JPH04308022A - Refractory for lining of ladle for producing high cleanness molten steel - Google Patents
Refractory for lining of ladle for producing high cleanness molten steelInfo
- Publication number
- JPH04308022A JPH04308022A JP3096184A JP9618491A JPH04308022A JP H04308022 A JPH04308022 A JP H04308022A JP 3096184 A JP3096184 A JP 3096184A JP 9618491 A JP9618491 A JP 9618491A JP H04308022 A JPH04308022 A JP H04308022A
- Authority
- JP
- Japan
- Prior art keywords
- refractory
- weight
- ladle
- al2o3
- lining
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 44
- 239000010959 steel Substances 0.000 title claims abstract description 44
- 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 91
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 52
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 52
- 239000002893 slag Substances 0.000 claims abstract description 9
- 229910000532 Deoxidized steel Inorganic materials 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 79
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 46
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 229910052681 coesite Inorganic materials 0.000 claims description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims description 31
- 229910052682 stishovite Inorganic materials 0.000 claims description 31
- 229910052905 tridymite Inorganic materials 0.000 claims description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims description 30
- 239000002994 raw material Substances 0.000 claims description 21
- 229910052845 zircon Inorganic materials 0.000 claims description 18
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 18
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000011819 refractory material Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 23
- 229910052596 spinel Inorganic materials 0.000 description 19
- 239000011029 spinel Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 238000004901 spalling Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000004927 clay Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 229910000655 Killed steel Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005491 wire drawing Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000005350 fused silica glass Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 238000009749 continuous casting Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011823 monolithic refractory Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- -1 2 (Al Inorganic materials 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009848 ladle injection Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、高清浄度鋼溶製用の耐
火物に関するものであって、特にｓｏｌ．Ａｌ．０．０
０２％以下の伸線加工性、疲労強度、あるいは被削性を
要求されるＳｉ脱酸鋼溶製用の取鍋内張り用耐火物に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to refractories for high-cleanliness steel melting, and particularly to sol. Al. 0.0
The present invention relates to a refractory for lining a ladle for producing Si-deoxidized steel, which requires wire drawability, fatigue strength, or machinability of 0.02% or less.
【０００２】0002
【従来の技術】今日の二次精練および連続鋳造を行なう
状況の下での取鍋は、出鋼温度の上昇、滞湯時間の延長
等を強いられるため耐火物にかかる負担が過酷なものに
なっている。そのために現在の取鍋内張り用耐火物は高
耐食性を指向したものが主流をしめている。例えば取鍋
の中で最も溶損の大きいスラグライン用の耐火物として
は、高アルミナ質またはＡｌ２Ｏ３−ＭｇＯ系及びジル
コン質耐火物が使用される場合が多く、最近ではカーボ
ン添加により耐スポーリング性を向上させた材質も使用
されている。また、溶鋼やスラグによる磨耗が大きい取
鍋一般壁用の耐火物としては、高アルミナ質、中アルミ
ナ質あるいはジルコン質のれんがが使用される場合が多
い。なお、一部では耐火物のコスト低減を目的に一般壁
の不定形化を進めるメーカーも増えている。主に流し込
み材が使用されるが、これについても高耐食性、高耐磨
耗性を目的に高アルミナ質、あるいはスピネル質が使用
されている。 敷耐火物については直接スラグに接す
る機会が少ないので、高耐スポーリング性指向によるジ
ルコン質、シャモット質、蝋石質耐火物が使用されてい
る。[Prior Art] Under today's conditions of secondary smelting and continuous casting, ladles are forced to raise the tapping temperature and extend the residence time, which places a severe burden on the refractories. It has become. For this reason, the current mainstream of ladle lining refractories are those that are oriented toward high corrosion resistance. For example, high alumina, Al2O3-MgO, and zircon refractories are often used as refractories for slag lines, which have the largest erosion loss in ladles.Recently, carbon has been added to improve spalling resistance. Materials with improved properties are also used. In addition, high alumina, medium alumina, or zircon bricks are often used as refractories for general walls of ladle, which are subject to significant wear due to molten steel and slag. In addition, an increasing number of manufacturers are making regular walls amorphous in order to reduce the cost of refractories. Pouring materials are mainly used, and high alumina or spinel materials are also used for the purpose of high corrosion resistance and high wear resistance. Since there are few opportunities for direct contact with slag, zircon-based, chamotte-based, and rouseki-based refractories are used because of their high spalling resistance.
【０００３】0003
【発明が解決しようとする課題】従来から高清浄度Ｓｉ
キルド鋼を製造するに当たっては耐火物の非アルミナ化
（純Ａｌ２Ｏ３を用いない）が望ましいと言われてきた
。
その理由は■介在物組成制御用の溶鋼酸素活量およびｓ
ｏｌ．Ａｌ．の微量コントロール（小山等：学振１９委
員会第３分科会・神戸製鋼所資料；Ｓ６２．９．３０）
、■耐火物を構成する純Ａｌ２Ｏ３粒子の脱落防止（市
橋等；鉄と鋼Ｖｏｌ．７１ Ｎｏ．２・８５−Ａ２５）
であった。従って、従来技術で可能な取鍋内張り耐火物
の非アルミナ化、例えばジルコン系耐火物の使用、タン
ディッシュ内張り耐火物の非アルミナ化、例えばＭｇＯ
系耐火物の使用等、部分的には非アルミナ化が行なわれ
、それなりの改善効果も認められていた（斉藤等；神戸
製鋼技報Ｖｏｌ．３４ Ｎｏ．２ ｐ９６）が、実
害介在物を皆無にし、実用上のトラブルを防止できるレ
ベルには至っていない（斉藤等；神戸製鋼技報Ｖｏｌ．
３４ Ｎｏ．２ ｐ９６）。その理由は、溶鋼注入
系の耐火物を非アルミナ化することが技術的に困難であ
ったことと、部分的な非アルミナ化（純Ａｌ２Ｏ３粒子
を用いない）では、本発明者等が明らかにしたように溶
鋼中および耐火物中カーボンとの反応で耐火物中のＳｉ
Ｏ２成分が還元されてＡｌ２Ｏ３成分が濃化する結果、
後述する実害となるＡｌ２Ｏ３粒子相及びスピネル（Ｍ
ｇＯ・Ａｌ２Ｏ３）相が生成することを防止できないか
らである。したがって溶鋼と接触する耐火物は、実害を
及ぼさないレベルにアルミナレス化する必要がある。Ｓ
ｉキルド鋼を溶製・鋳造した後のＡｌ２Ｏ３成分を含有
した蝋石質等の取鍋耐火物稼働面は、反応付着生成物が
少ないため、従来無害であると考えられていたが、本発
明者らの最近の調査結果では、耐火物稼働面にＡｌ２Ｏ
３が濃化して生成したアルミナ相、スピネル相が鋳造中
に脱落し、鋳片にトラップされて実害を生じる介在物に
なっていると推定される。[Problem to be solved by the invention] Conventionally, high cleanliness Si
In producing killed steel, it has been said that it is desirable to use non-aluminated refractories (not using pure Al2O3). The reason is ■ Molten steel oxygen activity and s for inclusion composition control.
