US20060033247A1

US20060033247A1 - Refractory material for casting a rare-earth alloy and its production method as well as method for casting the rare-earth alloys

Info

Publication number: US20060033247A1
Application number: US11/201,296
Authority: US
Inventors: Hiroshi Hasegawa; Nobuhiko Kawamura; Shiro Sasaki; Yoichi Hirose
Original assignee: Showa Denko KK
Current assignee: Resonac Holdings Corp
Priority date: 1998-06-22
Filing date: 2005-08-11
Publication date: 2006-02-16
Also published as: US20030109372A1

Abstract

Rare-earth alloy is cast into a sheet (6) or the like by using a tundish (3, 13). The refractory material of the tundish used for casting does not necessitate preheating for improving the flowability of the melt (2). The refractory material used essentially consists of 70 wt % or more of Al₂O₃and 30 wt % or less of SiO₂, or 70 wt % or more of ZrO₂and 30 wt % or less of one or more of Y₂O₃, Ce₂O₃, CaO, MgO, Al₂O₃, TiO₂and SiO₂. The refractory material has 1 g/cm³or less of bulk density, has 0.5 kcal/(mh° C.) or less of thermal conductivity in the temperature range of from 1200 to 1400° C., and has 0.5 wt % or less of ratio of ignition weight-loss under the heating condition of 1400° C. for 1 hour.

Description

TECHNICAL FIELD

The present invention relates to refractory material for casting a rare-earth alloy, which contains a rare-earth element (R) as one of the main components, such as an alloy for an R—Fe—B based magnet, an R—Ni based hydrogen-absorbing alloy and an alloy for an Sm—Co based magnet. The present invention also relates to a production method of the refractory material and a method for casting the rare earth-alloys.

BACKGROUND TECHNIQUE

Recently, attention has been paid to the rare-earth sintered magnet or rare-earth bond magnet, in which the excellent magnetic properties of the rare-earth alloys are utilized. Particularly, with regard to R—Fe—B based magnets, development for further enhancement of the magnetic properties has been conducted. There is in the R—Fe—B based magnets a ferromagnetic R₂Fe₁₄B phase, which is the basis of the magnetism, and an R-rich phase (a non-magnetic phase having high concentration of the rare-earth elements, such as Nd) which is the basis of liquid-phase sintering and greatly contributes to enhancement of the magnetic properties.
It is necessary to increase the volume fraction of the ferromagnetic R₂Fe₁₄B phase to attain higher performance of a magnet. This necessarily results in decrease of the volume fraction of the R-rich phase. Therefore, when the casting is carried out by a conventional method, the R-rich phase is so poorly dispersed that the R-rich phase is locally deficient, resulting in unsatisfactory properties in many cases.
Meanwhile, when the magnet composition has a higher volume fraction of the R₂Fe₁₄B phase, α-Fe is more liable to form in the alloy for the magnet. This α-Fe seriously impairs the crushability of the alloy for the magnet, and hence causes composition variation at the crushing process. This, in turn, incurs decrease of the magnetic properties and increase in variation of the magnetic properties.
Therefore, methods for solving these problems involved in the high-performance magnets have been proposed. A strip-casting method is proposed in Japanese Unexamined Patent Publications Nos. 5-222488 and 5-295490. Since this method attains, in the solidification, higher cooling speed than in the conventional book-mold casting method, it is possible to produce an alloy having refined structure and finely dispersed R-rich phase. The formation of a -Fe is difficult in such alloy.
A strip-casting method described in Japanese Unexamined Patent Publication No. 5-222488 resides in that: an alloy ingot for permanent magnet is produced by solidifying the rare earth metal-iron-boron alloy melt; the alloy melt is subjected, in the production, to cooling under condition of from 10 to 500° C./second of cooling speed, and 10 to 500° C. of the super cooling degree; the alloy melt is homogeneously solidified into an ingot having a thickness in the range of from 0.05 to 15 mm. The specific casting method is to flow down the melt from a tundish onto a rotary roll.
Japanese Unexamined Patent Publication No. 5-295490 exemplifies a rotary disc method for making an alloy in the form of fish scale and a twin-roll method for making an alloy in the form of a strip or pieces.
Meanwhile, the R—Ni based hydrogen-absorbing alloy having excellent hydrogen-absorbing property has recently attracted attention as the electrode material of the secondary battery. Such elements as Co, Mn, Al and the like are added into this alloy to enhance the hydrogen-absorbing property and other material properties. In the production by a conventional book-mold casting method, additive elements are liable to micro-segregate. Prolonged heat treatment is necessary to homogenize the crystal composition.
In addition, the hydrogen-absorbing alloy is usually pulverized in the pulverization step to a few tens of microns. An alloy obtained by the book-mold casting method is difficult to pulverize, is of large particle diameter and contains a phase with rich additive elements. The post-pulverizing distribution of the powder size is, therefore, non-uniform and exerts detrimental influence upon the hydrogen-absorbing property. The final resultant powder of the hydrogen-absorbing alloy exhibits disadvantageously insufficient hydrogen-absorbing property.
The strip-casting method is proposed to solve the above-described problems (Japanese Unexamined Patent Publication No. 5-3207920). Since higher cooling speed than in the conventional book-mold casting method is attained by solidification in the strip-casting method, homogeneity in the composition and structure of the alloy produced is improved. It is possible to produce, by using this alloy, the secondary battery having such characteristics as high initial charging speed, long battery life, and large electric capacity.
FIG. 1 illustrates the strip-casting method. Melt 2 is tapped from a melting furnace (not shown) to a tiltable ladle 1 into a tundish 3. The melt is then fed from there onto a water-cooled copper (single) roll 4 at a predetermined feeding speed. In accordance with the rotation of the roll, the melt 2 is cast-formed on the water-cooled copper roll 4 into a sheet 5. Subsequently, the sheet 5 is separated from the roll and is crushed by a hammer (not shown) into thin pieces 6 which are stored in the metal reservoir 7.
As above, the melt is fed onto a roll in such small amount that the alloy is ordinarily 1 mm or less thick. Heat of melt should, therefore, not be abstracted by the tundish and the like which guides the melt from a crucible to the cooling roll, thereby preventing the solidification.
When the melt is fed by a small amount into a tundish made of ordinary refractory material, such as alumina, mullite, alumina-mullite, magnesia, zirconia or calsia, the heat of the melt is abstracted by the tundish so that the melt solidifies and cannot be cast. In this case, if the amount of heat abstraction is decreased by reducing the thickness of the tundish, good flow of the melt can therefore be maintained. However, such thin tundish is not only difficult to produce but also would be difficult to handle as it may be liable to crack.
In order to prevent the above-described problems from occurring in a tundish made of ordinary refractory material as described above, it is necessary to heat at least the surface of the tundish to approximately the same temperature as that of the melt.
However, the following problems are involved in the tundish heating.
{circle around (1)} Since the melting temperature is usually 1200 to 1500° C., an apparatus for heating the entire tundish has a complicated structure. A heater capable of heating at this temperature is expensive.
{circle around (2)} An apparatus for heating the entire tundish is complicated.
{circle around (3)} Since the heat capacity of a tundish is large, heating takes long time and hence decreases the production efficiency.
{circle around (4)} The heater may discharge electricity depending upon the vacuum degree in the melting furnace. There incurs, thus, a safety problem.
The present applicant proposed in European publication EP 0784350A1: a rapid cooling and centrifugal casting method of hydrogen-absorbing alloy by means of pouring the melt into a rotating cylindrical mold; a casting method, in which the poured melt rotates together with the rotation of the mold and solidifies at its surface during one rotation, and the pouring is successively carried out on the solidified surface; and a method for feeding the melt onto the inner surface of a mold from two or more nozzles located within the mold. An apparatus for carrying out these methods is shown in FIG. 2.
In FIG. 2, a tiltable melting furnace 12, a primary stationary tundish 13 a, a secondary reciprocating tundish 13 b, and a rotary cylindrical mold 14 are equipped within a vacuum chamber 10. The rotary cylindrical mold 14 is rotated by the rotary mechanism 16.
The melt flows from the melting furnace 12 through the primary stationary tundish 13 a and a secondary reciprocating tundish 13 b and is then poured into the rotary cylindrical mold 14. The ingot 15, which is cylindrical material, is cast into the inner surface of the rotary cylindrical mold 14. The tundish 13 b inserted into the rotary cylindrical mold 14 is provided with several nozzles 17. The tundish 13 b is reciprocated so as to rapidly and uniformly feed the melt over the inner surface of the mold.
The present inventors considered the following refractory materials: refractory material for stably feeding the melt of a rare-earth alloy in the strip-casting method; refractory material for feeding a small amount of melt onto a rotary mold in the centrifugal casting method: refractory material for feeding the melt through a thin nozzle in the single-roll melt quenching method; and, in addition, the refractory material for decreasing the temperature drop of the melt fed in small amounts. As a result, the present inventors discovered that virtually no reaction between the melt and Al₂O₃—SiO₂based refractory material or ZrO₂based refractory material occurs; and, further, no preliminary heating is necessary in the casting. The present invention was thus arrived at.

