JPH0834666A - Refractory for steel making - Google Patents
Refractory for steel makingInfo
- Publication number
- JPH0834666A JPH0834666A JP6172742A JP17274294A JPH0834666A JP H0834666 A JPH0834666 A JP H0834666A JP 6172742 A JP6172742 A JP 6172742A JP 17274294 A JP17274294 A JP 17274294A JP H0834666 A JPH0834666 A JP H0834666A
- Authority
- JP
- Japan
- Prior art keywords
- refractory
- alumina
- thermal shock
- steel making
- mgo
- 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
- Compositions Of Oxide Ceramics (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
- Ceramic Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は製鋼用耐火物に関し、
特に耐熱衝撃性を保持しつつ耐蝕性を向上した耐火物
で、取鍋ノズル、ノズル受けなどの鋳造用耐火物に好適
な製鋼用耐火物に関する。BACKGROUND OF THE INVENTION This invention relates to a refractory material for steelmaking,
In particular, the present invention relates to a refractory for steel making suitable for a casting refractory such as a ladle nozzle and a nozzle receiver, which is a refractory having improved thermal shock resistance and corrosion resistance.
【０００２】[0002]
【従来の技術】従来、取鍋ノズル、ノズル受けレンガな
どの製鋼用耐火物は、高アルミナ質レンガ、高アルミナ
質キャスタブルブロックが使用されてきた。また最近で
は、特開平４−８３７５５で耐蝕性と耐熱衝撃性を向上
させるためにクロミア原料とアルミナ−ジルコニア系原
料を使用したアルミナ−クロミア−ジルコニア系耐火物
が提案されている。2. Description of the Related Art Hitherto, high-alumina bricks and high-alumina castable blocks have been used as refractories for steelmaking such as ladle nozzles and nozzle receiving bricks. Recently, JP-A-4-83755 proposes an alumina-chromia-zirconia-based refractory material using a chromia raw material and an alumina-zirconia-based raw material in order to improve corrosion resistance and thermal shock resistance.
【０００３】しかしながら、高アルミナ質レンガはスラ
グによる溶損及び熱衝撃による割れが著しいことが知ら
れ、またアルミナ−クロミア−ジルコニア系レンガは耐
熱衝撃性はある程度改善されてきたが、耐蝕性はいまだ
十分とまではいっていない。However, it is known that high-alumina bricks have significant erosion damage due to slag and cracking due to thermal shock. Alumina-chromia-zirconia bricks have been improved in thermal shock resistance to some extent, but still have corrosion resistance. Not enough.
【０００４】[0004]
【発明が解決しようとする課題】この発明は、取鍋ノズ
ル、ノズル受けレンガなどに好適な製鋼用耐火物とし
て、耐熱性を低下させることなく耐蝕性を向上させた耐
火物を得ようとするものである。DISCLOSURE OF THE INVENTION The present invention is intended to obtain a refractory for steelmaking which is suitable for ladle nozzles, bricks for receiving nozzles, etc. and has improved corrosion resistance without lowering heat resistance. It is a thing.
【０００５】[0005]
【課題を解決するための手段】この発明は、ＺｒＯ2 が
５〜１５重量％、Ｃｒ2 Ｏ3 が３〜２０重量％、スピネ
ル及び又はクロム鉱に由来するＭｇＯが１〜１０重量
％、残部がＡｌ2 Ｏ3 及び不可避的な不純物であること
を特徴とする製鋼用耐火物（請求項１）、Ｃｒ2Ｏ3 が
クロム鉱及び又は酸化クロムのいずれか一種であること
を特徴とする請求項１記載の製鋼用耐火物（請求項２）
及びＺｒＯ2 がアルミナ−ジルコニア系原料であること
を特徴とする請求項１記載の製鋼用耐火物（請求項３）
である。以下にこれらの発明をさらに説明する。According to the present invention, ZrO 2 is 5 to 15 wt%, Cr 2 O 3 is 3 to 20 wt%, MgO derived from spinel and / or chrome ore is 1 to 10 wt%, and the balance is Is a refractory for steel making (claim 1), characterized in that Al 2 O 3 and unavoidable impurities, and Cr 2 O 3 is one of chrome ore and chromium oxide. Refractory for steel making according to claim 1 (claim 2)
And ZrO 2 are alumina-zirconia-based raw materials, the refractory for steel making according to claim 1 (claim 3).
Is. These inventions will be further described below.