ol. Al. (Koyama et al.: JSPS 19 Committee Subcommittee 3/Kobe Steel Materials; S62.9.30)
, ■ Prevention of falling off of pure Al2O3 particles that constitute refractories (Ichihashi et al.; Tetsu to Hagane Vol. 71 No. 2/85-A25)
Met. Therefore, it is possible to use non-aluminated ladle lining refractories using conventional techniques, such as the use of zircon-based refractories, and non-aluminated tundish lining refractories, such as MgO.
Non-alumina was used in some areas, such as the use of refractories, and some improvement effects were recognized (Saito et al.; Kobe Steel Technical Report Vol. 34 No. 2 p. 96), but no actual harmful inclusions were present. However, it has not reached a level that can prevent practical problems (Saito et al., Kobe Steel Technical Report Vol.
34 No. 2 p96). The reason for this is that it was technically difficult to make the refractories of the molten steel injection system non-aluminated, and the inventors clearly found that partial non-aluminization (not using pure Al2O3 particles) As mentioned above, Si in the refractory is removed by reaction with carbon in molten steel and refractory.
As a result of the O2 component being reduced and the Al2O3 component being concentrated,
Al2O3 particle phase and spinel (M
This is because the formation of the gO.Al2O3) phase cannot be prevented. Therefore, refractories that come into contact with molten steel need to be alumina-free to a level that does not cause any actual damage. S
The working surface of ladle refractories made of rouseite containing Al2O3 components after melting and casting i-killed steel was conventionally thought to be harmless because there are few reaction products, but the present inventor According to recent research results, Al2O on the working surface of refractories
It is estimated that the alumina phase and spinel phase produced by the concentration of No. 3 fall off during casting, become trapped in the slab, and become inclusions that cause actual damage.
【０００４】0004
【課題を解決するための手段】本発明は従来技術の課題
を有利に解決するものであってｓｏｌ．Ａｌ．０．００
２％以下のＳｉ脱酸鋼を溶製する取鍋の内張り用耐火物
において、（１）溶鋼と接触する部分のＡｌ２Ｏ３含有
量を８重量％以下とし、望ましくはＺｒＯ２：３５重量
％以上、ＳｉＯ２：５５重量％以下、およびその他の耐
火成分：０〜５重量％からなることを特徴とする高清浄
度鋼溶製用取鍋の内張り用耐火物。（２）：（１）の取
鍋内張り用耐火物で、取鍋敷き部以外の溶鋼と接触する
耐火物中のＡｌ２Ｏ３含有量を４重量％以下とし、望ま
しくはジルコン原料７０重量％（ＺｒＯ２として４５重
量％）以上を含有し、さらにＳｉＯ２：１０〜２５重量
％含有することを特徴とするセミジルコン質の高清浄度
鋼溶製用取鍋の内張り用耐火物。（３）：（１）および
（２）の取鍋内張り耐火物で、スラグライン部の溶鋼と
接触する耐火物のＡｌ２Ｏ３含有量を２重量％以下とし
、望ましくはＺｒＯ２として６０〜８０重量％を含有し
、さらにＳｉＯ２を２０〜４０重量％含有し、さらにそ
の他の耐火成分を０〜５重量％含有することを特徴とす
る高清浄度鋼溶製用取鍋の内張り用耐火物である。SUMMARY OF THE INVENTION The present invention advantageously solves the problems of the prior art and solves the problems of the prior art. Al. 0.00
In a refractory for lining a ladle made of 2% or less Si deoxidized steel, (1) the Al2O3 content in the part that comes into contact with molten steel is 8% by weight or less, preferably ZrO2: 35% by weight or more, SiO2 : 55% by weight or less, and other refractory components: 0 to 5% by weight. (2): In the ladle lining refractory of (1), the Al2O3 content in the refractory that comes into contact with molten steel other than the ladle lining is 4% by weight or less, and preferably 70% by weight of the zircon raw material (as ZrO2). 45% by weight) and further contains 10 to 25% by weight of SiO. (3): In the ladle lining refractories of (1) and (2), the Al2O3 content of the refractory that comes into contact with the molten steel in the slag line is 2% by weight or less, and preferably 60 to 80% by weight as ZrO2. A refractory for lining a ladle for high-cleanliness steel melting, characterized by containing 20 to 40% by weight of SiO2, and 0 to 5% by weight of other refractory components.