DISCLOSURE OF INVENTION

The refractory material for casting a rare-earth alloy according to the present first invention is characterized by the following (1)-(3).
(1) The content of Al₂O₃and SiO₂
The refractory material of the present first invention is based on Al₂O₃—SiO₂. The content of Al₂O₃based on the weight of the total components including a binder and the like is 70 wt % or more. The content of SiO₂is 30 wt % or less. Since the heat resistance is enhanced with the increase in the content of the refractory constituent Al₂O₃, the Al₂O₃content amounting to 70 wt % or more is necessary to impart to the refractory material sufficient heat resistance in the temperature range of 1200° C. to 1500° C. On the other hand, the post-shaping formability of the refractory material is enhanced with the increase in the SiO₂content, and fracture of the refractory material is difficult to occur when subjected to thermal impact during casting. However, since the Al₂O₃content is lowered with the increase in the SiO₂content, the heat-resistant temperature of the refractory material is lowered. For this reason, the SiO₂content should be 30 wt % or less. Preferably, the Al₂O₃content is 80 wt % or more, and the SiO₂content is 20 wt % or less.
In the refractory material of the present first invention, the Al₂O₃and SiO₂are preferably 90 wt % or more of the total refractory material, the balance being impurities and incidental elements.
(2) Bulk Density and Thermal Conductivity
The heat of the rare-earth alloy melt is abstracted by the refractory material. A considerable temperature drop of the melt occurs during the casting process. In extreme cases, a state of complete solidification or semi-solidification is incurred. In order to prevent this, the refractory material should be as porous as possible so as to decrease the thermal conductivity. The thermal conductivity at from 1200 to 1400° C., which is a representative temperature range of the melt at the casting of a rare-earth alloy, is particularly important. Therefore, the bulk density of the refractory material is set at 1 g/cm³or less, and the thermal conductivity in the temperature range of from 1200 to 1400° C. is set at 0.5 kcal/(mh° C.) or less. Preferably, the bulk density of the refractory material is 0.5 g/cm³or less.
In order to decrease the thermal conductivity to as low a level as possible, alumina fiber (3.87 g/cm³of true density) is more preferred than alumina powder which is liable to be densely packed. The content of alumina fiber is preferably 70 wt % or more. Particularly, the direction of alumina fibers should not be aligned but the alumina fibers should be randomly arranged and entwined. Similarly, the thermal conductivity can be decreased by means of adjusting the refractory components such that 70 wt % or more of alumina fiber and mullite fiber (3.16 g/cm³of true density) in total is contained in the refractory material. Incidentally, the SiO₂is contained in the mullite fiber. In addition, the SiO₂may be contained in the refractory material as colloidal silica or colloidal mullite.
(3) Ignition Weight Loss
Ordinarily, the refractory material is shaped by using an organic binder such as resin or an inorganic binder such as water glass. The so-shaped refractory material is used without removing such binder. Therefore, when the refractory material as shaped is used, the organic binder is decomposed into such organic gases as N₂, CO, CO₂and the like and H₂O, which are brought into reaction with the melt, so that the flowability of the melt is impaired. In addition, bonded water, carbon dioxide and the like are dissociated from the easily decomposable inorganic compounds and exert similar influence. When the flowability of the melt is severely impaired, the melt solidifies in the tundish. It is, therefore, extremely important to preliminarily remove the organic binder and the like from the refractory material as completely as possible. The present invention is, therefore, characterized in that the ratio of ignition weight loss under the heating condition of 1400° C. for 1 hour is 0.5 wt % or less. Incidentally, a part of Al₂O₃may be replaced with ZrO₂, TiO₂, CaO and MgO provided that the conditions of the above-mentioned bulk density, thermal conductivity and ratio of ignition weight loss are fulfilled. Preferable upper limit of these component(s) is 5 wt % in total. Impurities such as FeO, Fe₂O₃, Fe₃O₄, Na₂O, K₂O and other inevitable impurities may be contained in a range not exceeding 5wt %.
Next, the refractory material for casting a rare-earth alloy according to the present second invention is characterized in the following (4)-(6).
(4) Contents of ZrO₂, and Y₂O₃, Ce₂O₃, CaO, MgO, Al₂O₃, TiO₂or SiO₂The refractory material, of the present second invention is based on ZrO₂. The content of ZrO₂based on the total components including a binder and the like is characterized by 70 wt % or more, and one or more of Y₂O₃, Ce₂O₃, CaO, MgO, Al₂O₃, TiO₂and SiO₂is characterized by 30 wt % or less. Pure ZrO₂has a monoclinic structure at from room temperature to 1170° C., is a distorted tetragonal at from 1170 to 2370° C., and is cubic in the form of a fluorite structure at 2370° C. or higher. Along with the transformation from the tetragonal to monoclinic structure at 1170° C. in the cooling, volume expansion by 4% takes place. ZrO₂cracks and finally is ruptured as long as it is kept pure (for example, K. Nakajima, S. Shimada: Solid State Ionics, Vol. 101-103, p 131-135 (1997)). Its structure is, therefore, modified to an isometric system, where no volume expansion takes place, to prevent rupture. For this purpose, one or more of Y₂O₃, Ce₂O₃, CaO or MgO, is added to and substitution-dissolved in ZrO₂. The so-stabilized zirconia is preferably used. In addition, addition of one or more of Al₂O₃, TiO₂and SiO₂is effective for improving the heat resistance and durability of the mechanical properties. Their addition amount is limited to 30 wt % or less, for the following reasons: rupture is satisfactorily prevented; the solute amount of these components in ZrO₂is limited; Y₂O₃and Ce₂O₃are expensive; and the further addition of CaO, MgO, Al₂O₃, TiO₂and SiO₂added in a large amount enhances reactivity with the melt. More preferable addition amount of these in large amount components is in the range of from 1 to 15 wt %.
