JPS59162174A - Continuous casting nozzle - Google Patents
Continuous casting nozzleInfo
- Publication number
- JPS59162174A JPS59162174A JP58037690A JP3769083A JPS59162174A JP S59162174 A JPS59162174 A JP S59162174A JP 58037690 A JP58037690 A JP 58037690A JP 3769083 A JP3769083 A JP 3769083A JP S59162174 A JPS59162174 A JP S59162174A
- Authority
- JP
- Japan
- Prior art keywords
- continuous casting
- cao
- zirconia
- aggregate
- casting nozzle
- 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
- Continuous Casting (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明は鋼の連続鋳造の操業に使用して、特に鍋スラグ
又は鋳型内パウダーと溶鋼との境界に接する部位(以下
P、L部と称する。)でも、きわめて優れた耐食性を有
すると共に耐スポール性にも優れた連続鋳造用ノズルに
係るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention can be used in the operation of continuous steel casting, and is extremely effective especially in areas that are in contact with the boundary between ladle slag or mold powder and molten steel (hereinafter referred to as P and L parts). This invention relates to a continuous casting nozzle that has excellent corrosion resistance and excellent spalling resistance.
鋼の連続鋳造用ノズルは、取鍋′からタンディツシュへ
又バタンディツシュカラモールドへ溶鋼全給送するため
に連結され、同時に溶鋼の酸化防止、鋳込時の溶鋼の乱
れの防止、スラグの巻き込み防止等に機能し、鋳片内の
非金属介在物を減少させ鋳片の品質向上に重要な役割を
果す部材である。The nozzle for continuous casting of steel is connected to completely feed the molten steel from the ladle to the tundish and to the tundish caramold, and at the same time prevents oxidation of the molten steel, prevents turbulence of the molten steel during pouring, and entrains slag. It is a member that plays an important role in improving the quality of slabs by reducing non-metallic inclusions in slabs.
従来、鋼の連続鋳造用ノズルの材料とし−(、〜されて
いる材質は、浴融シリカ質、アルミナ−黒鉛質、ジルコ
ニア−黒鉛質等があるがいずれのものも一長一短がある
。たとえば、溶融シリカ質は高温で結晶化するだめに、
定席的な操業を行なうには耐スポール性が不充分で、中
でも高マンガン鋼によって著しく溶損される欠点があシ
、又、アルミナ−黒鉛質は溶鋼に対する耐食性及び耐ス
ポール性には優れた特性を示すが%’ P、L部におい
ては著しく溶損し易い欠点がある等はその典型的なもの
である。Conventionally, the materials used for continuous steel casting nozzles include bath-fused silica, alumina-graphite, and zirconia-graphite, but each has its advantages and disadvantages. Because siliceous substances crystallize at high temperatures,
Spall resistance is insufficient for regular operation, and high manganese steel has the drawback of being severely eroded, and alumina-graphite has excellent corrosion resistance and spall resistance against molten steel. However, a typical example is that the P and L portions have a drawback that they are extremely susceptible to melting damage.
これらの欠点の解決策として、たとえば特公昭54−8
5579号及び特開昭56−37275号等によりジル
コニア−黒鉛質の浸漬ノズルが開示されている。しかし
、最近では鋼の連続鋳造における操業の安定化を図るた
めの溶鋼の温度、通過敏の増大等の多様化のために、こ
れらの部材に求められる特性もますます苛酷になり、上
記先行技術にみるジルコニア−黒鉛質であっても耐久力
が不充分で改善が求められているのが実態である。As a solution to these shortcomings, for example,
Zirconia-graphite immersion nozzles are disclosed in No. 5579 and Japanese Unexamined Patent Publication No. 56-37275. However, in recent years, due to the diversification of the temperature of molten steel, increase in passing sensitivity, etc. in order to stabilize operations in continuous steel casting, the properties required of these parts have become increasingly severe, and the above-mentioned prior art The reality is that even zirconia-graphite materials have insufficient durability, and improvements are needed.
