JP3363330B2 - Refractory for casting, nozzle for continuous casting and method for producing the same - Google Patents
Refractory for casting, nozzle for continuous casting and method for producing the sameInfo
- Publication number
- JP3363330B2 JP3363330B2 JP29793096A JP29793096A JP3363330B2 JP 3363330 B2 JP3363330 B2 JP 3363330B2 JP 29793096 A JP29793096 A JP 29793096A JP 29793096 A JP29793096 A JP 29793096A JP 3363330 B2 JP3363330 B2 JP 3363330B2
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- 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.)
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- 238000005266 casting Methods 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000009749 continuous casting Methods 0.000 title claims description 12
- 239000002994 raw material Substances 0.000 claims description 71
- 239000002245 particle Substances 0.000 claims description 62
- 239000000843 powder Substances 0.000 claims description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- 229910052582 BN Inorganic materials 0.000 claims description 11
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052580 B4C Inorganic materials 0.000 claims description 9
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000011819 refractory material Substances 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 description 35
- 238000005260 corrosion Methods 0.000 description 35
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 28
- 239000000292 calcium oxide Substances 0.000 description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 235000012255 calcium oxide Nutrition 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 239000002893 slag Substances 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 238000004901 spalling Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000035939 shock Effects 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 230000001687 destabilization Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- 230000003628 erosive effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000368 destabilizing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- VXPLXMJHHKHSOA-UHFFFAOYSA-N propham Chemical compound CC(C)OC(=O)NC1=CC=CC=C1 VXPLXMJHHKHSOA-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は鋳造用耐火物、連続
鋳造用ノズル及びその製造方法に関し、特にモールドパ
ウダーやスラグに対する耐溶損性・耐食性、鋼に対する
耐浸潤性を備える鋳造用耐火物、連続鋳造用浸漬ノズル
及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a refractory for casting, a nozzle for continuous casting, and a method for producing the same, and more particularly, a refractory for casting having continuous erosion resistance / corrosion resistance to mold powder and slag, and infiltration resistance to steel, continuous. The present invention relates to a dipping nozzle for casting and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】従来、鋳造用ノズル等においてモールド
・パウダーやスラグに接する部分、例えばパウダーライ
ン部の鋳造用耐火物としては、一般にＺｒＯ2 −Ｃ系の
材質が用いられている。ＺｒＯ2 原料としては、未安定
化原料と安定化原料が適宜用いられる。2. Description of the Related Art Conventionally, a ZrO 2 -C type material is generally used as a refractory for casting in a portion in contact with mold powder or slag in a casting nozzle or the like, for example, a powder line portion. As the ZrO 2 raw material, an unstabilized raw material and a stabilized raw material are appropriately used.
【０００３】また、特開昭６０−４１５３号、特開昭５
２−１３４５号、特開昭６３−５２９８６号公報に記載
された耐火物は、ＺｒＯ2 −Ｃ材質に対して窒化硼素、
マグネシア、カルシア、炭化珪素、金属シリコン等を加
えることによって、溶融金属やスラグパウダーに対する
耐食性と耐スポーリング性を向上している。特に、スラ
グパウダーは浸食性の大きなアルカリ成分やフッ素成分
を含む溶融スラグとなるため、高耐食性が要求される。Further, JP-A-60-4153 and JP-A-5
The refractory materials described in JP-A No. 2-1345 and JP-A No. 63-52986 are boron nitrides for ZrO 2 -C materials,
By adding magnesia, calcia, silicon carbide, metallic silicon, etc., corrosion resistance and spalling resistance to molten metal and slag powder are improved. In particular, the slag powder is a molten slag containing a highly erosive alkali component or fluorine component, and thus high corrosion resistance is required.
【０００４】ところで、ＺｒＯ2 −Ｃ系材質の耐火物に
おいては、耐スポーリング性を向上するために熱膨脹係
数を均一にすることが重要である。このため、近年は、
安定化ＺｒＯ2 原料を単独で用いるか、あるいは安定化
ＺｒＯ2 原料と未安定化ＺｒＯ2 原料を混合して使用す
ることが多い。By the way, in a refractory made of ZrO 2 -C type material, it is important to make the coefficient of thermal expansion uniform in order to improve the spalling resistance. Therefore, in recent years,
Alone or using a stabilizing ZrO 2 raw material, or is often used as a mixture of stabilized ZrO 2 raw material and unstabilized ZrO 2 raw material.
【０００５】従来、ＺｒＯ2 原料を安定化するための安
定化剤としてはＣａＯ、ＭｇＯ、Ｙ2 Ｏ3 等が知られて
いる。コスト的な観点からは、ＣａＯで安定化されたＺ
ｒＯ2 原料が有利である。Conventionally, CaO, MgO, Y 2 O 3 and the like are known as stabilizers for stabilizing the ZrO 2 raw material. From a cost perspective, Z stabilized with CaO
The rO 2 raw material is preferred.
【０００６】他方、特開平４−１８２０号、特開平５−
３６１号、特開平５−３６７号公報に記載の連続鋳造用
浸漬ノズルは、部分安定化ジルコニアの粒度を連続粒度
配合とすることによって耐火物特性を改善している。On the other hand, JP-A-4-1820 and JP-A-5-
The immersion nozzles for continuous casting described in Japanese Patent No. 361 and Japanese Patent Application Laid-Open No. 5-367 improve the refractory properties by blending the particle size of partially stabilized zirconia with a continuous particle size.
【０００７】また、特開昭６２−１４８０７６号公報
は、１００μｍ以下の未安定化ジルコニアを３５〜７０
重量％含むカーボン含有連続鋳造用耐火物を示してい
る。Further, Japanese Unexamined Patent Publication (Kokai) No. 62-148076 discloses that unstabilized zirconia of 100 μm or less is used in the range of 35 to 70.
1 shows a refractory material for continuous casting containing carbon by weight.
【０００８】さらに、特開平５−１７８１２号は、部分
安定化ジルコニアを５０〜９５重量％（未安定化ジルコ
ニアの残部）含み、１０μｍ以下の未安定化ジルコニア
を５〜５０重量％含む浸漬ノズルを開示している。Further, JP-A-5-17812 discloses an immersion nozzle containing 50 to 95% by weight of partially stabilized zirconia (the balance of unstabilized zirconia) and 5 to 50% by weight of unstabilized zirconia of 10 μm or less. Disclosure.
【０００９】[0009]
【発明が解決しようとする課題】しかし、従来の安定化
ＺｒＯ2 原料は、長時間の連続鋳造を行う場合に脱安定
化現象が生じ易い問題がある。However, the conventional stabilized ZrO 2 raw material has a problem that the destabilization phenomenon easily occurs when continuous casting is performed for a long time.
【００１０】すなわち、熱サイクル過程でノズルが高温
になるとＣａＯが分解してＺｒＯ2粒外に流出し、スラ
グ中のＡｌ2 Ｏ3 、ＳｉＯ2 等と反応して低融点物質が
生成されるのである。このように、ＺｒＯ2 −Ｃ材質中
に低融点物質が生成すると、材質自体が溶損し、ノズル
寿命が短くなってしまう。That is, when the temperature of the nozzle becomes high during the heat cycle process, CaO is decomposed and flows out of the ZrO 2 grains and reacts with Al 2 O 3 , SiO 2, etc. in the slag to form a low melting point substance. is there. As described above, when the low melting point substance is generated in the ZrO 2 -C material, the material itself is melted and the nozzle life is shortened.
