EP0846514B1

EP0846514B1 - A continuous casting nozzle for casting molten steel

Info

Publication number: EP0846514B1
Application number: EP97118925A
Authority: EP
Inventors: Toshiyuki Muroi; Shojiro Naito
Original assignee: Akechi Ceramics Co Ltd
Current assignee: Akechi Ceramics Co Ltd
Priority date: 1996-12-05
Filing date: 1997-10-30
Publication date: 2000-12-20
Anticipated expiration: 2017-10-30
Also published as: JPH10166116A; EP0846514A1; CA2223356C; ATE198172T1; DE69703729T2; AU4522997A; DE69703729D1; CA2223356A1; AU730801B2

Abstract

The invention is related to a continuous casting nozzle for casting of aluminum killed steel without clogging of the bore of the nozzle. The surface layer of the bore of the continuous casting nozzle contacting with the molten steel is formed of a refractory comprising graphite from 10 to 35 wt%, an aggregate of 10 to 60 wt% selected from from alumina matter, zirconia matter, zircon matter, or alumina-silica matter and roseki containing the pyrophyllite (Al2O3.4SiO2.H2O) as the main component as the rest part of the above mentioned materials.

Description

FIELD OF THE INVENTION

The present invention relates to a continuous casting nozzle for permitting effective prevention of narrowing, clogging of the nozzle bore or metal sticking to the nozzle bore through which molten steel passes in performing continuous casting of the molten steel containing aluminum such as aluminum-killed steel.

