WO2003086684A1 - Binding structure of refractory sleeve for inner hole of nozzle for continuous casting - Google Patents

Binding structure of refractory sleeve for inner hole of nozzle for continuous casting Download PDF

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Publication number
WO2003086684A1
WO2003086684A1 PCT/JP2003/004138 JP0304138W WO03086684A1 WO 2003086684 A1 WO2003086684 A1 WO 2003086684A1 JP 0304138 W JP0304138 W JP 0304138W WO 03086684 A1 WO03086684 A1 WO 03086684A1
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WO
WIPO (PCT)
Prior art keywords
sleeve
refractory
nozzle
inner hole
joint
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.)
Ceased
Application number
PCT/JP2003/004138
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English (en)
French (fr)
Inventor
Koji Ogata
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Krosaki Harima Corp
LWB Refractories Co
Original Assignee
Krosaki Harima Corp
LWB Refractories Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Krosaki Harima Corp, LWB Refractories Co filed Critical Krosaki Harima Corp
Priority to MXPA04009577A priority Critical patent/MXPA04009577A/es
Priority to KR1020047015291A priority patent/KR100647858B1/ko
Priority to JP2003583683A priority patent/JP4323962B2/ja
Priority to US10/509,638 priority patent/US7172013B2/en
Priority to DE60313446T priority patent/DE60313446T2/de
Priority to EP03715683A priority patent/EP1493516B1/en
Priority to BRPI0308907-0A priority patent/BR0308907B1/pt
Priority to AU2003221070A priority patent/AU2003221070A1/en
Publication of WO2003086684A1 publication Critical patent/WO2003086684A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/482—Refractories from grain sized mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/50—Pouring-nozzles
    • B22D41/52—Manufacturing or repairing thereof
    • B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/013—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/043—Refractories from grain sized mixtures
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/06—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on oxide mixtures derived from dolomite
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C04B35/103—Refractories from grain sized mixtures containing non-oxide refractory materials, e.g. carbon
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    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
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    • C04B37/005—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of glass or ceramic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/02—Ceramics
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
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    • C04B2237/04—Ceramic interlayers
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
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Definitions

  • the present invention prevents the adhesion of alumina to the inner holes of nozzles such as immersion nozzles, upper nozzles, sliding nozzles, lower nozzles, and long nozzles used for continuous steelmaking, and in particular, refractory sleeves for the inner holes.
  • nozzles such as immersion nozzles, upper nozzles, sliding nozzles, lower nozzles, and long nozzles used for continuous steelmaking, and in particular, refractory sleeves for the inner holes.
  • nozzles such as immersion nozzles, upper nozzles, sliding nozzles, lower nozzles, and long nozzles used for continuous steelmaking, and in particular, refractory sleeves for the inner holes.
  • Non-metallic inclusions such as alumina adhering to the inner hole of the immersion nozzle during the continuous manufacturing process of steel have a bad influence on the final quality, and in recent years, as the required quality of steel materials has become strict, Much effort has been put into reducing the adhesion of non-metallic inclusions. Further, the deposits on the inner hole of the immersion nozzle cause the inner hole to be closed in a long-time structure, making the structure difficult and hindering an improvement in productivity.
  • argon gas has been blown into molten steel from the inner surface of the nozzle in order to physically reduce the deposits such as alumina.
  • this method if the amount of argon gas blown is too large, bubbles are trapped in the piece and pinholes are formed in the structure, resulting in defects in the steel material. Therefore, since the amount of gas blown is limited, a sufficient reduction effect cannot always be obtained.
  • the refractory material constituting the immersion nozzle has an alumina adhesion preventing function.
  • a typical refractory material is disclosed in Japanese Patent Publication No. 2-32494.
  • this ZCG material has been put to practical use, but has not been widely applied.
