Large superconductor and its intermediate, and method for...

Superconductor technology: apparatus – material – process – Precursor of high temperature superconductor material or...

Reexamination Certificate

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C505S234000, C505S238000, C505S451000

Reexamination Certificate

active

06627582

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a large bulk material of a rare-earth-element oxide superconductor and a method for manufacturing the same.
2. Description of the Related Art
As a conventional method of manufacturing a superconductive bulk material of REBa
2
Cu
3
O
x
system with which the present invention is concerned, there has been a melting method as represented by the Quench and Melt Growth method (Patent Registration No. 1869884 and Patent Registration No. 2556401). This method is as follows: first, materials are heated up to a temperature of the region where RE
2
BaCuO
5
phase or RE
4
Ba
2
Cu
2
O
10
phase and a liquid phase including Ba—Cu—O compounds as a main component coexist, then, the materials are cooled to a level immediately above a peritectic temperature at which the REBa
2
Cu
3
O
x
phase generates, the material are further cooled slowly to generate crystals, and nucleus generation and crystal orientation in the material are controlled by the cooling to obtain a large bulk. Based on this manufacturing method, it is possible to obtain a relatively large superconductor having a high transition current density (a current density per unit cross section as one of superconductive characteristics).
Further, as a method for manufacturing a much larger superconductive bulk material, there has been known a method for using one seed crystal and sequentially combining materials having different starting-temperatures of crystal-growth together, and controlling a nucleus formation, a crystal orientation and a crystal growth direction (conventional method 1) (Japanese Patent Application Laid-open Publication No. 5-170598). According to this method, it is possible to manufacture a material having a diameter exceeding 100 mm. This method, however, has a problem in that it takes a long time for a crystal growth, one month as a maximum, and has low productivity.
In the mean time, there has also been known a method for manufacturing a large material by growing a crystal from various seed crystals (conventional method 2). According to this method, a region for growing a crystal from each seed crystal becomes small, and therefore, this method has an advantage that it is possible to achieve a crystal growth in a relatively short time. Further, according to this method, a transition current density is high within a region (A) in which a crystal has grown from each seed crystal. However, as shown in FIG.
1
and
FIG. 2
, mainly a Ba—Cu—O compound and a Cu—O compound, or a segregated RE
2
BaCuO
5
phase or RE
4
Ba
2
Cu
2
O
10
phase are precipitated as excluded phases between the regions (A). As a result, the transition current density between these regions is lowered extremely. Therefore, this method has had a problem in that the characteristics of a superconductive bulk material manufactured by this method are extremely inferior to those of a material manufactured by the conventional method 1, as a total superconductive bulk unit. As a method of improving this situation, it has been reported that the distributing the seed crystals with smaller intervals (about 5 mm) between them will make it difficult to generate impurity phases. According to this improvement method, the whole surface for a crystal growth must be embedded with the seed crystals. Thus, this method has not been practical from the viewpoint of productivity. Therefore, there has been demanded a superconductive bulk unit and a method for manufacturing this superconductive bulk unit that makes it difficult to generate, or that does not generate, an excluded phase between the regions (A).
SUMMARY OF THE INVENTION
It is, therefore, an object of the present invention to provide a large superconductive bulk material and a method for manufacturing this large superconductive bulk material capable of reducing or eliminating excluded phases such as a Ba—Cu—O compound and a Cu—O compound, or a segregated RE
2
BaCuO
5
phase or RE
4
Ba
2
Cu
2
O
10
phase that are precipitated between one region of crystal growth from one seed crystal and the other region of crystal growth from the other seed crystal, and capable of making a larger current to flow between the regions of crystal growth from the seed crystals.
The present invention solves the above problems. An oxide superconductor is structured by oxide superconductors of 123 phases of two or more kinds of different peritectic temperatures (Tp). Seed crystals are disposed at the oxide superconductor side having a highest Tp, and crystals are grown. Then, it has been found that excluded phases of a Ba—Cu—O compound and a Cu—O compound, or a segregated RE
2
BacuO
5
phase or RE
4
Ba
2
Cu
2
O
10
phase are generated in the layers of superconductors having a high Tp, and that these excluded phases do not propagate easily in the superconductor layers having a low Tp. Based on this finding, the present invention provides a superconductive bulk unit that has reduced or eliminated “excluded phases” that interrupt a current flow in the superconductive bulk unit, at the portion of the superconductive layers having lower Tp's. As a result, the superconductive bulk unit can make a larger current to flow based on the use of the superconductor layers having a low Tp.
According to a first gist of the present invention, there is provided a large superconductor intermediate of REBa
2
Cu
3
O
x
system (where RE is one kind or a combination of rare earth elements including Y), characterized by a structure that oxide superconductors having non-superconductive phases finely dispersed in REBa
2
Cu
3
O
x
phases (123 phases) of different peritectic temperatures (Tp) are laminated three-dimensionally in the order of Tp's, seed crystals mounted on the oxide superconductor layer having a highest Tp, and excluded phases included in at least the oxide superconductor having the high Tp.
In the present invention, the REBa
2
Cu
3
O
x
system (where RE is one kind or a combination of rare earth elements including Y) means that a base phase is not only REBa
2
Cu
3
O
x
, but also is (RE
1−z
Ba
z
)
1+y
Ba
2−y
Cu
3
O
x
(−0.5≦y≦1.0, 0≦z≦0.5). Further, this also includes a material of which a part of or the whole Ba has been substituted by Sr. Similarly, the REBa
2
Cu
3
O
x
(123) phases as the base phases include not only REBa
2
Cu
3
O
x
, but also (RE
1−z
Ba
z
)
1+y
Ba
2−y
Cu
3
O
x
(−0.5≦y≦1.0, 0≦z≦0.5). Further, they also include a material of which a part of or the whole Ba has been substituted by Sr.
The non-superconductive layer in the present invention means the RE
2
BaCuO
5
phase or the RE
4
Ba
2
Cu
2
O
10
phase finely distributed in the REBa
2
Cu
3
O
x
phases (123 phases) as the base phases. Further, the REBa
2
Cu
3
O
x
phases (123 phases) of different peritectic temperatures (Tp) means a oxide superconductor structured by composition powders of different Tp's having different peritectic temperatures (Tp) of the 123 phases by changing the RE compositions or changing the addition volumes of the added elements like Ag. Further, the structure obtained by a three-dimensional lamination means a lamination in layers, or a concentric structure, or a combination of these.
According to a second gist of the present invention, there is provided a large superconductor intermediate of the above first gist, wherein a deviation of a crystal orientation between the nearest seed crystals is within 30 degrees in the mounting of seed crystals. The nearest seed crystals in the present invention means the seed crystals that are located at the nearest positions among various disposed seed crystals. Further, the deviation in the crystal orientation means a minimum rotational angle that is necessary for matching a crystal orientation of a certain seed crystal with a crystal orientation of the nearest seed crystal by rotating these seed crystals in space.
According to a third gist of the present invention, there is provided a large superconductor intermediate of the above first or second gi

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