THE RELATED ART

A continuous casting nozzle for casting molten steel is used for the following purposes.
As for continuous casting molten steel, a continuous casting nozzle is used for such purpose of preventing the molten steel from being oxidized by contacting with the open air and from splashing when the molten steel is poured from a tundish to a mold, and rectifying the flow of the molten steel poured for preventing non-metallic inclusion and slag present near or on the mold surface from being entrapped in the cast steel strand.
Material of a conventional continuous casting nozzle of molten steel comprises such material as graphite, alumina, silica, silicon carbide and recently zirconia. However, there are following problems in the case of casting aluminum-killed steel and the like.
As for the aluminum-killed steel and the like, aluminum, which is added as a deoxidizer, reacts with oxygen existing in the molten steel to produce non-metallic inclusion such as α-alumina. Therefore, in casting the aluminum-killed steel and the like, the non-metallic inclusion such as α-alumina adheres and accumulates onto the surface of the bore of the continuous casting nozzle, so that the bore is narrowed or clogged up in the worst case, which makes stable casting to be difficult. Furthermore, the non-metallic inclusion such as α-alumina adhered or accumulated onto the surface of the bore peels off or falls down, and is entrapped in the cast steel strand, thus degrading the quality of the cast steel strand.
For the purpose of preventing the above-mentioned reduction or clogging of the bore caused by the non-metallic inclusion such as α-alumina, there is a commonly used method for preventing the non-metallic inclusion such as α-alumina existing in the molten steel from adhering or accumulating on the surface of the bore of the nozzle by ejecting inert gas from the inner surface of the nozzle bore toward the molten steel flowing through the bore (for example, Japanese Patent Publication No. Hei 6-59533/1994).
However, there are problems as described below for the above-mentioned method wherein inert gas is ejected from the inner surface of the nozzle.
A large amount of the ejected inert gas causes entrapment of bubbles produced by the inert gas into the cast steel strand, resulting in defects based on pinholes. On the other hand, a small amount of the ejected inert gas causes adhesion and accumulation of the non-metallic inclusion such as α-alumina onto the surface of the bore of the nozzle, thus causing narrowing or clogging, in the worst case, of the bore.
Additionally, it is constructionally difficult to uniformly eject the inert gas from the inner surface of the nozzle bore toward the molten steel flowing through the bore. And in the case that the casting is performed in a long period of time, a stable control of the amount of ejected inert gas becomes gradually more difficult as the composition and the structure of the material consisting of the continuous casting nozzle degrades. And moreover, it becomes difficult to eject inert gas uniformly from the inner surface to the nozzle bore. As a result, the non-metallic inclusion such as α-alumina adhere and accumulate onto the surface of the bore of the nozzle so that the bore is narrowed or clogged up in the end.
It is thought that the clogging of the nozzle by the non-metallic inclusion, specially by the alumina inclusion is caused as described below.
(1) Alumina inclusion is produced from aluminum in the steel by secondary oxidation, such as oxidation by entrapped air passing through a refractory junction and refractory structure or oxidation by supplying oxygen obtained from reduction of silica in a graphite- or carbon-containing refractory.
(2) Alumina inclusion is produced by diffusion and cohesion of the alumina produced in the above process.
(3) Graphite on the surface of the nozzle bore vanishes and the surface of the bore becomes rough and thus the alumina inclusion is apt to accumulate on the rough surface of the bore.
On the other hand, as a counterplan in view of nozzle material, a nozzle in which a non-oxide raw material (SiC, Si₃N₄, BN, ZrB₂, SIALON etc.) that has low reactivity with aluminum oxide is added to alumina-graphite or a nozzle consisting of the non-oxide material itself is proposed (for example, Japanese Patent Publication No. Sho 61-38158/1986).
However, this counterplan is not practical in the case of the alumina-graphite nozzle because the adhesion preventing effect is not recognized and further corrosion resistance is decreased unless much of the non-oxide material is added.
