The present invention relates to an oxide superconducting wire connection structure.
Oxide superconducting wires are used as power supply cables, magnetic coils and the like because of their low current loss. Currently, since oxide superconducting wires are produced through a number of processes, it is difficult to produce a defect-free long wire for the above-mentioned usage. For this reason, the wire of the length for the above-mentioned usage is constituted by connecting a plurality of wires. In addition, in order to apply to a coil used for an MRI, an NMR, and the like among magnetic coils, both ends may be connected in a loop shape with a low resistance to enable operation in a permanent current mode. Patent Document 1 describes a connection structure in which a groove leading to the outside is provided in at least one of the superconducting wires.
In the case of the connection structure described in Patent Document 1, since oxygen is supplied through the groove during an oxygen annealing process, the groove needs to be continuously formed in the longitudinal direction. For this reason, the width of a superconducting layer facing the wires becomes narrow. The oxide superconducting wire is used under a low temperature such as liquid nitrogen, and a mechanical or electromagnetic load is applied to the wire or coil. Therefore, the mechanical strength of a connection portion may be increased.
The present invention is made in view of the above-mentioned circumstances, and provides an oxide superconducting wire connection structure with high adhesion between superconducting layers.
In an oxide superconducting wire connection structure according to one or more embodiments of the present invention, a connection target wire comprising a first oxide superconducting wire comprising a first superconducting layer on a first substrate and a connection superconducting wire comprising a second superconducting wire comprising a second superconducting layer on a second substrate are connected such that the first superconducting layer faces the second superconducting layer, and in a portion of the connection superconducting wire at least facing the connection target wire, the second superconducting layer is divided into a plurality of portions in the width direction of the second substrate via non-orientation portions extending in a longitudinal direction of the second substrate, and the non-orientation portions are constituted by (i.e., contains) an oxide material which is same as the superconducting layer.
According to one or more embodiments of the present invention, the second superconducting layer has an orientation portion comprising an oxide superconductor constituted such that the oxide material is oriented on the second substrate, and the non-orientation portion have holes as compared with the orientation portion.
According to one or more embodiments of the present invention, current characteristics of the connection superconducting wires are equal to or greater than current characteristics of the connection target wire.
According to one or more embodiments of the present invention described above, an oxide superconducting wire connecting structure with high adhesion between superconducting layers can be provided.
Hereinafter, based on one or more embodiments, the present invention will be described with reference to the drawings. The drawings are schematic diagrams, and the dimensional ratios of the respective components are not necessarily the same as the actual dimensional ratios.
In
The connection target wires 10 has an oxide superconducting wire having superconducting layers 13 on the respective substrates 11. The connection target wires 20 has an oxide superconducting wire having superconducting layers 23 on the respective substrates 21. The connection target wires 10 has a laminated structure in which superconducting layer 13 is formed on one main surface of the substrates 11 via the intermediate layers 12. The connection target wires 20 has a laminated structure in which superconducting layer 23 is formed on one main surface of the substrates 21 via the intermediate layers 22. In addition, the connection superconducting wire 30 of one or more embodiments includes an oxide superconducting wire having a superconducting layer 33 on a substrate 31. The connection superconducting wire 30 has a laminated structure in which a superconducting layer 33 is formed on one main surface of a substrate 31 via an intermediate layer 32. Protection layers 14 and 24 having metal or the like are formed around the connection target wires 10 and 20, respectively.
In the connection structure 40 according to one or more embodiments, the connection target wires 10 and 20 are arranged so that end portions in the longitudinal direction are opposed to each other in the longitudinal direction. The end portions in the longitudinal direction of the connection target wire 10 and 20 may be brought into contact with each other, or a gap may be provided between the end portions in the longitudinal direction of the connection target wire 10 and 20. On the main surfaces of the substrates 11 and 21, the direction intersecting the longitudinal direction is the width direction.