【０００６】この発明の耐火物の構成成分であるアルミ
ナ原料は、ボ−キサイトやバン土頁岩などの天然原料を
使用することができるが、耐火物の耐蝕性を上げるうえ
からは焼結アルミナや電融アルミナなどのＡｌ2 Ｏ3 単
味からなる合成原料を用いることが好ましい。As the alumina raw material which is a constituent of the refractory of the present invention, natural raw materials such as bauxite and shale shale can be used, but in order to improve the corrosion resistance of the refractory, sintered alumina and It is preferable to use a synthetic raw material consisting of Al 2 O 3 plain such as fused alumina.
【０００７】ＺｒＯ2 成分は耐熱衝撃性を維持するため
のもので、従来と同様にアルミナ−ジルコニア系の原料
を使用するのが好ましい。ＺｒＯ2 成分が５重量％未満
では耐熱衝撃性が維持できず、またこれが１５重量％を
超えると耐火物のスラグに対する耐蝕性の低下ととも
に、転移に伴う体積変化の影響が大きく製造上好ましく
ない。The ZrO 2 component is for maintaining thermal shock resistance, and it is preferable to use an alumina-zirconia-based raw material as in the conventional case. If the ZrO 2 component is less than 5% by weight, the thermal shock resistance cannot be maintained, and if it exceeds 15% by weight, the corrosion resistance to the slag of the refractory material is deteriorated, and the influence of the volume change accompanying the transition is large, which is not preferable in manufacturing.
【０００８】Ｃｒ2 Ｏ3 は、クロム鉱又は酸化クロムを
用いることが出来る。Ｃｒ2 Ｏ3 は３重量％未満では耐
蝕性の向上は認められず、またこれが２０重量％を超え
るとこれが難焼結性の原料である故に焼成によって必要
な強度が得られない。As Cr 2 O 3 , chrome ore or chromium oxide can be used. If Cr 2 O 3 is less than 3% by weight, no improvement in corrosion resistance is observed, and if it exceeds 20% by weight, the required strength cannot be obtained by firing because it is a material that is difficult to sinter.
【０００９】また、ＭｇＯ成分はスピネル又はクロム鉱
のいずれか一種または２種に由来するもので、その使用
量は１〜１０重量％とする。これが１％未満では耐蝕性
の向上に不十分であり、これが１０重量％を超えるとＣ
ｒ2 Ｏ3 の場合と同様に最低限度必要な強度特性が得ら
れず、熱衝撃により割れを生じる恐れがある。The MgO component is derived from one or two of spinel and chrome ore, and the amount used is 1 to 10% by weight. If it is less than 1%, it is insufficient to improve the corrosion resistance, and if it exceeds 10% by weight, C
As in the case of r 2 O 3 , the minimum required strength characteristics cannot be obtained and there is a risk of cracking due to thermal shock.
【００１０】なお、ＭｇＯ単味を添加するとＡｌ2 Ｏ3
と反応してスピネルを生成し体積膨脹を生じるため実用
に使用できない。なお、Ｃｒ2 Ｏ3 が２０重量％を超え
る場合、又はＭｇＯが１０重量％を超える場合に、その
強度特性の低下を補うために高温焼成を行うと主成分で
あるＡｌ2 Ｏ3 が過焼結して耐熱衝撃性が低下する。When MgO alone is added, Al 2 O 3 is added.
It cannot be used in practice because it reacts with to form spinel and causes volume expansion. When Cr 2 O 3 exceeds 20% by weight, or when MgO exceeds 10% by weight, high temperature firing is performed to compensate for the deterioration of the strength characteristics of Al 2 O 3 which is the main component. When combined, the thermal shock resistance decreases.
【００１１】残部はＡｌ2 Ｏ3 及び不可避的な不純物で
あるが、その配合比はほぼ６５〜９２％の範囲である。
また不可避的な不純物としてはＦｅ2 Ｏ3 、ＳｉＯ2 、
ＣａＯなどがある。本発明の耐火物を得るための焼成温
度は１５００〜１７５０℃である。これが１５００℃未
満では最低限必要な強度特性が得られず、またこれが１
７５０℃を超えるとＡｌ2 Ｏ3 が過焼結して耐熱衝撃性
が低下する。なお、本発明の耐火物は不定形耐火物とし
て用いることもできる。The balance is Al 2 O 3 and unavoidable impurities, but the compounding ratio thereof is in the range of approximately 65 to 92%.
Inevitable impurities include Fe 2 O 3 , SiO 2 ,
For example, CaO. The firing temperature for obtaining the refractory material of the present invention is 1500 to 1750 ° C. If this is less than 1500 ° C, the minimum required strength characteristics cannot be obtained, and this is 1
When it exceeds 750 ° C, Al 2 O 3 is over-sintered and the thermal shock resistance is lowered. The refractory material of the present invention can also be used as an irregular refractory material.