Also, the nozzle consists of only the non-oxide material is not suitable for practical use in view of material cost and manufacturing cost, although a substantial effect is expected.
A nozzle consisting of graphite-oxide raw material containing CaO is proposed for producing low-melting-point material by a reaction of CaO in an oxide raw material containing CaO (CaO·ZrO₂, CaO·SiO₂, 2CaO·SiO₂ etc.) with Al₂O₃ and forming the low-melting-point material in the steel (for example, Japanese Patent Laid-Open Publication No. Sho 62-56101/1987).
However, reactivity of CaO with Al₂O₃ is apt to be influenced by a temperature condition of the molten steel in casting, and there is a case that amount of CaO is not sufficiently secured for satisfying spalling resistance and corrosion resistance when plenty of Al₂O₃ inclusion is contained in the steel.
A German laid open patent No. 1808778 disclosed a new open nozzle for casting liquid metal, wherein said nozzle is made of a refractory material consisting of a siliceous material, which is selected from pyrophillite, clay, fireclay or silica glass and carbon. No other component such as alumina, zirconia, zircon or alumina-silica is further used in this refractory material.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a continuous casting nozzle having features of forming a glass layer at the surface of the bore of the nozzle when the nozzle is used, thereby preventing air from being entrapped through refractory structure, smoothing the bore surface of the nozzle and preventing the accumulation of alumina. Also, the object of the present invention is to provide a continuous casting nozzle which prevents erosion by products having a low-melting point on account of a reaction between an aggregate in a refractory and alumina in the steel, and to provide the nozzle which is not influenced by a temperature of the molten steel in casting, and which is able to prevent the bore from narrowing or clogging economically, comparatively easy and stable.
In the present invention, the surface layer of the bore of a continuous casting nozzle contacting with molten steel is formed of a refractory comprising graphite from 10 to 35 wt%, an aggregate from 10 to 60 wt% selected from from alumina matter, zirconia matter, zircon matter, or alumina-silica matter and roseki containing the pyrophyllite (Al₂O₃·4SiO₂·H₂O) as the main component as the balance up to 100 wt% of the above mentioned materials.
In another embodiment of the present invention, the surface layer of the bore of a continuous casting nozzle contacting with molten steel is formed of a refractory comprising graphite from 10 to 35 wt%, an aggregate from 10 to 60 wt% selected from from alumina matter, zirconia matter, zircon matter, or alumina-silica matter and roseki containing the pyrophyllite (Al₂O₃·4SiO₂·H₂O) as the main component as the balance up to 100 wt% of the above mentioned materials, the said refractory being added binder, kneaded, formed, and sintered in the anti-oxidizing atmosphere.
It is preferable that the roseki containing the pyrophyllite as the main component is calcinated at a temperature equal to or more than 800°C so as to vanish crystal water and contain alkaline component from 1 to 5 wt%. As for the roseki having above mentioned component, it is preferable that a mixing weight ratio of roseki with an average grain diameter equal to or less than 250µm is equal to or less than 60% relative to the whole of the roseki content.
As for roseki having above mentioned component, it is preferable that the roseki containing the pyrophyllite as the main component is calcinated at a temperature equal to or more than 800°C so as to vanish crystal water and contains alkaline component from 1 to 5 wt %.
Furthermore, the mixing weight ratio of roseki whose average grain diameter equal to or less than 250µm, is equal to or less than 60% relative to the whole of the roseki content. And as for the binder a thermosetting resin, for example, phenol resin is preferable selected. With respect to forming process CIP (Cold isostatic process) should be preferably selected.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a longitudinal cross section of a nozzle according to the present invention comprising a invented refractory at the surface layer of the bore of the nozzle.
FIG. 2 shows a longitudinal cross section of a nozzle according to the present invention comprising a invented refractory at the surface layer of the bore of the nozzle and the lower part (a part immersed in the molten steel) of the nozzle.