In the connection superconducting wire 30, the superconducting layer 33 is arranged so as to face and overlap the superconducting layers 13 and 23 of the respective connection target wires 10 and 20. As a result, the connection target wires 10 and 20 are connected via the connection superconducting wire 30. The superconducting layer 13 of the connection target wire 10 and the superconducting layer 33 of the connection superconducting wire 30, and the superconducting layer 23 of the connection target wire 20 and the superconducting layer 33 may be in contact or integrated so that superconducting connection is possible. For this reason, a material having a greater electrical resistance than the superconducting layers 13, 23, and 33, such as solder, may not be interposed between the superconducting layer 13 of the connection target wire 10 and the superconducting layer 33 of the connection superconducting wire 30, and between the superconducting layer 23 of the connection target wire 20 and the superconducting layer 33.
The superconducting layer 33 of the connecting superconducting wire 30 has an orientation portion 34 and a non-orientation portion 35 in at least a portion of the connecting superconducting wire 30 that faces the connection target wires 10 and 20. The superconducting layer 33 is divided into a plurality of portions in the width direction of the substrate 31 via the non-orientation portions 35 extending in the longitudinal direction of the substrate 31. The superconducting layer 33 of the orientation portion 34 is constituted by an oxide superconductor in which an oxide material is oriented, for example, biaxially on the substrate 31.
In the example shown in
In the connection structure 40 according to one or more embodiments, the current characteristics of the connection superconducting wire 30 may be equal to or greater than the current characteristics of the connection target wires 10 and 20. Thereby, the current characteristics of the connection structure 40 are not limited to the current characteristics of the connection superconducting wires 30, and become equal to or greater than the current characteristics of the connection target wires 10 and 20. Specific examples of current characteristics include critical current (Ic) below the critical magnetic field.
When two or more orientation portions 34 of the connection superconducting wire 30 are provided in parallel in the width direction, the current characteristics of each of the orientation portions 34 may not be equal to or greater than the current characteristics of the connection target wires 10 and 20. The current characteristics obtained by adding two or more orientation portions 34 may be equal to or greater than the current characteristics of the connection target wires 10 and 20. When there is a difference in the current characteristics of the connection target wires 10 and 20, the current characteristics of the connection superconducting wire 30 may be at least equal to or greater than the lower current characteristics of the connection target wires 10 and 20. The current characteristics of the connection superconducting wire 30 may be equal to or greater than the average current characteristics of the connection target wires 10 and 20, or may be equal to or greater than the greater current characteristics of the connection target wires 10 and 20.
As a method of improving the current characteristics of the connection superconducting wire 30, for example, the following (1) to (3) or a combination of two or more of these can be provided.
(1) The superconducting layer 33 of the connection superconducting wire 30 has an oxide superconductor having a better crystal orientation as compared with the superconducting layers 13 and 23 of the respective connection target wires 10 and 20.
(2) The film thickness of the superconducting layer 33 of the connection superconducting wire 30 is thicker than the film thickness of the superconducting layers 13 and 23 of the respective connection target wires 10 and 20.
(3) The superconducting layer 33 of the connection superconducting wire 30 includes artificial crystal defects.
In the case (3), the superconducting layers 13 and 23 of the respective connection target wires 10 and 20 are not limited to the case where artificial crystal defects are not included, and the artificial crystal defects may be included. When all the superconducting layer 33 of the connection superconducting wire 30 and the superconducting layers 13 and 23 of the respective connection target wires 10 and 20 include the artificial crystal defects, due to a difference in the type or degree of the artificial crystal defects, the above-described (1), (2) or the like, a difference in current characteristics can be provided.
In the superconducting layer 33 of the connection superconducting wire 30, as an oxide superconductor having a good crystal orientation, for example, the orientation of the intermediate layer 32 of the connection superconducting wire 30 is greater than the intermediate layer 12 and 22 of the respective connection target wires 10 and 20. As the oxide superconductor constituting the superconducting layer 33 of the connection superconducting wire 30, a material having greater current characteristics than the oxide superconductor constituting the superconducting layers 13 and 23 of the respective connection target wires 10 and 20 may be used. The superconducting layers 13 and 23 of the respective connection target wires 10 and 20 may be a long and stable material, and the superconducting layer 33 of the connection superconducting wire 30 may be a short material having high current characteristics.