【０００５】以下本発明を図表を用いて説明する。表１
は本発明に適用する鋼種であって、特に低Ａｌに特徴が
ある。Ａｌは強脱酸元素で脱酸・酸素コントロール用に
有用であるが、ｓｏｌ．Ａｌ．が０．００２％以上にな
ると非延性硬質のＡｌ２Ｏ３系介在物を生じて、疲労特
性、伸線加工特性および被削性等を害するので、低Ａｌ
とする必要がある。Ｃは材質強度コントロ−ルに必要で
あり、用途によって必然的にその成分範囲が決定される
が、０．０５％未満では後述する本発明で問題にしてい
る耐火物稼働面のＡｌ２Ｏ３成分濃化も問題とならない
。
ＳｉはＣと共に脱酸・酸素コントロール上必要であり、
また靱性をあまり低下せずに強度を増加させる効果が有
り、 ０．０３〜２．５０％が実用化されている。Ｍｎ
は強度を増加させる効果が有り、また介在物の軟質化に
も効果が有り０．１５〜２．００％程度が実用化されて
いる。Ｐ，Ｓは偏析を悪化させ、材料特性を悪化させる
ので０．０３％以下が望ましい。Ｏは介在物組成コント
ロール上重要な成分でありＣ，Ｓｉ含有量に対して適当
な範囲が有るが安定して鋳造できるのは８０ｐｐｍ以下
である。これ以上では鋳片にブローホールが発生したり
して鋳造が不安定になる。その他Ｃｒ，Ｎｂ，Ｖ等材質
特性上有効で脱酸および介在物組成にあまり影響を及ぼ
さない元素は含有してもかまわない。The present invention will be explained below using diagrams. Table 1
is a steel type applicable to the present invention, and is particularly characterized by low Al content. Al is a strong deoxidizing element and is useful for deoxidizing and oxygen control, but sol. Al. If it exceeds 0.002%, non-ductile hard Al2O3 inclusions will occur, which will impair fatigue properties, wire drawing properties, machinability, etc.
It is necessary to do so. C is necessary for material strength control, and its component range is inevitably determined depending on the application, but if it is less than 0.05%, it will cause concentration of Al2O3 components in the operation of refractories, which will be discussed later in the present invention. is not a problem either. Si is necessary together with C for deoxidation and oxygen control,
It also has the effect of increasing strength without significantly reducing toughness, and 0.03 to 2.50% is in practical use. Mn
has the effect of increasing strength and also softening inclusions, and is in practical use at a content of about 0.15 to 2.00%. Since P and S worsen segregation and material properties, their content is preferably 0.03% or less. O is an important component for controlling inclusion composition, and there is an appropriate range for the C and Si contents, but stable casting is possible at 80 ppm or less. If it exceeds this range, blowholes may occur in the slab, making casting unstable. Other elements such as Cr, Nb, and V that are effective in terms of material properties and do not significantly affect deoxidation and inclusion composition may be included.
【０００６】[0006]
【表１】[Table 1]
【０００７】〈耐火物をアルミナレス化する必要性〉伸
線加工中の破断面、および疲労破面に認められる実害と
なる介在物は、殆どが純アルミナ、およびスピネル（Ａ
ｌ２Ｏ３・ＭｇＯ）である。Ｓｉキルド鋼を溶製、鋳造
した後の中アルミナ質および蝋石質の取鍋内張り耐火物
稼働面には耐火物基材の粒子とは形態が異なる数十μｍ
〜１５０μｍサイズのアルミナ相、およびスピネル相が
析出していることが検鏡調査、ＥＰＭＡ調査で確認され
た。その稼働面断面の模式図を図１に示す。図で１は溶
鋼と反応生成したアルミナ相であり、２は（Ａｌ，Ｓｉ
，Ｍｎ）Ｏ系主体のマトリックスである。３は耐火物基
材である。これらＡｌ２Ｏ３成分含有耐火物の稼働面に
アルミナ、スピネル相が生成する機構をＡｌ２Ｏ３−Ｓ
ｉＯ２系耐火物の場合を例にして述べる。この例は連鋳
タンディッシュ堰（５２％Ａｌ２Ｏ３，４８％ＳｉＯ２
）の場合であるが、取鍋内張り耐火物の場合も同じ反応
である。<Need to make refractories alumina-free> Inclusions that cause actual damage observed on fracture surfaces during wire drawing and fatigue fracture surfaces are mostly pure alumina and spinel (A
12O3・MgO). After melting and casting Si-killed steel, the working surface of the ladle lining refractory made of medium alumina and waxite contains particles several tens of μm in size that are different in shape from the particles of the refractory base material.
It was confirmed by microscopic examination and EPMA examination that an alumina phase and a spinel phase with a size of ~150 μm were precipitated. A schematic cross-sectional view of its operating surface is shown in Figure 1. In the figure, 1 is the alumina phase produced by reaction with molten steel, and 2 is (Al, Si).
, Mn) is an O-based matrix. 3 is a refractory base material. Al2O3-S
The case of iO2-based refractories will be described as an example. This example is a continuous casting tundish weir (52% Al2O3, 48% SiO2
), but the same reaction occurs in the case of ladle lining refractories.
【０００８】カーボンを含まないＡｌ２Ｏ３−ＳｉＯ２
系耐火物にアルミナ相が生成する機構について、 溶鋼
と耐火物との反応を熱力学的に検討した。その結果を表
２に示す（熱力学データは学振・製鋼第１９委員会「製
鋼反応の推奨平衡値」を使用した）。１５００℃の溶鋼
５０Ｔと耐火物１ｋｇが平衡に達するまで反応した結果
を反応後の欄に示してある。溶鋼５０Ｔはタンディッシ
ュ内の溶鋼、耐火物１ｋｇは堰表面の反応層の量を想定
している。表で水準■は高炭素鋼との反応の例である。
耐火物中のＳｉＯ２が還元されて消失し、アルミナが１
００％つまり純アルミナ相が生成することを示している
。
さらにアルミナの一部も還元されてｓｏｌ．Ａｌ．とし