【００１１】このような脱安定化を防止するために、次
のような方法が考えられる。
全てにＹ2 Ｏ3 単独の安定化剤を用いたＺｒＯ2 原料
を用いる。
全てに未安定化ＺｒＯ2 原料を用いる。
全てにＹ2 Ｏ3 −ＣａＯ安定化原料を用いる。
Ｙ2 Ｏ3 単独の安定化剤を用いたＺｒＯ2 原料と未安
定化ＺｒＯ2 原料を組み合わせる。
ＣａＯ安定化原料と未安定化ＺｒＯ2 原料を組み合わ
せる。In order to prevent such destabilization, the following method can be considered. A ZrO 2 raw material using a stabilizer of Y 2 O 3 alone is used for all. Unstabilized ZrO 2 raw material is used for all. A Y 2 O 3 —CaO stabilizing raw material is used for all. A ZrO 2 raw material using a stabilizer of Y 2 O 3 alone and an unstabilized ZrO 2 raw material are combined. A CaO stabilized raw material and an unstabilized ZrO 2 raw material are combined.
【００１２】しかし、このような〜の方法にも種々
の欠点がある。は、コストが高い割には耐食性向上効
果が少ない。は、１０００〜１２００℃で生じる単斜
晶系←→正方晶系の相転移に伴い体積変化が生じスポ−
リング特性が低下する。また、未安定化ＺｒＯ2 は製造
過程で粒子に入る亀裂が多く、大量に用いても耐食性向
上効果は得られない。は、耐食性の向上を得られる
が、未安定化ＺｒＯ2 原料との組み合せによる効果のほ
うがより大きい。は、コストが高い割には耐食性向上
効果が少ない。は、ある程度の効果は得られるが実用
的に十分な耐食性は得られない。However, the methods (1) to (3) have various drawbacks. Has a small effect of improving the corrosion resistance despite the high cost. Is a volume change due to the monoclinic ← → tetragonal phase transition occurring at 1000 to 1200 ° C.
Ring characteristics deteriorate. In addition, unstabilized ZrO 2 has many cracks that enter the particles during the manufacturing process, and the effect of improving corrosion resistance cannot be obtained even if used in large quantities. Improves the corrosion resistance, but the effect of the combination with the unstabilized ZrO 2 raw material is larger. Has a small effect of improving the corrosion resistance despite the high cost. Has a certain degree of effect, but practically sufficient corrosion resistance cannot be obtained.
【００１３】ところで、近年、鋳造工程における鋳込み
速度が速くなるに伴い、従来よりも粘性が低いモールド
パウダーが使用されるようになってきた。By the way, in recent years, as the casting speed in the casting process has increased, mold powder having a lower viscosity than before has been used.
【００１４】それゆえ、より耐食性に優れたパウダーラ
イン部用の耐火物の必要性は益々高まっている。Therefore, there is an ever-increasing need for refractory materials for powder line parts which are more excellent in corrosion resistance.
【００１５】本発明は、このような従来技術に鑑み、耐
スポーリング性、耐食性、耐酸化性に優れ、また、安定
化剤のＣａＯの流れ出しを抑制して脱安定化現象を極力
防止することが可能な、長寿命の鋳造用耐火物、連続鋳
造用ノズル及びその製造方法を提供することを目的とし
ている。In view of such prior art, the present invention is excellent in spalling resistance, corrosion resistance, and oxidation resistance, and suppresses outflow of CaO as a stabilizer to prevent destabilization phenomenon as much as possible. It is an object of the present invention to provide a refractory for casting, which has a long life, a nozzle for continuous casting, and a manufacturing method thereof.
【００１６】[0016]
【課題を解決するための手段】本願第１発明は、安定化
または部分安定化されたＺｒＯ2 原料３０〜７０重量
％、平均粒径７５μｍ以下の未安定化ＺｒＯ2 原料５〜
３０重量％、黒鉛１０〜４０重量％に対して外率で炭化
硼素、炭化珪素、窒化硼素、金属シリコン、アルミナ、
金属アルミニウムの少なくとも一種を１〜３０重量％
（ただし、金属シリコンと金属アルミニウムは合計で１
０重量％以下）添加した原料から製造し、かつ、ＺｒＯ
2 の安定化剤がＣａＯ１．０〜４．０重量％及びＹ 2 Ｏ
3 ０．５〜３．０重量％であることを特徴とする鋳造用
耐火物を要旨としている。本願第２発明は、部分安定化
ＺｒＯ 2 原料３０〜７０重量％と、平均粒径７５μｍ以
下、最大粒径８０μｍ以下の未安定化ＺｒＯ 2 ５〜３０
重量％と、黒鉛１０〜４０重量％と外率で、１〜３０重
量％の炭化珪素および／または金属シリコン（ただし、
金属シリコンは最大１０重量％以下）からなり、前記未
安定化ＺｒＯ 2 の平均粒径３μｍ以下の粒子が前記全構
成原料の１〜２０重量％を占め、かつ、ＺｒＯ 2 の安定
化剤がＣａＯ１．０〜４．０重量％及びＹ 2 Ｏ 3 ０．５
〜３．０重量％であることを特徴とする鋳造用耐火物。 According to the first invention of the present application, a stabilized or partially stabilized ZrO 2 raw material 30 to 70% by weight and an unstabilized ZrO 2 raw material 5 having an average particle size of 75 μm or less are used.
Boron carbide, silicon carbide, boron nitride, metallic silicon, alumina, with an external ratio of 30% by weight and 10 to 40% by weight of graphite,
1 to 30% by weight of at least one kind of metallic aluminum
(However, the total of metallic silicon and metallic aluminum is 1
0 wt% or less) manufactured from added raw material and ZrO
2 of stabilizing agent CaO1.0~4.0 wt% and Y 2 O
3 The gist is a refractory for casting, which is characterized by being 0.5 to 3.0% by weight . The second invention of the present application is partially stabilized.
30 to 70% by weight of ZrO 2 raw material and an average particle size of 75 μm or less
Lower unstabilized ZrO 2 5-30 with a maximum particle size of 80 μm or less
1% to 30% by weight, and 10% to 40% by weight of graphite and external ratio
% Silicon carbide and / or metallic silicon (however,
The maximum amount of metallic silicon is 10% by weight or less)
Stabilized ZrO 2 particles having an average particle size of 3 μm or less have the above-mentioned composition.
Occupies 1 to 20% by weight of raw materials and stabilizes ZrO 2 .
The agent is CaO 1.0 to 4.0% by weight and Y 2 O 3 0.5.
A refractory for casting, characterized in that the refractory for casting is 3.0% by weight.
