JP5841862B2 - High temperature superconducting wire and high temperature superconducting coil - Google Patents

Description

  The present invention relates to a high-temperature superconducting wire and a high-temperature superconducting coil.

  Conventionally used metal-based superconducting wires such as NbTi are provided in the form of round wires or square wires, and have a high degree of freedom in shape. On the other hand, in the high-temperature oxide superconductor having a critical temperature of about 90 to 100 K such as Bi-based and Y-based, the superconducting layer is formed of ceramics, and the wire structure is also in a tape shape. There is a drawback that mechanical properties such as bending and twisting are likely to deteriorate.

For example, as shown in FIG. 15, a Bi-based superconducting wire 100 has a structure manufactured by a Powder In Tube method (PIT method) or the like so that a Bi-based superconducting layer 101 is covered with an Ag sheath material 102. It has become. On the other hand, the rare earth-based superconducting wire 200 such as Y has a completely different structure as shown in FIG.
A superconducting wire 200 shown in FIG. 16 is formed by laminating an oxide superconducting layer 203 on a tape-shaped metal substrate 201 through an intermediate layer 202 by a film forming method, and covering stabilization layers 204 and 205 such as Ag and Cu. A laminated structure is adopted. Therefore, the Bi-based superconducting wire 100 having the structure shown in FIG. 15 is not symmetrical in the thickness direction, and a rare-earth superconducting wire 200 is used to form a superconducting coil such as bending or twisting. It is necessary to design in consideration of directionality.

In order to wind a tape-shaped superconducting wire into a coil, it is necessary to coat the superconducting wire with an insulating material in order to ensure electrical insulation between the superconducting wires.
As a method of insulatingly covering the superconducting wire, a method of winding a resin tape such as a polyimide tape around the outer periphery of the tape-shaped superconducting wire, or applying a resin to the outer peripheral surface of the superconducting wire and baking the resin, the superconducting wire A method of forming a resin film on the outer peripheral surface of the film (see Patent Document 1) is known.

JP 2000-31526 A

  The technique described in Patent Document 1 is a technique applied to a Bi-based superconducting wire formed by a PIT method in which a raw material powder to be an oxide superconductor is filled in a metal tube and diameter-reduced. The Bi-based superconducting wire formed by the PIT method has an elliptical cross section as shown in FIG. 15, and it is easy to form a resin film by applying and baking a resin on the entire outer periphery of the superconducting wire.

On the other hand, as shown in FIG. 16, a rare earth-based superconducting wire 200 in which an oxide superconducting layer 203 is laminated above a tape-like metal substrate 201 has a rectangular cross section, and its four corners are square. Therefore, if an attempt is made to form a resin coating by applying and baking a resin on the outer periphery of the superconducting wire 200 shown in FIG. 16, it is difficult to form the insulating coating 210 on the corner portion 200a of the superconducting wire 200 as shown in FIG. In some cases, the entire outer periphery of the wire 200 cannot be covered with insulation.
If the thickness of the insulating coating 210 is increased, the corner portion 200a can be covered. However, if the thickness of the insulating coating 210 becomes too thick, the coil section is occupied when the superconducting wire 200 is wound and coiled. The ratio of the oxide superconducting layer 203 decreases, and the current density of the coil decreases. In the example of Patent Document 1, the insulating coating layer is formed by baking the resin at a temperature of 300 ° C. or higher and 350 ° C. or lower. However, the rare earth oxide superconducting layer has characteristics at a temperature of 300 ° C. or higher. Therefore, it is difficult to apply this heat treatment condition as it is to rare earth-based superconducting wires having different wire composition and heat resistance.

By the way, when coiling by winding a superconducting wire with insulation coating, the winding state of the superconducting wire can be changed by applying or injecting a thermosetting resin between the superconducting wires in the wound state and then heat-curing. Keeping it is done. The following methods are known as methods for introducing and curing the thermosetting resin.
(1) A method in which a superconducting wire after winding is immersed in a thermosetting resin such as an epoxy resin, impregnated by pressurization in vacuum, and then heated to cure the thermosetting resin (vacuum pressure impregnation method) ).
(2) A method of winding a superconducting wire while applying a thermosetting resin such as an epoxy resin to the superconducting wire and then heating to cure the thermosetting resin.
(3) When winding a superconducting wire, a semi-cured thermosetting resin tape such as a semi-cured epoxy tape and a superconducting wire are wound together and wound, and then heated and thermoset. A method of curing a functional resin.

The method (1) has a problem that when the coil is enlarged, it is difficult to impregnate the coil with the thermosetting resin.
In the method (2), when a long superconducting wire is wound and coiled, the thermosetting resin may not be uniformly applied to the entire superconducting wire. In such a case, when the coil is cooled to about the liquid nitrogen temperature during operation of the superconducting coil, it is locally caused by the difference in coefficient of linear expansion between the metal material constituting the superconducting wire and the resin layer made of the thermosetting resin. There is a possibility that distortion is generated, and the oxide superconducting layer is deteriorated due to the distortion and the superconducting characteristics are deteriorated.
In the method (3), when the thickness of the semi-cured thermosetting resin tape is less than 100 μm, the workability when winding the superconducting wire tends to be extremely deteriorated. Further, when the thickness of the semi-cured thermosetting resin tape is 100 μm or more, the ratio of the oxide superconducting layer in the coil cross section is reduced, and the current density of the coil is lowered.

  The present invention has been made in view of such a conventional situation, and an object of the present invention is to provide a high-temperature superconducting wire having an insulation coating on the entire outer periphery, and a high-temperature superconducting coil using the high-temperature superconducting wire. Another object of the present invention is to provide a high-temperature superconducting coil that can suppress a decrease in current density.

In order to solve the above problems, the high-temperature superconducting wire of the present invention covers a superconducting laminate in which a substrate, an intermediate layer, an oxide superconducting layer, and a metal stabilizing layer are laminated in this order, and an outer peripheral surface of the superconducting laminate. An insulating coating layer formed by baking a resin, and a chamfer in which a corner in a cross section along the width direction of the superconducting laminate is a curved surface having a radius of curvature, and the thickness of the insulating coating layer is 12 μm or more The radius of curvature of the corner is 14.5 mm or more.
The high-temperature superconducting wire of the present invention has a superconducting structure in which the radius of curvature of the corners in the cross section along the width direction of the superconducting laminate is 14.5 mm or more and the thickness of the insulating coating layer is specified to be 12 μm or more. The insulating coating layer forming resin can be applied and baked so as to cover the corners of the laminate, and a structure in which the entire outer periphery including the corners of the superconducting laminate is completely covered with the insulating coating layer can be realized. Therefore, in the high-temperature superconducting wire of the present invention, the superconducting laminate is sealed from the outside by the insulating coating layer, so that moisture and the like can be prevented from entering the oxide superconducting layer, and deterioration of the superconducting characteristics can be suppressed.

In the high-temperature superconducting wire of the present invention, the metal stabilization layer has a structure in which a second stabilization layer is laminated on the first stabilization layer, and the second stabilization layer is attached to a metal tape via solder. The insulating coating layer may be formed of a resin that can be baked at a temperature of 170 ° C. to 200 ° C.
In this case, when the insulating coating layer is formed, the baking temperature does not become too high, and the second stabilization layer formed by bonding the metal tape through the solder melts and peels off when the resin is baked. Can be prevented.

In the high-temperature superconducting wire of the present invention, the metal stabilization layer has a structure in which a second stabilization layer is laminated on the first stabilization layer, and the second stabilization layer is formed by plating or vapor deposition, The insulating coating layer may be formed of a resin that can be baked at a temperature of 170 ° C. to 280 ° C.
In this case, when the insulating coating layer 7 is formed, the baking temperature does not become excessively high, and it is possible to prevent the oxide superconducting layer from deteriorating due to the loss of oxygen in the oxide superconducting layer during resin baking.

In the high-temperature superconducting wire of the present invention, a semi-cured resin layer made of a semi-cured thermosetting resin may be provided so as to cover the outer peripheral surface of the insulating coating layer.
In this case, after winding the high-temperature superconducting wire, the semi-cured resin layer is cured by heating as it is without impregnating the resin, and the high-temperature superconducting wire adjacent in the coil radial direction is fixed and coiled. Can do. Therefore, by producing a high-temperature superconducting coil from this form of high-temperature superconducting wire, the coil manufacturing process can be simplified, and the resin between the high-temperature superconducting wires adjacent in the coil radial direction can be compared with the conventional superconducting coil manufacturing method. Therefore, the current density of the superconducting coil is high and a high-performance superconducting coil can be realized.

In order to solve the above-mentioned problems, the high-temperature superconducting coil of the present invention is formed by winding the high-temperature superconducting wire of the present invention.
Since the high-temperature superconducting coil of the present invention is composed of the above-described high-temperature superconducting wire of the present invention, the superconducting laminate is sealed from the outside with an insulating coating layer, and moisture enters the oxide superconducting layer. Therefore, deterioration of superconducting characteristics can be suppressed.

In order to solve the above problems, in the high-temperature superconducting coil of the present invention, the metal stabilizing layer has a structure in which a second stabilizing layer is laminated on a first stabilizing layer, and the second stabilizing layer is the superconducting layer. It is arrange | positioned so that four corner | angular parts in the cross section along the width direction of a laminated body may occupy, and the corner | angular part of a said 2nd stabilization layer can be made into the curved surface which has the said curvature radius.
Since the four corners of the metal second stabilization layer are the corners of the specified curvature radius, the target structure is obtained by setting the four corners of the metal second stabilization layer to the specified curvature radius. Can be realized. That is, the resin for forming the insulating coating layer can be applied and baked so as to cover the corner portion, and a structure in which the entire outer periphery including the corner portion of the superconducting laminate is completely covered with the insulating coating layer can be realized.

In order to solve the above problems, in the high-temperature superconducting coil of the present invention, the metal stabilization layer has a structure including a second stabilization layer and a third stabilization layer on the first stabilization layer, and the second Just as the stabilization layer occupies two corners in the cross section along the width direction of the superconducting laminate, the third stabilization layer occupies the remaining two corners in the cross section along the width direction of the superconducting laminate. And the two corners of the second stabilization layer and the two corners of the third stabilization layer may be curved surfaces having the curvature radius.
Even in the structure in which the third stabilizing layer is added in addition to the second stabilizing layer, the target structure can be realized by setting the corners of the second stabilizing layer and the third stabilizing layer to a prescribed curvature radius. . That is, the resin for forming the insulating coating layer can be applied and baked so as to cover the corners, and a structure in which the entire outer periphery is completely covered with the insulating coating layer can be realized.

