JP2012164442A - Manufacturing method of tape-shaped oxide superconducting wire material, and thermal processing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve superconducting characteristics of a manufactured tape-shaped oxide superconducting wire material, in a TFA-MOD method.SOLUTION: In a thermal processing device 10, a cylindrical rotor 12 is disposed so as to rotate to a furnace core axis C, in a cylindrical thermal processing space 11a of a furnace core pipe 11. In the rotor 12, around a surface 12a on which a large number of through-holes 17 are formed, a tape-shaped wire material 50 formed with a film body of a superconductive precursor is wound. A gas supplying pipe 13 supplies atmosphere gas from a position opposing/separating to/from a film surface of the tape-shaped wire material 50 wound around the rotor 12. A separation distance S between the surface 12a of the rotor 12 and a gas jetting hole 20 of the gas supplying pipe 13 is made to be 10 mm to 150 mm, and the atmosphere gas supplied to the tape-shaped wire material 50 is discharged from the inside of the rotor 12 to the outside of the furnace core pipe 11, through a gas discharging pipe 14.

Description

  The present invention relates to a method for manufacturing a tape-shaped oxide superconducting wire and a heat treatment apparatus, and more particularly to a technique for forming a superconducting layer on a metal substrate on which an intermediate layer is formed using a MOD (Metal-organic Deposition) method.

Conventionally, as a method for producing a YBa ₂ Cu ₃ O _7-X (YBCO) -based tape-shaped oxide superconducting wire, an organic metal salt is thermally decomposed (MOD: Metal-organic) on a metal substrate on which an intermediate layer is formed. It is known to form a superconducting layer using the Deposition method (see Patent Documents 1, 2, and 3).

  In this MOD method, first, a tape-like base material on which an oxide intermediate layer is formed is octyl such as trifluoroacetate (TFA salt) containing each metal element constituting a superconductor in a predetermined molar ratio. It is immersed in a superconducting raw material solution which is a mixed solution of metal organic acid salts such as acid salts and naphthenates. Next, the mixed solution is applied to the surface of the substrate by pulling up the substrate from the superconducting raw material solution (so-called dip coating method). Next, an oxide superconducting layer is formed by performing preliminary firing and main firing.

  Since the MOD method can continuously form an oxide superconducting layer on a long substrate even in a non-vacuum state, the process is more effective than a gas phase method such as a PLD (Pulse Laser Deposition) method or a CVD (Chemical Vapor Deposition) method. It is attracting attention because it is simple and can be reduced in cost.

  Patent Documents 1 and 2 disclose a batch-type heat treatment apparatus that heat-treats a substrate having a superconducting raw material solution attached to the surface thereof. Compared with the reel-to-reel heat treatment apparatus as shown in Patent Document 3, the batch-type heat treatment apparatus has an advantage that a stable superconducting layer can be formed because the atmosphere in the furnace is easily controlled. In addition, the batch-type heat treatment apparatus has an advantage that the firing can be completed in a short time with a small-sized apparatus, compared with the reel-to-reel type heat treatment apparatus. Incidentally, the heat treatment equipment of the reel-to-reel method performs firing by installing a wire feeding mechanism and a winding mechanism at both ends of a tunnel-shaped furnace core tube, and moving the wire at a constant speed in the furnace. is there.

  The configuration of the heat treatment apparatus disclosed in Patent Documents 1 and 2 will be briefly described. This heat treatment apparatus winds a base material having a superconducting raw material attached to a surface of a cylindrical rotating body. The cylindrical rotating body around which the substrate is wound is rotated by a rotation driving mechanism. A large number of through holes are formed in the rotating body. The base material is heated by a heater provided in the surface direction of the base material while being wound around the rotating body. In addition, an atmospheric gas composed of an inert gas, oxygen gas, water vapor, and the like is ejected from the surface direction of the base material toward the base material, and this atmospheric gas is discharged through a through-hole formed in the cylindrical body.

