JPH0547245A - Manufacturing device for high-temperature superconductive wire rod - Google Patents

Abstract

PURPOSE:To form a superconductive layer in the state where a base material is curved, and work a compression stress onto the base material after passing it through a sup port device to make the superconductive layer fine by forming the contact surface of a base material support device making contact with the base material into a convex surface, and providing a feed-out part and winding part in such a manner as to be capable of vertically inclining. CONSTITUTION:The inner parts of a film forming chamber 1, a feed part 2, and a delivery part 3 are vacuumized, and a carrier gas such as Ar is sent to a feed source 4 to evaporate a material powder for an intermediate layer 23, which is then sent to the film forming chamber 1. A tape base material 22 is also sent to the film forming chamber 1, passed on a support device 7, heated by a heater, and wound on a winding device 20 at a fixed speed. At this time, a cylinder device 21 is operated to regulate the inclinations of a feed-out part 2 and a winding part 3, and the base material 22 is moved along a convex surface provided on the device 7 upper surface. After the intermediate layer 23 is thus formed, the base material 22 is again moved from the winding device 20 to a feed-out device 19 and returned to the linear form, and an oxide superconductive layer 24 is formed on the intermediate layer 23 by use of an oxygen gas feeding device 27.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for producing a long high-temperature superconducting wire, and more particularly to an apparatus for forming a dense oxide superconducting layer by applying compressive stress to the formed oxide superconducting layer.

[0002]

2. Description of the Related Art Conventionally, as an example of a method for producing an oxide superconducting wire, a powder of an oxide superconductor is filled in a tubular sheath material such as silver, and plastic working such as drawing, swaging or rolling is performed on the tubular sheath material. There is known a method in which an oxide superconducting wire is manufactured by subjecting it to a wire rod to consolidate the powder, and subsequently subjecting the powder to heat treatment to react the elements contained in the compacted powder.

[0003]

In the oxide superconducting wire obtained by this manufacturing method, since the crystal orientation of the oxide superconductor produced is not uniform, the oxide superconductor itself has There was a problem that a high critical current density could not be obtained due to the crystal anisotropy (the property in which there is a direction in which current easily flows and a direction in which current does not easily flow depending on the crystal direction of the oxide superconductor). And, in the oxide superconducting wire, it is difficult to align the crystal orientation in order to obtain a high critical current density, and there is a problem that a long time heat treatment is required even if the crystal orientation can be achieved. Even if the crystal orientation can be achieved, the orientation is not perfect, and it has been difficult to improve the critical current density to a level where it can be put to practical use (for example, 10,000 A). Therefore, conventionally, in order to solve the above-mentioned problem, a long tape-shaped substrate is continuously sent from a delivery device to a film forming chamber, a raw material gas is sent to the film forming chamber, and the substrate is continuously reacted by a chemical reaction. An apparatus has been developed in which a long oxide superconducting wire is obtained by winding the film with a winding device after the film is formed.

In this apparatus, as shown in FIG. 5, a support device 32 for a tape-shaped substrate 31 is provided in the center of a film forming chamber 30 capable of being evacuated, and the substrate is delivered to both sides of the support device 32. A device 33 and a winding device 34 are provided, and a raw material gas introduction pipe 35 is provided at the center of the film forming chamber 30. In the apparatus shown in FIG. 5, the film formation chamber 30 is evacuated and then the delivery apparatus 33 is used.
The tape-shaped base material 31 fed out from the support device 32 is guided to the support device 32, and while the base material 31 is heated by the heater incorporated in the support device 32, the raw material gas is introduced from the introduction pipe 35 to the upper surface of the base material 31 and reacted. An apparatus for obtaining a superconducting wire by forming an oxide superconducting layer on the upper surface of a base material.

However, in the manufacturing apparatus of the above-described type, the long base material 31 is in a straight line state from the exit of the feeding device 33 to the winding of the winding device 34.
Since it was first bent in No. 4, tensile stress acted on the superconducting layer at the time of winding, cracking occurred in the superconducting layer, and there was a problem of lowering the critical current density.