In order to solve the above problems, the high-temperature superconducting coil of the present invention is formed by winding the high-temperature superconducting wire of the present invention provided with the semi-cured resin layer, and the semi-cured between the high-temperature superconducting wires adjacent in the coil radial direction It is provided with the resin layer formed by heat-curing a resin layer.
Since the high-temperature superconducting coil of the present invention is formed from the high-temperature superconducting wire according to the present invention described above, the thickness of the cured resin layer for fixing the insulating coating layer and the wire in a coil shape as compared with the conventional superconducting coil. Is thinner than a conventional superconducting coil and can reduce variations in thickness. Therefore, since the interval between the high-temperature superconducting wires adjacent to each other in the coil radial direction can be reduced, the thickness of the insulating resin layer or the cured resin layer does not become too thick, and the superconducting coil can suppress the decrease in critical current density.
Conventionally, a superconducting coil has been manufactured through a process of winding a superconducting wire, impregnating it with a thermosetting resin, and further heat-curing it. In contrast, the high-temperature superconducting coil of the present invention can be manufactured by winding a high-temperature superconducting wire having a semi-cured resin layer and then heating to cure the semi-cured resin layer to form a cured resin layer. The impregnation step of the thermosetting resin necessary for the coil can be omitted. Therefore, the high temperature superconducting coil of the present embodiment can be manufactured by a simplified manufacturing process as compared with the conventional superconducting coil.

  ADVANTAGE OF THE INVENTION According to this invention, the high temperature superconducting wire with which the whole outer periphery was completely insulation-coated, and the high temperature superconducting coil which uses this high temperature superconducting wire can be provided. Further, according to the present invention, a small and high-performance high-temperature superconducting coil with a high current density can be provided.

It is a cross-sectional schematic diagram which shows 1st Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows 2nd Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows the other example of 2nd Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows 3rd Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows 4th Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a schematic perspective view which shows an example structure of the high temperature superconducting wire which concerns on this invention. FIG. 7 is a schematic cross-sectional view showing an example structure of a high-temperature superconducting wire adjacent to the coil radial direction in the high-temperature superconducting coil shown in FIG. 6. FIG. 8A is a partial cross-sectional view along the radial direction in an example structure of a conventional superconducting coil, and FIG. 8B is a partial cross-sectional view along the radial direction in another example of the conventional superconducting coil. It is a cross-sectional schematic diagram which shows 5th Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows 6th Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows 7th Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows 8th Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a cross-sectional schematic diagram which shows 9th Embodiment of the high-temperature superconducting wire which concerns on this invention. It is a graph which shows the result of the moisture resistance test of Example 6 and Comparative Example 1. It is a cross-sectional schematic diagram which shows an example structure of Bi type superconducting wire. It is a cross-sectional schematic diagram which shows an example structure of a rare earth-based superconducting wire. It is a cross-sectional schematic diagram which shows an example structure at the time of carrying out insulation coating to the superconducting wire shown in FIG.

Hereinafter, embodiments of a high-temperature superconducting wire and a high-temperature superconducting coil according to the present invention will be described with reference to the drawings.
[First Embodiment]
FIG. 1 is a schematic cross-sectional view along the width direction of the first embodiment of the high-temperature superconducting wire according to the present invention.
A high-temperature superconducting wire 10 shown in FIG. 1 has a superconducting laminate on an outer peripheral surface of a superconducting laminate 5 in which an intermediate layer 12, an oxide superconducting layer 13, and a metal stabilizing layer 4 are laminated in this order on a substrate 11. 5 is formed and configured to cover the entire outer peripheral surface 5. The metal stabilization layer 4 includes a first stabilization layer 14 formed on the oxide superconducting layer 13 and a second stabilization layer 15 formed on the first stabilization layer 14.

The substrate 11 may be any substrate that can be used as an ordinary superconducting wire substrate, and is preferably in the form of a long plate, sheet, or tape, and is preferably made of a heat-resistant metal. Among heat resistant metals, an alloy is preferable, and a nickel (Ni) alloy or a copper (Cu) alloy is more preferable. Among them, if it is a commercial product, Hastelloy (trade name, manufactured by Haynes) is suitable, and the amount of components such as molybdenum (Mo), chromium (Cr), iron (Fe), cobalt (Co) is different, Hastelloy B, Any kind of C, G, N, W, etc. can be used. Alternatively, an oriented metal substrate in which a texture is introduced into a nickel (Ni) alloy or the like may be used as the substrate 11, and the intermediate layer 12 and the oxide superconducting layer 13 may be formed thereon.
The thickness of the substrate 11 may be appropriately adjusted according to the purpose, and is usually preferably 10 to 500 μm, and more preferably 20 to 200 μm. By setting the lower limit value or more, the strength can be further improved, and by setting the upper limit value or less, the critical current density of the overall can be further improved.

The intermediate layer 12 controls the crystal orientation of the oxide superconducting layer 13 and prevents diffusion of the metal element in the substrate 11 into the oxide superconducting layer 13. Furthermore, it functions as a buffer layer that alleviates the difference in physical properties (thermal expansion coefficient, lattice constant, etc.) between the substrate 11 and the oxide superconducting layer 13, and the material has physical properties such as the substrate 11 and the oxide superconducting layer. A metal oxide showing an intermediate value of 13 is preferable. Specifically, preferred materials for the intermediate layer 12 are Gd ₂ Zr ₂ O ₇ , MgO, ZrO ₂ —Y ₂ O ₃ (YSZ), SrTiO ₃ , CeO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , Gd _2. Examples thereof include metal oxides such as O ₃ , Zr ₂ O ₃ , Ho ₂ O ₃ , and Nd ₂ O ₃ .
The intermediate layer 12 may be a single layer or a plurality of layers. For example, the layer made of the metal oxide (metal oxide layer) preferably has crystal orientation, and when it is a plurality of layers, the outermost layer (the layer closest to the oxide superconducting layer 13). Preferably have at least crystal orientation.

The intermediate layer 12 may have a multi-layer structure in which a bed layer is interposed on the substrate 11 side. The bed layer has high heat resistance and is used for reducing interfacial reactivity, and is used for obtaining the orientation of a film disposed thereon. Such a bed layer is arranged as necessary, and is made of, for example, yttria (Y ₂ O ₃ ), silicon nitride (Si ₃ N ₄ ), aluminum oxide (Al ₂ O ₃ , also referred to as “alumina”), or the like. Is done. The bed layer is formed by a film forming method such as a sputtering method, and has a thickness of 10 to 200 nm, for example.

Further, in the present invention, the intermediate layer 12 may have a multi-layer structure in which a diffusion prevention layer and a bed layer are laminated on the substrate 11 side. In this case, a diffusion preventing layer is interposed between the substrate 11 and the bed layer. The diffusion preventing layer is formed for the purpose of preventing the constituent elements of the substrate 11 from diffusing, and is composed of silicon nitride (Si ₃ N ₄ ), aluminum oxide (Al ₂ O ₃ ), or a rare earth metal oxide, The thickness is, for example, 10 to 400 nm. Note that since the crystallinity of the diffusion preventing layer is not questioned, it may be formed by a film forming method such as a normal sputtering method.
In this way, by interposing the diffusion preventing layer between the substrate 11 and the bed layer, when forming the other layer constituting the intermediate layer 12, the oxide superconducting layer 13, etc., it is inevitably heated, When receiving a thermal history as a result of the heat treatment, it is possible to effectively suppress a part of the constituent elements of the substrate 11 from diffusing to the oxide superconducting layer 13 side through the bed layer. As an example of the case where a diffusion preventing layer is interposed between the substrate 11 and the bed layer, a combination using Al ₂ O ₃ as the diffusion preventing layer and Y ₂ O ₃ as the bed layer can be exemplified.

  The intermediate layer 12 may have a multi-layer structure in which a cap layer is further laminated on the metal oxide layer. The cap layer has a function of controlling the orientation of the oxide superconducting layer 13, diffuses the elements constituting the oxide superconducting layer 13 into the intermediate layer 12, and uses a gas and an intermediate used when the oxide superconducting layer 13 is laminated. It has a function of suppressing the reaction with the layer 12 and the like.

The cap layer is formed through a process of epitaxially growing on the surface of the metal oxide layer, and then growing the grains in the lateral direction (plane direction) (overgrowth) and selectively growing the crystal grains in the in-plane direction. The ones made are preferred. Such a cap layer has a higher degree of in-plane orientation than the metal oxide layer.
The material of the cap layer is not particularly limited as long as it can exhibit the above functions, but specifically, preferred examples include CeO ₂ , Y ₂ O ₃ , Al ₂ O ₃ , Gd ₂ O ₃ , and Zr ₂ O. ₃ , Ho ₂ O ₃ , Nd ₂ O _{3 and the} like. When the material of the cap layer is CeO ₂ , the cap layer may contain a Ce—M—O-based oxide in which part of Ce is substituted with another metal atom or metal ion.
The cap layer can be formed by a PLD method (pulse laser deposition method), a sputtering method, or the like, but it is preferable to use the PLD method from the viewpoint of obtaining a high film formation rate.

The thickness of the intermediate layer 12 may be appropriately adjusted according to the purpose, but is usually 0.1 to 5 μm.
When the intermediate layer 12 has a multi-layer structure in which a cap layer is laminated on the metal oxide layer, the thickness of the cap layer is usually 0.1 to 1.5 μm.

The intermediate layer 12 is formed by physical vapor deposition such as sputtering, vacuum vapor deposition, laser vapor deposition, electron beam vapor deposition, ion beam assisted vapor deposition (hereinafter abbreviated as IBAD); chemical vapor deposition (CVD). ); Coating pyrolysis method (MOD method); lamination can be performed by a known method for forming an oxide thin film such as thermal spraying. In particular, the metal oxide layer formed by the IBAD method is preferable in that the crystal orientation is high and the effect of controlling the crystal orientation of the oxide superconducting layer 13 and the cap layer is high. The IBAD method is a method of orienting crystal axes by irradiating an ion beam at a predetermined angle with respect to a crystal deposition surface during deposition. Usually, an argon (Ar) ion beam is used as the ion beam. For example, the intermediate layer 12 made of Gd ₂ Zr ₂ O ₇ , MgO, or ZrO ₂ —Y ₂ O ₃ (YSZ) can reduce the value of ΔΦ (FWHM: full width at half maximum) that is an index representing the degree of orientation in the IBAD method. Therefore, it is particularly suitable.

The oxide superconducting layer 13 can be widely applied with an oxide superconductor having a generally known composition, such as REBa ₂ Cu ₃ O _y (RE is Y, La, Nd, Sm, Er, Gd, etc. A material made of a material that represents a rare earth element, specifically, Y123 (YBa ₂ Cu ₃ O _y ) or Gd123 (GdBa ₂ Cu ₃ O _y ) can be exemplified. Further, other oxide superconductors, for _{example, Bi 2 Sr 2 Ca n-} 1 Cu n for _{O 4 + 2n + δ} becomes may be used in compositions such as those made of other oxide superconductors having high critical temperatures representative Of course.
The oxide superconducting layer 13 is laminated by physical vapor deposition such as sputtering, vacuum vapor deposition, laser vapor deposition, or electron beam vapor deposition; chemical vapor deposition (CVD); coating pyrolysis (MOD). Of these, laser vapor deposition is preferred.
The oxide superconducting layer 13 has a thickness of about 0.5 to 5 μm and preferably a uniform thickness.