EMBODIMENTS OF THE INVENTION

A major characteristic of a continuous casting nozzle of the present invention is that the main component of a refractory of the surface layer of the bore of the nozzle is roseki. During usage, when silica in the above mentioned refractory coexisting with graphite or carbon , the following reactions are usually caused. SiO₂(S) + C(S) = SiO(g) + CO(g) 3SiO(g) + 2Al = Al₂O₃(S) + 3Si 3CO(g) + 2Al = Al₂O₃ (S) + 3C
As shown in the above reactions, decomposition of the silica produces SiO(g) and CO(g), which react with aluminum in the steel to form Al₂O₃ and it becomes the source of oxygen to the steel.
However, as for the roseki, the roseki particles do not decompose even if it is coexisting with graphite or carbon, namely SiO₂ in pyrophyllite (Al₂O₃·4SiO₂·H₂O) which is the main mineral of the roseki is stable. This fact is found from the facts that the particles do not decay and bubbles are not produced, which is confirmed by means of a microscope observation after forming a briquette consisting of the roseki, resin powders and carbon powders and performing heat-treatment at a temperature of 1500°C for 24 hours with burying it in a coke breeze.
The half-melting temperature of the roseki is about 1500°C, so that it melts at the bore surface contacting with the molten steel to form a glass coat for smoothing the structure of the surface of the bore and for preventing air from being entrapped through a refractory structure.
This is found from the fact that the permeability is decreased such that the permeability after performing heat-treatment at a temperature of 1500°C for 1 hours is as small as about 9.5x10^-5 darcy, in contrast the permeability after performing heat-treatment at a temperature of 1000°C for 1 hours is about 9.5x10^-4 darcy.
Although the mixing amount of the roseki is the rest part of the mixing amount of other components, a mixing weight ratio of the roseki is equal to or more than 30 wt% in order to actively form the glass coat on the surface of the bore in use as continuous casting nozzle, preferably. Also, it is preferably that the mixing weight ratio of the roseki is equal to or less than 80 wt% because degree of softening deformation is large with a range of over 80 wt%.
The most preferable mixing weight ratio of the roseki is from 30 wt% to 60 wt%.
In this case the aggregate of roseki particles does not decompose even coexisting with graphite.
As for kinds of roseki, it is possible to use three kinds of roseki, that is pyrophyllite matter roseki, kaolin matter roseki, and sericite matter roseki.
The pyrophyllite matter roseki with refractoriness from SK29 to SK32 (SK(Seger cone) is a Japanese Standard for refractoriness ) is suitable, considering formation of a glass layer and erosion resistance against the molten steel, as the surface of the bore contacting with the molten steel is half-molten in use. Both of the kaolin matter roseki and the sericite matter roseki is not preferable because the kaolin matter roseki has a greater refractoriness from SK33 to SK36, and the sericite matter roseki has a smaller refractoriness from SK26 to SK29.
As for the binder for forming the nozzle body a thermosetting resin, for example phenol resin, is preferably used and the mixing ratio is preferably 5 to 15 wt%. And the most preferable process of the mixed material is CIP(cold isostatic pressing) to produce the nozzle having a high heat resistance.
Sintering of the formed body is preferably performed in the nonoxidizing atmosphere to minimize the burning loss of the graphite mixed in the material, which is mixed to enhance the erosion resistance and oxidation resistance and the sintering temperature is preferably 1000 to 1200 °C to obtain a sufficient strength of the nozzle.
The reason for using the roseki calcinated at a temperature equal to or more than 800°C to vanish crystal water is that the crystal water is released from the roseki at a temperature in a range of from 500 to 800°C in sintering and the refractory cracks by virtue of an unusually large coefficient of thermal expansion in this range. The alkaline component of the roseki from 1 to 5 wt% is preferable to control the melting point of roseki adequdately
It is preferable that a mixing weight ratio of roseki with an average grain diameter equal to or less than 250µm is equal to or less than 60% relative to the whole of the roseki content because, in the range of over 60%, structural defects such as lamination are apt to be produced in molding and softening deformation of roseki particles is apt to happen when used in a continuous casting nozzle.
The half-melting temperature of the roseki is about 1500°C, and it melts at the bore surface contacting with the molten steel to form a glass coat for smoothing the structure of the surface of the bore and for preventing air from being entrapped through a refractory structure, so that it has the effect to depress the adherence of Al₂O₃ and metal.
To prevent the softening deformation and to maintain heat-impact resistance of the roseki, preferably, a mixing weight ratio of the graphite is equal to or more than 10 wt%. Also, it is preferably that the mixing weight ratio of the graphite is equal to or less than 35 wt% from the view point of manufacturing of the nozzle because the volume ratio of the graphite relative to the roseki is too large so that structural defects such as lamination are apt to be produced in the range of over 35 wt%. Considering thermal conductivity and oxidation resistance, natural graphite is suitable as the graphite to be mixed.
As for the aggregate to be mixed, an aggregate of 10 to 60 wt% selected from from alumina matter, zirconia matter, zircon matter, or alumina-silica matter should be selected, to obtain a sufficient erosion resistance of the nozzle against molten steel.
The continuous casting nozzle for steel according to the present invention will be described in detail with reference to the accompanying drawings of nozzle for continuous casting.
As shown in FIG. 1, a surface layer 2 of the bore 1, through which the molten steel flows, of the immersion nozzle 10 consists of a refractory having the chemical composition as described above. The rest part of the nozzle 3 is composed of regular refractory, for example, of alumina-graphite which is already known in public. The dimensions of the nozzle are about 1,000mm in total length, about 60mm in diameter of the bore, 160mm in outer diameter, and about 50mm in thickness.
FIG. 2 shows another embodiment of the invention, a nozzle comprising a refractory according to the present invention at the surface layer of the bore of the nozzle and the lower part (a part immersed in the molten steel) of the nozzle. In the bore 1 of the nozzle for continuous casting, the adherence and accumulation of non-metallic inclusion such as the α-alumina are depressed.