Japanese Patent No. 4468901 JP 2009-48817 A Japanese Patent No. 44011992

  A superconducting precursor obtained by pre-calcining a base material coated with a mixed solution containing trifluoroacetate using a heat treatment apparatus disclosed in Patent Documents 1 and 2, and a precursor containing fluorine (F) In the method (TFA-MOD method) for forming a YBCO film by subjecting this to a film on the intermediate layer and then subjecting it to firing, as the atmospheric gas (reactive gas) supplied to the precursor film during the firing Use water vapor.

The YBCO production reaction formula at this time is
1 / 2Y ₂ Cu ₂ O ₅ + 2BaF ₂ + 2CuO + 2H ₂ O → YBCO + 4HF
It becomes.

  Thus, during the main firing, since the precursor film is heat-treated using water vapor as an atmospheric gas, HF is generated, and HF gas is generated after this reaction.

In the TFA-MOD method, the fluorine removal rate when decomposing the fluorine compound (BaF ₂ ) is the reaction rate-limiting factor for YBCO formation. Therefore, there is a problem that the superconducting property of the YBCO film to be fired is deteriorated due to the influence of HF gas generated after the reaction.

  In particular, in order to obtain a long tape-shaped wire having a critical current density (Jc) of 2.0 or more and a critical current value (Ic) of 300 A or more, the superconducting layer is formed to a thickness of 1.5 μm or more. It is necessary to form a film. With the above film thickness, it becomes more difficult to completely remove fluorine gas, and the above characteristics cannot be obtained.

  For this reason, in order to improve the superconducting characteristics of the YBCO film, it is important how to remove fluorine contained in the precursor in the main firing.

  This invention is made | formed in view of this point, and it aims at providing the manufacturing method and heat processing apparatus of a tape-form oxide superconducting wire with which the superconducting characteristic was improved in TFA-MOD method.

  The method for producing a tape-shaped oxide superconducting wire according to the present invention includes a furnace core tube having a cylindrical heat treatment space, a rotatable arrangement with respect to the furnace core shaft inside the heat treatment space, and a large number of through holes. A cylindrical rotating body around which a tape-shaped wire having a superconducting precursor film formed thereon is wound on the surface on which the gas is formed, a gas supply pipe for supplying an atmospheric gas to the tape-shaped wire, and A film of the film body of the tape-shaped wire wound around the rotary body using a heat treatment apparatus including a gas discharge pipe for discharging atmospheric gas from the inside of the rotary body to the outside of the furnace core pipe In the method of manufacturing an oxide superconducting wire that supplies the atmospheric gas from a position spaced upward with respect to the surface, the separation distance between the surface of the rotating body and the gas ejection hole of the gas supply pipe is 10 mm to 150 mm. I made it. Preferably, the separation distance is 50 mm to 100 mm.

  One aspect of the heat treatment apparatus of the present invention is a furnace core tube having a cylindrical heat treatment space, and is disposed so as to be rotatable with respect to the furnace core shaft inside the heat treatment space, and a plurality of through holes are formed. A cylindrical rotating body on which a tape-shaped wire material in which a film body of a superconducting precursor is formed is wound, and a film surface of the film body of the tape-shaped wire material wound on the rotating body. A gas supply pipe for supplying an atmospheric gas to the film surface; and a gas discharge pipe for discharging the atmospheric gas from the inside of the rotating body. The gas ejection hole is configured such that a separation distance from the surface of the rotating body is provided at a position of 10 mm to 150 mm. Preferably, the separation distance is 50 mm to 100 mm.

  According to the present invention, a tape-shaped oxide superconducting wire with improved superconducting properties can be produced by the TFA-MOD method.

BRIEF DESCRIPTION OF THE DRAWINGS Schematic sectional drawing which shows the principal part structure of the heat processing apparatus of the tape-shaped oxide superconducting wire which concerns on one embodiment of this invention Schematic front view showing the main components of the heat treatment equipment Schematic showing the rotating body of the heat treatment equipment Schematic sectional view showing the gas supply pipe of the heat treatment apparatus Schematic showing the manufacturing method of YBCO superconducting wire by MOD method

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 5 shows an outline of a method for producing a tape-shaped oxide superconducting wire (YBCO superconducting wire) having a YBCO superconducting layer by the MOD method.