The first stabilization layer 14 laminated on the oxide superconducting layer 13 is made of a metal material having good conductivity, such as Ag or a noble metal, having a low contact resistance with the oxide superconducting layer 13 and a good compatibility.
The reason why the first stabilization layer 14 is made of Ag is that it has a property of making it difficult for escape of doped oxygen from the oxide superconducting layer 13 in the annealing step of doping the oxide superconducting layer 13 with oxygen. Can do. In order to form the Ag first stabilizing layer 14, a film forming method such as a sputtering method is employed, and the thickness thereof is set to about 1 to 30 μm.

The second stabilization layer 15 laminated on the first stabilization layer 14 is made of a highly conductive metal material. When the oxide superconducting layer 13 attempts to transition from the superconducting state to the normal conducting state, the first stabilizing layer 15 is formed. It functions as a bypass through which the current of the oxide superconducting layer 13 commutates together with the oxide layer 14.
The metal material constituting the second stabilization layer 15 is not particularly limited as long as it has good conductivity, but copper alloys such as copper, brass (Cu—Zn alloy), Cu—Ni alloy, stainless steel, and the like. It is preferable to use a material made of a relatively inexpensive material such as copper, and copper is preferable because it has high conductivity and is inexpensive.
In addition, when using the oxide superconducting wire 10 for a superconducting fault current limiter, the 2nd stabilization layer 15 is comprised from a resistance metal material, Ni-type alloys, such as Ni-Cr, etc. can be used.

The formation method of the 2nd stabilization layer 15 is not specifically limited, For example, it forms by laminating | stacking the metal tape which consists of highly conductive materials, such as copper, on the 1st stabilization layer 14 via bonding agents, such as solder. it can. Here, the solder that can be used when the second stabilization layer 15 is formed by laminating a metal tape on the first stabilization layer 14 via the solder is not particularly limited, and a conventionally known solder can be used. For example, lead-free solder made of an alloy containing Sn as a main component such as Sn—Ag alloy, Sn—Bi alloy, Sn—Cu alloy, Sn—Zn alloy, Pb—Sn alloy solder, Examples thereof include eutectic solder and low-temperature solder, and these solders can be used alone or in combination of two or more. Among these, it is preferable to use solder having a melting point of 300 ° C. or less. As a result, the metal tape and the first stabilizing layer 14 can be soldered at a temperature of 300 ° C. or lower, and the deterioration of the characteristics of the oxide superconducting layer 13 due to the heat of soldering can be suppressed.
The thickness of the 2nd stabilization layer 15 is not specifically limited, Although it can adjust suitably, it is preferable to set it as 10-300 micrometers. By setting the lower limit value or more, a higher effect of stabilizing the oxide superconducting layer 13 can be obtained, and by setting the upper limit value or less, the oxide superconducting wire 10 can be thinned.

Superconducting laminate 5 having a substantially rectangular cross section in which substrate 11, intermediate layer 12, oxide superconducting layer 13, first stabilizing layer 14, and second stabilizing layer 15 are laminated has a cross section along the width direction. The corners 5a on the four corner sides are curved surfaces having a radius of curvature, and the radius of curvature of the corner 5a is set to 14.5 mm or more. By setting the radius of curvature of the corner 5a of the superconducting laminate 5 to 14.5 mm or more, the resin is uniformly applied to the entire outer periphery including the corner 5a of the superconducting laminate 5 when the insulating coating layer 7 described later is formed. The insulating coating layer 7 that can be applied and baked and completely covers the entire outer periphery of the superconducting laminate 5 can be formed. Therefore, a structure in which the superconducting laminate 5 is completely sealed from the outside by the insulating coating layer 7 can be realized. When the curvature radius of the corner portion 5a of the superconducting laminate 5 is less than 14.5 mm, the resin for forming the insulating coating layer 7 cannot be applied so as to cover the corner portion 5a of the superconducting laminate 5, and insulation is provided on the corner portion 5a. The coating layer 7 may not be formed, which is not preferable.
The upper limit of the radius of curvature of the corner portion 5a of the superconducting laminate 5 is not particularly limited, and can be appropriately adjusted depending on the dimensions and aspect ratio (width / thickness) of the superconducting laminate 5.

As a method of processing the corner 5a of the superconducting laminate 5 into a curved surface having a curvature radius in the above range, a conventionally known chamfering method can be applied. It can process so that it may become a corner | angular part of a desired curvature radius by grind | polishing with an apparatus.
When the corner portion of the superconducting laminate 5 is processed into a curved surface, the corner portion may be processed after the superconducting laminate 5 is formed, and the corner portion 11a of the substrate 11 and the corner portion 15a of the second stabilization layer 15 are preliminarily formed. After processing into a curved surface, each layer may be laminated to form superconducting laminate 5.

The insulating coating layer 7 covering the entire outer periphery of the superconducting laminate 5 is formed by applying a resin to the entire outer periphery of the superconducting laminate 5 and then baking it, and its thickness is set to 12 μm or more. The insulating coating layer is formed so as to cover the corner portion 5a of the superconducting laminate 5 by setting the radius of curvature of the corner portion 5a of the superconducting laminate 5 to 14.5 mm or more and the thickness of the insulating coating layer 7 to 12 μm or more. 7 can be applied and baked, and a structure in which the entire outer periphery including the corner 5a of the superconducting laminate 5 is completely covered with the insulating coating layer 7 can be realized. When the radius of curvature of the corner portion 5a is less than 14.5 mm, the resin for forming the insulating coating layer 7 cannot be applied so as to cover the corner portion 5a of the superconducting laminate 5, and the insulating coating layer 7 is formed on the corner portion 5a. It may not be possible and is not preferable. Further, even when the radius of curvature of the corner is 14.5 mm or more, the corner 5a cannot be completely covered if the thickness of the insulating coating layer 7 is less than 12 μm, as shown in the examples described later.
The upper limit of the thickness of the insulating coating layer 7 is not particularly limited, but is preferably 20 μm or less. When the thickness of the insulating coating layer 7 is 20 μm or less, the area of the insulating coating layer 7 shown in the cross-sectional area can be reduced, so that the high-temperature superconducting wire 10 can be reduced in size and the high-temperature superconducting wire 10 is coiled In addition, the overall current density can be increased.

  The resin constituting the insulating coating layer 7 is not particularly limited as long as the layer can be formed by baking. For example, formal resin, urethane resin, polyamideimide resin, polyimide resin, polyester resin, polyether ether ketone Resin (PEEK resin), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), perfluoroalkoxy fluororesin (PFA), polytetrafluoroethylene (tetrafluorinated resin, PTFE), ethylene tetrafluoride Fluorine resin such as ethylene copolymer (ETFE) can be used. Among these, a resin that can be baked at a temperature of 170 to 200 ° C. is preferable. By using such a resin, when the insulating coating layer 7 is formed, the baking temperature does not become too high, and the second stabilization layer 15 formed by bonding metal tape through solder or the like is used as the resin. It is possible to prevent the solder from melting and peeling during baking.

The baking of the resin when forming the insulating coating layer 7 is preferably performed at a temperature of 200 ° C. or lower, for example, 170 to 200 ° C., and the baking time may be adjusted as appropriate. By baking the resin under such conditions, peeling of the second stabilization layer 15 due to melting of the solder and deterioration of the oxide superconducting layer 13 can be suppressed.
The method for applying the resin is not particularly limited, and conventionally known methods such as a dip coating method and a spray coating method can be applied.
The insulating coating layer 7 may be formed on the superconducting laminate 5 by applying and baking the resin only once, and a plurality of resin coating and baking processes may be performed until the insulating coating layer 7 having a desired thickness is formed. It may be repeated repeatedly.

  The high-temperature superconducting wire 10 of the present embodiment includes the corner 5a of the superconducting laminate 5 by defining the curvature radius of the corner 5a of the superconducting laminate 5 and the thickness of the insulating coating layer 7 within a predetermined range. A structure in which the entire outer periphery is completely covered with the insulating coating layer 7 can be realized. Therefore, in the high-temperature superconducting wire 10 of the present embodiment, the superconducting laminate 5 is sealed from the outside by the insulating coating layer 7, and it is possible to reduce the intrusion of moisture and the like into the oxide superconducting layer 13 and the deterioration of the superconducting characteristics. Can be suppressed.

[Second Embodiment]
FIG. 2 is a schematic cross-sectional view along the width direction of the second embodiment of the high-temperature superconducting wire according to the present invention.
A high-temperature superconducting wire 10B shown in FIG. 2 includes a laminated body S1 having a rectangular cross section in which an intermediate layer 12, an oxide superconducting layer 13, and a first stabilizing layer 14 are laminated in this order on a substrate 11, in the center. An insulating coating layer 7B covering the entire outer peripheral surface of the superconducting laminate 5B is formed on the outer peripheral surface of the superconducting laminate 5B having a substantially rectangular cross section whose entire outer periphery of the laminate S1 is covered with the second stabilization layer 15B. It is configured. The metal stabilization layer 4B includes a first stabilization layer 14 formed on the oxide superconducting layer 13 and a second stabilization layer 15B that covers the entire outer periphery of the multilayer body S1.

  In the high-temperature superconducting wire 10B of the present embodiment, the second stabilizing layer 15B covers the entire outer periphery of the multilayer body S1 in which the intermediate layer 12, the oxide superconducting layer 13, and the first stabilizing layer 14 are laminated on the substrate 11. This is different from the high-temperature superconducting wire 10 of the first embodiment. In the high temperature superconducting wire 10B shown in FIG. 2, the same components as those of the high temperature superconducting wire 10 shown in FIG.

The second stabilization layer 15B covering the entire outer periphery of the multilayer body S1 is used together with the first stabilization layer 14 and the current of the oxide superconducting layer 13 when the oxide superconducting layer 13 attempts to transition from the superconducting state to the normal conducting state. Functions as a bypass to commutate.
The second stabilization layer 15B is formed by electroplating or vapor deposition. The material constituting the second stabilizing layer 15B is preferably a highly conductive metal, such as copper or aluminum, and copper is particularly preferable because of high conductivity. The thickness of the second stabilization layer 15B is not particularly limited and can be changed as appropriate. However, the thickness can be set to about 10 to 100 μm, preferably 20 μm to 100 μm, and preferably 20 μm to 50 μm. More preferred. A higher effect of stabilizing the oxide superconducting layer 13 can be obtained by setting the thickness of the second stabilizing layer 15B to 10 μm or more, and the high-temperature superconducting wire 10B can be made thinner by setting the thickness to 100 μm or less.
In order to form the second metal stabilization layer 15B of copper by plating, the laminate S1 may be immersed in a plating bath of an aqueous copper sulfate solution and electroplated.