【００１７】本願第３発明は、安定化または部分安定化
されたＺｒＯ2 原料３０〜７０重量％、平均粒径７５μ
ｍ以下の未安定化ＺｒＯ2 原料５〜３０重量％、黒鉛１
０〜４０重量％に対して外率で炭化硼素、炭化珪素、窒
化硼素、金属シリコン、アルミナ、金属アルミニウムの
少なくとも一種を１〜３０重量％（ただし、金属シリコ
ンと金属アルミニウムは合計で１０重量％以下）添加し
た原料を混合して所定形状に成形し、還元雰囲気中にお
いて８００〜１２００℃の温度で焼成し、かつ、ＺｒＯ
2 の安定化剤がＣａＯ１．０〜４．０重量％及びＹ 2 Ｏ
3 ０．５〜３．０重量％であることを特徴とする鋳造用
耐火物の製造方法を要旨としている。本願第４発明は、
部分安定化ＺｒＯ 2 原料３０〜７０重量％と、平均粒径
７５μｍ以下、最大粒径８０μｍ以下の未安定化ＺｒＯ
2 ５〜３０重量％と、黒鉛１０〜４０重量％と外率で、
１〜３０重量％の炭化珪素および／または金属シリコン
（ただし、金属シリコンは最大１０重量％以下）からな
り、前記未安定化ＺｒＯ 2 の平均粒径３μｍ以下の粒子
が前記全構成原料の１〜２０重量％を占める原料を混合
して、所定形状に成形し、還元雰囲気中において８００
〜１２００℃の温度で焼成し、かつ、ＺｒＯ 2 の安定化
剤がＣａＯ１．０〜４．０重量％及びＹ 2 Ｏ 3 ０．５〜
３．０重量％であることを特徴とする鋳造用耐火物の製
造方法を要旨としている。 The third invention of the present application is that the stabilized or partially stabilized ZrO 2 raw material is 30 to 70% by weight, and the average particle diameter is 75 μ.
Unstabilized ZrO 2 raw material of m or less 5 to 30% by weight, graphite 1
An external ratio of at least one of boron carbide, silicon carbide, boron nitride, metallic silicon, alumina, and metallic aluminum to 0 to 40% by weight (however, metallic silicon and metallic aluminum are 10% by weight in total). Below) the added raw materials are mixed and shaped into a predetermined shape, fired at a temperature of 800 to 1200 ° C. in a reducing atmosphere , and ZrO 2
2 of stabilizing agent CaO1.0~4.0 wt% and Y 2 O
3 The gist is a method for manufacturing a refractory for casting , which is characterized by being 0.5 to 3.0% by weight . The fourth invention of the present application is
Partially stabilized ZrO 2 raw material 30 to 70 wt% and average particle size
Unstabilized ZrO with 75 μm or less and maximum particle size of 80 μm or less
And 2 5 to 30 wt%, graphite 10 to 40% by weight and an outer rate,
1 to 30% by weight of silicon carbide and / or metallic silicon
(However, the maximum amount of metallic silicon is 10% by weight or less)
The particles of the unstabilized ZrO 2 having an average particle size of 3 μm or less
Mixes the raw materials which occupy 1 to 20% by weight of all the constituent raw materials
Then, it is molded into a predetermined shape and 800
Calcination at temperatures up to 1200 ° C and stabilization of ZrO 2
Agent CaO1.0~4.0 wt% and Y 2 O 3 0.5 to
Made of refractory for casting, characterized by being 3.0% by weight
The method of construction is the gist.
【００１８】[0018]
【発明の実施の形態】本発明の鋳造用耐火物は、安定化
または部分安定化されたＺｒＯ2 原料３０〜７０重量
％、平均粒径７５μｍ以下の未安定化ＺｒＯ2 原料５〜
３０重量％、黒鉛１０〜４０重量％に対して外率で炭化
硼素、炭化珪素、窒化硼素、金属シリコン、アルミナ、
金属アルミニウムの少なくとも一種を１〜３０重量％
（ただし、金属シリコンと金属アルミニウムは合計で１
０重量％以下）添加した原料から製造される。BEST MODE FOR CARRYING OUT THE INVENTION The refractory for casting of the present invention comprises a stabilized or partially stabilized ZrO 2 raw material of 30 to 70% by weight, and an unstabilized ZrO 2 raw material having an average particle diameter of 75 μm or less.
Boron carbide, silicon carbide, boron nitride, metallic silicon, alumina, with an external ratio of 30% by weight and 10 to 40% by weight of graphite,
1 to 30% by weight of at least one kind of metallic aluminum
(However, the total of metallic silicon and metallic aluminum is 1
Manufactured from added raw materials (0% by weight or less).
【００１９】安定化または部分安定化されたＺｒＯ2 原
料が３０重量％未満の場合には、モールドパウダーやス
ラグ等に対する十分な耐食性が得られない。また、Ｚｒ
Ｏ2原料が７０重量％を超える場合には、耐スポーリン
グ性が劣化すると共に、鋼とのぬれ性が良くなり鋼の浸
潤を促す結果となる。When the amount of the stabilized or partially stabilized ZrO 2 raw material is less than 30% by weight, sufficient corrosion resistance to mold powder, slag and the like cannot be obtained. Also, Zr
When the O 2 raw material exceeds 70% by weight, the spalling resistance is deteriorated, the wettability with the steel is improved, and the infiltration of the steel is promoted.
【００２０】このような観点から、安定化または部分安
定化されたＺｒＯ2 原料のより好ましい配合量は、６０
〜９０重量％である。From this point of view, the more preferable amount of the stabilized or partially stabilized ZrO 2 raw material is 60.
Is about 90% by weight.
【００２１】未安定化ＺｒＯ2 原料の含有量が５重量％
未満の場合には、ＣａＯ低減の効果及び耐食性の向上効
果が得られない。また、未安定化ＺｒＯ2 原料の含有量
が３０重量％を超える場合にも、十分な耐食性が得られ
ないばかりか、１０００〜１２００℃で生じる相転移の
影響で耐スポーリング性も低下する。Content of unstabilized ZrO 2 raw material is 5% by weight
If it is less than the above, the effect of reducing CaO and the effect of improving corrosion resistance cannot be obtained. Further, even when the content of the unstabilized ZrO 2 raw material exceeds 30% by weight, not only sufficient corrosion resistance is not obtained, but also the spalling resistance is lowered due to the effect of the phase transition occurring at 1000 to 1200 ° C.
【００２２】このような観点から、未安定化ＺｒＯ2 原
料のより好ましい配合量は、５〜３０重量％である。From such a viewpoint, a more preferable blending amount of the unstabilized ZrO 2 raw material is 5 to 30% by weight.
【００２３】未安定化ＺｒＯ2 原料の平均粒径が７５μ
ｍを超える場合には、粒子に亀裂が入りやすくなり、耐
食性が低下する。未安定化ＺｒＯ2 原料の平均粒径は、
より好ましくは５５μｍ以下である。The average particle size of the unstabilized ZrO 2 raw material is 75 μm.
When it exceeds m, the particles are likely to be cracked and the corrosion resistance is lowered. The average particle size of the unstabilized ZrO 2 raw material is
It is more preferably 55 μm or less.
【００２４】ＺｒＯ2 原料は、ＺｒＯ2 を９０重量％以
上含むＺｒＯ2 質電融体骨材であることが望ましい。The ZrO 2 raw material is preferably a ZrO 2 Shitsuden melt aggregate containing ZrO 2 90% by weight or more.
【００２５】黒鉛は溶鋼およびスラグとの難濡れ性と熱
伝導率が高く、また熱膨張係数が小さい特徴を有してい
る。ＺｒＯ2 原料に配合する黒鉛が１０重量％未満の場
合には、ＺｒＯ2 原料が７０重量％を超えた場合と同様
の理由で、耐スポーリング性の低下及び鋼の浸潤が問題
となり易い。Graphite has the characteristics that it is difficult to wet molten steel and slag, has high thermal conductivity, and has a small coefficient of thermal expansion. When the amount of graphite blended in the ZrO 2 raw material is less than 10% by weight, the reduction in spalling resistance and the infiltration of steel are likely to be problems for the same reason as when the ZrO 2 raw material exceeds 70% by weight.