本発明は斯かる現況に鑑がみ、ジルコニア骨材の性状を
限定することによシ、溶鋼はもとよシ鍋スラグ又は鋳型
内パウダーに対しても耐用性に富み、特に懸案となって
いたP、L部でもきわめて優れた耐食性を有する連続鋳
造用ノズルを提案せんとしてなされたものであって、C
aOが結晶相中に安定に人込み分布されたZr O2固
溶体を主たる材料として得られる連続鋳造用ノズルの提
供を目的としている。In view of the current situation, the present invention has been developed by limiting the properties of zirconia aggregate, thereby making it highly resistant not only to molten steel but also to ladle slag or mold powder, which is a particular concern. This was done with the aim of proposing a continuous casting nozzle that has extremely excellent corrosion resistance even in the P and L parts.
The object of the present invention is to provide a continuous casting nozzle that can be obtained using a ZrO2 solid solution as a main material in which aO is stably distributed in a crowd in a crystalline phase.
以下本発明を、実施の1例に基づき説明する。The present invention will be explained below based on an example of implementation.
耐火物原料としてのジルコニア骨材としては、遊離のC
aOやカルシウムジルコネートを含まないで、 Ca
Oが安定な状態で結晶相中に分布し7’(ZrO2固溶
体のうちから、この安定状態のcao−iの好適なもの
を選択したものであシ、この骨材を用いることによりノ
ズルにはP、L部での溶損に対し優れた耐食性を付与さ
せることができる。As a zirconia aggregate as a raw material for refractories, free C
Without aO or calcium zirconate, Ca
O is distributed in the crystal phase in a stable state, and a suitable one of cao-i in this stable state is selected from 7' (ZrO2 solid solution), and by using this aggregate, the nozzle Excellent corrosion resistance against melting loss at the P and L parts can be imparted.
ところで、鋼の連続鋳造において在来のノズルが使用さ
れる場合にはP、L部において異常に溶損され、その結
果ノズルの寿命が限界とされることが多かった。この溶
損機構については明確に解析されていないが、溶鋼とス
ラグ等との界面で生起する活性の酸素イオンがジルコニ
ア−黒鉛質のカーボン成分を酸化し、その結果、局部的
に鍋スラグや鋳型内パウダーに濡れ易くなシ低融点化合
物を生成し、この酸化と低融点化合物生成の繰り返しに
よj5 P、L部の異常溶損につながるものと考えられ
る。By the way, when a conventional nozzle is used in continuous casting of steel, the P and L portions are abnormally damaged by melting, and as a result, the life of the nozzle is often limited. Although the mechanism of this erosion has not been clearly analyzed, active oxygen ions generated at the interface between molten steel and slag oxidize the carbon component of zirconia-graphite, and as a result, localized ladle slag and mold It is thought that a low melting point compound that is easily wetted by the inner powder is produced, and the repetition of this oxidation and production of the low melting point compound leads to abnormal melting loss of the j5 P and L parts.
このような知見に処して、本発明ではCaO安定化Zr
O2固溶体が、酸素イオン導電性を有すること、及び
この事象を更に有効に発現させるべく高位の酸素イオン
導電性を保有さぜるためにCaO分布蓋を検討すること
にょシ、ノズルの溶鋼とスラグ箋パウダー等との境界面
に接する部位の耐食性を向上させたものである。In view of these findings, the present invention uses CaO-stabilized Zr
The O2 solid solution has oxygen ion conductivity, and in order to make this phenomenon more effective, we will consider a CaO distribution lid to maintain high oxygen ion conductivity. This improves the corrosion resistance of the area that comes into contact with the interface with note powder, etc.