Superconducting laminate 5B composed of substrate 11, intermediate layer 12, oxide superconducting layer 13, first stabilizing layer 14, and second stabilizing layer 15B has a curved surface in which corner portion 5Ba in the cross section along the width direction has a radius of curvature. The curvature radius of the corner 5Ba is set to 14.5 mm or more. By setting the radius of curvature of the corner portion 5Ba of the superconducting laminate 5B to 14.5 mm or more, the resin is applied and baked on the entire outer periphery including the corner portion 5Ba of the superconducting laminate 5B when the insulating coating layer 7B is formed. Insulating coating layer 7B covering the entire outer periphery of superconducting laminate 5B can be formed.
The upper limit of the radius of curvature of the corner 5Ba of the superconducting laminate 5B is the same as that of the high-temperature superconducting wire 10 of the first embodiment.

As a method of processing the corner portion 5Ba of the superconducting laminate 5B into a curved surface having a curvature radius in the above range, a conventionally known chamfering method can be applied. For example, the corner portion of the superconducting laminate 5 can be a tool such as a scissors or polished. It can process so that it may become a corner | angular part of a desired curvature radius by grind | polishing with an apparatus. Since the second stabilizing layer 15B formed by plating or vapor deposition tends to have a curved corner, the second stabilizing layer 15B has a curved surface having a curvature radius in the above range with the second stabilizing layer 15B intact. Chamfering can be omitted. In addition, even if all the side surfaces do not match, a part of the curvature can be obtained because the effect is obtained by having a curved surface in a corresponding range.
The aspect ratio (width / thickness) of the superconducting laminate 5B is the same as that of the high-temperature superconducting wire 10 of the first embodiment.

  The insulating coating layer 7B covering the entire outer periphery of the superconducting laminate 5B is formed by applying a resin to the entire outer periphery of the superconducting laminate 5B and then baking, and the thickness thereof is set to 12 μm or more. The insulating coating layer 7 is formed so as to cover the corner portion 5a of the superconducting laminate 5 by setting the radius of curvature of the corner portion 5Ba of the superconducting laminate 5B within the above range and the thickness of the insulating coating layer 7B being 12 μm or more. Therefore, a structure in which the entire outer periphery including the corner portion 5Ba of the superconducting laminate 5B is completely covered with the insulating coating layer 7B can be realized. The upper limit of the thickness of the insulating coating layer 7B is not particularly limited, but is preferably 20 μm or less. When the thickness of the insulating coating layer 7B is 20 μm or less, the area of the insulating coating layer 7 shown in the cross-sectional area can be reduced, so that the high-temperature superconducting wire 10B can be downsized and the high-temperature superconducting wire 10B is coiled In addition, a high overall current density can be realized.

  The resin constituting the insulating coating layer 7B is not particularly limited as long as the layer can be formed by baking, and the same resin as the high-temperature superconducting wire 10 of the first embodiment can be mentioned. Among these, a resin that can be baked at a temperature of 280 ° C. or lower, for example, 170 to 280 ° C. is preferable. By using such a resin, the baking temperature does not become too high when the insulating coating layer 7B is formed, and the oxide superconducting layer 13 deteriorates due to the release of oxygen in the oxide superconducting layer 13 during resin baking. Can be prevented.

The baking of the resin when forming the insulating coating layer 7B is preferably performed at a temperature of 170 to 280 ° C., and the baking time may be adjusted as appropriate. By baking the resin under such conditions, deterioration of the oxide superconducting layer 13 can be suppressed.
The method for applying the resin is not particularly limited, and a conventionally known method such as a dip coating method or a spray coating method can be used.
The insulating coating layer 7B may be formed on the superconducting laminate 5B by applying and baking the resin only once. A plurality of resin coating and baking processes may be performed until the insulating coating layer 7B having a desired thickness is formed. It may be repeated repeatedly.

  The high-temperature superconducting wire 10B of the present embodiment covers the corner 5a of the superconducting laminate 5 by defining the curvature radius of the corner 5Ba of the superconducting laminate 5B and the thickness of the insulating coating layer 7B within a predetermined range. Thus, the resin for forming the insulating coating layer 7 can be applied and baked, and a structure in which the entire outer periphery including the corner portion 5Ba of the superconducting laminate 5B is completely covered with the insulating coating layer 7B can be realized. Therefore, in the high-temperature superconducting wire 10B of the present embodiment, the superconducting laminate 5B is sealed from the outside by the insulating coating layer 7B, so that moisture or the like can be prevented from entering the oxide superconducting layer 13 and the superconducting characteristics are deteriorated. Can be suppressed.

In the high-temperature superconducting wire 10B shown in FIG. 2, an example is shown in which four corners of a rectangular cross section along the width direction of the laminate S1 are angular, but the corners of the laminate S1 are chamfered as shown in FIG. It may be processed into a curved surface. In the high-temperature superconducting wire 10B ₂ shown in FIG. 3, although the radius of curvature of the corners of the stack S1 is not particularly limited, plating by the time of forming the second stabilizing layer 15B, automatically the second stabilizing layer 15B It is preferable that the corner is set to be a curved surface having a radius of curvature in the above range. In this way, the second stabilizing layer 15B formed on the outer periphery of the multilayer body S1 may be a curved surface having a curvature radius in the above range by chamfering so that the corners of the multilayer body S1 are curved in advance. it can.

As a method of processing the corner portion of the laminated body S1 into a curved surface, a conventionally known chamfering method can be applied. For example, a desired radius of curvature is obtained by polishing the corner portion of the laminated body S1 with a tool such as a scissors or a polishing apparatus. Can be processed to be the corners of
When processing the corners of the laminate S1 into a curved surface, the corners may be processed after forming the laminate S1, and after processing the corner 11a of the substrate 11 into a curved surface in advance, the layers are stacked to form a laminate. In addition, the corner portion 14a of the first stabilization layer 14 may be processed into a curved surface.

[Third Embodiment]
FIG. 4 is a schematic cross-sectional view along the width direction of the third embodiment of the high-temperature superconducting wire according to the present invention.
A high-temperature superconducting wire 10C shown in FIG. 4 has a superconducting laminate on the outer peripheral surface of a superconducting laminate 5C in which an intermediate layer 12, an oxide superconducting layer 13, and a first stabilizing layer 14 are laminated in this order on a substrate 11. An insulating coating layer 7C that covers the entire outer peripheral surface of the body 5C is formed and configured.

  The high temperature superconducting wire 10C of the present embodiment is different from the high temperature superconducting wire 10 of the first embodiment in that the metal stabilizing layer 4C is composed of one layer of the first stabilizing layer 14. In the high temperature superconducting wire 10C shown in FIG. 4, the same components as those of the high temperature superconducting wire 10 shown in FIG.

A superconducting laminate 5C having a substantially rectangular cross section composed of the substrate 11, the intermediate layer 12, the oxide superconducting layer 13, and the first stabilizing layer 14 has a curved surface in which the corner 5Ca in the cross section along the width direction has a radius of curvature. The radius of curvature of the corner 5Ca is set to 14.5 mm or more. By setting the curvature radius of the corner 5Ca of the superconducting laminate 5C to 14.5 mm or more, the resin is applied and baked on the entire outer periphery including the corner 5Ca of the superconducting laminate 5C when the insulating coating layer 7C is formed. Insulating coating layer 7C covering the entire outer periphery of superconducting laminate 5C can be formed.
The upper limit of the radius of curvature of the corner portion 5Ca of the superconducting laminate 5C is the same as that of the high temperature superconducting wire 10 of the first embodiment.

The method of processing the corner portion 5Ca of the superconducting laminate 5C into a curved surface having the radius of curvature in the above range is the same as that of the high temperature superconducting wire 10 of the first embodiment.
When processing the corner portion of the superconducting laminate 5C into a curved surface having the radius of curvature, the corner portion may be processed after forming the superconducting laminate 5C, or after processing the corner portion 11a of the substrate 11 into a curved surface in advance. Each layer may be laminated, and the corner portion 14a of the first stabilization layer 14 may be processed into a curved surface.
The aspect ratio (width / thickness) of the superconducting laminate 5C is the same as that of the high-temperature superconducting wire 10 of the first embodiment.

  The insulating coating layer 7C covering the entire outer periphery of the superconducting laminate 5C is formed by applying a resin to the entire outer periphery of the superconducting laminate 5C and then baking, and the thickness thereof is set to 12 μm or more. By setting the radius of curvature of the corner portion 5Ca of the superconducting laminate 5C within the above range and the thickness of the insulating coating layer 7C being 12 μm or more, the entire outer periphery including the corner portion 5Ca of the superconducting laminate 5C becomes the insulating coating layer 7C. The structure covered with can be realized. The upper limit of the thickness of the insulating coating layer 7C is not particularly limited, but is preferably 20 μm or less. When the thickness of the insulating coating layer 7C is 20 μm or less, the area of the insulating coating layer 7 shown in the cross-sectional area can be reduced, so that the high-temperature superconducting wire 10C can be reduced in size and the high-temperature superconducting wire 10C is coiled In addition, the overall current density can be increased.

  The resin constituting the insulating coating layer 7C is not particularly limited as long as the layer can be formed by baking, and the same resin as the high-temperature superconducting wire 10 of the first embodiment can be mentioned. Among these, a resin that can be baked at a temperature of 170 to 280 ° C. is preferable. By using such a resin, the baking temperature does not become too high when the insulating coating layer 7C is formed, and the oxide superconducting layer 13 deteriorates due to the release of oxygen in the oxide superconducting layer 13 during resin baking. Can be prevented.

  The high-temperature superconducting wire 10C of the present embodiment covers the corner 5a of the superconducting laminate 5 by defining the curvature radius of the corner 5Ca of the superconducting laminate 5C and the thickness of the insulating coating layer 7C within a predetermined range. Thus, the resin for forming the insulating coating layer 7 can be applied and baked, and a structure in which the entire outer periphery including the corner portion 5Ca of the superconducting laminate 5C is completely covered with the insulating coating layer 7C can be realized. Therefore, in the high-temperature superconducting wire 10C of the present embodiment, the superconducting laminate 5C is sealed from the outside by the insulating coating layer 7C, and it is possible to reduce the intrusion of moisture and the like into the oxide superconducting layer 13, thereby deteriorating the superconducting characteristics. Can be suppressed.

[Fourth Embodiment]
The first to the high temperature superconducting wire of the third embodiment 10 and _10B, 10B 2, 10C further insulating coating layer 7,7B, covers 7C outer peripheral surface of the semi-cured resin made of a semi-cured thermosetting resin It is also preferred to have a layer. As an example below, but the high-temperature superconducting wire 10B ₂ shown in FIG. 3 will be described for the case with a semi-cured resin layer, the present invention is not limited to this embodiment, high-temperature superconducting wire of the first to third embodiments Any of these can have a semi-cured resin layer.