Examples of the artificial crystal defects include artificial pins made of different materials. Examples of the different materials used for introducing the artificial pin into the superconducting layer include one kind or two or more kinds of BaSnO3(BSO), BaZrO3(BZO), BaHfO3(BHO), BaTiO3 (BTO), SnO2, TiO2, ZrO2, LaMnO3, ZnO, and the like.
Next, the oxide superconducting wire constituting the connection target wires 10 and 20 and the connection superconducting wire 30 will be described.
The substrates 11, 21, and 31 are tape-shaped metal substrates. Each substrate has main surfaces on both sides in the thickness direction. Specific examples of the metal constituting each substrate include nickel alloys such as Hastelloy (registered trademark), stainless steel, and oriented NiW alloys in which a texture is introduced into the nickel alloy. The thickness of the substrate may be appropriately adjusted according to the purpose, and is, for example, in the range of 10 to 1000 μm.
The intermediate layer 12 is provided between the substrate 11 and the superconducting layer 13. The intermediate layer 22 is provided between the substrate 21 and the superconducting layer 23. The intermediate layer 32 is provided between the substrate 31 and the superconducting layer 33. The intermediate layer may have a multilayer structure, and may include, for example, a diffusion prevention layer, a bed layer, an alignment layer, a cap layer, and the like in order from the substrate side to the superconducting layer side. These layers are not necessarily provided one by one, and some layers may be omitted, or two or more of the same kind of layers may be laminated repeatedly.
The superconducting layers 13, 23, and 33 are constituted by an oxide superconductor. Examples of the oxide superconductor include a RE-Ba—Cu—O-based oxide superconductor represented by a general formula REBa2Cu3O7−x (RE123). Examples of the rare earth element RE include one kind or two or more kinds of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The thickness of the oxide superconducting layer is, for example, appropriately 0.5 to 5 μm.
The protection layers 14 and 24 have functions such as bypassing overcurrent and reducing a chemical reaction that occurs between the superconducting layers 13, 23, and 33 and the layers provided on the protection layers 14 and 24. Examples of the material of the protection layers 14 and 24 include silver (Ag), copper (Cu), gold (Au), an alloy of gold and silver, other silver alloys, copper alloys, and gold alloys. The thickness of the protection layers 14 and 24 is, for example, approximately 1 to 30 μm. When the protection layers 14 and 24 are thinned, the thickness may be 10 μm or less.
Two or more protection layers 14 and 24 can be laminated in the thickness direction. For example, silver or a silver alloy that can transmit oxygen under high temperature conditions is laminated as the protection layers 14 and 24 before the oxygen annealing, and copper or the like may be laminated on the silver or silver alloy after the oxygen annealing. After the oxygen annealing, a metal layer similar to the protection layers 14 and 24 may be provided around the connection target wires 10 and 20, respectively, or the connection superconducting wire 30 in the connection structure 40 to coat the superconducting layers 13, 23, and 33 and the like. A stabilization layer (not shown) or the like may be provided on the protection layers 14 and 24. Examples of the stabilization layer include a plating layer of metal such as Cu, Ag, Al, Sn, Ti, and an alloy, or a metal foil. The stabilization layer may be constituted by laminating the two or more kinds of the above.
As a manufacturing method of the connection structure 40, the connection target wire 10 having the intermediate layers 12 and the superconducting layer 13 on the substrate 11 is manufactured, and the connection target wire 20 having the intermediate layers 22 and the superconducting layer 23 on the substrate 21 is manufactured. After laminating the protection layers 14 and 24 around the respective connection target wires 10 and 20 including at least the upper surface of the superconducting layers 13 and 23, respectively, the superconducting layers 13 and 23 of the respective connection target wires 10 and 20 are connected via the superconducting layer 33 of the connection superconducting wire 30.