  • Japanese Patent Application Laid-Open No. 62-24846 describes that by inserting a cylindrical sleeve made of calcareous refractory into the inner surface of the hole, it is excellent in the absorbency of alumina and the inner hole is closed. No continuous production nozzle is disclosed, but also in this case, since the calcareous refractory has a large thermal expansion coefficient, there is a problem that the nozzle body is cracked due to expansion of the refractory sleeve.
  • a first object of the present invention is to provide a continuous production nozzle in which a refractory sleeve containing CaO is inserted into a nozzle body to reduce the adhesion of alumina, and that the expansion of the refractory sleeve adversely affects the nozzle body. It is an object of the present invention to provide a joint structure between a refractory sleeve and a nozzle body, which does not have any problem.
  • Another object of the present invention is to provide a joining structure in which a refractory sleep attached to a nozzle body does not fall off due to thermal expansion.
  • Still another object of the present invention is to provide a nozzle for continuous production which can effectively reduce the adhesion of alumina and contribute to the stability of operation and the improvement of chip quality.
  • a porosity of an joint formed by the adhesive is used.
  • a continuous production nozzle in which a refractory sleeve containing 20% by mass or more of CaO is provided, wherein the outer peripheral surface of the sleeve or the inner wall surface of a main body hole on which the sleeve is mounted.
  • Adhesive mixture of fire-resistant aggregate and binder is applied to the joints formed between the entire part or the inserted sleeve and the inner wall surface of the main body bore, and the porosity of the dried joints at the joints was adjusted to 15 to 90%.
  • the sponge resistance as a nozzle for continuous construction in which the refractory sleeve containing C a 0 is integrated with the nozzle body is as follows: when the sleeve is integrally formed with the nozzle body, and when the sleeve is inserted as a sleeve and bonded. In this case, bonding is superior. This is presumably because the adhesive joint has a function of relieving thermal stress caused by rapid expansion caused by molten steel flowing into the inner hole during use. As a result of studying the material, configuration, and shape of the nozzle for continuous production, it was found that the porosity of the bonded joint portion was required to be 15% or more in order for the stress to be reduced.
  • the porosity is 90% or less in the practicable range, and 30 to 75% is particularly preferable.
  • the porosity in the present invention can be calculated from the filling weight of the adhesive if the true specific gravity of the adhesive and the volume of the joint between the nozzle body and the sleeve are measured in advance.
  • the adhesive examples include a mortar-like material in which a refractory aggregate is dispersed in a liquid binder dissolved in a solvent, and a dry eve in which a phenol resin is coated on the refractory aggregate. Can be used. Usually, after applying these adhesives, the solvent is removed or drying for curing the phenol resin is performed, but the porosity referred to in the present invention means the porosity after such a drying treatment is performed.
  • the particle size of the refractory aggregate is 0.5 mm or less, and the porosity can be adjusted by increasing or decreasing the amount of solvent and binder or changing the filling amount according to the joint thickness. Is set.
  • the method of applying the adhesive to the joints is to apply the coating to the outer peripheral surface of the sleeve or a part or the whole of the inner wall surface of the main body at the portion where the sleep is attached, and to spray or tape-like material in which the adhesive is dipped.
  • the joint portion made of the adhesive can be formed by filling the gap formed between the sleeve and the inner wall surface of the main body with the adhesive after the sleeve is inserted depending on the thickness of the joint.
  • the component of the refractory aggregate used for the adhesive of the sleeve includes a reactivity with CaO. It is desirable to consider That, S i 0 is 2, A 1 2 0 3, etc. In the high temperature region by the molten steel heat of generating a TeiTorubutsu react with C a O, when using some refractory aggregate containing these Requires careful consideration of the amount of components. On the other hand, Mg ⁇ , CaO, Zr ⁇ ⁇ 2, etc. are less reactive with CaO and therefore rarely produce low melts. It is preferred to use aggregate.
  • MgO material is suitable from the viewpoints of handleability and cost.