FIG. 5: is a cross-sectional schematic diagram along the width direction of 4th Embodiment of the high-temperature superconducting wire which concerns on this invention.
A high-temperature superconducting wire 10D shown in FIG. 5 includes a laminated body S1 in which an intermediate layer 12, an oxide superconducting layer 13, and a first stabilizing layer 14 are laminated in this order on a substrate 11, and this laminated body S1. An insulating covering layer 7B is formed on the outer peripheral surface of the superconducting laminate 5B having a substantially rectangular cross section and the entire outer periphery of the superconducting laminate 5B is covered with the second stabilizing layer 15B. A semi-cured resin layer 9 covering the entire outer periphery of the insulating coating layer 7B is formed on the outer peripheral surface of the coating layer 7B. The same symbols are attached to the same components as HTS wire 10B ₂ shown in FIG. 3 in a high temperature superconducting wire 10C shown in FIG. 5, the description thereof is omitted.

The semi-cured resin layer 9 covering the entire outer periphery of the insulating coating layer 7B is obtained by applying a thermosetting resin to the entire outer periphery of the high-temperature superconducting wire 10B ₂ shown in FIG. It is formed by doing.
Heating of the thermosetting resin when forming the semi-cured resin layer 9 is preferably performed at a temperature of 150 to 200 ° C., and the heating time may be appropriately adjusted. By heating the thermosetting resin under such conditions, the thermosetting resin can be brought into a semi-cured state, and the oxide superconducting layer 13 can be prevented from being deteriorated by heating.

The thermosetting resin that can be used for forming the semi-cured resin layer 9 is not particularly limited as long as it is a thermosetting resin that becomes a semi-cured state under the above-described heating conditions, and examples thereof include an epoxy resin.
The method for applying the thermosetting resin is not particularly limited, and a conventionally known method such as a dip coating method or a spray coating method can be used.

  When coiling the high-temperature superconducting wire 10D of this embodiment, after winding the high-temperature superconducting wire 10D, the semi-cured resin layer 9 is cured and heated in the coil radial direction without being impregnated with resin. Adjacent high temperature superconducting wire 10 can be fixed. Therefore, by manufacturing a high-temperature superconducting coil from the high-temperature superconducting wire 10D of the present embodiment, the coil manufacturing process can be simplified and, as will be described later, compared to a conventional superconducting coil manufacturing method, a high temperature adjacent to the coil radial direction. Since the thickness of the resin between the superconducting wires can be reduced, the current density of the superconducting coil can be increased.

  The thickness of the semi-cured resin layer 9 is not particularly limited and can be appropriately adjusted, but is preferably 2 to 20 μm, and more preferably 2 to 5 μm. By setting the thickness of the semi-cured resin layer 9 in the above range, the overall current density can be increased when the high-temperature superconducting wire 10D is coiled.

Next, an embodiment of a superconducting coil according to the present invention will be described.
FIG. 6 is a schematic perspective view showing an embodiment of the high-temperature superconducting coil according to the present invention.
The high temperature superconducting coil 50 shown in FIG. 6 is configured by coaxially laminating a second coil body 52 on a first coil body 51.
The first coil body 51 is a pancake-type coil body configured by winding the above-described high-temperature superconducting wire of the present invention many times concentrically and counterclockwise. The second coil body 52 is a pancake type coil body formed by concentrically winding the high-temperature superconducting wire of the present invention described above many times in a clockwise direction.

  The outer peripheral end portion 51a that is the winding end of the first coil body 51 and the outer peripheral end portion 52a that is the winding end portion of the second coil body 52 are arranged so as to be adjacent to each other. On the side of the parts 51a and 52a, the insulating coating layer 7 is removed and the superconducting laminate 5 is drawn out, and the adjacent metal stabilization layers 4 are electrically connected by a highly conductive connection plate (not shown). Connected mechanically and mechanically.

  Since the high-temperature superconducting wire constituting the high-temperature superconducting coil 50 of the present embodiment is composed of the above-described high-temperature superconducting wire of the present invention, the superconducting laminate 5 is sealed from the outside by the insulating coating layer 7. For this reason, moisture permeation into the oxide superconducting layer 13 can be reduced, and deterioration of the superconducting characteristics can be suppressed.

The high temperature superconducting coil 50 of the present embodiment is preferably composed of a wire material in which a semi-cured resin layer 9 is formed on the outer periphery of the insulating coating layer 7B like the high temperature superconducting wire material 10D of the fourth embodiment.
FIG. 7 is a cross-sectional view schematically showing the state of the high-temperature superconducting wire 10D adjacent in the coil radial direction when the high-temperature superconducting coil 50 of the present embodiment is constituted by the high-temperature superconducting wire 10D shown in FIG. .

  The high temperature superconducting coil 50 shown in FIG. 7 can be manufactured by curing the semi-cured resin layer 9 of the high temperature superconducting wire 10D by heating the high temperature superconducting wire 10D shown in FIG. 5 after concentric winding. The high-temperature superconducting wire 10D adjacent in the coil radial direction is fixed by a cured resin layer 9G obtained by curing the semi-cured resin layer 9.

  Conventionally, the production of a superconducting coil has been performed through a process of winding a superconducting wire, impregnating it with a thermosetting resin, and further heat-curing it. On the other hand, in the high temperature superconducting coil 50 of this embodiment shown in FIG. 6, after winding the high temperature superconducting wire 10D provided with the semi-cured resin layer 9, the semi-cured resin layer 9 is cured by heating to cure the cured resin layer. It can be manufactured by using 9G, and the impregnation step of the thermosetting resin that is necessary in the conventional coil can be omitted. Therefore, the high-temperature superconducting coil 50 of the present embodiment can be manufactured by a simplified manufacturing process as compared with the conventional superconducting coil. Further, since the manufacturing process can be simplified, the manufacturing cost can be suppressed.

FIG. 8A is a partial cross-sectional view along the radial direction in an example structure of a conventional superconducting coil, and FIG. 8B is a partial cross-sectional view along the radial direction in another example of the conventional superconducting coil.
The superconducting coil 310 shown in FIG. 8A has a superconducting wire 311 in which an intermediate layer, an oxide superconducting layer, and a metal stabilizing layer are sequentially laminated on a substrate, and an insulating resin tape 312 overlaid. It is formed by winding concentrically into a coil shape and then fixing it with a resin layer 315 which is impregnated with a thermosetting resin and heat-cured. In the superconducting coil 310 of this form, when the thickness of the resin tape 312 to be used is less than 50 μm, the workability during winding tends to deteriorate, and the thickness of the resin tape 312 exceeds 50 μm and becomes too thick. Then, the critical current density of the superconducting coil 310 is lowered. Furthermore, the thickness of the resin layer 315A in the longitudinal direction of the superconducting wire 311 tends to be non-uniform.

    A superconducting coil 320 shown in FIG. 8B is obtained by winding an insulating resin tape 322 around the outer periphery of a superconducting wire 321 in which an intermediate layer, an oxide superconducting layer, and a metal stabilizing layer are sequentially laminated on a substrate. Are coiled to form a coil shape, and then the coiled material is impregnated with a thermosetting resin and fixed by a heat-cured resin layer 325. In the superconducting coil 320 of this form, when the thickness of the resin tape 322 to be used is less than 50 μm, the workability at the time of winding around the superconducting wire 321 tends to deteriorate, and the thickness of the resin tape 322 becomes too thick. Then, the critical current density of the superconducting coil 320 is lowered. Furthermore, the thickness of the resin layer 325A in the longitudinal direction of the superconducting wire 321 tends to be non-uniform.

  Since the high-temperature superconducting coil 50 of this embodiment is formed by winding the high-temperature superconducting wire according to the present invention described above, it is compared with the superconducting coils 310 and 320 shown in FIGS. 8 (a) and 8 (b). Thus, the insulating coating layer 7 formed by applying and baking the resin is thin, and the semi-cured resin layer 9 formed by applying and heating the thermosetting resin is thin, and the thickness variation is small. Therefore, the thickness of the insulating coating layer 7 and the cured resin layer 9G in the superconducting coil 50 is smaller than the thickness of the resin tapes 312 and 322 and the resin layers 315 and 325 of the superconducting coils 310 and 320 shown in FIG. There can be less variation. Therefore, since the interval between the high-temperature superconducting wires (superconducting laminate 5B) adjacent in the coil radial direction can be reduced, the thickness of the insulating resin layer 7 and the cured resin layer 9G does not become too thick, and the critical current density is increased. It becomes the superconducting coil 50 which can do.

[Fifth Embodiment]
FIG. 9 is a schematic cross-sectional view of a fifth embodiment of the high-temperature superconducting wire according to the present invention.
In the high-temperature superconducting wire 10E shown in FIG. 9, the intermediate layer 12, the oxide superconducting layer 13, and the first stabilizing layer 14 are laminated in this order on one surface of the substrate 11, and the peripheral surface of the laminate is formed as the second surface. An insulating coating layer 7E is formed on the peripheral surface of the superconducting laminate 5E covered with the stabilization layer 15E. The second stabilization layer 15E covers the peripheral surface of the laminate so as to form a C-shaped cross section except for the central portion of the other surface of the substrate 11, and the second stabilization layer of the first embodiment described above. The layer 15 is made of the same material. The central portion of the other surface of the substrate 11 that is not covered by the second stabilization layer 15E is covered by the solder layer 25, and the solder layer 25 fills the recess formed by the edges of the second stabilization layer 15E. Is formed. The insulating coating layer 7E is equivalent to the insulating coating layer 7 of the first embodiment.
In the high temperature superconducting wire 10E shown in FIG. 9, the same components as those of the high temperature superconducting wire 10 shown in FIG.

In the superconducting laminate 5E having a substantially rectangular cross section composed of the substrate 11, the intermediate layer 12, the oxide superconducting layer 13, the first stabilizing layer 14, and the second stabilizing layer 15E, the corner 5Ea in the cross section along the width direction thereof. Is a curved surface having a radius of curvature, and the radius of curvature of the corner 5Ea is set to 14.5 mm or more. By setting the radius of curvature of the corner portion 5Ea of the superconducting laminate 5E to 14.5 mm or more, the resin is applied and baked on the entire outer periphery including the corner portion 5Ea of the superconducting laminate 5E when the insulating coating layer 7E is formed. Insulating coating layer 7E covering the entire outer periphery of superconducting laminate 5E can be formed. The upper limit of the radius of curvature of the corner 5Ea of the superconducting laminate 5E is the same as that of the high-temperature superconducting wire 10 of the first embodiment.
Also in the structure of the fifth embodiment, the same effect as that of the structure of the first embodiment can be obtained.