Actually, SiO₂is bonded with ZrO₂and is present as ZrSiO₄. In the refractory material of the present second invention, the total of ZrO₂, and one or more of Y₂O₃, Ce₂O₃, CaO, MgO, Al₂O₃, TiO₂and SiO₂is preferably 85 wt % or more based on the total of the refractory material. The balance is impurities and incidental elements.
(5) Bulk Density and Thermal Conductivity
This is the same as in the first invention and hence its description is omitted.
(6) Ignition Weight Loss
Impurities, such as FeO, Fe₂O₃, Fe₃O₄, Na₂O, K₂O, HfO₂, C and other inevitable impurities may be contained in an amount not exceeding 5 wt %. Except this point, the same as in item (3), above.
Production Method of Refractories
Next, the method for producing the refractory material according to the present first invention resides in a method in which one or more selected from alumina, mullite and silica, and one or more binders selected from an inorganic binder and an organic binder are mixed to prepare a mixture, so as to provide 70 wt % or more of Al₂O₃and 30 wt % or less of SiO₂in the refractory material, and the mixture is shaped, dried and is further heat-treated at 1000° C. to 1400 ° C.
Although alumina, silica and mullite are not limited the fiber material, it is preferable to use the fiber material in the mixture at least one of alumina fiber, silica fiber and mullite fiber.
According to one embodiment of the production method of the present invention, one or more selected from alumina fiber, mullite fiber and silica fiber is first blended. For example, a combination of alumina fiber and silica fiber and a combination of alumina fiber and mullite fiber are possible. In addition, one or more of an organic binder and an inorganic binder are mixed to prepare a mixture, which is then shaped. It is necessary that the blending amount of the respective components in the mixture is such as to provide 70 wt % or more of Al₂O₃and 30 wt % or less of SiO₂in the refractory material. In a case of using a SiO₂-containing binder such as water glass, the total amount of SiO₂from the binder and fiber should attain the predetermined amount.
For example, water glass, colloidal silica and the like can be used as the inorganic binder. For example, ethyl silicate, ethyl cellulose and triethylene glycol can be used as the organic binder. These two kinds of binder may be used together. In this case, the dried strength of a shaped body and its bonding strength at high temperature can be further enhanced. Here, the amount of binder is preferably from 1 to 30 weight parts based on 100 weight parts of the fiber. With regard to the proportion within a binder, the organic binder is preferably from 50 to 100 weight parts based on 100 weight parts of the total binder.
Subsequently, the mixture of fiber and binder is shaped by means of a press, stamp or the like into the shape of a tundish, trough, nozzle and the like. Alternatively, the mixture may be shaped into a simple shape such as a sheet, a cylindrical column or a cylindrical tube, which enables the post-heating forming into a tundish, a trough, a nozzle and the like. Subsequently, sufficient natural drying is carried out to attain hardness which would withstand subsequent handling. The heat treatment is then carried out, thereby promoting the bonding of the fiber and, in addition, decomposing the organic matters in the shaped body to form a porous structure. Since the organic matter decomposes at approximately 400-800° C., the porous structure is obtained by the heat treatment at this temperature. However, in order to sufficiently remove the organic binder, the shaped body must be heat-treated at 1000° C. to 1400° C. When the heating temperature is less than 1000° C., the decomposition of the organic matter is incomplete, resulting in impairment of the flowability of the melt. On the other hand, when the heating temperature exceeds 1400° C., the shaped body is sintered and embrittles, thereby making its handling difficult. In addition, the shaped body is not resistant against the thermal impact while the melt is flowing and is liable to crack.
Subsequently, according to the method for producing refractory material of the present second invention, one or more selected from the zirconia fiber, the zirconia whisker, stabilized zirconia fiber and stabilized zirconia whisker, and inorganic and/or organic binder are mixed in such a manner to provide 70 wt % or more of ZrO₂, and 30 wt % or less of one or more of Y₂O₃, Ce₂O₃, CaO, MgO, Al₂O₃, TiO₂and SiO₂in the refractory material, the mixture is shaped, dried and hardened and then heat-treated at 1000° C. to 1400° C.
In the method according to the present invention, one or more selected from zirconia and stabilized zirconia is blended. A part or all of either or both of the zirconia and stabilized zirconia is preferably fiber and/or whisker. For example, only stabilized zirconia fiber may be used, or the zirconia fiber and stabilized zirconia fiber may be combined. Further, a mixture, in which one or more of the organic and inorganic binder is mixed, is shaped. The blending amount of the respective components in the mixture must be to provide 70 wt % or more of ZrO₂, and 30 wt % or less of total of one or more of Y₂O₃, Ce₂O₃, CaO, MgO, Al₂O₃, TiO₂and SiO₂in the refractory material. When a SiO₂-containing binder is used such as water glass, the total of SiO₂from the binder, fiber and whisker should attain the predetermined amount.
The other matters are the same as in the first invention.