The present invention has been made in view of the above circumstances, and a compressive stress can be applied to an oxide superconducting layer after film formation, whereby a dense superconducting layer can be formed and cracks can be formed. An object of the present invention is to provide an apparatus for producing an oxide superconducting wire, which can obtain an oxide superconducting layer free from defects.

[0007]

In order to solve the above-mentioned problems, the invention described in claim 1 supplies a film-forming chamber in which the inside can be evacuated, and a source gas of an oxide superconductor is supplied to the film-forming chamber. And a supply unit connected to the side of the film forming chamber and a lead-out unit. The film forming chamber is provided with a substrate supporting device having a heater, and the supply unit has a tape. A delivery device for delivering the substrate in the shape of a film to a substrate supporting device in the film forming chamber, a winding device for winding the substrate having passed through the substrate supporting device is housed in the outlet part, and the feeding and The lead-out portion is vertically slidably connected at a connecting portion to the film forming chamber, and the contact surface of the substrate supporting device is formed into a convex curved surface.

[0008]

The contact surface of the base material supporting device that contacts the base material is formed into a convex curved surface, and the sending portion and the winding portion are configured to be tiltable up and down, so that the upper surface of the base material is curved. A superconducting layer can be formed on. Therefore, since the base material after passing through the base material supporting device becomes linear, compressive stress acts on the superconducting layer after passing through the base material supporting device. For this reason, the oxide superconducting layer becomes dense and a layer in which cracks are hard to occur can be obtained.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a manufacturing apparatus according to an embodiment of the present invention. In the drawing, reference numeral 1 denotes a film forming chamber, 2 denotes a supply unit connected to the left side of the film forming chamber 1, 3 Is a lead-out section connected to the right side of the film forming chamber 1, and 4 is a source of the source gas.

The film forming chamber 1 is connected to an evacuation device such as a vacuum pump (not shown) through an evacuation unit 6, and has an airtight structure so that the inside can be evacuated. A base supporting device 7 in the form of a support is supported by a supporting rod 8 inside the film forming chamber 1, and a heater for heating is built in the base supporting device 7. An elastic member 9 such as a bellows is provided at the base end of the support rod 8, and the support device 7 is supported so as to be slightly movable vertically and slightly swingably to the left and right. Further, the upper surface of the base material supporting device 7 is formed into a convex curved surface having an arcuate cross section.

The supply unit 2 on the left side and the lead-out unit 3 on the right side of the film forming chamber 1 are configured as described below. First, the film forming chamber 1
A supply cylinder 10 is integrated with the left side wall of the support device 7 according to the installation height of the support device 7, and a discharge cylinder 11 is integrated with the right side wall of the support device 7 according to the installation height of the support device 7. Supply cylinder 10
The connecting tube 13 and the storage container 14 are airtightly flange-coupled to the tip of the connecting tube 13 via the bellows tube 10a.
The connecting cylinders 15 and 16 and the storage container 17 are airtightly flange-coupled to the tip end of each of the cylinders 10a, 11a, 11a, 13, 15 and 1 through a bellows cylinder 11a.
The interior of 6 and the storage containers 14 and 17 can be kept in the same atmosphere as the interior of the film forming chamber 1. The bellows tube 10
Reference characters a and 11a are flexible such as stainless bellows, and the supply unit 2 and the lead-out unit 3 are connected to the film forming chamber 1 so as to be vertically inclined. Further, a supporting bracket 13a is fixed to the lower portion of the connecting cylinder 13, a supporting bracket 16a is fixed to the lower portion of the connecting cylinder 16, and a cylinder device 21 is provided below each supporting bracket. An elongated hole is formed in each of the support brackets 13a and 16a, and the tip of the output shaft of each cylinder device 21 is pin-connected to the elongated hole of the support bracket 13a or the elongated hole of the support bracket 16b. By extending and contracting the output shaft of the above, the supply part 2 or the lead-out part 3 can be vertically tilted at a required angle.