EXAMPLES

The present invention is explained with examples as described below.
The samples Nos. 1 to 5 (hereinafter referred to as the "sample of the present invention") having the chemical compositions within the scope of the present invention, and the samples Nos. 6 to 8 (hereinafter referred to as "sample for comparison") having chemical compositions out of the scope of the present invention were prepared as shown in Table 1, and phenol resin in the state of powder and liquid was added in an amount within a range of from 5 to 10 wt% to each of the mixed materials. From the mixed materials above, the following formed bodies were prepared.
A first formed body (hereinafter referred to as the "formed body 1") with dimensions of 30mm by 30mm by 230mm for examining an amount of adhesion of non-metallic inclusion such as alumina and corrosion resistance against the molten steel, a second formed body (hereinafter referred to as the "formed body 2") with dimensions of 50mm ⊘ by 20mm for examining permeability, and a third formed body (hereinafter referred to as the "formed body 3") with dimensions of 100mm in outer diameter, 60mm in inner diameter and 250mm in length for examining spalling resistance, were respectively prepared, and then the bodies were sintered in reducing atmosphere at a temperature in a range from 1000 to 1200°C and samples 1 to 8 were prepared.
Physical properties (porosity and bulk density) for each of the above-mentioned samples of the present invention Nos. 1 to 5 and the samples for comparison Nos. 6 to 8 are shown in Table 1.
The spalling resistance of each of the sintered formed bodies 3 of the samples of the present invention Nos. 1 to 5 and the samples for comparison Nos. 6 to 8 were examined after heating at a temperature of 1500°C for 80 minutes in an electric furnace and then rapidly cooling by water. The results are shown in Table 1.
An erosion ratio (%) and an amount of adhesion of non-metallic inclusion such as alumina of each of the sintered formed bodies 1 of the samples of the present invention Nos. 1 to 5 and the samples for comparison Nos. 6 to 8 were examined after immersing in molten steel, which contains aluminum in a range from 0.02 to 0.05 wt%, at a temperature of 1550°C for 180 minutes. The results are shown in Table 1.
The permeability for each of the sintered formed bodies 2 of the samples of the present invention Nos. 1 to 5 and the samples for comparison Nos. 6 to 8 were examined after heating at a temperature of 1500°C for 60 minutes in an electric furnace and then cooling. The results are shown in Table 1.
It is easily understood from Table 1 that the samples of the present invention are superior in the spalling resistance so the nozzle is not destroyed at the beginning of casting. Also, the non-metallic inclusion such as alumina does not adhere in spite of the low erosion ration, thereby effectively preventing narrowing or clogging of the continuous casting nozzle of the molten steel.
And also, it is possible for the samples of the present invention to prevent air from being entrapped through the refractory in practical use because of small permeability.
On the other hand, it is obvious that the sample for comparison No. 6 is remarkably inferior in the spalling resistance and the corrosion resistance against the molten steel, although a small amount of alumina adheres due to much roseki content.
As for the sample for comparison No. 7, the amount of adhesion of alumina is remarkably large, because it contains Al₂O₃ and SiO₂, which decomposes to supply oxygen in the steel, instead of the roseki.
As for the sample for comparison No. 8, it does not contain SiO₂ instead of roseki and contains only Al₂O₃ and it has high permeability and the amount of adhesion of alumina is remarkably large, although it contains no mineral source of oxgen to the steel.
Therefore, with the use of the continuous casting nozzle for casting steel according to the present invention, it is possible to perform stable casting with preventing narrowing or clogging of the bore caused by the non-metallic inclusion such as alumina without deterioration of the refractory structure.
According to the present invention, approximately 300 ton of a low carbon aluminum killed steel of 5 to 7 charges is continuously cast with one nozzle without clogging by 2 strand slab caster in real operation, though with conventional nozzle, clogging up in the nozzle were occurred within 2 to 4 charges under same condition.

Claims

A continuous casting nozzle for casting molten steel from tundish to mould, wherein the surface layer of the bore of said continuous casting nozzle contacting with the molten steel is formed of a refractory comprising graphite from 10 to 35 wt%, an aggregate from 10 to 60 wt% selected from alumina, zirconia, zircon, or alumina-silica and roseki containing the pyrophyllite (Al₂O₃ 4SiO₂ H₂O) as the main component as the balance up to 100 wt% of the above mentioned materials.
A continuous casting nozzle for casting molten steel from a tundish to mould as defined in Claim 1, wherein said refractory is being added binder, kneaded, formed and sintered in the anti-oxidizing atmosphere.
A continuous casting nozzle for casting molten steel from a tundish to mould according to claim 2, wherein the roseki containing the pyrophyllite as the main component, is calcinated at a temperature equal to or more than 800 °C so as to vanish crystal water and contains alkaline component from 1 to 5 wt%.
A continuous casting nozzle for casting molten steel from a tundish to mould according to claim 2, wherein a mixing weight ratio of the roseki, whose average grain diameter equal to or less than 250µm, is equal to or less than 60% relative to the whole of the roseki content.
A continuous casting nozzle for casting molten steel from a tundish to mould according to claim 2, wherein said binder is a thermosetting resin.
A continuous casting nozzle for casting molten steel from a tundish to mould according to claim 2, wherein said refractory is formed by CIP process.