  • the main component of the mortar-like adhesive is mainly MgO
  • more than 70% by mass of the refractory aggregate uses magnesia materials such as sintered magnesia, calcined magnesia, and fused magnesia.
  • the refractory aggregate composed mainly of Mg_ ⁇ , combination with if more than one kind of substance containing alumina and Z or A 1 in 30 wt% or less A 1 2 0 3, the heat load of the molten steel Spinel is formed, and the expansion during the formation reduces the porosity of the joints and further increases the bonding strength between the nozzle body and the sleeve.
  • This spinel is formed gradually after relaxing the thermal stress at the start of injection, and does not adversely affect the spall at the start of injection.
  • Na husk, combined to material in the sleeve exceeds 3 0% by mass as A 1 2 0 3 It is not preferable because the amount of low melt produced by the reaction with C a O increases.
  • the thickness of the joint is not particularly limited, but is preferably in the range of 0.5 to 2.5 mm in consideration of the stress relaxation function and the adhesiveness of the joint.
  • the porosity of the joint is high in order to enhance the stress relaxation function, and when the joint thickness is large, it is preferable that the porosity of the joint be low in order to enhance the bonding function.
  • FIG. 1 shows an example in which the present invention is applied to an immersion nozzle.
  • 1 denotes a nozzle body
  • 2 denotes a ZG material used for a slag line
  • 3 denotes a sleeve
  • 4 denotes an adhesive joint.
  • a to F shown in Table 1 show examples of materials used for each part of the immersion nozzle.
  • the immersion nozzles as shown in Fig. 1 were manufactured by combining the materials of A to F shown in Table 1 with the combinations shown in Tables 2 and 3.
  • the ZG material used in the slag line, (: 1 6%, 2 1 " ⁇ 2 8 0 mass%, C a O is commonly used ones 4 wt%.
  • the joint 4 between the nozzle body 1 and the sleeve 3 was 1.5 mm thick, and the porosity of the joint was adjusted by changing the filling amount of the adhesive.