First, a composite in which a Gd ₂ Zr ₂ O ₇ intermediate layer was formed as a template by a IBAD method on a tape-shaped Ni alloy substrate (base material), and further a CeO ₂ intermediate layer was formed thereon by a sputtering method On the substrate, Y: TFA salt (trifluoroacetate salt), Ba-TFA salt and Cu-naphthenate salt in an organic solvent were applied in the coating step (a) with Y: Ba: Cu = 1: 1.5: 3. A mixed solution (superconducting raw material solution) 8 dissolved at a ratio is applied by a dip coating method. After the mixed solution 8 is applied, it is temporarily fired in the temporary firing step (b). This coating step (a) and pre-baking step (b) are repeated a predetermined number of times to form a film body as a superconducting precursor on the intermediate layer in the tape-shaped wire 50. Thereafter, in the main firing step (c), a heat treatment for crystallizing the superconducting precursor film in the tape-shaped wire 50, that is, a heat treatment for generating a YBCO superconductor is performed. Next, in step (d), an Ag stabilizing layer is applied on the generated YBCO superconductor by sputtering, and then in step (e), post-heat treatment is performed to manufacture a YBCO superconducting wire.

  The heat treatment apparatus according to the embodiment of the present invention is used for the crystallization heat treatment in the step (c), and heat-treats the precursor of the superconductor formed in the tape-shaped wire to generate a YBCO superconductor. . Note that the heat treatment apparatus may also be applied to the formation of the intermediate layer.

  The Ni alloy substrate may have a biaxial orientation or may have a biaxial orientation intermediate layer formed on a non-oriented metal substrate. Further, the intermediate layer is formed of one layer or a plurality of layers. As an application method, it is possible to use an inkjet method, a spray method, etc. in addition to the dip coating method described above, but basically, this example is applicable as long as it is a process capable of continuously applying a mixed solution onto a composite substrate. Not constrained by. The film thickness to be applied at one time is 0.01 μm to 2.0 μm, preferably 0.1 μm to 1.0 μm.

  The superconducting raw material solution used here is a mixed solution in which a metal organic acid salt or an organic metal compound containing Y, Ba, and Cu in a predetermined molar ratio is dissolved in an organic solvent. When the number of moles is Y: Ba: Cu = 1: a: 3, a raw material solution having a Ba molar ratio in the range of <2 is used. In this case, in order to obtain high Jc and Ic values, the Ba molar ratio in the raw material solution is preferably in the range of 1.0 ≦ a ≦ 1.8, and more preferably the Ba molar ratio in the raw material solution. Is in the range of 1.3 ≦ a ≦ 1.7. Thereby, the segregation of Ba can be suppressed, and as a result, the precipitation of Ba-based impurities at the grain boundaries is suppressed. Therefore, generation of cracks is suppressed and electrical connectivity between crystal grains is improved. By forming a superconducting film by the MOD method, a tape-like oxide having a high-speed uniform thick film and excellent superconducting characteristics. Superconductors can be easily manufactured. In addition, examples of the metal organic acid salt include octyl acid salt, naphthenic acid salt, neodecanoic acid salt, and trifluoroacetic acid salt of each element, but one or more kinds of the salts are uniformly dissolved in an organic solvent, Any material that can be applied on the composite substrate can be used.

<Configuration of heat treatment equipment>
A heat treatment apparatus 10 shown in FIG. 1 performs a baking of a raw material solution (superconducting raw material solution) applied as a film body of a superconducting precursor in a tape-shaped wire 50 in a batch type. The heat treatment apparatus 10 includes a furnace core tube 11 having a cylindrical heat treatment space 11 a, a cylindrical rotating body 12, a gas supply pipe 13, and a gas discharge pipe 14.

  The heat treatment space 11a of the furnace core tube 11 is configured so that a reduced-pressure atmosphere or vacuum in the furnace can be maintained. The furnace core tube 11 is provided with a heater 15 around it, and the inside of the heat treatment space 11 a is heated by the heater 15.