【００２６】このような観点から、黒鉛のより好ましい
配合量は、１０〜４０重量％である。From this point of view, the more preferable blending amount of graphite is 10 to 40% by weight.
【００２７】金属シリコンは、炭素成分の酸化防止や、
熱間での強度保持に役立つ。Metallic silicon is used to prevent oxidation of carbon components and
Helps maintain strength during heat.
【００２８】炭化珪素は、耐スポーリング性の向上及び
酸化防止に役立つ。Silicon carbide serves to improve spalling resistance and prevent oxidation.
【００２９】金属シリコンおよび／または金属アルミニ
ウムの合計を１０重量％以下としたのは、例えば閉塞
（ノズルの場合）や、動弾性率の上昇になる耐スポーリ
ング性の低下等の不具合を招かないためである。The reason that the total amount of metallic silicon and / or metallic aluminum is set to 10% by weight or less does not cause problems such as blockage (in the case of a nozzle) and deterioration of spalling resistance that increases dynamic elastic modulus. This is because.
【００３０】本発明の好ましい実施態様では、部分安定
化ＺｒＯ2 原料３０〜７０重量％と、平均粒径７５μｍ
以下、最大粒径８０μｍ以下の未安定化ＺｒＯ2 ５〜３
０重量％と、黒鉛１０〜４０重量％と外率で、１〜３０
重量％の炭化珪素および／または金属シリコン（ただ
し、金属シリコンは最大１０重量％以下）からなり、前
記未安定化ＺｒＯ2 の平均粒径３μｍ以下の粒子が前記
の全構成原料の１〜２０重量％を占めることを特徴とし
ている。In a preferred embodiment of the present invention, the partially stabilized ZrO 2 raw material is 30 to 70% by weight and the average particle size is 75 μm.
Hereinafter, unstabilized ZrO 2 5 to 3 having a maximum particle size of 80 μm or less
0% by weight, 10 to 40% by weight of graphite, and an external ratio of 1 to 30
% Of silicon carbide and / or metal silicon (however, the maximum amount of metal silicon is 10% by weight or less), and the unstabilized ZrO 2 particles having an average particle size of 3 μm or less are 1 to 20% by weight of all the constituent raw materials. It is characterized by occupying%.
【００３１】未安定化ＺｒＯ2 の最大粒径が８０μｍを
超えたり、平均粒径３μｍ以下の粒子が前記の全構成原
料の１重量％未満または２０重量％を超える場合には、
耐熱衝撃性と耐食性が低下する恐れがある。If the maximum particle size of the unstabilized ZrO 2 exceeds 80 μm, or if the particles having an average particle size of 3 μm or less are less than 1% by weight or more than 20% by weight of all the constituent raw materials,
Thermal shock resistance and corrosion resistance may decrease.
【００３２】このように未安定化ＺｒＯ2 の粒度配合を
微粉側にシフトさせた理由を、以下に述べる。The reason why the particle size composition of the unstabilized ZrO 2 is shifted to the fine powder side is described below.
【００３３】一般に、ＺｒＯ2 −Ｃ系材質の耐火物にお
いては、ジルコニア粒子の粒子間にカーボン等が存在し
ている。耐火物が溶融スラグと接触すると、ジルコニア
のうち粒度配合の粗い粒子がそのまま溶融スラグ中へ流
れ出すことにより、材料の溶損が進行していく。Generally, in a refractory made of a ZrO 2 —C-based material, carbon or the like exists between the zirconia particles. When the refractory comes into contact with the molten slag, coarse particles of zirconia with a mixed particle size flow out into the molten slag as they are, and the melting loss of the material proceeds.
【００３４】このような不具合を解消するため、粒度配
合を、連続的な粒度配合のまま微粉側へシフトさせるこ
とが考えられる。しかしながら、全てのジルコニアを微
粉にした場合にはジルコニアとしての含有量が同じでも
粒子の比表面積が増大し、前述の脱安定化現象が生じ易
くなり、反って耐食性が低下してしまう。In order to solve such a problem, it is possible to shift the particle size blending to the fine powder side while maintaining the continuous grain size blending. However, when all of the zirconia is pulverized, even if the content of zirconia is the same, the specific surface area of the particles increases, the above-mentioned destabilization phenomenon easily occurs, and the corrosion resistance decreases on the contrary.
【００３５】そこで、本発明の好適な実施態様では、未
安定化ＺｒＯ2 原料５〜３０重量％の平均粒径を７５μ
ｍ以下、最大粒径を８０μｍ以下とし、さらに平均粒径
３μｍ以下の粒子が前記の全構成原料の１〜２０重量％
を占めるように粒度配合を設定する。Therefore, in a preferred embodiment of the present invention, the average particle size of the unstabilized ZrO 2 raw material of 5 to 30% by weight is 75 μm.
m or less, the maximum particle size is 80 μm or less, and particles having an average particle size of 3 μm or less are 1 to 20% by weight of all the constituent raw materials.
Set the particle size formulation so that
【００３６】前述のような粒度配合を採用することによ
り、原料の充填性を向上して耐火物を緻密化できる利点
も得られる。By adopting the particle size composition as described above, there is an advantage that the filling property of the raw material can be improved and the refractory can be densified.
【００３７】このような観点から、未安定化ＺｒＯ2 原
料のより好ましい最大粒径は８０μｍである。また、平
均粒径３μｍ以下の粒子の全構成原料に対する配合量
は、より好ましくは１〜２０重量％とする。From such a viewpoint, the more preferable maximum particle size of the unstabilized ZrO 2 raw material is 80 μm. Further, the blending amount of particles having an average particle diameter of 3 μm or less with respect to all the constituent raw materials is more preferably 1 to 20% by weight.
【００３８】本発明の好ましい実施態様では、ＺｒＯ2
の安定化剤としてＣａＯ１．０〜４．０重量％とＹ2 Ｏ
3 ０．５〜３．０重量％を用いる構成になっている。In a preferred embodiment of the invention ZrO 2
As a stabilizer of 1.0 to 4.0% by weight of CaO and Y 2 O
3 0.5 to 3.0% by weight is used.
【００３９】従来技術でも述べたように、ＣａＯを安定
化剤として用いたＺｒＯ2 −Ｃ材質の耐火物では、熱サ
イクル時に脱安定化現象が生じ易い。一方、Ｙ2 Ｏ3 の
場合には、高温での脱安定化現象は防止できるが、十分
な効果を得るには５重量％以上の添加が必要でありコス
ト高となる。また、ＺｒＯ2 の正味の含有量も少なくな
ってしまう。As described in the prior art, the destabilization phenomenon is likely to occur in the refractory made of ZrO 2 -C material using CaO as a stabilizer during the thermal cycle. On the other hand, in the case of Y 2 O 3 , the destabilization phenomenon at high temperature can be prevented, but in order to obtain a sufficient effect, it is necessary to add 5% by weight or more, resulting in high cost. In addition, the net content of ZrO 2 also decreases.
【００４０】そこで、本発明の実施態様では、ＣａＯと
Ｙ2 Ｏ3 を適量づつ混合して用いることによって、Ｙ2
Ｏ3 を単独で用いた場合と同様の脱安定化抑制効果が得
られ、かつ高耐食性を実現できる構成になっている。[0040] Therefore, in embodiments of the present invention, by using a CaO and Y 2 O 3 were mixed proper amount at a time, Y 2
The destabilizing effect is the same as when O 3 is used alone, and high corrosion resistance is realized.