  • a mortar consisting of 10 parts by weight of nopolak phenol resin, 1 part by weight of hexamine and 10 parts by weight of ethanol with respect to 100 parts by weight was used.
  • the present invention relates to various types of nozzles for which metal is expected to adhere to various nozzle inner holes, such as nozzles for metal fabrication, especially immersion nozzles, upper nozzles, sliding nozzles, lower nozzles, and long nozzles used for continuous fabrication of molten steel. Applicable to the site.

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Description

明 細 書 連続铸造用ノズル内孔用耐火物製スリーブの接合構造 技術分野
本発明は、 鋼の連続铸造に使用する浸漬ノズル、 上ノズル、 スライディ ングノズル、 下部ノズル、 ロングノズル等のノズルの内孔へのアルミナ付 着を防止、 とくに、 そのための内孔用耐火物製スリーブのノズルへの接合 構造に関する。 背景技術
鋼の連続铸造過程で浸漬ノズルの内孔に付着するアルミナ等の非金厲介 在物は、 その最終品質に悪影響を与え、 近年、 要求される鋼材の品質が厳 格になるに伴い、 この非金属介在物の付着を減少させることに多くの努力 が払われている。 また、 この浸漬ノズルの内孔への付着物は、 長時間の铸 造においては内孔が閉塞をもたらし、 铸造を困難にし、 生産性向上への障 害をもたらす。
このアルミナ等の付着物を物理的に低減するために、 従来から、 ァルゴ ンガスをノズルの内面から溶鋼中に吹き込むことが行われてきた。 しかし、 この手法はアルゴンガスの吹き込み量が多すぎると気泡が铸片内に取り込 まれて铸造物中にピンホールを生じ、 鋼材の欠陥をもたらすこととなる。 従って、 ガスの吹き込み量は制約されるため必ずしも十分な低減の効果は 得られない。
また、 アルミナ等の付着物を化学的に低減するための手法として、 浸漬 ノズルを構成する耐火材にアルミナ付着防止機能を持たせる手法もある。 それの代表的な耐火材が特公平 2— 2 3 4 9 4号公報に開示されている。 この耐火材は、 C a Z r O 3を主成分とした C a〇一 Z r〇2クリンカーを 使用した C a O— Z r〇2—黒鉛材質、 いわゆる、 Z C G材質であって、 こ の Z C Gを浸漬ノズルの内孔に適用すしたものである。 この Z C G材質は、 現在のところ、 一部実用化されているものの広く一 般には適用されていない。 その理由の一つは、 アルミナの付着量が多い場 合に付着防止の効果が十分発揮されないことにある。 そのため、 アルミナ の付着量が多い場合には、 付着防止効果を発揮する C a Oの量を増量した り、 あるいは、 カーボン量を減量して相対的に C a O量を増加させる手法 が採用される。 しかし、 C a O量の増量は耐火物の熱膨張率の増大をもた らすことになり、 そのため、 ノズル本体に適用した場合には熱スポールが 発生し易くなる。 また、 内孔にのみに適用した場合にも、 その膨張により ノズル本体部分を押し割る危険性がある。
また、 特開昭 6 2— 2 4 8 4 6号公報には内孔面に石灰質の耐火物製の 円筒状スリーブを挿入することによって、 アルミナの吸収性に優れ、 内孔 が閉塞することのない連続鍀造用ノズルが開示されているが、 この場合も、 石灰質耐火物の熱膨張率が大きいために、 耐火物製スリーブの膨張により ノズル本体を押し割ってしまう問題がある。
発明の開示
本発明の第 1の目的は、 C a O含有の耐火物製スリーブをノズル本体に 内挿してアルミナの付着を低減する連続铸造用ノズルにおいて、 耐火物製 スリーブの膨張によりノズル本体に悪影響を及ぼすことのない耐火物製ス リーブとノズル本体との接合構造を提供することにある。
本発明の他の目的は、 ノズル本体に取り付けた耐火物製スリープが熱膨 張によっても脱落することのない接合構造を提供することにある。
さらに、 本発明の他の目的は、 アルミナの付着を効果的に低減できて、 操業の安定性と铸片の品質向上に寄与する連続铸造用ノズルを提供するこ とにある。