て溶鋼に入っていることが分かる。水準■は溶鋼中カー
ボンが０．２％の場合であるが、この場合でも純アルミ
ナ相が生成する。水準■および■は溶鋼中Ｍｎ含有量を
変更した場合であるが、あまり変化は認められない。こ
の結果から、耐火物中のＳｉＯ２成分は溶鋼中のカーボ
ンで還元されて、Ａｌ２Ｏ３成分が濃化し純アルミナ相
が生成することがわかる。従来溶鋼中のＭｎでＳｉＯ２
が還元されると言う文献が多く見られる（成田：耐火物
，３０〔１４〕，ｐ１４（１９７８）等）が、本発明の
場合にはカーボンの方が還元力が大きいことが分かる。
この全体の反応をムライト組成の例で示すと（３）式で
表わされる。
〈３Ａｌ２Ｏ３・２ＳｉＯ２〉 ＋ ４〔Ｃ〕 ＝ ３
Ａｌ２Ｏ３ ＋ ２〔Ｓｉ〕 ＋ ４｛ＣＯ｝
（３）この場合、耐火物中のＡｌ２Ｏ３成分が濃化
してアルミナ相が生成するので、実害となるアルミナ相
の生成を防止するためには、Ａｌ２Ｏ３成分を極力含有
しない耐火物を使用する必要がある。取鍋内張り耐火物
がジルコン系の場合も、ジルコン（ＳｉＯ２・ＺｒＯ２
）が高温の稼働面でＳｉＯ２とＺｒＯ２に解離したＳｉ
Ｏ２が溶鋼カーボンで還元され、耐火物に含まれるＡｌ
２Ｏ３成分が濃化するため、Ａｌ２Ｏ３含有量を少なく
する必要がある。[0008] Carbon-free Al2O3-SiO2
Regarding the mechanism by which alumina phase is formed in refractories, we thermodynamically investigated the reaction between molten steel and refractories. The results are shown in Table 2 (the thermodynamic data used was the ``Recommended Equilibrium Values for Steelmaking Reactions'' by the 19th JSPS Steelmaking Committee). The results of a reaction between 50T of molten steel at 1500° C. and 1 kg of refractory until reaching equilibrium are shown in the column after the reaction. 50T of molten steel is assumed to be the molten steel in the tundish, and 1kg of refractory is assumed to be the amount of reaction layer on the weir surface. In the table, level ■ is an example of reaction with high carbon steel. SiO2 in the refractory is reduced and disappears, and alumina becomes 1
00%, that is, pure alumina phase is generated. Furthermore, some of the alumina is reduced to sol. Al. It can be seen that it is contained in the molten steel. Level (3) is a case where the carbon content in the molten steel is 0.2%, but even in this case, a pure alumina phase is generated. Levels ■ and ■ are cases where the Mn content in the molten steel was changed, but no significant change was observed. This result shows that the SiO2 component in the refractory is reduced by the carbon in the molten steel, the Al2O3 component is concentrated, and a pure alumina phase is produced. Conventionally, Mn in molten steel is used as SiO2
There are many documents that say that carbon is reduced (Narita: Refractories, 30 [14], p. 14 (1978), etc.), but in the case of the present invention, it is found that carbon has a greater reducing power. This overall reaction is expressed by equation (3) using an example of mullite composition. <3Al2O3・2SiO2> + 4[C] = 3
Al2O3 + 2[Si] + 4{CO}
(3) In this case, the Al2O3 component in the refractory will be concentrated and an alumina phase will be produced, so in order to prevent the formation of the alumina phase which can cause actual damage, it is necessary to use a refractory that contains as little Al2O3 component as possible. be. Even if the ladle lining refractory is zircon-based, zircon (SiO2/ZrO2
) is dissociated into SiO2 and ZrO2 on the high-temperature operating surface.
O2 is reduced with molten steel carbon, and Al contained in the refractory is reduced.
Since the 2O3 component is concentrated, it is necessary to reduce the Al2O3 content.
【０００９】[0009]
【表２】[Table 2]
【００１０】一方、耐火物中にカーボンを含有した耐火
物の場合も、例えばＳｉキルド鋼を鋳造したアルミナ−
黒鉛質の浸漬ノズル稼働面には、ノズル基材に用いられ
ているアルミナ粒子とは形態が異なる数十〜数百μｍサ
イズのアルミナ相、およびスピネル相が生成しているこ
とが検鏡調査・ＥＰＭＡ分析で確認された。耐火物を構
成する純アルミナ粒子が脱落して硬質の実害介在物にな
るのは当然として、アルミナ相およびＡｌ２Ｏ３成分を
含有し、かつカーボンを含有する浸漬ノズル等の耐火物
稼働面にＡｌ２Ｏ３相及びスピネル（ＭｇＯ・Ａｌ２Ｏ
３）相が生成するのは次の機構によると考えられる。ア
ルミナ−黒鉛質の浸漬ノズルの様に耐火物中にカーボン
を含有する場合は、浸漬ノズル内のＡｌ２Ｏ３およびＳ
ｉＯ２成分がＣおよびＣＯガスで還元されてＡｌ２Ｏガ
ス、ＳｉＯガスとして稼働面に移動してＡｌ２Ｏガスは
溶鋼側から酸素を得てＡｌ２Ｏ３として析出し、ＳｉＯ
はさらにカーボン，およびＣＯガスで還元されてＳｉと
してメタル中へ移行する（福田等：鉄と鋼′８６−Ｓ２
８０等）。
全体の反応式は次の様に表わされる。
〈Ａｌ２Ｏ３〉 ＋ ４〈Ｃ〉 ＋ ２〈ＳｉＯ２〉
→ （Ａｌ２Ｏ３） ＋ ２〔Ｓｉ〕 ＋ ４｛ＣＯ｝
（１）ＳｉＯ２を含まないカーボン含有耐火物の反
応式も同様に（２）式（Ｈａｕｃｋら：Ｅｉｓｅｎｈｕ
ｔｔｅｎｗｅｓ．５３（１９８２）Ｎｒ．４Ａｐｒｉｌ
，Ｐ１２７）で表わされる。
３〈Ａｌ２Ｏ３〉 ＋ ６〈Ｃ〉 → ４〔Ａｌ〕 ＋
（Ａｌ２Ｏ３） ＋ ６｛ＣＯ｝ （
２）従ってＳｉＯ２を含まない場合でもカーボンを含有
していれば稼働面にＡｌ２Ｏ３が生成することになる。
稼働面にアルミナ相の生成を防止するには、Ａｌ２Ｏ３
成分を極力含有しない耐火物、すなわちアルミナレス耐
火物とする必要がある。また、耐火物稼働面にスピネル
（ＭｇＯ・Ａｌ２Ｏ３）相の生成がしばしば認められる
のは、転炉スラグ、およびＭｇＯ系耐火物成分や脱酸生
成物中のＭｇＯ成分と耐火物稼働面に生成したＡｌ２Ｏ
３が反応してスピネルが生成するためであると推定され
る。[0010] On the other hand, in the case of refractories containing carbon, for example, Si-killed steel is cast into alumina.