A delivery device 19 such as a forward / reverse rotatable carry-out roller is provided inside the storage container 14, and a take-up device 20 such as a forward / reverse rotatable winding roller 20 is provided inside the storage container 17. Is provided. In addition, each of the cylinders 10 and 1
0a, 11, 11a, 13, 15, 16 and storage container 1
Inside the rollers 4 and 17, conveying rollers 18 are horizontally provided. With the above configuration, the base material 22 such as a metal tape wound around the delivery device 19 is sent to the support device 7 of the film forming chamber 1 along the roller 18 of the supply unit 2 and further the rollers 18 of the lead-out unit 3. The winding device 20 can be wound in the opposite direction, and can be wound in the opposite direction.

The source gases 4 and 4 for supplying the raw material gas supply the gas of the element forming the oxide superconductor or the raw material gas of the intermediate layer to the film forming chamber 1. This supply source 4 is provided with a raw material feeder containing a raw material powder and a vaporizer, and a carrier gas such as argon gas is sent to the raw material feeder so that it can be sent to the vaporizer and vaporized and then sent to the film forming chamber 1. It has become.

The raw material supplied to the vaporizer of the one supply source 4 is the raw material of the intermediate layer formed on the base material 22.
As the raw material, it is preferable to use a material having an intermediate coefficient of thermal expansion between the elements constituting the base material 22 and the oxide superconducting layer. Specifically, M as the intermediate layer
Since gO and SrTiO ₃ are used, these powders are stored in the raw material feeder of the vaporizer.

The raw material supplied to the vaporizer of the other supply source 4 is a raw material for forming a Y-based, La-based, Bi-based, Tl-based oxide superconductor or the like. As the oxide superconductor manufactured by the present invention, Y ₁ Ba ₂ Cu ₃ Ox, Y ₂ Ba
₄ Cu ₈ Ox, Y ₃ Ba ₃ Cu ₆ Ox, (Bi, P
b) ₂ Ca ₂ Sr ₂ Cu ₃ Ox, (Bi, Pb) ₂ Ca ₂ Sr ₃
Composition of Cu ₄ Ox, Tl ₂ Ba ₂ Ca ₂ Cu ₃ Ox, Tl ₁
Examples thereof include oxide superconductors having a high critical temperature represented by compositions such as Ba ₂ Ca ₂ Cu ₃ Ox and Tl ₁ Ba ₂ Ca ₃ Cu ₄ Ox. Therefore, powders of oxides, sulfides, carbonates, etc. of the respective elements constituting the oxide superconductor are used as the raw material used in manufacturing these.

Next, a case where a tape-shaped oxide superconducting wire is manufactured using the apparatus having the above-mentioned structure will be described.

To manufacture an oxide superconducting wire using the apparatus shown in FIG. 1, the inside of the film forming chamber 1, the inside of the supply section 2 and the outlet section 3 are exhausted from the exhaust section 6 by an exhaust apparatus such as a vacuum pump.
While the inside of the chamber is evacuated, a carrier gas such as argon gas is sent to the supply source 4 to vaporize the raw material powder of the intermediate layer and send the raw material gas of the intermediate layer to the film forming chamber 1. Further, the tape-shaped base material 22 is sent from the delivery device 19 to the film forming chamber 1 and passed over the supporting device 7 of the film forming chamber 1, and the base material 22 is heated by the heater of the supporting device 7 and then wound. It is wound around the take-up device 20 side at a constant speed. Further, the cylinder devices 21 and 21 are operated to adjust the inclination angles of the feeding part 2 and the winding part 3 so that the base material 22 is along the convex curved surface of the upper surface of the supporting device 7 as shown in FIG. By the above operation, the intermediate layer 23 is continuously formed on the base material 22 on the base material support device 7.