本発明は、 アルミナ付着防止効果の高い C a O含有の耐火物製スリーブ (以下スリーブとも言う） をノズル本体に接着材を用いて接着するに際し て、 接着材により形成される目地部の気孔率を調整することで上記目的を 達成した。 本発明の実施の態様として、 C a Oを 2 0質量％以上含有する耐火物製 スリーブを内装した連続铸造用ノズルであって、 スリ一ブ外周面若しくは スリーブを装着する本体内孔壁面の一部または全体、 あるいは挿入したス リーブと本体内孔壁面間に形成された目地部に、 耐火性骨材とバインダー とを混合した接着材を施して、 乾燥後の接着材の目地部における気孔率を 1 5〜9 0 %に調整したものである。
C a 0含有耐火物製スリーブをノズル本体と一体化した連続铸造用ノズ ルとしての耐スポ一ル性は、 スリーブをノズル本体とを一体成形した場合 と、 スリーブとして挿入して接着した場合とでは、 接着した場合の方が優 れている。 これは、 接着目地部が、 使用時の内孔に溶鋼が流入して発生す る急激な膨張による熱応力を緩和する機能を有するためと考えられる。 連続铸造用ノズルの材質、 構成、 形状によって検討を行った結果、 この 応力緩和の作用させるためには、 接着目地部の気孔率は 1 5 %以上必要で あることを見出した。 1 5 %未満では接着目地部が応力を緩和する能力が 小さく、 ノズル本体を押し割る可能性が大きくなり適当ではない。 また、 一方気孔率が大きすぎた場合、 接着力が不足してスリーブの一部が脱落す るなどの問題が生じる。 使用中は耐火物製スリ一ブの膨張によりノズル本 体と密着状態に近くなることを考慮すると、 気孔率は 9 0 %以下が実用可 能範囲であり、 3 0〜 7 5 %がとくに好ましい。
本発明における気孔率は、 あらかじめ接着材の真比重とノズル本体とス リーブ間の目地の体積を測定しておけば、 接着材の充填重量から算出する ことができる。
接着材としては、 耐火性骨材を溶剤で溶かれた液状のバインダ一中に分 散させたモルタル状の物や、 耐火性骨材にフエノールレジンをコ一ティン グさせたドライ夕イブなどを使用できる。 通常はこれら接着材を塗布した 後、 溶剤の除去あるいはフエノールレジンを硬化させるための乾燥を行う が、 本発明で言う気孔率はこのような乾燥処理を実施した後の気孔率を意 味する。 耐火性骨材の粒度は 0 . 5 mm以下のものが使用され、 気孔率は 目地厚に合わせ溶剤とバインダ一の増減あるいは充填量を変えることによ つて設定される。
目地部への接着材の施すための方法としては、 スリーブ外周面若しくは スリープが装着される部分の本体内孔壁面の一部または全体に塗布する他、 吹付、 接着材を浸したテープ状の物をスリーブへ巻き付けるなどの方法を 採用できる。 さらには、 接着材による目地部は、 目地厚の大きさによって はスリーブ挿入後、 目地部として本体内孔壁面との間に形成される間隙に 接着材を充填することによつても形成できる。
本発明のように、 C a O含有量が 20質量％以上のスリープをノズル本 体に接着する場合、 スリーブの接着材に使用する耐火性骨材の成分として は、 C a Oとの反応性を考慮することが望ましい。 すなわち、 S i 02, A 1203等は溶鋼熱による高温域では C a Oと反応して低融物を生成するの で、 これらを含有する耐火性骨材を一部使用する場合は成分量を十分に考 慮する必要がある。 これに対し、 Mg〇、 C aO、 Z r〇2などは、 C aO と反応性が小さいために低融物を生成することが少なく、 これらを単独あ るいは複合された主成分の耐火性骨材を使用することが好ましい。
とくに、 MgO材質は取り扱い性、 コストの面から好適である。 例えば、 モルタル状の接着材の主要成分が M g Oを主体とする場合、 耐火性骨材の 70質量％以上が焼結マグネシア、 仮焼マグネシア、 電融マグネシア等の マグネシア質原料を使用する。 溶鋼による熱負荷による溶損の発生を避け るためには、 ^[8〇の純度95%以上、 また、 C aO、 Z r 02などにおい ても、 S i 02、 A 12〇3などの不純成分が少ないものであることが好まし い。
さらに、 Mg〇を主成分とした耐火性骨材と、 アルミナおよび Zまたは A 1を含む物質の 1種以上を A 1203として 30質量％以下で併用した場 合、 溶鋼の熱負荷によってスピネルを生成し、 その生成の際の膨張によつ て目地部の気孔率が低下し、 さらにノズル本体とスリーブの接着強度が増 大する。 このスピネルの生成は注入開始時の熱応力を緩和した後に徐々に 生成するため、 注入開始時のスポールには悪影響を及ぼさない。 しかしな がら、 併用する物質が A 1203として 3 0質量％を越えるとスリーブ中の C a Oとの反応による低融物の生成量が多くなるため好ましくない。