The refractory material according to the present first and second invention, for casting the melt of rare-earth alloys is limited from the aspects of composition, bulk density, thermal conductivity and ignition weight loss as described above. Thus, the requirements of heat resistance, flowability of melt, fracture resistance and the thermal impact resistance can be met.
Casting Method
The method for casting a rare-earth alloy according to the present invention is characterized in that the melt of a rare-earth alloy is poured onto the surface of a rotary roll via a pouring means, such as a tundish, a trough and a nozzle, which are the shaped refractory material of the first and second invention, thereby producing a sheet, a strip, thin pieces and the like having preferably from 0.1 to 1 mm of thickness. In addition, the method according to the present invention is characterized in that a cylindrical material having preferably from 1 to 20 mm of thickness is produced by means of pouring melt on the inner surface of a rotary cylinder.
The rare-earth alloy indicates an alloy for the rare earth magnets, particularly an alloy for an R—Fe—B based magnet, an R—Ni based hydrogen-absorbing alloy, alloy for an Sm—Co based magnet and the like. Alloy for an R—Fe—B magnet having a composition of 23.0% of Nd, 6.0% of Pr, 1.0% of Dy, 1.0% of B, 0.9% of Co, 0.1% of Cu, 0.3% of Al, and the balance of Fe can be cast. An R—Ni based hydrogen-absorbing alloy having a composition of 8.7% of La, 17.1% of Ce, 2.0% of Pr, 5.7% of Nd, 1.-3% of Co, 5.3% of Mn, 1.9% of Al, and the balance of Ni can be cast. Alloy for an Sm—Co magnet having a composition of 25.0% of Sm, 18.0% of Fe, 5.0% of Cu, 3.0% of Zr, and the balance of Co can be cast. The present invention is, however, not limited to these compositions.
The above-described tundish is a vessel which receives a melt of the rare-earth alloy from a melting furnace or a ladle, and which is provided with a pouring aperture for adjusting the pouring speed required for obtaining a thin-cast product. Since the amount of melt flowing on a tundish is small in the centrifugal casting method or a strip-casting method, the above-described heat-abstraction problems of the melt occur. Next, a trough is a form of the tundish used in the centrifugal casting method and the strip-casting method for guiding the melt into a tundish, in a case where the melting furnace and the tundish are located considerably distant. A nozzle is a pouring aperture provided in the tundish or trough described above or a passage means for guiding the melt onto a rotary roll. Particularly, the nozzles of a tundish used for the centrifugal casting enable control of the accumulating speed of the melt on the inner surface of the rotary cylinder. In addition, when a tundish is used for the strip-casting, the melt in the form of laminar flow can be poured on a single roll or twin rolls at a constant speed. When the amount of melt per pouring is as small as a few tens of kg, the melt may be directly fed from a vessel such as a ladle onto the rotary roll or the like and not via a tundish or trough. When the refractory material according to the present invention is used for a tundish or the like, since the flowability of the melt is improved, the thickness distribution of the thin pieces produced by the casting as well as its structure is homogeneous. In addition, the particle size of the alloy powder for the magnet prepared by crushing the thin pieces, is constant. The final product, i.e., a magnet, can be expected to attain such effects that the magnetic properties are stabilized. Furthermore, by means of controlling the feeding speed of the melt, thin pieces can be easily thinned as small as 0.3 mm or less, in the case of, for example, a strip-casting method. In this case, since the solidification speed of the rare-earth alloy is rapid, fine microstructure can be formed.
Preferable conditions in the casting method are described. Appropriate pouring temperature of the melt into a tundish or the like is 1300 to 1600° C. Preferably, the temperature is from 1350 to 1500° C. in the case of an alloy for an R—Fe—B magnet, an example of which composition is shown above, the temperature is from 1350 to 1500° C. in the case of the R—Ni based hydrogen-absorbing alloy, an example of the composition is shown above, and the temperature is from 1350 to 1500° C. in the case of alloy for the Sm—Co based magnet, an example of the composition is shown above.
In the case of strip casting, the tapping temperature of the melt into a tundish or the like is as follows: 1300˜1450° C. in the case of an alloy for an R—Fe—B magnet, an example of which composition is shown above, the temperature is from 1300 to 1450° C. in the case of the R—Ni based hydrogen-absorbing alloy, an example of the composition is shown above, and the temperature is from 1300 to 1450° C. in the case of alloy for the Sm—Co based magnet, an example of the composition is shown above.
The pouring amount of the melt is determined from the area of a rotary cylinder, its rotation speed, and the desired casting thickness. After pouring of the melt, a sheet, a strip, a cylindrical material and the like can be crushed into flake form.
In the present invention, although the pouring speed of the melt is very low, the melt of a rare-earth alloy can be cast without preliminarily heating the tundish, the trough and the like. In addition, improved flow of the melt can be realized during the casting without thermally insulating the tundish, trough and the like. Considerable time and caution are required for such preparation operations as pre-heating. Thermal insulation of a tundish necessary to maintain the casting condition relies on experience, in the case of a conventional casting method. When these facts are considered, the casting method according to the present invention can be said to be considerably advanced from the aspects of operability and stability.