  Inside the furnace core tube 11, a rotating body 12 is rotatably arranged around a furnace core axis C that is an axis of the furnace core tube 11. The rotating body 12 has a cylindrical body 12b around which a tape-shaped wire 50 on which a precursor is formed is wound on the surface 12a. The tape-shaped wire 50 is obtained by applying a mixed solution and calcining as described above to form a YBCO superconducting product precursor on a base material. The tape-shaped wire 50 is spirally wound around the surface 12a of the cylindrical body 12b (the surface of the rotating body 12) with the film surface of the precursor exposed.

  As shown in FIG. 3, a large number of through holes 17 are formed in the cylindrical body 12 b of the rotating body 12. The diameter of the through hole 17 is preferably equal to the tape width of the tape-shaped wire 50. Moreover, the hole area ratio is 50 to 95%, and the hole area ratio in the range of 89 to 91% is particularly preferable. The rotating body 12 is rotated at a constant speed during the heat treatment by a rotating mechanism (not shown). The rotating body 12 is made of a material that is resistant to high temperatures and hardly oxidizes, such as ceramics such as quartz glass and alumina, or metals such as Hastelloy and Inconel.

  One end side of the cylindrical body 12b is closed by a lid body 12c. The other end side of the cylindrical body 12b is closed by a lid body 12d. A gas discharge pipe 14 for discharging the atmospheric gas inside the cylindrical body 12b to the outside of the furnace core pipe 11 is inserted into the lid body 12d.

  As shown in FIGS. 1 and 2, a plurality of gas supply pipes 13 are disposed in the furnace core tube 11 so as to be separated from the surface 12 a of the cylindrical body 12 b. The plurality of gas supply pipes 13 are arranged in parallel to the furnace core axis C and are arranged symmetrically in a cross section perpendicular to the furnace core axis C. Here, four gas supply pipes 13 are arranged in the furnace core tube 11 symmetrically with respect to the furnace core axis C and parallel to each other. That is, in the furnace core tube 11, the plurality of gas intake pipes 13 are arranged at a pitch of 90 ° in the circumferential direction around the furnace core axis C.

  Each gas supply pipe 13 includes a large number of gas ejection holes 20 that eject atmospheric gas to the rotator 12.

  As shown in FIG. 4, the gas ejection holes 20 in the gas supply pipe 13 are uniformly formed in the main body portion of the gas supply pipe 13 at regular intervals along the longitudinal direction. Each gas ejection hole 20 is a circular hole and ejects atmospheric gas uniformly. In order to uniformly eject the atmospheric gas and to further remove the fluorine gas, the flow rate when supplying the atmospheric gas, specifically, the flow rate at which the film surface of the film body wound around the rotating body contacts However, it is preferable that they are 200 m / s or more and 500 m / s or less. If it is less than 200 m / s, not only the atmosphere gas cannot be uniformly supplied to the superconducting precursor, but also the exhaust gas (HF gas) staying on the surface of the film body cannot be removed. Therefore, desired superconducting characteristics cannot be obtained. On the other hand, if it exceeds 500 m / s, the atmospheric gas can be uniformly ejected, but the crystallization reaction proceeds rapidly, so that it is difficult to control the epitaxial growth rate. Therefore, desired superconducting characteristics cannot be obtained.

  As shown in FIGS. 1, 2, and 4, each gas supply pipe 13 has gas ejection holes 20 on the surface of the cylindrical body 12b so as to supply atmospheric gas from the vertical direction to the surface 12a of the cylindrical body 12b. It arrange | positions so that it may be located in the position spaced apart upwards with respect to 12a.

  The gas supply pipe 13 is provided in the furnace core pipe 11 so that the separation distance S between the gas ejection hole 20 and the surface 12a of the rotating body 12 is 10 mm to 150 mm. A preferable range of the separation distance is 50 mm to 100 mm. Within the above range, the atmospheric gas can be uniformly ejected to the superconducting precursor, so that the fluorine gas can be further removed. If it is less than the above range, the atmosphere gas ejected only to a part of the film surface of the film body of the tape-shaped wire 50 wound around the rotating body 12 does not come into contact with the superconducting wire in the longitudinal direction. Superconducting properties cannot be obtained. When the above range is exceeded, not only the gas flow rate increases and the production cost improves, but also the crystallization reaction proceeds rapidly, making it difficult to control the epitaxial growth rate. Therefore, desired superconducting characteristics cannot be obtained.