目地部の厚みはとくには制限されるものではないが、 目地による応力緩 和機能と接着性を考慮すると 0 . 5 〜 2 . 5 mmの範囲が好ましい。 目地 厚が小さい場合には応力緩和機能を高めるために目地部の気孔率は高い方 が好ましく、 目地厚が大きい場合には接着機能を高めるため目地部の気孔 率は低い方が好ましい。 図面の簡単な説明
図 1は 本発明を浸漬ノズルに適用した例を示す。 発明を実施するための最良の形態
図 1において、 1はノズル本体を、 2はスラグラインに用いた Z G材質 を、 3はスリーブを、 そして、 4は接着目地部を示す。
表 1に示す A〜 Fは、 浸漬ノズルの各部分に使用する材質例を示す。
【表 1】
Figure imgf000007_0001
比較例 .本 発 明 比較例 本 発 明 . 比較例
1 1 2 3 4 5 6 7 2 3 8 9 1 0 1 1 1 2 1 3 1 4 4 丰体材 A A A A A A A A A A A A A A A A A A スリーブ材質 C C C C C C C C C D D D D D D D D D 目地部の気孔率 1 0 1 5 2 0 3 0 4 5 6 0 7 5 9 0 9 5 1 0 1 5 2 0 3 0 4 5 6 0 7 5 9 0 •9 5 スホ。 X
母材の押割り 〇 〇 〇 〇 〇 〇 0 〇 X Δ 〇 〇· 〇 〇 〇 0 o
-ル
スリ-フ'の剥落 0 0 o 0 〇 0 0 〇 X 0 〇 〇 0 0 〇 0 0 X 験 試験結果で、 〇は問題なし、 △は微細な問題発生、 Xは大きな問題発生を示す。
¾2 比較例 本 明 比較例 本 明 比較例
5 1 5 1 6 1 7 1 8 1 9 2 n 2 1 6 7 9 9 0 A
ώ Q 乙 u 9 7 9 δ ο ο CO 本体材貲 B B B B B B B B B B B Β Β B Β Β Β Β スリーブ材質 E E E E E E E E E F . F F F F F F F F 目地部の気孔率 1 0 1 5 2 0 3 0 4 5 6 0 7 5 9 0 9 5 1 0 1 5 2 0 3 0 4 5 6 0 7 5 9 0 9 5 スホ' 母材の押割り X 厶 〇 〇 〇 〇 0 〇 0 X Δ 〇 〇 〇 〇 〇 〇 0
-ル
試 スリ-フ'の剥落 〇 〇 0 〇 〇 0 0 Δ X 〇 〇 〇 〇 〇 〇 〇 Δ X 験 試験結果で、 〇は問題なし、 △は微細な問題発生、 Xは大きな問題発生を示す。
表 1に示す A〜Fの材質を、 表 2、 3に示す組み合わせによって、 図 1 に示すような浸漬ノズルを作製した。 これらの例において、 スラグライン に用いた Z G材質としては、 （：が1 6質量％、 2 1"〇2が8 0質量％、 C a Oが 4質量％のものを共通して使用した。 ノズル本体 1とスリーブ 3間 の接着用目地 4は 1 . 5 mm厚とし、 接着材の充填量を変えることで、 目 地部の気孔率を調整した。 接着材としては M g O骨材 1 0 0重量部に対し てノポラック型フエノールレジン 1 0重量部、 へキサミン 1重量部、 エタ ノール 1 0重量部からなるモルタルを使用した。
これらの浸漬ノズルの試料に 1 5 5 0 °Cの溶鋼を注入しスポ一ルテスト を行い、 母材の押し割りとスリーブの剥落について評価を行った。 問題が なかった場合を〇、 微小な問題が発生した場合を△、 大きな問題が発生し た場合を Xとした。
表 2、 3に示すように、 実施例として示す組み合わせにおいて、 目地部 の気孔率が 1 5〜 9 0 %であれば、 スポール試験結果が、 母材の押し割り、 スリーブの剥落について良好な物および微小な問題しか発生していないも のも含めて、 適応可能であった。 産業上の利用可能性
本発明は、 金属の銬造用ノズル、 とくに溶鋼の連続铸造に使用する浸漬 ノズル、 上ノズル、 スライディングノズル、 下部ノズル、 ロングノズル等 の各種ノズル内孔へのアルミナの付着が予想される各種の部位に適用でき る。

Claims

請 求 の 範 囲
1 . C a Oを 2 0質量％以上含有する耐火物製スリーブを内装した連続铸 造用ノズルにおいて、 前記スリーブ外周面若しくは前記スリーブが装着さ れる部分の本体内孔壁面の一部または全体、 あるいは挿入された前記スリ —ブと本体内孔壁面間に形成される目地部に対して、 耐火性骨材とバイン ダ一とを混合した接着材を施して、 乾燥された目地部接着材の気孔率を 1 5〜9 0 %に調整した連続铸造用ノズル内孔用耐火物製スリーブの接合構 造。
2 . 気孔率は、 接着材を構成する溶剤とバインダーの増減あるいは充填量 を変えることで調整した請求項 1に記載の連続铸造用ノズル内孔用耐火物 製スリーブの接合構造。