Microscopic investigation revealed that on the graphite immersion nozzle operating surface, an alumina phase with a size of several tens to hundreds of micrometers and a spinel phase were formed, which had a different morphology from the alumina particles used in the nozzle base material. Confirmed by EPMA analysis. It goes without saying that the pure alumina particles constituting the refractory fall off and become hard harmful inclusions, but the Al2O3 phase and the Al2O3 phase and the carbon-containing refractory working surface, such as a submerged nozzle, contain an alumina phase and an Al2O3 component. Spinel (MgO・Al2O
3) The formation of phases is thought to be due to the following mechanism. When the refractory contains carbon, such as an alumina-graphite immersion nozzle, Al2O3 and S in the immersion nozzle
The iO2 component is reduced with C and CO gas and moves to the working surface as Al2O gas and SiO gas, and the Al2O gas obtains oxygen from the molten steel side and precipitates as Al2O3, forming SiO.
is further reduced with carbon and CO gas and migrates into the metal as Si (Fukuda et al.: Tetsu-to-Hagane '86-S2
80 etc.). The overall reaction formula is expressed as follows. 〈Al2O3〉 + 4〈C〉 + 2〈SiO2〉
→ (Al2O3) + 2[Si] + 4{CO}
(1) The reaction equation of a carbon-containing refractory that does not contain SiO2 is also the same as equation (2) (Hauck et al.: Eisenhu
ttenwes. 53 (1982) Nr. 4April
, P127). 3〈Al2O3〉 + 6〈C〉 → 4〔Al〕 +
(Al2O3) + 6{CO} (
2) Therefore, even if SiO2 is not contained, Al2O3 will be generated on the working surface if carbon is contained. To prevent the formation of alumina phase on the working surface, Al2O3
It is necessary to create a refractory that contains as few components as possible, that is, an alumina-free refractory. In addition, the formation of a spinel (MgO/Al2O3) phase on the working surface of the refractory is often observed due to the formation of the spinel (MgO/Al2O3) phase on the working surface of the refractory and the MgO components in the converter slag, MgO-based refractory components, and deoxidized products. Al2O
It is presumed that this is because 3 reacts to produce spinel.
【００１１】本発明による取鍋内張り耐火物は（１）溶
鋼と接触する部分のＡｌ２Ｏ３含有量を８重量％以下と
し、望ましくはＺｒＯ２：３５重量％以上、ＳｉＯ２：
５５重量％以下、およびその他の耐火成分：０〜５重量
％からなり、また（２）取鍋敷き部以外の溶鋼と接触す
る耐火物中のＡｌ２Ｏ３含有量を４重量％以下とし、望
ましくはジルコン原料７０重量％（ＺｒＯ２として４５
重量％）以上を含有し、さらにＳｉＯ２：１０〜２５重
量％含有するセミジルコン質用の耐火物、さらに（３）
スラグライン部の溶鋼と接触する耐火物のＡｌ２Ｏ３含
有量を２重量％以下とし、望ましくはＺｒＯ２として６
０〜８０重量％を含有し、さらにＳｉＯ２を２０〜４０
重量％含有し、さらにその他の耐火成分を０〜５重量％
含有する耐火物であるために、溶鋼との反応で耐火物稼
働面に実害となるアルミナ相やスピネル相が生成するこ
とがない。アルミナを含有しない耐火性原料としてはジ
ルコン、 ジルコニア、溶融シリカ、珪石等がある。本
発明の耐火物はこれらの耐火原料を主に使用してなる。
耐火物が上記耐火原料で構成される場合、ＳｉＯ２含有
量が６５％を超えると耐食性の低下が著しくなるので５
５％以下が望ましい。また１０％未満では耐スポーリン
グ性が低下する。残部は主としてＺｒＯ２成分で、３５
〜９０％となる。上記耐火性原料のみで耐火物を製造す
ることも可能であるが、定形耐火物はその製造時に作業
性が安定せず、混練、成形に熟練を要する。また、不定
形耐火物の場合には、主として炉前で混練、養生されて
使用されるため、特にその作業性の不安定さが問題とな
る。
この難点を解決するために、耐火粘土を使用することが
出来る。しかしこの場合耐火物中のＡｌ２Ｏ３含有量が
１０％を超えるほどに多くなると、（Ａｌ，Ｓｉ，Ｚｒ
）Ｏ系の低融点生成物が多くなり耐食性の低下をもたら
すので少ない方が望ましい。以上述べたように、本発明
成分系による取鍋内張り用耐火物は、耐食性や、耐スポ
ーリング性の点で従来の耐火物と同等以上の耐用性があ
り、しかもＳｉキルド鋼の鋳造に於いてアルミナ相やス
ピネル相等の実害となる高融点・硬質介在物を生成しな
いため、鋼材品質向上の上で大きな利点がある。The ladle lining refractory according to the present invention has (1) an Al2O3 content of 8% by weight or less in the portion that comes into contact with molten steel, preferably 35% by weight or more of ZrO2, and SiO2:
55% by weight or less, and other refractory components: 0 to 5% by weight, and (2) the Al2O3 content in the refractory that comes into contact with molten steel other than the ladle bedding part is 4% by weight or less, and preferably zircon. Raw material 70% by weight (45% as ZrO2
(wt%) or more, and further contains SiO2: 10 to 25 wt%, a refractory for semizircon, and (3)
The Al2O3 content of the refractory that comes into contact with the molten steel in the slag line should be 2% by weight or less, preferably 6% as ZrO2.
0 to 80% by weight, and further contains 20 to 40% SiO2.
Contains 0 to 5% by weight of other fire-resistant components.
Because it is a refractory containing refractories, alumina and spinel phases that cause actual damage to the working surfaces of refractories are not generated due to reaction with molten steel. Examples of refractory raw materials that do not contain alumina include zircon, zirconia, fused silica, and silica. The refractory of the present invention is mainly made of these refractory raw materials. When the refractory is composed of the above-mentioned refractory raw materials, if the SiO2 content exceeds 65%, the corrosion resistance will be significantly reduced.
