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

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 Al2O3 and 30 wt % or less of SiO2, or 70 wt % or more of ZrO2 and 30 wt % or less of one or more of Y2O3, Ce2O3, CaO, MgO, Al2O3, TiO2 and SiO2. The refractory material has 1 g / cm3 or 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 [0001] 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 [0002] 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 ...

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Benefits of technology

[0026] The refractory material of the present first invention is based on Al2O3—SiO2. The content of Al2O3 based on the weight of the total components including a binder and the like is 70 wt % or more. The content of SiO2 is 30 wt % or less. Since the heat resistance is enhanced with the increase in the content of the refractory constituent Al2O3, the Al2O3 content 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 SiO2 content, and fracture of the refractory material is difficult to occur when subjected to thermal impact during casting. However, since the Al2O3 content is lowered with the increase in the SiO2 content, the heat-resistant temperature of the refractory material is lowered. For this reason, the SiO2 content should be 30 wt % or less. Preferably, the Al2O3 content is 80 wt % or more, and the SiO2 content is 20 wt % or less.

[0034] (4) Contents of ZrO2, and Y2O3, Ce2O3, CaO, MgO, Al2O3, TiO2 or SiO2 The refractory material, of the present second invention is based on ZrO2. The content of ZrO2 based 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, TiO2 and SiO2 is characterized by 30 wt % or less. Pure ZrO2 has 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. ZrO2 cracks 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, TiO2 and SiO2 is 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 ZrO2 is limited; Y2O3 and Ce2O3 are expensive; and the further addition of CaO, MgO, Al2O3, TiO2 and SiO2 added 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 %.

[0043] 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.

[0051] 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.

[0055] 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.

Problems solved by technology

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.

This α-Fe seriously impairs the crushability of the alloy for the magnet, and hence causes composition variation at the crushing process.

The formation of a -Fe is difficult in such alloy.

In the production by a conventional book-mold casting method, additive elements are liable to micro-segregate.

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.

However, such thin tundish is not only difficult to produce but also would be difficult to handle as it may be liable to crack.

However, the following problems are involved in the tundish heating.

A heater capable of heating at this temperature is expensive.

② An apparatus for heating the entire tundish is complicated.

③ Since the heat capacity of a tundish is large, heating takes long time and hence decreases the production efficiency.

There incurs, thus, a safety problem.

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