3 . 接着材を構成する主な耐火性骨材が、 M g Oを主成分とする耐火性骨材 である請求項 1に記載の連続铸造用ノズル内孔用耐火物製スリーブの接合構 造。
4 . 接着材が、 粒径 0 . 5 mm以下で構成する M g Oを主成分とした耐火 性骨材を 7 0質量％以上とし、 アルミナ及び Zまたは A 1を含む物質の一 種以上を A 1 20 3として 3 0質量％以下含有する請求項 3に記載の連続铸 造用ノズル内孔用耐火物製スリーブの接合構造。
PCT/JP2003/004138 2002-04-02 2003-03-31 Binding structure of refractory sleeve for inner hole of nozzle for continuous casting Ceased WO2003086684A1 (en)

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JP2003583683A JP4323962B2 (ja) 2002-04-02 2003-03-31 連続鋳造用ノズル内孔用耐火物製スリーブの接合構造
US10/509,638 US7172013B2 (en) 2002-04-02 2003-03-31 Binding structure of refractory sleeve for inner hole of nozzle for continuous casting
DE60313446T DE60313446T2 (de) 2002-04-02 2003-03-31 Bindestruktur einer feuerfesten hülse für das innenloch einer düse zum stranggiessen
EP03715683A EP1493516B1 (en) 2002-04-02 2003-03-31 Binding structure of refractory sleeve for inner hole of nozzle for continuous casting
BRPI0308907-0A BR0308907B1 (pt) 2002-04-02 2003-03-31 estrutura de ligação de uma luva refratária fixada à parte interna de um bocal para lingotamento contìnuo.
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JP6396889B2 (ja) 2013-03-19 2018-09-26 日本碍子株式会社 接合体及びその製造方法
US20160361758A1 (en) * 2014-02-28 2016-12-15 Krosakiharima Corporation Refractory for steel casting, plate for sliding nozzle device, and method for producing refractory for steel casting
KR102007575B1 (ko) 2017-11-15 2019-10-01 한국가스공사 절연 와셔
CN111940715B (zh) * 2019-05-17 2022-07-08 宝山钢铁股份有限公司 防堵塞浸入式水口
JP7068255B2 (ja) * 2019-10-31 2022-05-16 黒崎播磨株式会社 ＣａＯ－ＺｒＯ２組成物，ＣａＯ－ＺｒＯ２組成物の製造方法，ＣａＯ－ＺｒＯ２含有耐火物及び鋳造用ノズル

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KR100647858B1 (ko) 2006-11-23
US20050067746A1 (en) 2005-03-31
JP4323962B2 (ja) 2009-09-02
JPWO2003086684A1 (ja) 2005-08-18
KR20050004827A (ko) 2005-01-12
US7172013B2 (en) 2007-02-06
EP1493516A4 (en) 2005-04-20
BR0308907A (pt) 2005-01-04
DE60313446T2 (de) 2008-07-24
EP1493516B1 (en) 2007-04-25
CN1642675A (zh) 2005-07-20
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EP1493516A1 (en) 2005-01-05
BR0308907B1 (pt) 2011-08-23

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