After the intermediate layer 23 is formed on the base material 22, the base material having the intermediate layer formed thereon is again moved from the winding device 20 to the delivery device 19 side. Then, when the base material 22 having the intermediate layer passes over the base material supporting device 7, the supply of the raw material gas for the intermediate layer from one supply source 4 is stopped prior to the passage, and the vaporization of the other is performed. The supply of the source gas from the device 4 is started, and at the same time, the supply of the oxygen gas from the oxygen gas supply device 27 is started to form the oxide superconducting layer on the intermediate layer. Of course, the base material 22 is heated by the heater of the base material support device 7. When forming the oxide superconducting layer, the base material 22 is provided between the delivery device 19 and the winding device 20.
And the like is repeated a required number of times to stack an oxide superconducting layer having a required thickness.

By the way, since the upper surface of the base material supporting device 7 has a convex curved surface as shown in FIG. 2, the base material 22 passes over the base material supporting device 7 in a curved state and the intermediate layer 23 An oxide superconducting layer 24 is deposited on the upper surface as shown in FIG.
After that, when the base material 22 passes through the base material supporting device 7, the base material 2
Since 2 is made linear, compressive stress acts on this oxide superconducting layer 24 as shown in FIG. Therefore, the oxide superconducting layer 24 becomes dense and has no defects.

Even when forming the intermediate layer 23, since the substrate 22 is linearly deformed after passing through the substrate supporting device 7 and a compressive stress acts on the intermediate layer 23, the intermediate layer 23 is also dense. Will be things.

Since the oxide superconducting wire manufactured as described above has the intermediate layer 23 interposed, it is resistant to bending, and the intermediate layer 23 and the oxide superconducting layer 24 do not separate even when subjected to a heat cycle. It has advantages. Further, according to the above-mentioned manufacturing method, since the base material 22 repeatedly passes through the film forming chamber 1 to form the oxide superconducting layer, the vacuum condition is changed while the film forming chamber 1 is always kept in the same vacuum state. The oxide superconducting layer can be stacked without any change (that is, without needing to perform the setup change), the oxide superconducting layer 24 to be laminated has no film thickness unevenness, and the setup change for each stack is not necessary and continuous film formation is possible. There is an effect that can be done. .. Further, when the oxide superconducting layer 24 is laminated, it is possible to introduce impurities or pining sites for improving the magnetic characteristics for each layer, and it is possible to improve the critical current density.

[0022]

[Production Example] A tape-shaped substrate made of Hastelloy C276 having a width of 5 mm and a thickness of 0.1 mm is sent from the delivery device shown in FIG. 1 to the film forming chamber at a speed of 1 mm / min, and the substrate is 700 in the film forming chamber.
An oxide having a composition of Y ₁ Ba ₂ Cu ₃ O _y is formed on the substrate by forming an intermediate layer of YSZ on the substrate in a film forming chamber by heating to ℃ to form a film and then winding the film into a winding device. A superconducting layer was formed.

At this time, the film forming chamber was decompressed to 1 × 10 ^-4 Torr, and the raw material feeder of one supply source was filled with a mixed powder of Y (thd) 3 and Zr (thd) 4 for forming an intermediate layer. Then, in order to form the oxide superconducting layer on the other material feeder, Y (thd) 3, Ba (thd) 2, Cu (thd)
The mixed powder of No. 2 was filled and pressure-fed to the vaporizer by Ar gas. In the vaporizer, the powder was gasified by heating to 250 ° C.

When forming an oxide superconducting film, the film formation was repeated three times to form an oxide superconducting layer having a thickness of 6 μm.
Further, the angle θ with respect to the horizontal plane when the base material is separated from the upper surface of the base material support device is adjusted to 1 by adjusting the angle between the supply portion and the outlet portion.
Deposition was performed at various times. The oxide superconducting wire obtained by the above treatment had a critical temperature of 90K and a critical current density of 1000A / mm ² .