5% or less is desirable. Moreover, if it is less than 10%, spalling resistance decreases. The remainder is mainly ZrO2 component, 35
~90%. Although it is possible to manufacture refractories using only the above-mentioned refractory raw materials, the workability of shaped refractories is unstable during manufacture, and skill is required for kneading and shaping. Moreover, in the case of monolithic refractories, since they are mainly kneaded and cured before use in a furnace, instability in their workability is a particular problem. To overcome this difficulty, fireclay can be used. However, in this case, if the Al2O3 content in the refractory increases to more than 10%, (Al, Si, Zr
) Since the amount of O-based low-melting point products increases, resulting in a decrease in corrosion resistance, it is desirable that the amount is less. As described above, the refractory for ladle lining made of the composition system of the present invention has durability equivalent to or higher than conventional refractories in terms of corrosion resistance and spalling resistance, and is also effective in casting Si-killed steel. Since it does not produce harmful high-melting-point, hard inclusions such as alumina phase or spinel phase, it has a great advantage in improving the quality of steel materials.
【００１２】0012
【実施例】以下、本発明例を実施例に基ずいて説明する
。表３に定形耐火物の例を示す。実施例Ａは、ジルコニ
ア原料１７重量％、溶融シリカ８重量％、ジルコン原料
７５重量％からなる配合を、バインダーとしてフェノー
ル樹脂を添加して混練・成形・焼成して得られるもので
ある。化学成分はＺｒＯ２が６７％、ＳｉＯ２が３２％
であり、不可避的なＡｌ２Ｏ３含有量は０．３％である
。
実施例Ｂはジルコン原料６０重量％、珪石２５重量％、
可塑材としての粘土１５％からなるものである。化学成
分はＺｒＯ２が４０％、ＳｉＯ２が５３％であり、粘土
によるＡｌ２Ｏ３含有量は６％である。実施例Ａ，Ｂは
耐食性、耐スポーリング性も良好であり、鋼材品質への
影響も問題がなかった。比較例Ｃは化学成分としてＳｉ
Ｏ２が過剰な材質であり、ジルコン原料４５％、溶融シ
リカ５０重量％、珪石５重量％からなる配合をバインダ
ーとしてフェノール樹脂を添加して混練・成形・焼成し
て得られるものである。 化学成分はＺｒＯ２が３０％
、ＳｉＯ２が７０％であり、不可避的Ａｌ２Ｏ３含有量
は０．４％である。この比較例Ｃは、本発明を適用した
実施例と比較して耐食性に劣り、溶鋼を汚染し鋼材の品
質を低下せしめる。比較例Ｄは化学成分としてＳｉＯ２
が不足している材質であり、ジルコニア原料７７重量％
、珪石３重量％、ジルコン原料２０重量％からなるもの
である。
化学成分はＺｒＯ２が９０％、ＳｉＯ２が９％であり、
不可避的成分としてのＡｌ２Ｏ３含有量が０．３％であ
る。
この比較例Ｄは、本発明を適用した実施例と比較して、
耐スポーリング性に劣り寿命が短い。比較例Ｅは化学成
分としてのＡｌ２Ｏ３含有量が過剰な材質であり、粘土
を３５重量％使用している。この比較例Ｅは本発明を適
用した実施例と比較して、耐スポーリング性に劣り、ま
た稼働面に品質上有害なアルミナ相、スピネル相の生成
が認められた。比較例Ｆは高アルミナ質煉瓦であり、バ
ンケツ８０重量％、アルミナ原料１０重量％、粘土１０
重量％からなる。本発明を適用した実施例と比較して、
耐スポーリング性が劣り、 有害なアルミナ、スピネル
相の生成も多数認められた。[Examples] The present invention will be explained below based on Examples. Table 3 shows examples of shaped refractories. Example A is obtained by kneading, molding, and firing a composition consisting of 17% by weight of zirconia raw material, 8% by weight of fused silica, and 75% by weight of zircon raw material, with the addition of a phenol resin as a binder. Chemical composition: 67% ZrO2, 32% SiO2
and the unavoidable Al2O3 content is 0.3%. Example B includes 60% by weight of zircon raw material, 25% by weight of silica stone,
It consists of 15% clay as a plasticizer. The chemical components are 40% ZrO2, 53% SiO2, and the Al2O3 content due to clay is 6%. Examples A and B had good corrosion resistance and spalling resistance, and there was no problem in affecting the quality of the steel material. Comparative example C contains Si as a chemical component.
It is a material with an excess of O2, and is obtained by kneading, molding, and firing a mixture of 45% zircon raw material, 50% fused silica, and 5% silica stone by adding phenolic resin as a binder. Chemical composition is 30% ZrO2
, SiO2 is 70% and the inevitable Al2O3 content is 0.4%. Comparative Example C is inferior in corrosion resistance compared to Examples to which the present invention is applied, contaminating the molten steel and degrading the quality of the steel material. Comparative example D uses SiO2 as a chemical component.
is a material in short supply, and 77% by weight of zirconia raw material
, 3% by weight of silica stone, and 20% by weight of zircon raw material. The chemical composition is 90% ZrO2 and 9% SiO2,
The content of Al2O3 as an inevitable component is 0.3%. This comparative example D is compared with the example to which the present invention is applied,
Poor spalling resistance and short lifespan. Comparative Example E is a material with excessive Al2O3 content as a chemical component, and uses 35% by weight of clay. Comparative Example E was inferior in spalling resistance compared to Examples to which the present invention was applied, and formation of alumina phase and spinel phase, which were detrimental to operational quality, was observed. Comparative Example F is a high alumina brick, containing 80% by weight of banquette, 10% by weight of alumina raw material, and 10% by weight of clay.
It consists of % by weight. Compared to the embodiment to which the present invention is applied,
The spalling resistance was poor, and many harmful alumina and spinel phases were observed.