すなわち、CaOが人込み分布したZ r O2固溶体
はCaR+がZr’+の位置に置換した立方螢石構造の
置換型固溶体を生成する。この場合、Zr O2結晶内
のZr’+の格子位置に、Ca2“なる原子価の小さい
陽イオンが一部置換固俗したので正電荷が不足するとと
になシ、結晶全体の電気的中性を保たうとするために陰
イオン(酸素イオン)の位置に不足型荷分の空格子をつ
くり、酸素イオン導電性を有するようになる。That is, a Z r O2 solid solution in which CaO is crowdedly distributed produces a substitutional solid solution having a cubic fluorite structure in which CaR+ is substituted at the position of Zr'+. In this case, the lattice positions of Zr'+ in the ZrO2 crystal are partially replaced by cations with a low valence of Ca2, so if there is a lack of positive charge, the entire crystal becomes electrically neutral. In order to maintain this, a vacancy with a deficient charge is created at the position of anions (oxygen ions), resulting in oxygen ion conductivity.
ジルコニア骨材については、骨材中のCaO量が13m
o1%前後のときに、導電率が最高になると報告(セラ
ミックス、■(8) (1976)僕達、池田、P19
8〜210)されておシ、酸素イオン導電性も当然その
性向であり、このことは、第1図に示すように、ジルコ
ニア−黒鉛質のP、L部での耐食性はCaO量が10〜
20.11101%の範囲で良好であった本発明者の実
験結果とも合致する。Regarding zirconia aggregate, the amount of CaO in the aggregate is 13m
It is reported that the electrical conductivity reaches its maximum when the temperature is around 1% (Ceramics, ■(8) (1976) Bokutachi, Ikeda, P19
8-210) Oxygen ion conductivity is also a natural tendency, and as shown in FIG.
This agrees with the inventor's experimental results, which were good in the range of 20.11101%.
一方、この場合、CaZrO3等のカルシウム・ジルコ
ネート化合物や遊離のCaOを含むクリンカーを使用す
ると、たとえCaO量、が10〜20 mol %であ
っても、クリンカーの酸素イオン導電性も低下し、又、
溶損機構から考えても鍋スラグや鋳型内パウダーに会合
してより低融点化合物をつくり好ましくない。On the other hand, in this case, if a clinker containing a calcium zirconate compound such as CaZrO3 or free CaO is used, even if the amount of CaO is 10 to 20 mol %, the oxygen ion conductivity of the clinker will also decrease.
Considering the erosion mechanism, it is undesirable because it associates with the pot slag and the powder in the mold, creating a lower melting point compound.
本発明は、この酸素゛イオン空格子を利用して、上記溶
鋼の界面で生起する活性な酸素イオンの何割かがZr
O2結晶中の空格子点を移動することになり、ジルコニ
ア−黒鉛質中のカーボンの酸化ヲ少なくし、最終的に耐
火物のP、L部での耐食性を向上させることに立脚して
いる。従って、本発明は遊離のCaOやカルシウム・ジ
ルコネート化合物全介在させることなく、CaOをlθ
〜20 mol %分布含有せしめたZ r 02固溶
体をジルコニア骨材として使用するものであシ、そして
このジルコニア骨材を60〜90鼠重価と黒@10〜4
0重量%及び必要に応じ−(Si 、AI 、B4C、
5in2、SiC等(7)IFJ又’fd2槓以上を0
〜10重量%に通常のバインダーを添加混練し、成形乾
燥後、還元雰囲気で焼成してなる連続鋳造用ノズルであ
る。In the present invention, by utilizing this oxygen ion vacancy, some of the active oxygen ions generated at the interface of the molten steel are
This is based on moving the vacancies in the O2 crystal, reducing the oxidation of carbon in the zirconia-graphite, and ultimately improving the corrosion resistance in the P and L parts of the refractory. Therefore, the present invention can convert CaO to lθ without intervening free CaO or calcium zirconate compounds.
Z r 02 solid solution containing ~20 mol % distribution is used as zirconia aggregate, and this zirconia aggregate has a weight value of 60~90 and black @10~4.
0% by weight and as necessary -(Si, AI, B4C,
5in2, SiC, etc. (7) IFJ or 'fd2 or more 0
This is a continuous casting nozzle made by adding and kneading 10% by weight of a normal binder, molding and drying, and then firing in a reducing atmosphere.