  Therefore, in order to obtain a long tape-shaped wire superconducting layer having a thick film of 1.5 μm or more, it is necessary to eject atmospheric gas to the superconducting precursor at an appropriate gas flow rate at a separation distance in the above range. In this way, it is possible to obtain a superconducting wire having the characteristics that the film thickness critical current density (Jc) is 2.0 or more and the critical current value (Ic) is 300 A or more.

  The gas supply pipe 13 ejects atmospheric gas from the gas ejection hole 20 in the direction indicated by the arrow D in each figure.

  Thereby, the gas supply pipe 13 supplies the atmospheric gas vertically from a position spaced upward to the film surface of the precursor in the tape-shaped wire 50 wound around the surface 12a of the cylindrical body 12b. The diameter of the gas ejection hole 20 needs to be designed so that the gas pressure and the gas flow rate are uniform.

  The atmospheric gas is supplied from an atmospheric gas supply device (not shown) disposed outside the furnace core tube 11 via a connection tube (not shown) connected to the gas supply pipe 13. Incidentally, the gas supply device generates an atmospheric gas composed of an inert gas, oxygen gas, water vapor, or the like, and the atmospheric gas is ejected from the gas supply pipe 13.

  Further, the length of the gas supply pipe 13 is preferably longer than the length of the rotating body 12. That is, the length between the gas ejection holes 20 located at both ends of the gas supply pipe 13 is longer than the length of the rotating body 12. This makes it possible to cause a uniform reaction over the entire length of the tape-shaped wire 50 wound around the cylindrical rotating body 12.

  The gas discharge pipe 14 is continuous with the internal space of the cylindrical body 12b and is connected to the other end side of the cylindrical body 12b. Specifically, the lid body 12 d is inserted from the inside of the cylindrical body 12 b and led out to the outside of the furnace core tube 11. The gas exhaust pipe 14 exhausts the atmospheric gas inside the cylindrical body to the outside of the furnace core pipe. Here, the gas discharge pipe 14 is formed on the rotating shaft (corresponding to the furnace core axis C) of the cylindrical body 12b.

  The gas supply pipe 13 and the gas discharge pipe 14 are made of a material that is resistant to high temperatures and hardly oxidizes, such as quartz glass, ceramics such as alumina, or metals such as Hastelloy and Inconel.

  In the heat treatment apparatus 10 described above, the cylindrical rotating body 12 around which the tape-like wire 50 is wound is rotated at a constant speed. In addition, the atmosphere gas supplied from a gas supply device (not shown) enters the heat treatment space 11 a held in the heating atmosphere by the heater 15 through the numerous gas ejection holes 20 of the gas supply pipe 13 to the tape. It is sprayed evenly against the film surface of the wire rod 50. The blown atmospheric gas reacts with the film surface and then enters the inside of the cylindrical body 12b through the numerous through holes 17 of the cylindrical body 12b in the rotating body 12. The gas after reaction inside the cylindrical body 12b is discharged out of the furnace via the gas discharge pipe 14 connected on the other end side of the cylindrical body 12b.

In the heat treatment apparatus 10, the gas supply pipes 13 are formed with a length of 2 m and an inner diameter of 20 mmφ, and the gas injection holes 20 are formed in the gas supply pipes 13 at a pitch of 30 mm in the longitudinal direction of the gas supply pipes 13. (Nozzle diameter) was formed at 1.0 mmφ. At this time, the pressure in the furnace core tube 11, that is, the pressure in the heat treatment space 11a, was set to 50 to 200 torr, and the gas flow rate was set to 250 to 1000 L / min (converted value at normal temperature and normal pressure). Then, the flow rate of the atmospheric gas ejected from the gas ejection holes 20 in the heat treatment apparatus 10 and supplied to the surface 12a of the rotator 12 (the flow rate in contact with the film surface of the film body wound around the rotator) is: The separation distance S between the gas ejection hole 20 and the surface 12a of the rotating body 12 disposed in the heat treatment apparatus 10 was set to 80 m / s. The film body of the tape-shaped wire 50 wound around the rotating body 12 is formed by forming a Gd ₂ Zr ₂ O ₇ intermediate layer as a template on the tape-shaped Ni alloy substrate (base material) by the IBAD method, Further, a Y-TFA salt (trifluoroacetate salt), a Ba-TFA salt, and a Cu-naphthenate salt are added in an organic solvent on a composite substrate on which a CeO ₂ intermediate layer is formed by sputtering. A film body obtained by applying a mixed solution (superconducting raw material solution) dissolved at a ratio of Y: Ba: Cu = 1: 1.5: 3 by a dip coating method and then pre-baking in a pre-baking step. The film body was heat-treated by a main baking step at a furnace temperature of 750 ° C. to obtain a 1.5 μm superconducting layer.

