74 μm alone.
Grind into the following (compound lime in terms of CaO content, the lime material may be lime hydroxide, lime carbonate, etc.), mix and knead with a mixer, and 6 × 6 × with a briquette machine. After granulating to 8 mm, it is dried, then melted using a three-phase electric furnace, tilted and transferred to a ladle, and cooled in the ladle for production. A heat resistance test cuts out a test piece of 30 × 30 × 30 mm from this melt, and a hydration resistance test material is crushed to prepare a sample of 3 to 2 mm, and the stability of crystals by heating and cooling, a ridge The composition is also changed using the same sample. The functional test is to pulverize the molten material to 3-1mm 45%, 1.0-0.1mm 15%, 0.1mm
Then, 5% of resin is added to 40%, mixed and kneaded in a wet pan, molded at a pressure of 1000 kg / cm 2 , and fired in a tunnel kiln having a maximum temperature of 1450 ° C. to produce a sample for evaluation test. The evaluation test results are shown in Table 2.

【0012】[0012]

【表2】 [Table 2]

【0013】[0013]

【発明の効果】本発明の耐火材料は溶鋼中の非金属介在
物の主成分であるアルミナとの反応性の高いCaO,S
iO2とB23を必須成分として構成し、しかもCaO
とSiO2の比をモル比で2:1〜3:2としB23
%〜5%と限定したことにより耐熱性耐消化性および結
晶形の安定性にも優れ加熱,冷却の繰り返しにおいても
2CaOSiO2等の結晶形の転移もなくγ2CaOS
iO2生成も全く認められない等、種々耐火材としての
特性を充分に備え持ち、アルミナとの接触反応性も非常
に高い等の機能性をも充分備えている。尚本材は電気炉
にて溶融して製造しているため、均質かつ高い結晶度を
有し、安定した品質を保つ素材となる。この材料を用い
て製造したノズル材は溶鋼中に介在するアルミナを主成
分とした非金属介在物との間で非常に高い反応性を有す
るので連鋳用のロングノズル,浸漬ノズルのノズル孔内
壁に付着堆積するアルミナ系の非金属介在物の付着堆積
防止に非常に有効である。尚表2において 〈耐熱性〉(所定温度で3時間保持炉内冷却後の状態を示す。) A 変化なし B 軟化状態 をそれぞれ示す C 半溶融状態 D シキ台に溶融浸透している状態 試料は溶融物から30×30×30mmの大きさに切り出し造る。 〈耐水和性〉電気溶融物を粉砕して3〜2mmに調整し
て試料とする。この試料を水中に入れ、煮沸30分後1
05℃の恒温槽中で10時間乾燥を行う。 a.重量増加量(消化量) b.粉化率(2mm以下となった量(重量パーセント)) 〈砿物組成〉 a.元材料のX線回折試験のよる b.水和試験−乾燥後材のX線回折試験による 1.CaO 2.3CaOSiO2 3.2CaOSiO2 4.3CaO2SiO2 5.CaOSiO2 〈機能性試験〉溶融材料を粉砕し、3〜1mm45%,1
〜0.1mm15%,0.1mm以下40%を配合し樹脂5
%を添加混練後1000kg/cm2の圧力で加圧成形した
後、1450℃で焼成し試料とする。試料の大きさ50
×50×20mmにアルミナ44ミクロン下を2mm厚に塗布し
て30分間1550℃で保持し炉内冷却後の状態を示
す。 A 変化なし B 1/3変化有り 状態を示す C 2/3変化有り D ほとんど反応する
INDUSTRIAL APPLICABILITY The refractory material of the present invention is CaO, S which has high reactivity with alumina which is a main component of non-metallic inclusions in molten steel.
Consists of iO 2 and B 2 O 3 as essential components, and CaO
And SiO 2 in a molar ratio of 2: 1 to 3: 2 and B 2 O 3 1
% To 5%, it has excellent heat resistance and digestion resistance and stability of crystal form. Γ2CaOS has no transition of crystal form such as 2CaOSiO 2 even after repeated heating and cooling.
It has sufficient characteristics as various refractory materials, such as no generation of iO 2 , and has sufficient functionality such as very high contact reactivity with alumina. Since this material is manufactured by melting in an electric furnace, it has a uniform and high crystallinity, and is a material that maintains stable quality. Nozzle materials manufactured using this material have extremely high reactivity with non-metallic inclusions mainly composed of alumina that are present in molten steel, so the inner wall of the nozzle hole of long nozzles for continuous casting and immersion nozzles It is very effective in preventing the adhesion and accumulation of alumina-based non-metallic inclusions that adhere and accumulate on the surface. In Table 2, <Heat resistance> (indicates the state after cooling in the holding furnace at a predetermined temperature for 3 hours) A: No change B: Softened state C: Semi-melted state It is cut out from the melt and cut into a size of 30 × 30 × 30 mm. <Hydration resistance> The electric melt is crushed and adjusted to 3 to 2 mm to prepare a sample. Put this sample in water and boil 30 minutes later 1
Dry for 10 hours in a constant temperature bath at 05 ° C. a. Weight increase (digestion amount) b. Pulverization rate (amount (less than 2 mm) (weight percent)) <Mind composition> a. By X-ray diffraction test of the original material b. Hydration test-by X-ray diffraction test of the material after drying 1. CaO 2.3CaOSiO 2 3.2CaOSiO 2 4.3CaO 2SiO 2 5. CaOSiO 2 <Functional test> The molten material is crushed and crushed by 3 to 1 mm 45%, 1
Resin 5 containing ~ 0.1mm 15% and 0.1mm or less 40%
%, Added and kneaded, pressure-molded at a pressure of 1000 kg / cm 2 , and fired at 1450 ° C. to obtain a sample. Sample size 50
It shows the state after applying 44 μm of alumina and 2 mm thickness to 50 × 20 mm and keeping it at 1550 ° C. for 30 minutes and cooling in the furnace. A No change B 1/3 change is present C 2/3 change is present D Mostly react

Claims (1)

【特許請求の範囲】[Claims] CaO,SiO2,B23の3成分を必須成分とした耐
火材料において、CaOとSiO2比がモル比で2:1
〜3:2の範囲の耐火材料95%〜99%とB23が1
%〜5%で構成されCaO,SiO2,B23の合量が
95%以上であることを特徴とするCaO,SiO2
23系の電融耐火材料。
In a refractory material containing three components, CaO, SiO 2 and B 2 O 3 , as essential components, the molar ratio of CaO to SiO 2 is 2: 1.
To 3: 95% to 99% refractory material 2 in the range and B 2 O 3 is 1
% To 5%, and the total amount of CaO, SiO 2 , B 2 O 3 is 95% or more, CaO, SiO 2 ,
B 2 O 3 based fused refractory material.
JP3708992A 1992-01-27 1992-01-27 Refractory material Expired - Lifetime JPH0723253B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3708992A JPH0723253B2 (en) 1992-01-27 1992-01-27 Refractory material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3708992A JPH0723253B2 (en) 1992-01-27 1992-01-27 Refractory material

Publications (2)

Publication Number Publication Date
JPH05201759A JPH05201759A (en) 1993-08-10
JPH0723253B2 true JPH0723253B2 (en) 1995-03-15

Family

ID=12487835

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3708992A Expired - Lifetime JPH0723253B2 (en) 1992-01-27 1992-01-27 Refractory material

Country Status (1)

Country Link
JP (1) JPH0723253B2 (en)

Also Published As

Publication number Publication date
JPH05201759A (en) 1993-08-10

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