【００１２】[0012]
【作用】この発明はＡｌ2 Ｏ3 とジルコニア系原料を用
いて耐熱衝撃性と耐スラグ性を保持し、さらにＣｒ2 Ｏ
3 とＭｇＯによって耐蝕性の向上を図ったものである。
以下に実施例及び比較例をあげてこの発明をさらに説明
する。[Action] The present invention maintains a thermal shock resistance and slag resistance with Al 2 O 3 and zirconia material, further Cr 2 O
3 and MgO are intended to improve the corrosion resistance.
The present invention will be further described below with reference to Examples and Comparative Examples.
【００１３】[0013]
（実施例１〜７、比較例１〜８）表１に示す化学組成と
なるように、高アルミナ原料として焼結アルミナ、アル
ミナ−ジルコニア原料、酸化クロム、スピネル、クロム
鉱を所定量配合し、パルプ廃液をバインダーとして混練
し、JIS R 2101の並形状に成形した。これを１７００℃
で４時間焼成してレンガを得た。(Examples 1 to 7 and Comparative Examples 1 to 8) Sintered alumina, alumina-zirconia raw material, chromium oxide, spinel, and chrome ore were blended in predetermined amounts as high alumina raw materials so as to have the chemical compositions shown in Table 1, The pulp waste liquid was kneaded as a binder and molded into a JIS R 2101 normal shape. This is 1700 ℃
And baked for 4 hours to obtain a brick.
【００１４】このレンガの見掛気孔率（％）、かさ比
重、圧縮強さ（ＭＰａ）を測定した。その後、このもの
の浸蝕試験と熱衝撃試験を行った。浸蝕試験は、回転炉
にて浸蝕剤としてＣａＯ／ＳｉＯ2 が３．３の合成スラ
グを用いて１７００℃で１０時間実施し、試験後に溶損
量を測定し、溶損指数を算出することで耐蝕性を評価し
た。溶損指数の値が小さい程耐蝕性に優れていることを
示す。結果を表１に示す。 熱衝撃試験は、所定形状に
切り出したテストピースの一端を１２００℃に保持した
電気炉中へ５分間挿入し、次に炉外へ取りだし５分間放
冷する間に発生したＡＥ（Acoustic emission) を、他
端に取付けたＡＥセンサーからカウントした。このカウ
ント数を指数化することで耐熱衝撃性を評価した。この
場合、小さい値程耐熱性が優れていることを示す。The apparent porosity (%), bulk specific gravity and compressive strength (MPa) of this brick were measured. Then, an erosion test and a thermal shock test of this product were performed. The erosion test is performed by using a synthetic slag of CaO / SiO 2 3.3 as an erosion agent in a rotary furnace at 1700 ° C. for 10 hours, measuring the amount of erosion after the test, and calculating the erosion index. The corrosion resistance was evaluated. The smaller the value of the melt index is, the more excellent the corrosion resistance is. The results are shown in Table 1. In the thermal shock test, one end of a test piece cut out into a predetermined shape was inserted into an electric furnace maintained at 1200 ° C for 5 minutes, then taken out of the furnace and allowed to cool for 5 minutes. , Counted from the AE sensor attached to the other end. The thermal shock resistance was evaluated by converting this count number into an index. In this case, the smaller the value, the better the heat resistance.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【表２】 [Table 2]
【００１７】表１から明らかなように、本発明の実施例
品はいずれも耐熱衝撃性を低下させることなく耐蝕性が
向上されていることが分かる。一方、表２に示されてい
る比較例は本願発明で規定する要件を欠くものでいずれ
も耐蝕性が劣っている。即ち、比較例１はＭｇＯが含ま
れておらず、また比較例２はＺｒＯ2 が２％と本願発明
で規定した範囲の下限未満である。As can be seen from Table 1, all the products of the present invention have improved corrosion resistance without lowering thermal shock resistance. On the other hand, the comparative examples shown in Table 2 lack the requirements specified in the present invention, and are inferior in corrosion resistance. That is, Comparative Example 1 does not contain MgO, and Comparative Example 2 has ZrO 2 of 2%, which is less than the lower limit of the range specified in the present invention.