[Sixth Embodiment]
FIG. 10 is a schematic cross-sectional view of a sixth embodiment of the high-temperature superconducting wire according to the present invention.
In the high-temperature superconducting wire 10F shown in FIG. 10, the intermediate layer 12, the oxide superconducting layer 13, and the first stabilizing layer 14 are laminated in this order on one surface of the substrate 11, and the peripheral surface of this laminate is formed as the second surface. The superconducting laminate 5F is configured by covering with the stabilization layer 15F and further laminating the third stabilization layer 16F on one surface thereof. The second stabilization layer 15F covers the peripheral surface of the laminate so as to form a C-shaped cross section except for the central portion of the other surface of the substrate 11, and the second stabilization layer of the first embodiment. The layer 15 is made of the same material. The central portion of the other surface of the substrate 11 that is not covered by the second stabilization layer 15F is covered by the solder layer 25, and the solder layer 25 fills the recess formed by the edges of the second stabilization layer 15F. Is formed. Further, the superconducting laminate 5F is arranged along the third stabilization layer 16F made of a copper tape having the same width as the second stabilization layer 15F outside the position where the solder layer 25 is provided with respect to the second stabilization layer 15F. An insulating coating layer 7E is formed outside the superconducting laminate 5F. In the high-temperature superconducting wire 10F shown in FIG. 10, the same components as those in the high-temperature superconducting wire 10E shown in FIG. 9 are denoted by the same reference numerals, and detailed description thereof is omitted.

In the superconducting laminate 5F having a substantially rectangular cross section composed of the substrate 11, the intermediate layer 12, the oxide superconducting layer 13, the first stabilizing layer 14, the second stabilizing layer 15F, and the third stabilizing layer 16F, its width direction The corner 5Fa in the cross-section along the line is a curved surface having a radius of curvature, and the radius of curvature of the corner 5Fa is set to 14.5 mm or more. By setting the curvature radius of the corner portion 5Fa of the superconducting laminate 5F to 14.5 mm or more, the resin is applied and baked on the entire outer periphery including the corner portion 5Fa of the superconducting laminate 5F when the insulating coating layer 7E is formed. Insulating coating layer 7E covering the entire outer periphery of superconducting laminate 5F can be formed. The upper limit of the radius of curvature of the corner portion 5Fa of the superconducting laminate 5F is the same as that of the high temperature superconducting wire 10E of the previous embodiment. In the present embodiment, of the four corners of the superconducting laminate 5F, two corners are constituted by the second stabilization layer 15F, and the other two corners are constituted by the third stabilization layer 16F. ing. In the structure shown in FIG. 10, the third stabilization layer 16 </ b> F is disposed outside the solder layer 25, but the third stabilization layer 16 </ b> F may be disposed near the oxide superconducting layer 13. That is, the third stabilization layer 16F may be laminated so as to be in contact with the outside of the second stabilization layer 15F laminated on the outside of the first stabilization layer 14. It is advantageous in terms of stabilizing the superconducting characteristics that the third stabilizing layer 16F is disposed at a position close to the oxide superconducting layer 13.
Also in the structure of the sixth embodiment, the same effect as that of the structure of the first embodiment can be obtained.

[Seventh Embodiment]
FIG. 11 is a schematic cross-sectional view of a seventh embodiment of the high-temperature superconducting wire according to the present invention.
In the high-temperature superconducting wire 10G shown in FIG. 11, an intermediate layer 12, an oxide superconducting layer 13, and a first stabilizing layer 14 are laminated in this order on one surface of the substrate 11, and tin is formed on the other surface of the substrate 11. An insulating coating layer 7E is formed on the peripheral surface of the superconducting laminate 5G in which the peripheral surface of the laminate formed by forming the bonding layer 17 by forming the foil is covered with the second stabilization layer 15G. The second stabilization layer 15G covers the peripheral surface of the laminate so as to form a C-shaped cross section except for the central portion on the other surface side of the substrate 11, and the second stabilization layer 15G of the previous first embodiment. It is made of the same material as the chemical layer 15. The central portion of the bonding layer 17 on the other side of the substrate 11 that is not covered by the second stabilization layer 15E is covered by the solder layer 25, and the solder layer 25 is formed by the edges of the second stabilization layer 15G. It is formed so as to fill the recess. Since the bonding layer 17 and the solder layer 25 can be made of the same material, the bonding layer 17 and the solder layer 25 have an integral structure when they are made of the same material.
In the high-temperature superconducting wire 10G shown in FIG. 11, the same components as those of the high-temperature superconducting wire 10E shown in FIG. 9 are denoted by the same reference numerals, and detailed description thereof is omitted.

A cross section along the width direction of a superconducting laminate 5G having a substantially rectangular cross section comprising a substrate 11, an intermediate layer 12, an oxide superconducting layer 13, a first stabilizing layer 14, a bonding layer 17, and a second stabilizing layer 15G. The corner 5Ga is a curved surface having a radius of curvature, and the radius of curvature of the corner 5Ga is set to 14.5 mm or more. By setting the radius of curvature of the corner portion 5Ga of the superconducting laminate 5G to 14.5 mm or more, the resin is applied and baked on the entire outer periphery including the corner portion 5Ga of the superconducting laminate 5G when the insulating coating layer 7E is formed. Insulating coating layer 7E covering the entire outer periphery of superconducting laminate 5G can be formed. The upper limit of the radius of curvature of the corner portion 5Ga of the superconducting laminate 5G is the same as that of the high temperature superconducting wire 10E of the previous embodiment.
Also in the structure of the seventh embodiment, the same effect as that of the structure of the first embodiment can be obtained.

[Eighth Embodiment]
FIG. 12 is a schematic cross-sectional view of an eighth embodiment of the high-temperature superconducting wire according to the present invention.
In the high-temperature superconducting wire 10H shown in FIG. 12, the intermediate layer 12, the oxide superconducting layer 13, and the first stabilizing layer 14 are laminated in this order on one surface of the substrate 11, and the tin foil is laminated on the other surface of the substrate 11. A superconducting laminate 5H is formed by covering the peripheral surface of the laminate formed by forming the bonding layer 17 with the second stabilizing layer 15H and further laminating the third stabilizing layer 16H on the one surface. ing. The second stabilizing layer 15H covers the peripheral surface of the laminate so as to form a C-shaped cross section except for the outer central portion of the bonding layer 17 on the other surface of the substrate 11, and the first embodiment described above. The second stabilizing layer 15 is made of the same material. The outer central portion of the bonding layer 17 that is not covered by the second stabilization layer 15H is covered by the solder layer 25, and the solder layer 25 is formed so as to fill the recess formed by the edges of the second stabilization layer 15H. ing. Further, the third stabilization layer 16H made of a copper tape or the like having the same width as the C-shaped second stabilization layer 15H is placed outside the position where the solder layer 25 is provided with respect to the second stabilization layer 15H. A laminated body 5H is configured, and an insulating coating layer 7E is formed outside the superconducting laminated body 5H.
In the high-temperature superconducting wire 10H shown in FIG. 12, the same components as those in the high-temperature superconducting wire 10E shown in FIG.

The superconducting laminate 5H having a substantially rectangular cross section composed of the substrate 11, the intermediate layer 12, the oxide superconducting layer 13, the first stabilizing layer 14, the second stabilizing layer 15H, and the third stabilizing layer 16H has a width direction. The corner 5Ha in the cross section along the line is a curved surface having a radius of curvature, and the radius of curvature of the corner 5Ha is set to 14.5 mm or more. By setting the radius of curvature of the corner portion 5Ha of the superconducting laminate 5H to 14.5 mm or more, the resin is applied and baked on the entire outer periphery including the corner portion 5Ha of the superconducting laminate 5H when the insulating coating layer 7E is formed. Insulating coating layer 7E covering the entire outer periphery of superconducting laminate 5H can be formed. The upper limit of the radius of curvature of the corner 5Ha of the superconducting laminate 5H is the same as that of the high-temperature superconducting wire 10E of the previous embodiment. In the structure shown in FIG. 12, the third stabilization layer 16H is disposed outside the solder layer 25. However, the third stabilization layer 16H may be disposed near the oxide superconducting layer 13. That is, the third stabilization layer 16H may be laminated so as to be in contact with the outside of the second stabilization layer 15F laminated on the outside of the first stabilization layer 14.
In the structure of the eighth embodiment, the same effect as that of the first embodiment can be obtained.

[Ninth Embodiment]
FIG. 13: is a cross-sectional schematic diagram of 9th Embodiment of the high temperature superconducting wire which concerns on this invention.
In the high-temperature superconducting wire 10J shown in FIG. 13, on the outer peripheral surface of the superconducting laminate 5J in which the intermediate layer 12, the oxide superconducting layer 13, and the first stabilizing layer 14 are laminated in this order on one surface of the substrate 11. In addition, a second stabilizing layer 15J is formed which covers the whole with a C-shaped cross section by abutting the end edge to the center of one side surface of the superconducting laminate 5J and soldering or welding, and further to the outside. An insulating coating layer 7E is formed. The second stabilization layer 15J is made of the same material as the second stabilization layer 15 of the first embodiment.
In the high-temperature superconducting wire 10J shown in FIG. 13, the same components as those in the high-temperature superconducting wire 10E shown in FIG.

The superconducting laminate 5J having a substantially rectangular cross section composed of the substrate 11, the intermediate layer 12, the oxide superconducting layer 13, the first stabilizing layer 14, and the second stabilizing layer 15J has a corner portion 5Ja in a section along the width direction. Is a curved surface having a radius of curvature, and the radius of curvature of the corner 5Ja is set to 14.5 mm or more. By setting the curvature radius of the corner portion 5Ja of the superconducting laminate 5J to 14.5 mm or more, the resin is applied and baked on the entire outer periphery including the corner portion 5Ja of the superconducting laminate 5J when the insulating coating layer 7E is formed. Insulating coating layer 7E covering the entire outer periphery of superconducting laminate 5J can be formed. The upper limit of the radius of curvature of the corner 5Ja of the superconducting laminate 5J is the same as that of the high-temperature superconducting wire 10E of the previous embodiment.
Also in the structure of the ninth embodiment, the same effect as that of the structure of the first embodiment can be obtained.
As described above, the high temperature superconducting wire and the high temperature superconducting coil of the present invention have been described. It is possible.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to these Examples. The evaluation methods in the following examples and comparative examples are as follows.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to these Examples. The evaluation methods in the following examples and comparative examples are as follows.

[1] Appearance The coating state of the insulating coating layer in the high-temperature superconducting wire was confirmed by visual inspection of the appearance and measurement with a micrometer. “○” indicates that there is no abnormality in the appearance (covering), “△” indicates that there is a portion where the coating is thin but the coating thickness is thin, and “×” indicates that there is an uncovered portion that is not covered. Judged.