この組成の範囲はジルコニア骨材が60重量%以下であ
ると耐食性が向上する効果がなく、また、90車量チ以
上になれば黒鉛量が少なくなりすぎ、濡れ性や耐スポー
ル性に難点が生じ2、この範囲を脱することは好ましく
ない。In this composition range, if the zirconia aggregate is less than 60% by weight, there is no effect of improving corrosion resistance, and if it is more than 90% by weight, the amount of graphite becomes too small, causing problems in wettability and spall resistance. Occurrence 2: Exceeding this range is not desirable.
次にこのように策定された耐火材料を用いた本発明の多
様な具体例を示す。第1表に示すような配合で鋼の連続
鋳造用浸漬ノズルを製造し、同時に本発明の範囲外とな
る材料による比較ノズルも製造し、共にタンディツシュ
とモールドとの間に取付け100を溶鋼鍋での実湯テス
トをした。その結果は第1表に併せて示すように本発明
の連続鋳造用ノズルは、特に鍋スラグ又は鋳型内パウダ
ーと解剖との境界面に接する部位での溶損速度は比較例
のものの40チ程度に止まシ、耐食性が優れていること
が判る。Next, various specific examples of the present invention using the fireproof material formulated in this way will be shown. An immersion nozzle for continuous casting of steel was manufactured with the composition shown in Table 1, and at the same time a comparative nozzle made of a material outside the scope of the present invention was also manufactured, and both were installed between the tundish and the mold, and the immersion nozzle was installed in a molten steel ladle. I did a real hot water test. The results are shown in Table 1. The continuous casting nozzle of the present invention has a melting rate of about 40 mm, especially in the area where it touches the interface between the pot slag or the powder in the mold and the dissection, compared to the comparative example. It can be seen that it has excellent corrosion resistance.
第1図はジルコニア骨材たるZr○2固溶体中に含まれ
るCa0iB4(と溶損指数との関係を表すグラフであ
る。
第1図
CユO童覚oj!%
手続補正書(自船
発明の名称 連続鋳造用ノズル
補11)をする者
事1′1・との関1系 特許出願入代 理
人
ほか1名
1−1 イ・J 昭和 年 月 口補、
正の対象 明細書、特許請求の範囲の欄、■ 特許請
求の範囲を下記のとおシ補正します。
「CaOを10〜20 mo1%含有し、遊離(D C
aOやカルシウムジルコネート化合物を生成しないZ
rO2固溶体を骨材として50〜9Qwt96と、黒鉛
で焼成してなる連続鋳造用ノズル。」
■ 明#l書、第6頁第9行目から第13行目まで、「
このジルコニア骨材を・・・・・・添加混練し、」とあ
るを、「このジルコニアミt材ヲso〜90wt%と黒
鉛10〜4Qwt%及びSt 、 AI 、 B4C%
5i02 。
SiC等の1種又は2種以上をθ〜10wtチに通常め
バインダーを添加混練し、」と補正します。
■ 明細書、第6頁第15行目、「ジルコニア骨材が6
0]i量チ」とあるを、「ジルコニア骨材が50wtチ
」と補正します。
■ 明細書、第6頁第17行目、「90重量%」とある
を、「9Qwtチ」と補正します。
450Figure 1 is a graph showing the relationship between Ca0iB4 (contained in Zr○2 solid solution, which is zirconia aggregate), and the erosion index. Name: Person responsible for continuous casting nozzle supplement 11) 1'1/Relationship with 1 system Patent application agency
1 person and 1 other person 1-1 Lee J. Showa 1999 Monthly oral assistance,
Positive subject matter Description, claims column, ■ The scope of claims will be amended as follows. "Contains 10 to 20 mo1% of CaO, free (D C
Z that does not generate aO or calcium zirconate compounds
Continuous casting nozzle made by firing rO2 solid solution as aggregate with 50-9Qwt96 and graphite. ” ■ Ming #l, page 6, line 9 to line 13, “
This zirconia aggregate was added and kneaded, and the phrase ``This zirconia aggregate was mixed with ~90wt%, graphite 10~4Qwt%, and St, AI, B4C%.