【００４１】このように、高温下で低融点物質を作りう
るＣａＯの含有量を極力抑える目的で粗粒にＹ2 Ｏ3 −
ＣａＯ安定化原料を用い、微粉に全くＣａＯを含まない
未安定原料を使用することで材質全体のＣａＯ量を極力
抑えるのである。Thus, for the purpose of suppressing the content of CaO capable of forming a low melting point substance at high temperature as much as possible, Y 2 O 3
By using a CaO-stabilized raw material and an unstable raw material that does not contain CaO at all in the fine powder, the amount of CaO in the entire material is suppressed as much as possible.
【００４２】ＺｒＯ2 原料の安定化剤として用いるＣａ
ＯとＹ2 Ｏ3 の量は、［（Ｉc ＋Ｉt ）／（Ｉc ＋Ｉt
＋Ｉm ）］×１００で表される安定化度が５０〜９８％
となるような範囲である。なお、Ｉは粉末Ｘ線ピーク強
度、ｃはcubic 、ｔはtetragonal、ｍはmonoclinicを意
味している。Ca used as a stabilizer for ZrO 2 raw material
The amounts of O and Y 2 O 3 are [(Ic + It) / (Ic + It)
+ Im)] × 100, the degree of stabilization is 50 to 98%.
The range is such that In addition, I means powder X-ray peak intensity, c means cubic, t means tetragonal, and m means monoclinic.
【００４３】ところで、本発明において、外率で１〜３
０重量％添加される炭化硼素、炭化珪素、窒化硼素、金
属シリコン、アルミナ、金属アルミニウムの少なくとも
一種は、耐酸化特性を強める作用を有する。特に、アル
ミナを添加する場合には、ＺｒＯ2 −Ｃ材質中に在っ
て、特に粘性の小さいパウダーと反応してパウダーの粘
性を増加させ、材質中へのパウダーの侵入を防止する効
果も期待できる。By the way, in the present invention, the external ratio is 1 to 3.
At least one of boron carbide, silicon carbide, boron nitride, metallic silicon, alumina, and metallic aluminum added in an amount of 0% by weight has an action of enhancing the oxidation resistance property. In particular, when alumina is added, it is also expected to have the effect of increasing the viscosity of the powder by reacting with the powder having a particularly low viscosity existing in the ZrO 2 -C material and preventing the powder from entering the material. it can.
【００４４】しかし、一般に、アルミナを含む前記物質
を添加すると、耐酸化効果を奏する過程でＢ2 Ｏ3 、Ｓ
ｉＯ、ＳｉＯ2 、Ａｌ2 Ｏ3 等の酸化物が生成し、Ｚｒ
Ｏ2中より生じたＣａＯと反応して低融点物質を作り、
耐食性を劣化させる不具合が生じる場合がある。つま
り、前記物質の添加によって得られる効果の他に、弊害
が生じることもある。However, in general, when the above-mentioned substance containing alumina is added, B 2 O 3 and S are added in the process of exhibiting an oxidation resistance effect.
Oxides such as iO, SiO 2 , and Al 2 O 3 are generated, and Zr
It reacts with CaO generated from O 2 to make a low melting point substance,
Problems that deteriorate corrosion resistance may occur. That is, in addition to the effect obtained by adding the substance, an adverse effect may occur.
【００４５】このため、本発明の好ましい実施態様で
は、安定化剤として適量のＹ2 Ｏ3 とＣａＯを用い、前
記不具合の発生を確実に防止する構成になっている。す
なわち、Ｙ2 Ｏ3 はＢ2 Ｏ3 、ＳｉＯ2 、Ａｌ2 Ｏ3 等
と結合し、それぞれの融点を上げる特性を持ち、耐酸化
性を与えるために添加した炭化硼素、炭化珪素、窒化硼
素、金属シリコン、アルミナ、金属アルミニウム等から
発生するＢ2 Ｏ3 、ＳｉＯ2 、Ａｌ2 Ｏ3 とＺｒＯ2 中
のＣａＯによって生成される低融点化合物の発生を抑制
するのである。このため、耐食性を劣化させずに、確実
に耐酸化性を高めることができる。Therefore, in a preferred embodiment of the present invention, suitable amounts of Y 2 O 3 and CaO are used as stabilizers, and the above-mentioned problems are surely prevented. That is, Y 2 O 3 has the property of combining with B 2 O 3 , SiO 2 , Al 2 O 3, etc. to raise the melting point of each, and boron carbide, silicon carbide, boron nitride added to impart oxidation resistance. , B 2 O 3 , SiO 2 , Al 2 O 3 generated from metallic silicon, alumina, metallic aluminum, etc. and the low melting point compound generated by CaO in ZrO 2 are suppressed. Therefore, the oxidation resistance can be surely increased without deteriorating the corrosion resistance.
【００４６】本発明の鋳造用耐火物の製造方法は、安定
化または部分安定化されたＺｒＯ2原料３０〜７０重量
％、平均粒径７５μｍ以下の未安定化ＺｒＯ2 原料５〜
３０重量％、黒鉛１０〜４０重量％に対して外率で炭化
硼素、炭化珪素、窒化硼素、金属シリコン、アルミナ、
金属アルミニウムの少なくとも一種を１〜３０重量％
（ただし、金属シリコンと金属アルミニウムは合計で１
０重量％以下）添加した原料を混合して所定形状に成形
し、還元雰囲気中において８００〜１２００℃の温度で
焼成することを特徴としている。The method for producing a refractory for casting according to the present invention comprises 30 to 70% by weight of a stabilized or partially stabilized ZrO 2 raw material and an unstabilized ZrO 2 raw material 5 having an average particle diameter of 75 μm or less.
Boron carbide, silicon carbide, boron nitride, metallic silicon, alumina, with an external ratio of 30% by weight and 10 to 40% by weight of graphite,
1 to 30% by weight of at least one kind of metallic aluminum
(However, the total of metallic silicon and metallic aluminum is 1
It is characterized in that the added raw materials are mixed, shaped into a predetermined shape, and fired at a temperature of 800 to 1200 ° C. in a reducing atmosphere.
【００４７】前記焼成温度が８００℃未満の場合には使
用するレジンバインダーの炭化が十分でなくなり、ま
た、焼成温度が１２００℃を超える場合には使用原料が
熱変化を起こす恐れがある。If the firing temperature is lower than 800 ° C., the carbonization of the resin binder to be used is insufficient, and if the firing temperature exceeds 1200 ° C., the raw materials used may undergo thermal change.
【００４８】この発明の耐火物はモールドパウダーやス
ラグに接する部分に用いると、特に効果がある。The refractory material of the present invention is particularly effective when it is used in a portion in contact with mold powder or slag.
【００４９】本発明の耐火物は、特にパウダーライン部
など特にモールドパウダーやスラグに対する耐溶損性、
耐食性が必要とされるところに部分的に用いることが好
ましい。The refractory material of the present invention has a erosion resistance to the mold powder and slag, especially the powder line part,
It is preferably used partially where corrosion resistance is required.
【００５０】[0050]
【実施例】以下、表１を参照して本発明の実施例１〜５
及び比較例１〜１０を説明する。EXAMPLES Examples 1 to 5 of the present invention will be described below with reference to Table 1.
Also, Comparative Examples 1 to 10 will be described.