BRIEF EXPLANATION OF DRAWINGS

FIG. 1 is a drawing for illustrating a strip casting method.
FIG. 2 is a drawing for illustrating a conventional centrifugal casting method.
FIG. 3 is a drawing of a tundish used in the examples and comparative examples.

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES AND COMPARATIVE EXAMPLES OF FIRST INVENTION

The present invention is described more in detail by way of examples.
The constituent components of the refractory material used in Examples 1-4 and Comparative Examples described below had the following properties.
Alumina fiber: 5 μm of average diameter, 0.5 mm of average length.
Mullite fiber: 5 μm of average diameter, 0.5 mm of average length.
Colloidal silica: 3 to 4 μm of average diameter
Colloidal mullite: 3 to 4 μm of average diameter
Alumina particle: 3 to 4 μm of average diameter
Mullite particle: 3 to 4 μm of average diameter
Ethyl silicate 40, which is a representative ethyl silicate, was used as the binder.

Example 1

Alumina, mullite and silica were blended to provide the refractory construction as described in Table 1. A binder in 15 weight parts was blended to 100 weight parts of the resultant fiber mixture. The fiber mixture and the binder were sufficiently mixed to provide a slurry mixture. It was then shaped by a press machine into material in the form of a trough-shaped tundish. After hardening by natural drying, heat treatment was carried out at the heat-treating temperature shown in Table 1. The tundish 1 has a shape shown in FIG. 3. The dimension of the respective parts was: 360 mm of width (w), 125 mm of height (h), 900 mm of length (l), 100 mm of depth of the melt-flowing portion (h₁), 310 mm of the upper width (w₁), and 300 mm of the bottom width (w₂).
In Table 1 are shown the chemical analysis results of Al₂O₃and SiO₂, bulk density, and the maximum thermal conductivity at 1200 to 1400° C. In addition, a sample was taken from the tundish and was ignited at 1400° C. for 1 hour. The measured weight loss is also shown in Table 1.
NdFeB alloy, having 1450° C. of temperature directly before the casting (tapping temperature) was caused to flow from one end of the tundish 3, while adjusting the melt feeding amount in such a manner to attain 0.5 mm of thickness of the melt 2. The melt was cast from the other end of the tundish onto a strip-casting roll in total amount of 100 kg. The melt flowed normally without solidification on the tundish. Incidentally, no preliminary heating of the tundish was carried out. When the condition of the tundish was examined after completion of casting, neither discoloring nor foreign matters suggesting its reaction with the melt, were recognized.
In addition, the easiness of melt flow was defined by the following formula. The defined flowing coefficient was 0.67.
Flowing coefficient=actual flowing speed of melt through a nozzle, which melt is stored in the tundish and generating a constant head pressure/theoretical flowing speed of melt under the same condition flowing through a nozzle, calculated by Bernoulli's theorem.
The theoretical flowing speed (v) shown in this equation is calculated by the following formula, provided that the gravitational acceleration is expressed by g and the height of melt stored in a tundish is expressed by h.
V=√(2 gh)

Example 2

A tundish consisting of the same refractory material as in Example 1 was used in the same strip-casting method as in Example 1 to cast a Mm (misch metal) Ni-based alloy (1450° C. of tapping temperature). The melt flowed normally on the tundish without solidifying on the tundish. The flowing coefficient at this time was 0.67.
When the condition of the tundish was examined after completion of casting, neither discoloring nor foreign matters suggesting its reaction with the melt, were recognized.

Example 3

A tundish consisting of the same refractory material as in Example 1 was used in the same strip-casting method as in Example 1 to cast an Sm Co-based alloy (1450° C. of tapping temperature). The melt flowed normally on the tundish without solidifying on the tundish. The flowing coefficient at this time was 0.71.
When the condition of the tundish was examined after completion of casting, reaction with the melt was not recognized.

Comparative Example 1

A tundish consisting of the refractory material described in Table 1 was manufactured by the same method as in Example 1. It was attempted to cast an NdFeB-based alloy by the same strip-casting method as in Example 1. However, during the course of casting, the flowability of the melt was gradually impaired, finally resulting in solidification. The flowing coefficient during the melt flow with difficulty was 0.26. Incidentally, the heating condition of this refractory material was 800° C. for 1 hour. The ratio of ignition weight loss at 1400° C. was 4.0 wt %.

Comparative Example 2

The refractory material having the same composition as that of Example 1 was formed into the same tundish as in Example 1. The heating temperature of the refractory material was 1500° C. for 1 hour. The refractory material was frequently broken during the forming.

Example 4

A tundish consisting of the refractory material described in Table 1 was produced by the same method as in Example 1 and was used to cast an NdFeB-based alloy by the same strip-casting method as in Example 1. The melt flowed normally on the tundish without solidifying on the tundish. The temperature of the melt directly before the casting (tapping temperature) was 1450° C. The flowing coefficient at this time was 0.77. Preliminary heating of the tundish was not carried out.
When the condition of the tundish was examined after completion of casting, its reaction with the melt was not recognized.

Comparative Example 3

A tundish consisting of the refractory material described in Table 1 as Comparative Example 3 was manufactured by the same method as in Example 1. It was attempted to cast NdFeB based alloy by the same strip-casting method as in Example 1 using the tundish. However, during the course of casting, the flowability of the melt was gradually impaired, finally resulting in solidification. The flowing coefficient during the melt flow with difficulty was 0.29. Incidentally, the heating condition of this refractory material was 800° C. for 1 hour. The ratio of ignition weight loss at 1400° C. was 4.0 wt %.