5i02. One or more types of SiC etc. are added to θ~10wt and a regular binder is added and kneaded. ■ Specification, page 6, line 15, “zirconia aggregate is 6
0] Correct the statement ``i amount q'' to ``zirconia aggregate is 50 wt q.'' ■ In the specification, page 6, line 17, "90% by weight" should be corrected to "9Qwt". 450
Claims (1)
やカルシウムジルコネート化合物を生成しないZr O
2固溶体を骨材として60〜9Q wt %と、黒鉛ヲ
10〜40゛wt%とを通常のバインダーで混練成形後
、還元界囲気で焼成してなる連続鋳造ノズル。Contains 10-20 mol% of CaO, free CaO
ZrO does not produce calcium zirconate compounds or calcium zirconate compounds.
A continuous casting nozzle made by kneading and molding 60 to 9 Q wt % of 2 solid solution as aggregate and 10 to 40 Q wt % of graphite with a normal binder, and then firing in a reducing atmosphere.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58037690A JPS59162174A (en) | 1983-03-07 | 1983-03-07 | Continuous casting nozzle |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58037690A JPS59162174A (en) | 1983-03-07 | 1983-03-07 | Continuous casting nozzle |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59162174A true JPS59162174A (en) | 1984-09-13 |
JPH0238541B2 JPH0238541B2 (en) | 1990-08-30 |
Family
ID=12504557
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58037690A Granted JPS59162174A (en) | 1983-03-07 | 1983-03-07 | Continuous casting nozzle |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59162174A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4846145A (en) * | 1985-10-11 | 1989-07-11 | Katsuyoshi Inouci | Infrared ray radiation sauna device with heat source of combustion heat |
FR2642687A1 (en) * | 1989-02-07 | 1990-08-10 | Akechi Ceramics Kk | CAST NOZZLE OF MOLTEN STEEL |
JPH0347671A (en) * | 1989-07-14 | 1991-02-28 | Harima Ceramic Co Ltd | Refractory for flow rate control device for molten metal |
JPH03221249A (en) * | 1990-01-23 | 1991-09-30 | Akechi Ceramics Kk | Submerged nozzle for continuous casting |
JPH0428462A (en) * | 1990-05-24 | 1992-01-31 | Harima Ceramic Co Ltd | Immersion nozzle for continuous casting and production thereof |
WO1999014005A1 (en) * | 1997-09-17 | 1999-03-25 | Ishikawajima-Harima Heavy Industries Company Limited | Immersion nozzle for casting steel strip |
-
1983
- 1983-03-07 JP JP58037690A patent/JPS59162174A/en active Granted
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4846145A (en) * | 1985-10-11 | 1989-07-11 | Katsuyoshi Inouci | Infrared ray radiation sauna device with heat source of combustion heat |
FR2642687A1 (en) * | 1989-02-07 | 1990-08-10 | Akechi Ceramics Kk | CAST NOZZLE OF MOLTEN STEEL |
JPH0347671A (en) * | 1989-07-14 | 1991-02-28 | Harima Ceramic Co Ltd | Refractory for flow rate control device for molten metal |
JPH03221249A (en) * | 1990-01-23 | 1991-09-30 | Akechi Ceramics Kk | Submerged nozzle for continuous casting |
JPH0478392B2 (en) * | 1990-01-23 | 1992-12-11 | Akechi Ceramics Kk | |
JPH0428462A (en) * | 1990-05-24 | 1992-01-31 | Harima Ceramic Co Ltd | Immersion nozzle for continuous casting and production thereof |
JPH0734978B2 (en) * | 1990-05-24 | 1995-04-19 | ハリマセラミック株式会社 | Immersion nozzle for continuous casting and manufacturing method thereof |
WO1999014005A1 (en) * | 1997-09-17 | 1999-03-25 | Ishikawajima-Harima Heavy Industries Company Limited | Immersion nozzle for casting steel strip |
US5924476A (en) * | 1997-09-17 | 1999-07-20 | Ishikawajima-Harima Heavey Industries Co. Ltd. | Casting steel strip |
Also Published As
Publication number | Publication date |
---|---|
JPH0238541B2 (en) | 1990-08-30 |
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