  Thus, the thing which set the separation distance S to 80 mm is made into Example 1, and the example which changed only the separation distance S in the structure of the heat processing apparatus 10 of Example 1 from Example 2 to Example 7 is shown in the following table | surface. .

  In Example 2, the separation distance S = 50 mm, in Example 3, the separation distance S = 100 mm, and in Example 4, the separation distance S = 30 mm. In the fifth embodiment, the separation distance S = 120 mm, in the sixth embodiment, the separation distance S = 10 mm, and in the seventh embodiment, the separation distance S = 150 mm.

  The characteristics of the superconducting wires made by the heat treatment apparatuses of Examples 1 to 7 were as follows. The characteristics of the superconducting wire made by the heat treatment apparatus 10 of Example 1 were Jc2.5 and Ic370A, and the characteristics of the superconducting wire made by the heat treatment apparatus of Example 2 were Jc2.2 and Ic330A. The characteristics of the superconducting wire made by the heat treatment apparatus of Example 3 were Jc2.1 and Ic315A, and the characteristics of the superconducting wire made by the heat treatment apparatus of Example 4 were Jc2.0 and Ic300A. The characteristics of the superconducting wire completed by the heat treatment apparatus of Example 5 were Jc2.0 and Ic300A, and the characteristics of the superconducting wire completed by the heat treatment apparatus of Example 6 were Jc2.0 and Ic300A. The characteristics of the superconducting wire completed by the heat treatment apparatus of Example 7 were Jc2.0 and Ic300A.

  Further, in the heat treatment apparatus of Example 1, the superconducting wire completed by the heat treatment apparatus of Comparative Example 1 in which the separation distance S between the gas ejection hole 20 and the surface 12a of the rotating body 12 disposed in the heat treatment apparatus 10 is 200 mm. The characteristics were Jc1.1 and Ic165A. Further, in the heat treatment apparatus of Example 1, the superconducting wire produced by the heat treatment apparatus of Comparative Example 2 in which the separation distance S between the gas ejection hole 20 and the surface 12a of the rotating body 12 disposed in the heat treatment apparatus 10 is 5 mm. The characteristics were Jc1.2 and Ic180A.

  As shown in Example 1 to Example 7, when the separation distance S between the surface 12a of the rotating body 12 and the gas ejection hole 20 of the gas supply pipe 13 is 10 mm to 150 mm, “◯” in the “Evaluation” column, As indicated by “線”, a superconducting wire excellent in superconducting properties was produced. In particular, when the separation distance S was 50 mm to 100 mm, a superconducting wire having particularly excellent superconducting characteristics was obtained as indicated by “◎” in the “Evaluation” column. In addition, when the separation distance S between the surface 12a of the rotating body 12 and the gas ejection hole 20 of the gas supply pipe 13 is not in the range of 10 mm to 150 mm, the superconductivity of the resulting superconducting wire is indicated by “x” in “Evaluation” The property was not the desired value.

  Thus, the method for producing a tape-shaped oxide superconducting wire using the heat treatment apparatus of the example increases the fluorine reaction rate more than the method for producing a tape-shaped oxide superconducting wire using the heat treatment apparatus of the comparative example. The superconducting properties of the tape-shaped oxide superconducting wire to be manufactured can be improved.