Comparative Example 4

The refractory material having the composition described in Table 1 as Comparative Example 4 was formed into a tundish by the same method, as in Example 1. The heat treating condition of the refractory material was 1500° C. for 1 hour. The refractory material was frequently broken during the forming.

Comparative Example 5

The refractory material described in Table 1 as Comparative Example 5 was used to form a tundish by the same method as in Example 1. NdFeB-based alloy was cast by the same strip-casting method as in Example 1. The melt flowed on the tundish without solidification. However, during the course of casting, melt leaked through the bottom of the tundish. The flowing coefficient, in which the melt leakage was corrected, was 0.45. When the condition of the tundish was examined after completion of casting, the tundish was broken to form an aperture. The circumference of the aperture was discolored in a broad range. When the tundish was broken to examine the fractured plane, it turned out that almost all parts of the tundish brought into contact with the melt, but not the aperture portion, were discolored. It turned out, thus, a reaction between the melt and the tundish occurred during the casting. It was presumed from this fact that a reason for the lower flowing coefficient than in Example 1 was attributable to the reaction of the melt with the tundish, which impaired melt flowability.

Comparative Example 6

The refractory material described in Table 2 as Comparative Example 6 consisted of alumina fiber, colloidal mullite and crushed particles of the ordinary alumina refractory material. The refractory material was formed into a tundish by the same, method as in Example 1. NdFeB-based alloy was cast by the same strip-casting method as in Example 1 while using the tundish mentioned above. From the beginning, the melt flowability was poor, and the melt solidified before it was appreciably cast. The flowing coefficient during the melt flow with difficulty was 0.24.

Comparative Example 7

The refractory material described in Table 2 as Comparative Example 7 consisted of alumina fiber, mullite fiber,- colloidal mullite and crushed particles of the ordinary alumina refractory material. The refractory material was formed into a tundish by the same method as in Example 1. NdFeB alloy was cast by the same strip casting method as in Example 1. From the beginning, the melt flowability was poor, and the melt solidified before it was appreciably cast. The flowing coefficient during the melt flow with difficulty was 0.24.

Comparative Example 8

The ordinary refractory material described in Table 3 as Comparative Example 8 was formed into a tundish as in Example 1. It was attempted to produce NdFeB-based alloy by the same strip-casting method as in Example 1. However, as soon as the melt began to flow on the tundish, solidification took place. The casting became thus impossible. After that, the alloy left in the tundish was removed and the condition of the tundish was examined. No reaction of the tundish with the melt was recognized.

Comparative Example 9

The ordinary refractory material described in Table 3 as Comparative Example 9 was formed into a tundish as in Example 1. It was attempted to produce NdFeB-based alloy by the same strip-casting method as in Example 1. However; as soon as the melt began to flow on the tundish, solidification took place. The casting became thus impossible. After that, the alloy left in the tundish was removed and the tundish was broken to observe the fractured plane. Discoloring extended partly into the inner portion of the tundish. The reaction of the tundish with the melt was, therefore, recognized.

EXAMPLES AND COMPARATIVE EXAMPLES OF SECOND INVENTION

The constituent components of refractory material used in Examples 5-26 and Comparative Examples 10-29 described below had the following properties.
Zirconia fiber: 5 μm of average diameter, 1.5 mm of average length.
Zirconia whisker: 5 μm of average diameter, 500 μm of average length.
Stabilized zirconia fiber: 5 μm of average diameter, 1.5 mm of average length.
Stabilized zirconia whisker: 5 μm of average diameter, 500 μm of average length.
Ethyl silicate 40, which is a representative ethyl silicate, was used as the binder.

Example 5

ZrO₂, Y₂O₃and SiO₂were blended to provide the refractory construction as described in Table 4. A binder in 15 weight parts was blended with 100 weight parts of the resultant fiber mixture. The fiber mixture and the binder were sufficiently mixed to provide a slurry mixture. It was then shaped by a press machine into material in the form of a trough-shaped tundish. After hardening by natural drying, heat treatment was carried out at the heat-treating temperature shown in Table 4. The tundish 3 had the shape shown in FIG. 3. The dimensions of the respective parts were the same as that of the examples and comparative examples of the first invention.
In Table 4 are shown the chemical analysis results of ZrO₂, Y₂O₃and SiO₂, bulk density, and the maximum thermal conductivity at 1200 to 1400° C. In addition, a sample was taken from the tundish and was ignited at 1400° C. for 1 hour. The measured weight loss is also shown in Table 4.
NdFeB alloy, having 1450° C. of temperature directly before the casting (tapping temperature) was caused to flow from one end of the tundish 1, while adjusting the melt feeding amount to attain 0.5 mm of thickness of the melt 2. The melt was cast from the other end of tundish onto a strip-casting roll in total amount of 100 kg. The melt flowed normally without solidification on the tundish. Incidentally, no preliminary heating of the tundish was carried out. When the condition of the tundish was examined after completion of casting, neither discoloring nor foreign matters suggesting its reaction with the melt, were recognized.
In addition, the easiness of melt flow in terms of the flowing coefficient defined in Example 1 was 0.71.

Example 6

A tundish consisting of the same refractory material as in Example 5 was used in the same strip-casting method as in Example 5 to cast a Mm (misch metal) Ni-based alloy (1450° C. of tapping temperature). The melt flowed normally on the tundish without solidifying on the tundish. The flowing coefficient at this time was 0.71.
When the condition of the tundish was examined after completion of casting, reaction of the tundish with the melt was not recognized.

Example 7

A tundish, consisting of the same refractory material as in Example 5, was used in the same strip-casting method as in Example 5 to cast an Sm Co-based alloy (1450° C. of tapping temperature). The melt flowed normally on the tundish without solidifying on the tundish. The flowing coefficient at this time was 0.77.
When the condition of the tundish was examined after completion of casting, reaction of the tundish with the melt was not recognized.