【００１３】[0013]
【表３】[Table 3]
【００１４】表４．には不定形耐火物の例を示す。実施
例Ｇはジルコニア原料１７重量％、溶融シリカ８重量％
、ジルコン原料７５％からなる配合を、水を添加して混
練・施工・養生して使用されるものである。化学成分は
ＺｒＯ２が６７％、ＳｉＯ２が３２％であり、不可避的
なＡｌ２Ｏ３含有量は０．３％である。実施例Ｈはジル
コン原料６３重量％、珪石２７重量％、可塑材としての
粘土１０重量％からなるものである。化学成分はＺｒＯ
２が４２％、ＳｉＯ２が５４％であり、粘土によるＡｌ
２Ｏ３含有量は４％である。実施例Ｇ、Ｈは耐食性が良
好であり、特にＨは作業性も良好である。比較例Ｉは化
学成分としてのＳｉＯ２が過剰な材質であり、ジルコン
原料４５重量％、珪石５５重量％、から成るものである
。化学成分はＺｒＯ２が３０％、ＳｉＯ２が６９％であ
り、不可避的なＡｌ２Ｏ３含有量は０．６％である。こ
の比較例Ｉは、本発明を適用した実施例と比較して耐食
性に劣り、 溶鋼を汚染して品質を低下させた。 比較
例Ｊは化学成分としてＳｉＯ２が不足している材質であ
り、ジルコニア原料７７重量％、珪石３重量％、ジルコ
ン原料２０重量％からなるものである。化学成分はＺｒ
Ｏ２が９０％、ＳｉＯ２が９％であり、不可避成分とし
てのＡｌ２Ｏ３含有量が０．３％である。この比較例Ｊ
は、本発明を適用した実施例と比較して耐スポーリング
性に劣り、寿命が著しく短くなる。比較例Ｋは化学成分
としてＡｌ２Ｏ３が過剰な材質であり、粘土を３５重量
％使用している。この比較例Ｋは本発明を適用した実施
例と比較して、耐スポーリング性に劣り、また稼働面に
有害なアルミナ相、スピネル相の生成も認められた。比
較例Ｌは従来の蝋石タイプの流し込み材であり、 蝋石
８０重量％、アルミナ原料１０重量％、粘土１０重量％
からなる。化学成分はＳｉＯ２が６２重量％、Ａｌ２Ｏ
３が３１重量％であり、稼働面に有害なアルミナ相、ス
ピネル相が多数生成した。Table 4. shows an example of monolithic refractories. Example G contains 17% by weight of zirconia raw material and 8% by weight of fused silica.
, a formulation consisting of 75% zircon raw material is used by adding water, kneading, applying, and curing. The chemical components are 67% ZrO2, 32% SiO2, and the inevitable Al2O3 content is 0.3%. Example H consists of 63% by weight of zircon raw material, 27% by weight of silica stone, and 10% by weight of clay as a plasticizer. Chemical composition is ZrO
2 is 42%, SiO2 is 54%, and Al due to clay
The 2O3 content is 4%. Examples G and H have good corrosion resistance, and H in particular has good workability. Comparative Example I is a material containing excessive SiO2 as a chemical component, and is composed of 45% by weight of zircon raw material and 55% by weight of silica stone. The chemical components are 30% ZrO2, 69% SiO2, and the inevitable Al2O3 content is 0.6%. Comparative Example I was inferior in corrosion resistance compared to Examples to which the present invention was applied, and contaminated the molten steel, degrading its quality. Comparative Example J is a material lacking SiO2 as a chemical component, and consists of 77% by weight of zirconia raw material, 3% by weight of silica stone, and 20% by weight of zircon raw material. Chemical component is Zr
O2 is 90%, SiO2 is 9%, and the content of Al2O3 as an inevitable component is 0.3%. This comparative example J
Compared to the examples to which the present invention is applied, the spalling resistance is inferior and the life span is significantly shortened. Comparative Example K is a material containing excessive Al2O3 as a chemical component, and uses 35% by weight of clay. Comparative Example K was inferior in spalling resistance as compared to Examples to which the present invention was applied, and formation of alumina and spinel phases, which were harmful to operation, was also observed. Comparative example L is a conventional Rouseki type pouring material, which contains 80% by weight Rouseki, 10% by weight alumina raw material, and 10% by weight clay.
Consisting of Chemical composition is 62% by weight of SiO2, Al2O
3 was 31% by weight, and a large amount of alumina phase and spinel phase, which were harmful to the operating surface, were generated.
【００１５】[0015]
【表４】[Table 4]
【００１６】図２は、本発明対象成分の鋼材を、約２０
０ミクロンまで伸線加工をしたときの介在物性断線指数
と耐火物改善経過との関連を調査した結果を示す。従来
品は鍋から、タンディッシュ、および注入系耐火物とし
て、Ａｌ２Ｏ３含有耐火物を使用したものである。比較
例１は鍋注入系ノズル、ロングノズル、タンディッシュ
内壁、タンディッシュ上ノズル、ストッパー、浸漬ノズ
ル、タンディッシュカバー等の耐火物をＡｌ２Ｏ３含有
量１０％以下に少なくし、取鍋内張り耐火物のみを従来
の蝋石質主体の物を用いた場合である。鍋耐火物の稼働
面に生成したアルミナ、スピネル相が溶損脱落して断線
を生じた実害介在物になったことを示している。 本発
明１は、本発明の取鍋内張り耐火物を従来品に替えて使
用した例である。その他は従来耐火物であるが若干の改
善効果が認められる。本発明２は本発明の考えを発展さ
せ、取鍋から浸漬ノズルまでの溶鋼と接触する全ての耐
火物のＡｌ２Ｏ３含有量を１０％以下にした例で大幅に
改善されている。これは溶鋼と耐火物の反応で生じるア
ルミナ、スピネルの実害介在物を無くすることが出来た
からである。本発明２でも極僅かに介在物性の断線が認
められるが、これは脱酸生成物系、及びスラグ系の大型
介在物起因によるものである。このレベルになると表面
欠陥起因、 及び中心偏析起因の断線の方が圧倒的に多
く、従来問題となっていた介在物性起因の断線トラブル
は殆ど生じなくなった。同様に、硬質介在物が大幅に減
少した結果疲労限が向上し、また硬質介在物に起因する
伸線時のダイスの寿命が延長し、切削時の工具刃先の傷
みが減少した結果、被削性も向上した。なお、図３に取
鍋およびタンディッシュ耐火物の構造例を示す。FIG. 2 shows the steel material containing the target components of the present invention in approximately 20%
The results of an investigation into the relationship between the inclusion breakage index and the progress of refractory improvement when wire-drawing down to 0 microns are shown. Conventional products use Al2O3-containing refractories for pots, tundishes, and injection refractories. In Comparative Example 1, the refractories such as the ladle injection nozzle, long nozzle, tundish inner wall, tundish upper nozzle, stopper, immersion nozzle, and tundish cover were reduced to less than 10% Al2O3 content, and only the ladle lining refractory was used. This is the case when a conventional material mainly composed of Roiseki is used. This indicates that the alumina and spinel phases that formed on the working surface of the pot refractory were melted and fell off, becoming the actual damaging inclusions that caused the disconnection. Present invention 1 is an example in which the ladle lining refractory of the present invention is used in place of a conventional product. The rest are conventional refractories, but some improvements can be seen. Present invention 2 develops the idea of the present invention and is greatly improved in an example in which the Al2O3 content of all refractories that come into contact with molten steel from the ladle to the immersion nozzle is reduced to 10% or less. This is because harmful inclusions of alumina and spinel produced by the reaction between molten steel and refractories can be eliminated. Even in Invention 2, a very slight inclusion-related disconnection is observed, but this is due to large inclusions of the deoxidation product system and the slag system. At this level, the number of wire breaks caused by surface defects and center segregation is overwhelmingly higher, and the problem of wire breaks caused by inclusions, which was a problem in the past, almost no longer occurs. Similarly, the fatigue limit is improved as a result of a significant reduction in hard inclusions, the life of the die during wire drawing due to hard inclusions is extended, and damage to the tool edge during cutting is reduced, resulting in Sexuality also improved. Note that FIG. 3 shows an example of the structure of the ladle and tundish refractories.