[0025]

Comparative Example Using the apparatus shown in FIG. 1, the operation of forming the oxide superconducting layer is repeated by setting the angle θ between the base material and the upper surface of the supporting device when forming the oxide superconducting layer to 0 degree. Then, the same number of laminated layers as the oxide superconducting wire was obtained. The moving speed of the substrate and the film forming conditions were the same as in the previous example.
The obtained oxide superconducting wire had a critical temperature of 89K and a critical current density of 100A / mm ² . As is clear from the above comparison, it has been revealed that the oxide superconducting wire obtained by the method of the present invention exhibits superconducting characteristics superior to those of the superconducting wire obtained in the comparative example.

As described above, according to the present invention, a compressive stress can be applied after forming a film on a substrate,
A superconducting wire having a dense oxide superconducting layer having a high critical current density can be obtained. Further, it is possible to obtain an oxide superconducting wire having a dense and thick laminated oxide superconducting layer in which cracks are not generated. Furthermore, since a plurality of oxide superconducting layers can be laminated in the same film forming chamber under the same conditions, a laminated film having no unevenness in film thickness can be obtained. Further, if a laminated film is formed in the same film forming chamber, even if a defective portion is formed in the oxide superconducting layer formed previously, the oxide superconducting layer is laminated on the defective portion to re-form a film in the defective portion during manufacturing. be able to.

[Brief description of drawings]

FIG. 1 is a block diagram showing an apparatus according to an embodiment of the present invention.

FIG. 2 is an enlarged side view of a base material supporting device of the device shown in FIG.

FIG. 3 is a cross-sectional view showing a curved state of a base material.

FIG. 4 is a cross-sectional view of a base material in a linear state.

FIG. 5 is a sectional view showing an example of a conventional film forming apparatus.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 film-forming chamber 2 supply part 3 derivation part 4 supply source 7 base material support device 10 supply cylinder 10a bellows cylinder 11 derivation cylinder 11a bellows cylinder 13 connection cylinder 13a support bracket 15 connection cylinder 16 connection cylinder 16a support bracket 19 derivation device 20 rolls Taking device 21 Cylinder device 22 Base material 23 Intermediate layer 24 Oxide superconducting layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyuki Tadakata 1-5-1, Kiba, Koto-ku, Tokyo Within Fujikura Electric Wire Co., Ltd. (72) Takashi Saito 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Electric Line Co., Ltd. (72) Inventor Satoshi Kono 1-5-1, Kiba, Koto-ku, Tokyo Fujikura Electric Line Co., Ltd. (72) Inventor Saji Akira 20 Kitakanzan, Otakamachi, Midori-ku, Nagoya-shi, Aichi No. 1 Chubu Electric Power Co., Inc. Electric Power Technology Research Institute (72) Inventor Noboru Kuroda No. 20 Kitakanyama, Otaka-cho, Midori-ku, Nagoya-shi, Aichi No. 1 Chubu Electric Power Co. Electric Power Technology Research Lab (72) Inventor Hiroshi Yoshida Aichi Chubu Electric Power Co., Inc. Electric Power Technology Research Institute, 1-20, Kitakanyama, Otaka-cho, Midori-ku, Nagoya, Japan

Claims (1)

[Claims] 1. A film forming chamber capable of evacuating the interior, and a supply source for supplying a raw material gas of an oxide superconductor to the film forming chamber,
A base material supporting device having a heater and a heater is provided, which is connected to a side portion of the film forming chamber, and is provided with a heater in the film forming chamber. A delivery device for delivering to the base material support device in the film forming chamber is provided, and a winding device for winding the base material that has passed through the base material support device is housed in the delivery portion, and the supply portion and the delivery portion are provided. An apparatus for manufacturing a high-temperature superconducting wire, which is vertically slantably connected at a connection portion with respect to a film forming chamber, and a base material contact surface of a base material support device is a convex curved surface.