【００５１】実施例１〜５及び比較例１〜１０の鋳造用
ノズルのサンプルは、パウダーライン部に使用するもの
であり、表１に示す比率で耐火物原料を配合し、レジン
バインダーを添加し、静水圧プレスで成形したのち、還
元雰囲気中、１０００℃で焼成することによって得たも
のである。サンプルの寸法は、直径が２５ｍｍ、全長が
１５０ｍｍであった。The samples of the casting nozzles of Examples 1 to 5 and Comparative Examples 1 to 10 were used for the powder line portion, and the refractory raw materials were blended in the ratio shown in Table 1, and the resin binder was added. After being molded by isostatic pressing, it was obtained by firing at 1000 ° C. in a reducing atmosphere. The dimensions of the sample were 25 mm in diameter and 150 mm in total length.
【００５２】そして、実施例１〜５及び比較例１〜１０
の鋳造用ノズルのサンプルに対して、誘導炉浸食テスト
を行って、パウダーライン部の耐食性を比較した。Then, Examples 1 to 5 and Comparative Examples 1 to 10
An induction furnace erosion test was performed on the sample of the casting nozzle of No. 1 to compare the corrosion resistance of the powder line portion.
【００５３】誘導炉浸食テストは、ＳＳ４００、１００
Ｋｇを溶解し、１５５０℃に保持した溶鋼中に、塩基度
（ＣａＯ／ＳｉＯ2 ）＝１．１、粘性１．５ポイズ（１
３００℃において）のパウダー１Ｋｇを投入し、サンプ
ルを３０分間浸漬し、ベース材質を１００とした時の溶
損量を求めたものである。つまり、表１に示す耐食性指
数は、比較例１を１００としたものであり、指数が大き
い程耐食性に優れていることになる。The induction furnace erosion test is SS400, 100
Kg was melted, and in molten steel held at 1550 ° C., basicity (CaO / SiO 2 ) = 1.1, viscosity 1.5 poise (1
1 Kg of powder (at 300 ° C.) was added, the sample was immersed for 30 minutes, and the amount of erosion loss was calculated when the base material was set to 100. That is, the corrosion resistance index shown in Table 1 is based on Comparative Example 1 as 100, and the larger the index, the better the corrosion resistance.
【００５４】表１から分かるように、実施例１〜５のサ
ンプルは、比較例３に比べてパウダーライン部の耐食性
指数が約３０％程度優れていた。As can be seen from Table 1, the samples of Examples 1 to 5 were superior to Comparative Example 3 in the corrosion resistance index of the powder line portion by about 30%.
【００５５】また、実施例３〜５のサンプルは、パウダ
ーライン部の耐火物がそれぞれ、炭化硼素３重量％、炭
化珪素３重量％、窒化硼素３重量％を含むため、耐酸化
特性にも優れていた。ここで注意すべきは、これらの酸
化防止剤を加えたにも拘らず、十分な耐食性を得ること
ができた点である。Further, in the samples of Examples 3 to 5, the refractory material in the powder line portion contained 3% by weight of boron carbide, 3% by weight of silicon carbide and 3% by weight of boron nitride, respectively, so that the samples had excellent oxidation resistance. Was there. What should be noted here is that sufficient corrosion resistance could be obtained despite the addition of these antioxidants.
【００５６】因みに、比較例８等は、窒化硼素を３重量
％含むので耐酸化特性に優れているが、その反面、耐食
性が劣っていた。その理由は、前述したとおりである。Incidentally, Comparative Example 8 and the like contained 3% by weight of boron nitride and thus were excellent in oxidation resistance, but were inferior in corrosion resistance. The reason is as described above.
【００５７】次に、表２を参照して本発明の実施例１１
〜１７及び比較例１１〜１３を説明する。Next, referring to Table 2, Example 11 of the present invention
17 and Comparative Examples 11 to 13 will be described.
【００５８】表２の＊１は、熱衝撃抵抗係数＝曲げ強さ
／（熱膨張率×動弾性率）によって算出され、この数値
が大きいほど耐熱衝撃性に優れている。同じく＊２の耐
食性指数については、高周波誘導炉を用いて溶解した鋼
中に浸漬させることにより評価したもので、比較例１１
を１００とした時の溶損比により算出した。この数値が
大きい程、耐食性に優れている。* 1 in Table 2 is calculated by thermal shock resistance coefficient = bending strength / (thermal expansion coefficient × dynamic elastic modulus), and the larger this value, the better the thermal shock resistance. Similarly, the corrosion resistance index of * 2 was evaluated by immersing in a molten steel using a high frequency induction furnace, and Comparative Example 11
It was calculated from the melt loss ratio when the value was set to 100. The larger this value, the better the corrosion resistance.
【００５９】表２に示す粒度の原料を配合し、混練後、
成形圧１．５トン／ｃｍ2 の静水圧プレスにて成形し、
還元雰囲気下１０００℃で焼成を行い、ノズルのパウダ
ーライン部用の試料耐火物を得た。The raw materials having the particle sizes shown in Table 2 were blended, and after kneading,
Molded with a hydrostatic press with a molding pressure of 1.5 tons / cm 2 ,
Firing was performed at 1000 ° C. in a reducing atmosphere to obtain a sample refractory for the powder line part of the nozzle.
【００６０】原料の配合は、比較例１１を基本材質と
し、実施例１１、実施例１２、比較例１２では、部分安
定化ジルコニアを順次、各粒度において未安定化ジルコ
ニアで置換した。The raw materials were compounded using Comparative Example 11 as a basic material, and in Examples 11, 12 and 12, the partially stabilized zirconia was sequentially replaced with unstabilized zirconia at each particle size.
【００６１】表２に示す物理特性を測定した結果、比較
例１２では耐食性が低下した。これより、未安定化ジル
コニアは、平均粒径５５μｍ以下（ｍａｘ８０μｍ以
下）の粒子による置換が適正であることが確認された。As a result of measuring the physical properties shown in Table 2, in Comparative Example 12, the corrosion resistance was lowered. From this, it was confirmed that the unstabilized zirconia was appropriately replaced with particles having an average particle size of 55 μm or less (max 80 μm or less).
【００６２】また、実施例１３〜１７及び比較例１３で
は、粒度配合を微粉側にシフトさせる効果と、未安定化
ジルコニアの適正含有量を調べた。実施例１３のよう
に、粒度配合を微粉側にシフトさせることにより、耐食
性指数が大きくなり、耐食性を向上できることが確認さ
れた。In addition, in Examples 13 to 17 and Comparative Example 13, the effect of shifting the particle size composition to the fine powder side and the appropriate content of unstabilized zirconia were investigated. It was confirmed that by shifting the particle size composition to the fine powder side as in Example 13, the corrosion resistance index was increased and the corrosion resistance could be improved.
【００６３】また，実施例１３〜１７及び比較例１３で
は、未安定化ジルコニアの含有量を増大させて、適正値
を超えると、熱衝撃抵抗係数が減少して耐スポーリング
性が低下することが確認された。比較例３では、熱衝撃
抵抗係数が大幅に減少している。Further, in Examples 13 to 17 and Comparative Example 13, when the content of unstabilized zirconia was increased to exceed the appropriate value, the thermal shock resistance coefficient decreased and the spalling resistance decreased. Was confirmed. In Comparative Example 3, the thermal shock resistance coefficient is significantly reduced.