【００１７】[0017]
【発明の効果】本発明によって、耐火物稼働面に実害を
及ぼす硬質のアルミナ相やスピネル相が生成しなくなり
、鋳片内の硬質介在物が減少した結果、伸線加工中の断
線トラブルが減少し、また疲労限が向上し、さらに被削
性も向上させることが出来た。[Effects of the invention] The present invention prevents the formation of hard alumina and spinel phases that cause actual damage to the working surfaces of refractories, and reduces the number of hard inclusions in the slab, resulting in fewer wire breakage problems during wire drawing. In addition, the fatigue limit was improved, and machinability was also improved.
【図１】高アルミナ質稼働面における断面模式図、[Figure 1] Schematic cross-sectional diagram of high alumina operating surface,
【図
２】本発明と比較例との介在物性の断線指数を示す図、FIG. 2 is a diagram showing the breakage index of inclusion properties between the present invention and a comparative example;
【図３】取鍋およびタンデッシュ耐火物の構造例を示す
。FIG. 3 shows an example of the structure of a ladle and a tundish refractory.
１ 溶鋼と反応生成したアルミナ相、２ （Ａｌ，
Ｓｉ，Ｍｎ）Ｏ系主体のマトリックス、３ 耐火物基
材。1 Alumina phase produced by reaction with molten steel, 2 (Al,
Si, Mn) O-based matrix, 3. Refractory base material.
Claims (3)
ｉ脱酸鋼を溶製する取鍋の内張り用耐火物において、溶
鋼と接触する部分のＡｌ２Ｏ３含有量を８重量％以下と
し、望ましくはＺｒＯ２：３５重量％以上、ＳｉＯ２：
５５重量％以下、およびその他の耐火成分：０〜５重量
％からなることを特徴とする高清浄度鋼溶製用取鍋の内
張り用耐火物。[Claim 1] sol. Al. S less than 0.002%
i In a refractory for lining a ladle for melting deoxidized steel, the Al2O3 content in the part that comes into contact with molten steel is 8% by weight or less, preferably ZrO2: 35% by weight or more, SiO2:
55% by weight or less, and other refractory components: 0 to 5% by weight. A refractory for lining a ladle for high-cleanliness steel melting.
、取鍋敷き部以外の溶鋼と接触する耐火物中のＡｌ２Ｏ
３含有量を４重量％以下とし、望ましくはジルコン原料
７０重量％（ＺｒＯ２として４５重量％）以上を含有し
、さらにＳｉＯ２：１０〜２５重量％含有することを特
徴とするセミジルコン質の高清浄度鋼溶製用取鍋の内張
り用耐火物。2. In the ladle lining refractory according to claim 1, Al2O in the refractory that comes into contact with molten steel other than the ladle lining part.
3 content is 4% by weight or less, desirably contains 70% by weight or more of zircon raw material (45% by weight as ZrO2), and further contains 10 to 25% by weight of SiO2. Refractory for lining ladle for steel melting.
物で、スラグライン部耐火物のＡｌ２Ｏ３含有量を２重
量％以下とし、望ましくはＺｒＯ２として６０〜８０重
量％を含有し、さらにＳｉＯ２を２０〜４０重量％含有
し、さらにその他の耐火成分を０〜５重量％含有するこ
とを特徴とする高清浄度鋼溶製用取鍋の内張り用耐火物
。3. In the ladle lining refractory according to claims 1 and 2, the Al2O3 content of the slag line refractory is 2% by weight or less, preferably 60 to 80% by weight as ZrO2, and further contains SiO2. A refractory for lining a ladle for high-cleanliness steel melting, characterized by containing 20 to 40% by weight of , and further containing 0 to 5% by weight of other refractory components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3096184A JP2510898B2 (en) | 1991-04-03 | 1991-04-03 | Refractory for lining of ladle for melting high-cleanliness molten steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3096184A JP2510898B2 (en) | 1991-04-03 | 1991-04-03 | Refractory for lining of ladle for melting high-cleanliness molten steel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04308022A true JPH04308022A (en) | 1992-10-30 |
| JP2510898B2 JP2510898B2 (en) | 1996-06-26 |
Family
ID=14158232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3096184A Expired - Lifetime JP2510898B2 (en) | 1991-04-03 | 1991-04-03 | Refractory for lining of ladle for melting high-cleanliness molten steel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2510898B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1018565A4 (en) * | 1998-06-23 | 2003-07-23 | Sumitomo Metal Ind | Steel wire rod and method of manufacturing steel for the same |
-
1991
- 1991-04-03 JP JP3096184A patent/JP2510898B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1018565A4 (en) * | 1998-06-23 | 2003-07-23 | Sumitomo Metal Ind | Steel wire rod and method of manufacturing steel for the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2510898B2 (en) | 1996-06-26 |
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