Examples 8-26

The tundishes consisting of the refractory material described in Table 4 were produced by the same method as in Example 5 and were used in the same strip-casting method as in Example 1 to cast an NdFeB-based alloy. The melt flowed normally on every tundish without solidifying on it. The tapping temperature was 1450° C. The flowing coefficients at these castings are shown in Table 4. Incidentally, preliminary heating of the tundishes was not carried out.
When the condition of the tundish was examined after completion of casting, reaction of the tundish with the melt was not recognized.

Comparative Examples 10-17

The tundishes consisting of the refractory material described in Table 5 were used. It was attempted to cast an NdFeB-based alloy by the same strip-casting method as in Example 5. However, in case of each tundish, during the course of casting, the flowability of melt was gradually impaired, finally resulting in solidification. The flowing coefficient during the melt flow with difficulty was 0.27-0.30. Incidentally, the heating condition of this refractory material was 800° C. for 1 hour. The ignition weight loss at 1400° C. was 4.0 wt % in each tundish.

Comparative Examples 18-25

The refractory materials having the compositions shown in Table 5 were formed into tundishes as in Example 5. The heating temperature of the refractory material was 1500° C. for 1 hour. Every tundish was frequently broken during the forming.

Comparative Example 26

A tundish consisting of refractory material described in Table 5 as Comparative Example 26 was used. NdFeB-based alloy was cast by the same strip casting method as in Example 5. The melt flowed on the tundish without solidification. However, during the course of casting, melt leaked through the bottom of the tundish. The flowing coefficient, in which the melt leakage was corrected, was 0.43. When the condition of the tundish was examined after completion of casting, the tundish was broken to form an aperture. The circumference of the aperture was discolored in a broad range. When the tundish was broken to examine the fractured plane, it turned out that almost all parts of the tundish brought into contact with the melt but not the aperture portion was discolored. It turned out, thus, a reaction between the melt and tundish occurred during the casting. It was presumed from this fact that a reason for the lower flowing coefficient than in Example 5 was attributable to the reaction of the melt with the tundish, which impaired melt flowability.

Comparative Examples 27-28

The ordinary refractory material described in Table 6 as Comparative Examples 27-28 were formed into tundishes as in Example 5. It was attempted to produce NdFeB based alloy by the same strip-casting method as in Example 5. However, as soon as the melt began to flow on the tundish, solidification took place and the casting was impossible. After that, the alloy left in the tundish was removed and the condition of tundish was examined. No reaction of the tundish with the melt was recognized.

Comparative Example 29

The ordinary refractory material described in Table 6 as Comparative Example 29 was formed into a tundish as in Example 5. It was attempted to produce NdFeB-based alloy by the same strip-casting method as in Example 5. However, as soon as the melt began to flow on the tundish, solidification took place and the casting was impossible.

INDUSTRIAL APPLICABILITY

According to the present invention, it is possible to stably produce the alloys, which are optimum for the raw materials of rare-earth magnets, without a complicated process and apparatus. The present invention is, therefore, extremely useful. In addition to this alloy, quality control at the casting of various rare-earth alloys is facilitated.

TABLE 4


Main Components and Properties of Refractories

Construction, Construction

Stabilized

Zirconia

Main Components

Fiber

Whisker

Fiber

Whisker

ZrO₂

Y₂O₃

Ce₂O₃

CaO

MgO

Al₂O₃

TiO₂

SiO₂

wt %

Example 5	—	—	100	—	91	8	—	—	—	—	—	0.2
Example 6	—	—	100	—	91	8	—	—	—	—	—	0.2
Example 7	—	—	100	—	91	8	—	—	—	—	—	0.2
Example 8	—	—	100	—	86	13	—	—	—	—	—	0.2
Example 9	10	—	90	—	92	7	—	—	—	—	—	0.2
Example 10	40	—	60	—	94	5	—	—	—	—	—	0.2
Example 11	—	—	100	—	91	—	8		—	—	—	0.2
Example 12	—	—	100	—	94	—	—	5	—	—	—	0.2
Example 13	—	—	100	—	94	—	—	—	5	—	—	0.2
Example 14	—	—	100	—	94	—	—	—	—	5	—	0.2
Example 15	—	—	100	—	94	—	—	—	—	—	5	0.2
Example 16	—	—	100	—	88	8	—	—	—	—	—	5
Example 17	—	—	100	—	75	4	—	—	—	20	—	—
Example 18	—	—	100	—	91	8	—	—	—	—	—	0.2
Example 19	—	—	100	—	91	8	—	—	—	—	—	0.2
Example 20	10	—	90	—	82	7	—	—	—	5	—	5
Example 21	—	—	90	10	91	8	—	—	—	—	—	0.2
Example 22	—	—	50	50	91	8	—	—	—	—	—	0.2
Example 23	—	—	—	100	91	8	—	—	—	—	—	0.2
Example 24	—	10	90	—	91	8	—	—	—	—	—	0.2
Example 25	5	5	90	—	92	7	—	—	—	—	—	0.2
Example 26	5	5	80	10	92	7	—	—	—	—	—	0.2

	Ratio of
	Ignition

Bulk	Thermal		Weight		Flowing
Density	Conductivity	Heat	Loss	Cost	Coefficient
g/cm³	kcal/(mh ° C.)	Treatment	wt %	Alloy	of Melt

Example 5	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 6	0.48	0.16	1300° C. 1 hour	<0.1	Mn-Ni	0.71
Example 7	0.48	0.16	1300° C. 1 hour	<0.1	SmCo	0.77
Example 8	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 9	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 10	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 11	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 12	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.66
Example 13	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.65
Example 14	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.63
Example 15	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.64
Example 16	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.62
Example 17	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.67
Example 18	1.1	0.25	1300° C. 1 hour	<0.1	NdFeB	0.66
Example 19	1.4	0.44	1300° C. 1 hour	<0.1	NdFeB	0.59
Example 20	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 21	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 22	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 23	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 24	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 25	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71
Example 26	0.48	0.16	1300° C. 1 hour	<0.1	NdFeB	0.71