【００６４】以上より、未安定化ジルコニアの粒径は平
均粒径５５μｍ以下がより好ましく、その添加量は５〜
３０重量％が適正範囲であることが確認された。ただ
し、添加量が５０重量％以下であれば、それなりの効果
は得られる。From the above, the average particle size of unstabilized zirconia is more preferably 55 μm or less, and the addition amount is 5 to 5 μm.
It was confirmed that 30% by weight was within the proper range. However, if the addition amount is 50% by weight or less, a certain effect can be obtained.
【００６５】次に、表３を参照して本発明の実施例１８
〜２１及び比較例１４〜１５を説明する。Next, referring to Table 3, Example 18 of the present invention
21 and Comparative Examples 14 to 15 will be described.
【００６６】表３に示すように、未安定化ジルコニアの
粒径３μｍ以下の割合を変化させて、ノズルのパウダー
ライン部用の試料耐火物を製造し、熱衝撃抵抗係数と耐
食性指数の評価を行った。As shown in Table 3, a sample refractory for the powder line portion of the nozzle was manufactured by changing the ratio of the unstabilized zirconia with a particle size of 3 μm or less, and the thermal shock resistance coefficient and the corrosion resistance index were evaluated. went.
【００６７】その結果、全構成粒子のうち、未安定化Ｚ
ｒＯ2 の粒径３μｍ以下の占める割合が０．６５％の比
較例１４、および２６％の比較例１５では、比較例１１
よりも熱衝撃抵抗係数が小さく、粒度配合の変更および
未安定化ジルコニア使用の効果は確認できなかった。こ
れに対して、その添加量が３．３％、６．５％、１３
％、１９．５％である実施例１８〜２１では、いずれも
熱衝撃抵抗係数が大きかった。As a result, of all the constituent particles, the unstabilized Z
In Comparative Example 14 in which the proportion of rO 2 having a particle diameter of 3 μm or less was 0.65% and Comparative Example 15 in which it was 26%, Comparative Example 11
The thermal shock resistance coefficient was smaller than that, and the effects of changing the particle size composition and using unstabilized zirconia could not be confirmed. On the other hand, the added amount is 3.3%, 6.5%, 13
%, The thermal shock resistance coefficient was large in each of Examples 18 to 21, which were 19.5%.
【００６８】以上の結果より、全構成出発原料のうち、
未安定化ＺｒＯ2 の粒径３μｍ以下の粒子の割合は、１
〜２０重量％が適正であることが確認された。From the above results, of all the constituent starting materials,
The ratio of particles of unstabilized ZrO 2 having a particle size of 3 μm or less is 1
It was confirmed that -20 wt% was appropriate.
【００６９】なお、本発明のより良い理解のために（特
に１３００℃以上の高温時におけるＺｒＯ2 安定化材の
パウダー、スラグ成分との反応を推定するために）、Ｙ
2 Ｏ3 とＡｌ2 Ｏ3 −ＳｉＯ2 、Ｂ2 Ｏ3 、ＣａＯ−Ｓ
ｉＯ2 との状態図、ＣａＯ−Ａｌ2 Ｏ3 −ＳｉＯ2 の状
態図を参照できる。これらの状態図は、例えば、「セラ
ミック工学ハンドブック」（技報堂発行）や「Ｐｈａｓ
ｅ Ｄｉａｇｒａｍｓｆｏｒ Ｃｅｒａｍｉｓｔｓ」
（ＡＭＥＲＩＣＡＮ ＣＥＲＡＭＩＣ ＳＯＣＩＥＴＹ
発行）等の文献に記載されている。For a better understanding of the present invention (especially for estimating the reaction with the powder of the ZrO 2 stabilizer and the slag component at a high temperature of 1300 ° C. or higher), Y
2 O 3 and Al 2 O 3 -SiO 2, B 2 O 3, CaO-S
Reference can be made to the state diagram of iO 2 and the state diagram of CaO—Al 2 O 3 —SiO 2 . These state diagrams are, for example, “Ceramic Engineering Handbook” (published by Gihodo) and “Phas”.
e Diagrams for Ceramics "
(AMERICAN CERAMIC SOCIETY
Issue) etc.
【００７０】[0070]
【表１】 [Table 1]
【００７１】[0071]
【表２】 [Table 2]
【００７２】[0072]
【表３】 [Table 3]
【００７３】[0073]
【発明の効果】本発明の鋳造用耐火物、連続鋳造用ノズ
ル及びその製法によれば、耐食性を損わずに、耐酸化
性、耐スポーリング性を高めることが可能である。それ
ゆえ、本発明の鋳造用耐火物は連続鋳造用ノズルのパウ
ダーライン部の耐火物として最適である。According to the refractory for casting, the nozzle for continuous casting and the method for producing the same of the present invention, it is possible to enhance the oxidation resistance and spalling resistance without impairing the corrosion resistance. Therefore, the casting refractory of the present invention is most suitable as the refractory for the powder line portion of the continuous casting nozzle.
【００７４】請求項３、６に記載の鋳造用耐火物及びそ
の製法によれば、安定化剤のＣａＯの流れ出しを抑制
し、脱安定化現象を極力防止することによって、耐食性
を高め長寿命としたパウダーライン部を有する鋳造用ノ
ズルを製造することが可能である。According to the refractory for casting and the method for producing the same according to claims 3 and 6, by suppressing the outflow of the stabilizer CaO and preventing the destabilization phenomenon as much as possible, the corrosion resistance is improved and the life is extended. It is possible to manufacture a casting nozzle having the powder line part.
【００７５】また、安定化剤のＹ2 Ｏ3 を高々３．０重
量％しか添加しないので、従来の同程度の耐食性を有す
る鋳造用ノズルよりも安価に提供できる。Further, since the stabilizer Y 2 O 3 is added only at most 3.0% by weight, it can be provided at a lower cost than the conventional casting nozzle having the same degree of corrosion resistance.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 伏見 哲郎 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 (56)参考文献 特開 昭57−7367（ＪＰ，Ａ) 特開 平３−66462（ＪＰ，Ａ) 特開 平４−100661（ＪＰ，Ａ) 特開 平１−176271（ＪＰ，Ａ) 特開 昭62−202860（ＪＰ，Ａ) 特公 昭60−4153（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 35/48 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuro Fushimi No. 1 Minamito, Ogakie-cho, Kariya city, Aichi Toshiba Ceramics Co., Ltd. Kariya factory (56) Reference JP-A-57-7736 (JP, A) JP-A-3 -66462 (JP, A) JP-A-4-100661 (JP, A) JP-A-1-176271 (JP, A) JP-A-62-202860 (JP, A) JP-B-60-4153 (JP, B1) ) (58) Fields investigated (Int.Cl. 7 , DB name) C04B 35/48
Claims (6)
原料３０〜７０重量％、平均粒径７５μｍ以下の未安定
化ＺｒＯ2 原料５〜３０重量％、黒鉛１０〜４０重量％
に対して外率で炭化硼素、炭化珪素、窒化硼素、金属シ
リコン、アルミナ、金属アルミニウムの少なくとも一種
を１〜３０重量％（ただし、金属シリコンと金属アルミ
ニウムは合計で１０重量％以下）添加した原料から製造
し、かつ、ＺｒＯ 2 の安定化剤がＣａＯ１．０〜４．０
重量％及びＹ 2 Ｏ 3 ０．５〜３．０重量％であることを
特徴とする鋳造用耐火物。1. Stabilized or partially stabilized ZrO 2
Raw material 30 to 70% by weight, unstabilized ZrO 2 raw material having an average particle size of 75 μm or less 5 to 30% by weight, graphite 10 to 40% by weight
The raw material to which at least one of boron carbide, silicon carbide, boron nitride, metallic silicon, alumina, and metallic aluminum is added in an external ratio of 1 to 30% by weight (however, the total of metallic silicon and metallic aluminum is 10% by weight or less). And a stabilizer of ZrO 2 made of CaO 1.0 to 4.0.