【００１８】比較例３は逆にＺｒＯ2 が２０％と本願発
明で規定した範囲の上限を超えている。比較例４もＭｇ
Ｏが１５％と本願発明で規定した範囲の上限を超えてい
る。比較例５は、Ｃｒ2 Ｏ3 が１％で本願発明で規定し
た範囲の下限未満である。比較例６及び７は、いずれも
Ｃｒ2 Ｏ3 が２５％で本願発明で規定した範囲の上限を
超えている。比較例８のＺｒＯ2 が含まれていない。In Comparative Example 3, conversely, ZrO 2 is 20%, which exceeds the upper limit of the range specified in the present invention. Comparative Example 4 is also Mg
O is 15%, which exceeds the upper limit of the range specified in the present invention. In Comparative Example 5, Cr 2 O 3 is 1%, which is less than the lower limit of the range specified in the present invention. In each of Comparative Examples 6 and 7, Cr 2 O 3 was 25% and exceeded the upper limit of the range specified in the present invention. ZrO 2 of Comparative Example 8 is not included.
【００１９】[0019]
【発明の効果】以上の通り本発明の製鋼用耐火物によれ
ば、従来のアルミナ−ジルコニア原料添加によって得ら
れる耐熱衝撃性を低下させることなく、クロム鉱、酸化
クロムとスピネル、これらの全てを併用することによっ
て、さらに耐蝕性を著しく向上させることが出来るよう
になった。As described above, according to the refractory material for steelmaking of the present invention, chromium ore, chromium oxide and spinel, all of them can be obtained without lowering the thermal shock resistance obtained by adding the conventional alumina-zirconia raw material. By using them together, the corrosion resistance can be further improved.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 寺西 久広 愛知県刈谷市小垣江町南藤１番地 東芝セ ラミックス株式会社刈谷製造所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hisahiro Teranishi 1st Nanto, Ogakie-cho, Kariya city, Aichi Prefecture Toshiba Ceramics Co., Ltd. Kariya factory
Claims (3)
が３〜２０重量％、スピネル及び又はクロム鉱に由来す
るＭｇＯが１〜１０重量％、残部がＡｌ2 Ｏ3 及び不可
避的な不純物であることを特徴とする製鋼用耐火物。1. ZrO 2 is 5 to 15 wt%, Cr 2 O 3
Is 3 to 20% by weight, MgO derived from spinel and / or chrome ore is 1 to 10% by weight, and the balance is Al 2 O 3 and unavoidable impurities.
ムのいずれか一種であることを特徴とする請求項１記載
の製鋼用耐火物。2. The refractory material for steel making according to claim 1, wherein Cr 2 O 3 is one of chrome ore and / or chromium oxide.
であることを特徴とする請求項１記載の製鋼用耐火物。3. The refractory for steel making according to claim 1, wherein ZrO 2 is an alumina-zirconia-based raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6172742A JP2975849B2 (en) | 1994-07-25 | 1994-07-25 | Refractories for steelmaking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6172742A JP2975849B2 (en) | 1994-07-25 | 1994-07-25 | Refractories for steelmaking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0834666A true JPH0834666A (en) | 1996-02-06 |
| JP2975849B2 JP2975849B2 (en) | 1999-11-10 |
Family
ID=15947482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6172742A Expired - Lifetime JP2975849B2 (en) | 1994-07-25 | 1994-07-25 | Refractories for steelmaking |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2975849B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10160366A1 (en) * | 2001-12-08 | 2003-06-26 | Refractory Intellectual Prop | Fired refractory ceramic molded part used for lining waste incineration furnaces has a spinel matrix |
| JP2007001827A (en) * | 2005-06-24 | 2007-01-11 | Asahi Glass Ceramics Co Ltd | Alumina-chromia based monolithic refractory |
| US11746053B2 (en) * | 2018-02-09 | 2023-09-05 | Vesuvius Usa Corporation | Refractory compositions and in situ anti-oxidation barrier layers |
-
1994
- 1994-07-25 JP JP6172742A patent/JP2975849B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10160366A1 (en) * | 2001-12-08 | 2003-06-26 | Refractory Intellectual Prop | Fired refractory ceramic molded part used for lining waste incineration furnaces has a spinel matrix |
| DE10160366C2 (en) * | 2001-12-08 | 2003-10-02 | Refractory Intellectual Prop | Fired fireproof ceramic molded part, its use and offset for the production of the molded part |
| US6982233B2 (en) * | 2001-12-08 | 2006-01-03 | Refractory Intellectual Property Gmbh & Co. | Fire refractory ceramic molded piece, use thereof and composition for production of molded pieces |
| JP2007001827A (en) * | 2005-06-24 | 2007-01-11 | Asahi Glass Ceramics Co Ltd | Alumina-chromia based monolithic refractory |
| US11746053B2 (en) * | 2018-02-09 | 2023-09-05 | Vesuvius Usa Corporation | Refractory compositions and in situ anti-oxidation barrier layers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2975849B2 (en) | 1999-11-10 |
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