[2] Superconducting characteristics Measure the critical current value Ic0 at 77K of the superconducting laminate before forming the insulating coating layer and the critical current value Ic at 77K of the high-temperature superconducting wire after forming the insulating coating layer to form the insulating coating layer. The ratio Ic / Ic0 between the front and rear critical current values was determined, and a case where Ic / Ic0 was 0.95 or more was determined as “◯”, and a case where Ic / Ic0 was less than 0.95 was determined as “x”.

[3] Solvent resistance test Using a standard solvent of JIS C 3003, the presence or absence of the insulation coating layer of the high-temperature superconducting wire after immersion of the high-temperature superconducting wire in a solvent (xylene) at 60 ° C. for 30 minutes is visually or optical microscope Observed at.
The case where there was no abnormality in the coating was determined as “◯”, and the case where there was an abnormality such as melting of the coating was determined as “x”.

[4] Chemical resistance test In accordance with JIS C 3003, the high-temperature superconducting wire was immersed in dilute sulfuric acid at room temperature for 24 hours, and then the coating state of the insulating coating layer of the high-temperature superconducting wire was confirmed visually or with an optical microscope.
The case where there was no abnormality in the coating was determined as “◯”, and the case where there was an abnormality such as melting of the coating was determined as “x”.

(Example 1: Samples 1 to 5)
On the substrate made of tape-like Hastelloy (trade name, manufactured by Haynes, USA) having a width of 5 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) was formed on the bed layer by ion beam assisted sputtering (IBAD method), and then 1.0 μm thick CeO ₂ (PLD method) was formed by pulsed laser deposition (PLD method). (Cap layer) was formed. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer). Thereafter, a 0.1 mm thick copper tape (second stabilizing layer) is laminated on the silver layer with tin solder (melting point 230 ° C.), and the corners (four corners) in the width direction of the laminate are polished. Thus, a superconducting laminate having a width of 5 mm, a thickness of 0.21 mm, and an aspect ratio of 24 was prepared by setting the radius of curvature of the corner of the cross section along the width direction to 14.5 mm.

Next, a formal resin (manufactured by Chisso Corporation, Vinylec F) is baked on the produced superconducting laminate at the baking temperature shown in Table 1 for 30 minutes to form an insulating coating layer having a thickness of 20 μm and shown in FIG. A high-temperature superconducting wire with a structure was prepared.
Table 1 also shows the results of evaluating the appearance, superconducting properties, and solvent resistance test of the produced high-temperature superconducting wires of Samples 1 to 5.

From the results of Table 1, in the high-temperature superconducting wire of Example 1 in which the second stabilizing layer was formed by laminating copper tape, the resin was baked at 170 to 200 ° C. when forming the insulating coating layer as shown in Samples 2 to 4. As a result, good appearance, superconducting properties and solvent resistance were obtained.
On the other hand, in sample 5 having a baking temperature of 155 ° C., the resin was not sufficiently baked when forming the insulating coating layer, and the solvent resistance of the formed insulating coating layer was low. In sample 1 with a baking temperature of 230 ° C., the tin solder melted during the baking of the resin and the copper tape peeled off, and the appearance and superconducting properties deteriorated.
From this result, in the high-temperature superconducting wire according to the present invention, when the second stabilizing layer is formed by laminating a metal tape, the insulating coating layer is formed from a resin that can be baked at a temperature of 170 to 200 ° C. Is clearly preferred.

(Example 2: Samples 6 to 12)
On a substrate made of tape-shaped Hastelloy (trade name, manufactured by Haynes, USA) having a width of 10 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) is formed on the bed layer by ion beam assisted sputtering (IBAD), and then 1.0 μm thick CeO ₂ (cap layer) is formed by PLD. did. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer) to form a laminate. Thereafter, the laminate is immersed in a copper sulfate aqueous plating bath and electroplated to form a copper layer (second stabilizing layer) having a thickness of 20 μm on the outer peripheral surface of the laminate. A superconducting laminate having a curvature radius of 25 mm, a width of 10 mm, a thickness of 0.15 mm, and an aspect ratio of 66 at the corner of the cross section along the line A was prepared.

Next, a formal resin (manufactured by Chisso Corp., Vinylec F) is baked on the produced superconducting laminate for 30 minutes at the baking temperature shown in Table 2 to form an insulating coating layer having a thickness of 20 μm and shown in FIG. A high-temperature superconducting wire with a structure was prepared.
Table 2 also shows the results of evaluating the appearance, superconducting properties, and solvent resistance test of the produced high-temperature superconducting wires of Samples 6 to 12.

From the results of Table 2, in the high-temperature superconducting wire of Example 2 in which the second stabilizing layer was formed by plating, as shown in Samples 7 to 11, the resin was baked at 170 to 280 ° C. when forming the insulating coating layer. It had good appearance, superconducting properties and solvent resistance.
On the other hand, in sample 12 having a baking temperature of 155 ° C., the resin was not sufficiently baked when forming the insulating coating layer, and the solvent resistance of the formed insulating coating layer was low. Further, in sample 6 having a baking temperature of 300 ° C., oxygen was lost from the oxide superconducting layer when the resin was baked, resulting in deterioration of superconducting properties.

  From this result, when the second stabilization layer is formed by plating in the high-temperature superconducting wire of the present invention, it is preferable that the insulating coating layer be formed from a resin that can be baked at a temperature of 170 to 280 ° C. Is clear.

(Example 3: Samples 13 to 19)
On the substrate made of tape-like Hastelloy (trade name, manufactured by Haynes, USA) having a width of 5 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) is formed on the bed layer by ion beam assisted sputtering (IBAD), and then 1.0 μm thick CeO ₂ (cap layer) is formed by PLD. did. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer). Thereafter, a 0.1 mm thick copper tape (second stabilizing layer) is laminated on the silver layer with tin solder (melting point 230 ° C.), and the corners (four corners) in the width direction of the laminate are polished. Thus, a superconducting laminate having a width of 5 mm, a thickness of 0.21 mm, and an aspect ratio of 24 was prepared using the curvature radius of the corner as shown in Table 3.

Next, a formal resin (manufactured by Chisso Corporation, Vinylec F) is baked on the produced superconducting laminate at 185 ° C. for 30 minutes to form an insulating coating layer having a thickness shown in Table 3 and shown in FIG. A high-temperature superconducting wire was prepared. In addition, the thickness of the insulating coating layer was performed by adjusting the number of times of baking.
Table 3 also shows the results of evaluation of appearance, superconducting characteristics, and chemical resistance test for the produced high-temperature superconducting wires of Samples 13 to 19.

From the results of Table 3, in the high-temperature superconducting wires of Samples 15 to 19 according to the present invention, the radius of curvature of the cross section along the width direction of the superconducting laminate is 14.5 mm or more, and the thickness of the insulating coating layer By setting the thickness to 12 μm or more, good appearance, superconducting properties, and chemical resistance were obtained.
On the other hand, the thickness of the insulating coating layer is 20 μm and satisfies the predetermined range of the present invention. However, the sample 13 having a corner radius of curvature of 12 mm and smaller than the predetermined range of the present invention does not cover the corners. In addition, the chemicals penetrated from the corners, and the chemical resistance was low. Further, in the sample 14 where the radius of curvature of the corner portion is 14.5 mm and satisfies the predetermined range of the present invention, but the thickness of the insulating coating layer is 7 μm and is thinner than the predetermined range of the present invention, the corner portion is barely covered in the appearance test. However, the result of the chemical resistance test was deteriorated, and it was revealed that the corners were not completely covered.

(Example 4: Samples 20 to 22)
On a substrate made of tape-shaped Hastelloy (trade name, manufactured by Haynes, USA) having a width of 10 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) is formed on the bed layer by ion beam assisted sputtering (IBAD), and then 1.0 μm thick CeO ₂ (cap layer) is formed by PLD. did. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer) to form a laminate. Thereafter, the laminate is immersed in a plating bath of an aqueous copper sulfate solution and electroplated to form a copper layer (second stabilizing layer) having a thickness of 20 μm on the outer peripheral surface of the laminate. The superconducting laminate having a width of 10 mm, a thickness of 0.15 mm, and an aspect ratio of 66 is obtained by polishing the corners (four corners) in the width direction as shown in Table 4. The body was made.

Next, a formal resin (for example, Vinylec F manufactured by Chisso Co., Ltd.) is baked on the produced superconducting laminate for 30 minutes at 185 ° C. to form an insulating coating layer having a thickness of 15 μm. A superconducting wire was produced.
Table 4 shows the results of evaluation of the appearance, superconducting characteristics, and chemical resistance test of the produced high-temperature superconducting wires of Samples 20 to 22.

  From the results of Table 4, in the high-temperature superconducting wires of Samples 20 to 22 according to the present invention, the curvature radius of the corner portion of the cross section along the width direction of the superconducting laminate is 14.5 mm or more, and the thickness of the insulating coating layer By setting the thickness to 12 μm or more, good appearance, superconducting properties, and chemical resistance were obtained.

(Example 5: Samples 23 to 25)
On a substrate made of tape-shaped Hastelloy (trade name, manufactured by Haynes, USA) having a width of 10 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) is formed on the bed layer by ion beam assisted sputtering (IBAD), and then 1.0 μm thick CeO ₂ (cap layer) is formed by PLD. did. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer) to form a laminate. Then, by polishing the corners (four corners) in the width direction of this laminate, the radius of curvature of the corners of the cross section along the width direction is set to the values shown in Table 5, and the width is 10 mm, the thickness is 0.11 mm, the aspect A superconducting laminate having a ratio of 91 was produced.

Next, a formal resin (for example, Vinylec F, manufactured by Chisso Corporation) is baked on the produced superconducting laminate for 30 minutes at 185 ° C. to form an insulating coating layer having a thickness of 15 μm. A superconducting wire was produced.
Table 5 also shows the results of evaluation of appearance, superconducting characteristics, and chemical resistance test for the produced high-temperature superconducting wires of Samples 23 to 25.

From the results of Table 5, in the high-temperature superconducting wires of Samples 23 to 25 according to the present invention, the radius of curvature of the cross section along the width direction of the superconducting laminate is 14.5 mm or more, and the thickness of the insulating coating layer By setting the thickness to 12 μm or more, good appearance, superconducting properties, and chemical resistance were obtained.

(Example 6)
On the substrate made of tape-like Hastelloy (trade name, manufactured by Haynes, USA) having a width of 5 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) is formed on the bed layer by ion beam assisted sputtering (IBAD), and then 1.0 μm thick CeO ₂ (cap layer) is formed by PLD. did. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer). Thereafter, a 0.1 mm thick copper tape (second stabilizing layer) is laminated on the silver layer with tin solder (melting point 230 ° C.), and the corners (four corners) in the width direction of the laminate are polished. Thus, a superconducting laminate having a width of 5 mm, a thickness of 0.21 mm, and an aspect ratio of 24 was prepared by setting the radius of curvature of the corner of the cross section along the width direction to 14.5 mm.