TABLE 5


Construction, Main Components and Properties of Refractories

Construction

			Stabilized	Stabilized
	Zirconia	Zirconia	Zirconia	Zirconia	Main Components

	Fiber	Whisker	Fiber	Whisker	ZrO₃	Y₁O₁	Cr₂O₃	CaO	MgO	Al₃O₃	TiO	SiO₃
	wt %	wt %	wt %	wt %	wt %	wt %	wt %	wt %	wt %	wt %	wt %	wt %

Comparative	—	—	100	—	91	8	—	—	—	—	—	0.2
Example 10
Comparative	10	—	90	—	82	7	—	—	—	5	—	5
Example 11
Comparative		10	90	—	82	7	—	—	—	5	—	5
Example 12
Comparative	—	—	90	10	91	8	—	—	—	—	—	0.2
Example 13
Comparative	—	—	80	80	91	8		—	—	—	—	0.2
Example 14
Comparative	—	—	—	100	91	8	—	—	—	—	—	0.2
Example 15
Comparative	8	8	90	—	82	7	—	—	—	5	—	5
Example 16
Comparative	8	8	80	10	92	7	—	—	—	—	—	0.2
Example 17
Comparative	—	—	100	—	91	8	—	—	—	—	—	0.2
Example 18
Comparative	10	—	90	—	82	7	—			6	—	5
Example 19
Comparative	—	10	90	—	82	7	—	—		6	—	5
Example 20
Comparative	—	—	90	10	91	8	—	—	—	—	—	0.2
Example 21
Comparative	—	—	80	80	91	8	—	—	—	—	—	0.2
Example 22
Comparative		—	—	100	91	8	—	—	—	—	—	0.2
Example 23
Comparative	6	6	90	—	82	7	—	—	—	8	—	6
Example 24
Comparative	6	6	80	10	92	7		—	—	—	—	0.2
Example 25
Comparative	—	—	100	—	89	—	—	—	—	20		20
Example 26

				Ratio of
				Ignition
	Bulk	Thermal		Weight		Flowing
	Density	Conductivity	Heat	Loss	Coal	Coefficient
	g/cm³	kcal(mA ° C.)	Treatment	wt %	Alloy	of Melt	Remarks

Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.27	Melt modified
Example 10							during coating
Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.30	Melt modified
Example 11							during coating
Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.30	Melt modified
Example 12							during coating
Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.27	Melt modified
Example 13							during coating
Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.27	Melt modified
Example 14							during coating
Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.27	Melt modified
Example 15							during coating
Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.30	Melt modified
Example 16							during coating
Comparative	0.48	0.16	800° C. 1 hour	4.0	NedFeB	0.30	Melt modified
Example 17							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 18							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 19							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 20							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 21							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 22							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 23							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 24							during coating
Comparative	0.48	0.16	1600° C. 1 hour	<0.1	—	—	Refractories fracial
Example 25							during coating
Comparative	0.48	0.16	1300° C. 1 hour	<0.1	NedFeB	0.43	Maltreated with
Example 26							refractories

TABLE 6


Main Components and Properties of Refractories

Main Components

Bulk

Thermal

ZrO₂	Y₂O₃	Ce₂O₃	CaO	MgO	Al₂O₃	TiO	SiO₂	Density	Conductivity
wt %	wt %	wt %	wt %	wt %	wt %	wt %	wt %	g/cm³	kcal/(mh ° C.)

Comparative Example 27	91	8	—	—	—	—	—	—	2.4	3.4
Comparative Example 28	93	—	—	5	—	—	—	—	2.4	3.4
Comparative Example 29	91	—	—	5	—	—	—	—	5.3	7.6

Ratio of

Ignition

Flowing

Heat	Weight Loss	Cost	Coefficient
Treatment	wt %	Alloy	of Melt	Remarks

Comparative Example 27	none	<0.1	NdFeB	—	After casting start, immediate
					solidification
Comparative Example 28	none	<0.1	NdFeB	—	After casting start, immediate
					solidification
Comparative Example 29	none	<0.1	NdFeB	—	After casting start, immediate
					solidification

Claims

1-20. (canceled)

21. An apparatus for casting rare earth alloy comprising:

pouring means for receiving and pouring molten alloy, wherein said pouring means is composed of refractory material that consists of 70 wt % or more of Al₂O₃and 30 wt % or less of SiO₂has 1 g/cm³or less of bulk density, has 0.5 kcal/(mh° C.) or less of thermal conductivity in the temperature range from 1200 to 1400° C., and has 0.5 wt % or less of ratio of ignition weight-loss under the heating condition of 1400° C. for 1 hour.

22. The apparatus according to claim 21, wherein said refractory material contains 70 wt % or more of alumina fiber.

23. The apparatus according to claim 21, wherein said refractory material contains 70 wt % of alumina fiber and mullite fiber in total.

24. An apparatus for casting rare earth alloy, comprising:

pouring means for receiving and pouring molten alloy, wherein said pouring means is composed of refractory material that consists of 70 wt % or more of ZrO₂and 30 wt % or less of one or more of Y₂O₃, Ce₂O₃, CaO, MgO, Al₂O₃, TiO₂and SiO₂has 2 g/cm³or less of bulk density, has 0.5 kcal/(mh° C.) or less of thermal conductivity in the temperature range of from 1200 to 1400° C., and has 0.5 wt % or less of ratio of ignition weight loss under the heating condition of 1400° C. for 1 hour.

25. The apparatus according to claim 24, wherein said refractory material contains 70 wt % or more of one or more of zirconia fiber, zirconia whisker, stabilized zirconia fiber and stabilized zirconia whisker.

26. The apparatus according to claim 21, wherein said pouring means is a tundish.

27. The apparatus according to claim 26, wherein the refractory material contains 70 wt % of alumina fiber.

28. The apparatus according to claim 26, wherein the refractory material contains 70 wt % of alumina fiber and mullite fiber in total.

29. The apparatus according to claim 24, wherein said pouring means is a tundish.

30. The apparatus according to claim 29, wherein the refractory material contains 70 wt % or more of one or more of zirconia fiber, zirconia whisker, stabilized zirconia fiber and stabilized whisker.