  As described above, according to the present embodiment, at the time of the main firing, the rotating body wound with the tape-shaped base material is accommodated in the heat treatment space of the furnace core tube, and the heat treatment space is heated while being in a tape shape. The wire is supplied from a position that is 10 mm to 150 mm apart from the film surface of the superconducting precursor. Thereby, the reaction rate of fluorine can be increased, the decomposition of the fluorine compound (barium fluoride) can be accelerated, and a tape-shaped oxide superconducting wire excellent in superconducting characteristics can be produced.

  Furthermore, since firing is performed in a batch mode, the atmosphere in the furnace can be controlled more easily than in the case of firing in a reel-to-reel mode, so a stable superconducting layer can be formed, and the oxide can be formed in a short time. Superconducting wire can be manufactured.

  The present invention can be variously modified without departing from the spirit of the present invention, and the present invention naturally extends to the modified ones.

  The method for producing a tape-shaped oxide superconducting wire and the heat treatment apparatus according to the present invention are widely applicable when forming a tape-shaped oxide superconducting wire using the MOD method.

DESCRIPTION OF SYMBOLS 10 Heat processing apparatus 11 Furnace core pipe 12 Rotor 12a Surface 12b Cylindrical body 13 Gas supply pipe 14 Gas discharge pipe 20 Gas ejection hole 50 Tape-shaped wire C Furnace core axis | shaft S Separation distance

Claims (7)

A furnace core tube with a cylindrical heat treatment space;
A cylindrical shape in which a tape-like wire rod having a superconducting precursor film formed thereon is wound around a surface on which a large number of through-holes are formed and is rotatable with respect to the furnace core shaft inside the heat treatment space. A rotating body of
A gas supply pipe for supplying atmospheric gas to the tape-shaped wire;
A gas discharge pipe for discharging the atmospheric gas from the inside of the rotating body to the outside of the furnace core pipe;
A method of manufacturing an oxide superconducting wire that supplies the atmospheric gas from a position spaced upward with respect to the film surface of the film body of the tape-shaped wire wound around the rotating body using a heat treatment apparatus comprising: In
The separation distance between the surface of the rotating body and the gas ejection hole of the gas supply pipe is 10 mm to 150 mm.
Tape-like oxide superconducting wire manufacturing method. The separation distance is from 50 mm to 100 mm;
A method for producing a tape-shaped oxide superconducting wire according to claim 1. The flow rate of supplying the atmospheric gas to the tape-shaped wire is 200 m / s or more and 500 m / s or less.
The manufacturing method of the tape-shaped oxide superconducting wire of Claim 1 or 2. The superconducting precursor film body forms an intermediate layer on the substrate, and after applying a mixed solution prepared by dissolving a metal organic acid salt or organic metal compound containing a metal element in an organic solvent on the intermediate layer, pre-baking A film body formed by
The manufacturing method of the tape-shaped oxide superconducting wire of any one of Claims 1 thru | or 3. The metal organic acid salt containing a metal element in the mixed solution consists of one or more selected from octylate, naphthenate, neodecanoate or trifluoride acetate.
The manufacturing method of the tape-shaped oxide superconducting wire of Claim 4. The oxide superconducting wire comprises an intermediate layer formed on the substrate, a REBa _y Cu ₃ O _z- based superconducting layer formed on the intermediate layer, a stabilization layer formed on the superconducting layer, The tape-shaped oxide superconducting wire according to any one of claims 1 to 5, wherein the RE is made of at least one element selected from Y, Nd, Sm, Eu, Gd, and Ho. Production method. A furnace core tube with a cylindrical heat treatment space;
A cylindrical shape in which a tape-like wire material in which a film body of a superconducting precursor is formed is wound around the surface of the heat treatment space, which is rotatably arranged with respect to the furnace core shaft and in which a large number of through holes are formed. A rotating body,
A gas supply pipe disposed at a position spaced upward from the film surface of the film body of the tape-shaped wire wound around the rotating body, and for supplying an atmospheric gas to the film surface;
A gas discharge pipe for discharging the atmospheric gas from the inside of the rotating body;
With
The gas ejection hole of the gas supply pipe is provided at a position where the distance from the surface of the rotating body is 10 mm to 150 mm.
Heat treatment equipment for tape-shaped oxide superconducting wire.

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