  Next, a formal resin (for example, Vinylec F manufactured by Chisso Co., Ltd.) is baked on the produced superconducting laminate for 30 minutes at 185 ° C. to form an insulating coating layer having a thickness of 15 μm. A superconducting wire was produced.

(Comparative Example 1)
A high-temperature superconducting wire was produced in the same manner as in Example 6 except that the insulating coating layer was not formed.

The high-temperature superconducting wire of Example 6 and Comparative Example 1 was subjected to a moisture resistance test in which it was allowed to stand for 0 to 48 hours under a high temperature and high humidity of 126 ° C., 85% humidity and 2 atmospheres, and a critical current value Ic0 (77K) before the test. The ratio Ic / Ic0 of the critical current value Ic (77K) after the test was calculated. The results are plotted in FIG. In FIG. 14, the closer Ic / Ic0 is to 1.0, the higher the superconducting property retention ratio and the higher the moisture resistance.
From the result of FIG. 14, the high temperature superconducting wire of Example 6 has a structure having an insulating coating layer, and therefore has a higher superconducting property retention ratio and moisture resistance than Comparative Example 1 having no insulating coating layer. The nature was getting higher.

(Example 7)
On a substrate made of tape-shaped Hastelloy (trade name, manufactured by Haynes, USA) having a width of 10 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) is formed on the bed layer by ion beam assisted sputtering (IBAD), and then 1.0 μm thick CeO ₂ (cap layer) is formed by PLD. did. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer) to form a laminate. Thereafter, the laminate is immersed in a plating bath of an aqueous copper sulfate solution and electroplated to form a copper layer (second stabilizing layer) having a thickness of 20 μm on the outer peripheral surface of the laminate. A superconducting laminate having a width of 10 mm, a thickness of 0.15 mm, and an aspect ratio of 66 is obtained by polishing the corners (four corners) in the width direction so that the radius of curvature of the corners of the cross section along the width direction is 14.5 mm. Produced.

  Next, a formal resin (for example, Vinylec F, manufactured by Chisso Corporation) was baked on the produced superconducting laminate at 185 ° C. for 30 minutes to form an insulating coating layer having a thickness of 15 μm. Subsequently, an epoxy-containing resin (manufactured by Tohoku Paint Co., Ltd., TCVU2) is applied on the outer peripheral surface of the formed insulating coating layer and heated at 150 to 160 ° C. for 20 minutes to make the epoxy resin semi-cured and thick. A semi-cured resin layer having a thickness of 5 μm was formed to produce a high-temperature superconducting wire shown in FIG.

  The produced high-temperature superconducting wire is concentrically wound 100 times with an inner diameter of 70 mm, heated in this state for 180 minutes at 150 ° C. to cure the semi-cured resin layer, and the coil body having the internal structure shown in FIG. Created. Next, another coil body is produced in the same procedure, and the obtained two coil bodies are coaxially laminated as shown in FIG. 6 to obtain a height of 20.1 mm and a total number of turns of 200 turns ( A high temperature superconducting coil of 100 turns × 2) was produced.

(Example 8)
High-temperature superconductivity having a height of 20.1 mm and a total number of turns of 200 (100 turns × 2) in the same manner as in Example 6 except that the number of times the formal resin was baked was adjusted to a thickness of 20 μm. A coil was produced.

(Comparative Example 2)
On a substrate made of tape-shaped Hastelloy (trade name, manufactured by Haynes, USA) having a width of 10 mm and a thickness of 0.1 mm, an Al ₂ O ₃ (diffusion prevention layer; film thickness of 150 nm) film was formed by sputtering. Y ₂ O ₃ (bed layer; film thickness: 20 nm) was formed by ion beam sputtering. Next, MgO (intermediate layer; film thickness: 10 nm) is formed on the bed layer by ion beam assisted sputtering (IBAD), and then 1.0 μm thick CeO ₂ (cap layer) is formed by PLD. did. Next, a 1.0 μm-thick GdBa ₂ Cu ₃ O ₇ (oxide superconducting layer) is formed on the CeO ₂ layer by the PLD method, and an 8 μm-thick silver layer (first stabilization) is formed on the oxide superconducting layer by the sputtering method. Layer) to form a laminate. Thereafter, the laminate is immersed in a copper sulfate aqueous plating bath and electroplated to form a copper layer (second stabilizing layer) having a thickness of 20 μm on the outer peripheral surface of the laminate. A superconducting wire having a thickness of 10 mm, a thickness of 0.15 mm, and an aspect ratio of 66 was produced.

Next, a superconducting wire with an insulating tape was produced by winding two 12.5 μm thick polyimide tapes on the outer peripheral surface of the produced superconducting wire. In addition, the polyimide tape was wound so that the polyimide tape adjacent to the longitudinal direction of a superconducting wire might be in the state which contact | connects without the space | interval edge parts overlapping each other.
Next, the produced superconducting wire with insulating tape is concentrically wound 100 times with an inner diameter of 70 mm, immersed in a thermosetting resin in this state and impregnated, and further heated at 80 ° C. for 12 hours. Thus, the thermosetting resin was cured to produce a coil body having the internal structure shown in FIG. Next, another coil body is produced in the same procedure, and the obtained two coil bodies are coaxially laminated as shown in FIG. 6 so that the height is 21.0 mm and the total number of turns is 200 turns ( A high temperature superconducting coil of 100 turns × 2) was produced.

(Comparative Example 3)
A superconducting wire having a width of 10 mm, a thickness of 0.15 mm, and an aspect ratio of 66 was produced in the same manner as in Comparative Example 2.
Next, on the copper layer on the silver layer side of the produced superconducting wire, a polyimide tape having a thickness of 50 μm and a width of 10 mm is overlaid, and concentrically wound 100 times with an inner diameter of 70 mm (co-winding), In this state, after being immersed and impregnated in a thermosetting resin, the thermosetting resin is further cured by heating at 80 ° C. for 12 hours to have the internal structure shown in FIG. A coil body was created. Next, another coil body is produced in the same procedure, and the two obtained coil bodies are coaxially laminated as shown in FIG. 6 to obtain a height of 20.5 mm and a total number of turns of 200 turns ( A high temperature superconducting coil of 100 turns × 2) was produced.

For the high-temperature superconducting coils of Examples 7 and 8 and Comparative Examples 2 and 3, the critical current density (A / mm ² ) and the central magnetic field (T) of each high-temperature superconducting coil when a current of 300 A was applied at 20 K were measured. did. The results are shown in Table 6. The coil dimensions and the wire lengths used in Examples 7 and 8 and Comparative Examples 2 and 3 are also shown in Table 6.

From the results of Table 6, it is confirmed that the high-temperature superconducting coil of Example 7 according to the present invention has a stronger central magnetic field because the current density is larger for the same energization current than Comparative Examples 2 and 3. It was done. Moreover, since the thickness of the resin layer which fixes an insulation coating layer and a coil is thinner than the high temperature superconducting coil of the comparative examples 2 and 3, the superconducting coil of Example 7 is higher than the high temperature superconducting coil of the comparative examples 2 and 3. The outer diameter of the coil was small and the length of the wire used was also small.
It was confirmed that the high-temperature superconducting coil of Example 8 according to the present invention has a higher central magnetic field than the high-temperature superconducting coil of Comparative Example 3 because the current density increases for the same energization current. Further, the high-temperature superconducting coil of Example 8 had a smaller coil height than the high-temperature superconducting coils of Comparative Examples 2 and 3, and the coil could be miniaturized.
Furthermore, the high-temperature superconducting coils of Examples 7 and 8 are manufactured by a process simplified more than the high-temperature superconducting coils of Comparative Examples 2 and 3, and the curing time of the thermosetting resin as in Comparative Examples 2 and 3 Thus, it was confirmed that it can be produced with good productivity without requiring a long time.

  The present invention can be used for a superconducting coil used in various superconducting devices such as a superconducting motor and a current limiting device.

4, 4B, 4C ... metal stabilizing layer, 5, 5B, 5C ... superconducting laminate, 5a, 5Ba, 5Ca ... corner, 7, 7B, 7C ... insulating coating layer, 9 ... semi-cured resin layer, 9G ... cured resin layer, 10 and _10B, 10B 2, 10C, 10D ... HTS wire, 11 ... substrate, 12 ... middle layer, 13 ... oxide superconducting layer, 14 ... first stabilizing layer layer, 15 and 15b ... second stable 50 ... high temperature superconducting coil, 51 ... first coil body, 52 ... second coil body.

Claims (8)

A superconducting laminate in which a substrate, an intermediate layer, an oxide superconducting layer and a metal stabilizing layer are laminated, and an outer peripheral surface of the superconducting laminate, and an insulating coating layer formed by baking a resin;
The corners in the cross section along the width direction of the superconducting laminate are chamfered so that the curved surface has a curvature radius, the thickness of the insulating coating layer is 12 μm or more, and the curvature radius of the corners is 14.5 mm or more. A high-temperature superconducting wire characterized by being.   The metal stabilization layer has a structure in which a second stabilization layer is laminated on the first stabilization layer, the second stabilization layer is formed by bonding a metal tape through solder, and the insulating coating layer The high-temperature superconducting wire according to claim 1, wherein is formed from a resin that can be baked at a temperature of 170 ° C. to 200 ° C.   The metal stabilization layer has a structure in which a second stabilization layer is laminated on the first stabilization layer, the second stabilization layer is formed by plating or vapor deposition, and the insulating coating layer is 170 ° C. to 280 ° C. The high-temperature superconducting wire according to claim 1, wherein the high-temperature superconducting wire is formed of a resin that can be baked at a temperature of 5.   The high-temperature superconducting wire according to any one of claims 1 to 3, further comprising a semi-cured resin layer that covers an outer peripheral surface of the insulating coating layer and is made of a semi-cured thermosetting resin.   The metal stabilization layer has a structure in which a second stabilization layer is laminated on the first stabilization layer, and the second stabilization layer occupies four corners in a cross section along the width direction of the superconducting laminate. The high-temperature superconducting wire according to claim 1, wherein the second stabilization layer is a curved surface having the radius of curvature.   The metal stabilization layer has a structure including a second stabilization layer and a third stabilization layer on the first stabilization layer, and the second stabilization layer is in a cross section along the width direction of the superconducting laminate. The third stabilization layer is disposed so as to occupy the remaining two corners in the cross section along the width direction of the superconducting laminate so as to occupy two corners, and the two corners of the second stabilization layer 2. The high-temperature superconducting wire according to claim 1, wherein two corners of the third stabilizing layer are curved surfaces having the radius of curvature.   A high temperature superconducting coil formed by winding the high temperature superconducting wire according to any one of claims 1 to 6.   A high-temperature superconductivity comprising a resin layer formed by winding the high-temperature superconducting wire according to claim 4 and heat-curing the semi-cured resin layer between the high-temperature superconducting wires adjacent to each other in the coil radial direction. coil.

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