A refractory for casting, characterized in that it is 0.5% by weight and Y 2 O 3 is 0.5 to 3.0% by weight .
％と、平均粒径７５μｍ以下、最大粒径８０μｍ以下の
未安定化ＺｒＯ2 ５〜３０重量％と、黒鉛１０〜４０重
量％と外率で、１〜３０重量％の炭化珪素および／また
は金属シリコン（ただし、金属シリコンは最大１０重量
％以下）からなり、前記未安定化ＺｒＯ2 の平均粒径３
μｍ以下の粒子が前記全構成原料の１〜２０重量％を占
め、かつ、ＺｒＯ 2 の安定化剤がＣａＯ１．０〜４．０
重量％及びＹ 2 Ｏ 3 ０．５〜３．０重量％であることを
特徴とする鋳造用耐火物。2. A partially stabilized ZrO 2 raw material 30 to 70% by weight, an unstabilized ZrO 2 having an average particle size of 75 μm or less and a maximum particle size of 80 μm or less, and graphite of 10 to 40% by weight. The average particle size of the unstabilized ZrO 2 is 3 to 30% by weight of silicon carbide and / or metallic silicon (however, the maximum amount of metallic silicon is 10% by weight or less).
Particles having a size of less than or equal to μm occupy 1 to 20% by weight of all the constituent raw materials , and the ZrO 2 stabilizer is CaO 1.0 to 4.0.
A refractory for casting, characterized in that it is 0.5% by weight and Y 2 O 3 is 0.5 to 3.0% by weight .
請求項１〜２のいずれか１項に記載の鋳造用耐火物で形
成されている連続鋳造用ノズル。3. A continuous casting nozzle in which the powder line portion of the continuous casting nozzle is formed of the casting refractory according to any one of claims 1 and 2 .
原料３０〜７０重量％、平均粒径７５μｍ以下の未安定
化ＺｒＯ2 原料５〜３０重量％、黒鉛１０〜４０重量％
に対して外率で炭化硼素、炭化珪素、窒化硼素、金属シ
リコン、アルミナ、金属アルミニウムの少なくとも一種
を１〜３０重量％（ただし、金属シリコンと金属アルミ
ニウムは合計で１０重量％以下）添加した原料を混合し
て所定形状に成形し、還元雰囲気中において８００〜１
２００℃の温度で焼成し、かつ、ＺｒＯ 2 の安定化剤が
ＣａＯ１．０〜４．０重量％及びＹ 2 Ｏ 3 ０．５〜３．
０重量％であることを特徴とする鋳造用耐火物の製造方
法。 4. Stabilized or partially stabilized ZrO 2
Raw material 30 to 70% by weight, unstabilized ZrO 2 raw material having an average particle size of 75 μm or less 5 to 30% by weight, graphite 10 to 40% by weight
The raw material to which at least one of boron carbide, silicon carbide, boron nitride, metallic silicon, alumina, and metallic aluminum is added in an external ratio of 1 to 30% by weight (however, the total of metallic silicon and metallic aluminum is 10% by weight or less). Are mixed to form a predetermined shape, and 800 to 1 in a reducing atmosphere
Baking at a temperature of 200 ° C. and a stabilizer for ZrO 2
CaO1.0~4.0 wt% and Y 2 O 3 0.5~3.
Manufacturing method of refractory for casting characterized by 0% by weight
Law.
％と、平均粒径７５μｍ以下、最大粒径８０μｍ以下の
未安定化ＺｒＯ2 ５〜３０重量％と、黒鉛１０〜４０重
量％と外率で、１〜３０重量％の炭化珪素および／また
は金属シリコン（ただし、金属シリコンは最大１０重量
％以下）からなり、前記未安定化ＺｒＯ2 の平均粒径３
μｍ以下の粒子が前記全構成原料の１〜２０重量％を占
める原料を混合して、所定形状に成形し、還元雰囲気中
において８００〜１２００℃の温度で焼成し、かつ、Ｚ
ｒＯ 2 の安定化剤がＣａＯ１．０〜４．０重量％及びＹ
2 Ｏ 3 ０．５〜３．０重量％であることを特徴とする鋳
造用耐火物の製造方法。5. A partially stabilized ZrO 2 raw material 30 to 70% by weight, an unstabilized ZrO 2 having an average particle size of 75 μm or less and a maximum particle size of 80 μm or less, and graphite of 10 to 40% by weight and outside. The average particle size of the unstabilized ZrO 2 is 3 to 30% by weight of silicon carbide and / or metallic silicon (however, the maximum amount of metallic silicon is 10% by weight or less).
Raw materials in which particles having a size of μm or less account for 1 to 20% by weight of all the constituent raw materials are mixed, shaped into a predetermined shape, fired at a temperature of 800 to 1200 ° C. in a reducing atmosphere, and Z
The stabilizer of rO 2 is 1.0 to 4.0% by weight of CaO and Y.
2 O 3 0.5 to 3.0% by weight, a method for manufacturing a refractory for casting.
法によって製造された鋳造用耐火物で連続鋳造用ノズル
のパウダーライン部を形成する連続鋳造用ノズルの製造
方法。6. A method for producing a continuous casting nozzle, which comprises forming a powder line portion of the continuous casting nozzle with a refractory material for casting produced by the method according to any one of claims 4 to 5 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29793096A JP3363330B2 (en) | 1996-05-01 | 1996-10-22 | Refractory for casting, nozzle for continuous casting and method for producing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8-132567 | 1996-05-01 | ||
| JP13256796 | 1996-05-01 | ||
| JP25224596 | 1996-09-04 | ||
| JP8-252245 | 1996-09-04 | ||
| JP29793096A JP3363330B2 (en) | 1996-05-01 | 1996-10-22 | Refractory for casting, nozzle for continuous casting and method for producing the same |
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| Publication Number | Publication Date |
|---|---|
| JPH10130053A JPH10130053A (en) | 1998-05-19 |
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|---|---|---|---|---|
| JP3722405B2 (en) * | 1999-10-19 | 2005-11-30 | 品川白煉瓦株式会社 | Steel continuous casting method |
| JP5309916B2 (en) * | 2008-04-01 | 2013-10-09 | Ｊｆｅスチール株式会社 | Refractories for shaft furnace outlets and shaft furnace outlets |
| JP5168080B2 (en) * | 2008-10-22 | 2013-03-21 | Ｊｆｅスチール株式会社 | Unshaped refractories for vertical furnaces |
| KR101639754B1 (en) * | 2014-11-21 | 2016-07-22 | 주식회사 포스코 | Submerged entry nozzle for continuous casting, Continuous casting method using same and Method for manufacturing submerged entry nozzle |
| JP6464831B2 (en) * | 2015-03-04 | 2019-02-06 | 品川リフラクトリーズ株式会社 | Immersion nozzle for continuous casting and method for continuous casting of steel |
-
1996
- 1996-10-22 JP JP29793096A patent/JP3363330B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10130053A (en) | 1998-05-19 |
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