In the connection target wires 10 and 20 before the connection, when the protection layers 14 and 24 are formed on the respective superconducting layers 13 and 23 where the connection superconducting wire 30 is overlapped, at least a portion of the overlapped portion of the protection layers 14 and 24 may be removed. After the superconducting layers 13 and 23 of the respective connection target wires 10 and 20 are overlapped on superconducting layer 33 of connection superconducting wire 30, the superconductor may be diffusion-bonded in order to reduce the electrical resistance at an interface. In addition, the deterioration of the superconducting layers 13, 23, and 33 may be recovered by performing oxygen annealing after the connection. In the diffusion bonding, the superconductors included in the opposing superconducting layers may be the same or similar materials. The ratio of the oxide to the metal element of the oxide superconductor can be optimized by the oxygen annealing.
If there is a continuous hole in the non-oriented portion 35 of the connection superconducting wires 30, oxygen can be circulated through the superconducting layers 13, 23 and 33 during the oxygen annealing after the connection. Even after the connection, the introduction of oxygen is not hindered, and the introduction of oxygen does not require a great deal of time. The oxygen annealing of the connection target wires 10 and 20 and the connection superconducting wire 30 may be performed at least once after the connection target wires 10 and 20 are connected to the connection superconducting wire 30. After connecting the wire with the superconducting layer exposed, a protection layer of silver or the like may be laminated on at least the exposed superconducting layer so that the superconducting layer is not exposed.
When there is a gap between the longitudinal ends of the connection target wires 10 and 20, a filler or the like (not shown) may be interposed in these gaps. Examples of the filler include metals, resins, and the like. When the superconducting layers 13 and 23 of the respective connection target wires 10 and 20 and the superconducting layer 33 of the connection superconducting wire 30 are superconductingly connected, even a conductor or an electrical insulator exists around the superconducting layers 13, 23 and 33, the superconducting properties of the wire are not affected.
As mentioned above, although the present invention has been described based on one or more embodiments, the present invention is not limited to the above-mentioned embodiments, and a various modifications are possible in the range which does not deviate from the summary of the present invention. Examples of the modifications include addition, replacement, omission, and other changes of components in one or more embodiments. Moreover, it is also possible to combine the component used for two or more embodiments appropriately.
When obtaining a wire in which two or more oxide superconducting wires are connected in the longitudinal direction via the connection portion, a long connection target wire and a short connection superconducting wire may be alternately and repeatedly connected. Alternatively, when the end portion of the long connection superconducting wire is connected to the end portion of the long connection target wire, a non-oriented portion may be provided at the end portion of the connection superconducting wire. Two or more superconducting wires having a non-oriented portion at the first end and no non-oriented portion at the second end are prepared, and between the wires adjacent in the longitudinal direction, a connection structure may be provided in which the first end having the non-oriented portion and the second end having no non-oriented portion are opposed.
To fabricate a superconducting coil using an oxide superconducting wire, for example, after a wire is wound around the outer peripheral surface of a winding frame to form a coil-shaped multilayer winding coil, the wire can be fixed by impregnating with a resin such as an epoxy resin so as to cover the wound wire. A plurality of coils may be arranged in the axial direction. In such a case, since each coil is adjacent in the width direction of the wire, both ends in the width direction of the connection superconducting wire may not protrude from both ends in the width direction of the connection target wire.
Hereinafter, the present invention will be specifically described with reference to examples. Here, an example is shown in which a superconducting wire having a width of 4 mm is used as a connection target wire, and ends of the connection target wire are connected in a bridge shape by the connection superconducting wires. The electrical characteristics were measured at the liquid nitrogen temperature at which the wire became superconductive.
(1-1) A substrate having Hastelloy (registered trademark) C-276 having a width of 12 mm, a length of 5 m, and a thickness of 0.75 mm (750 μm) was prepared as a substrate, and the main surface of the substrate was polished using alumina (Al2O3) particles having an average particle diameter of 3 μm.
(1-2) The substrate was degreased and washed with an organic solvent such as ethanol or acetone.
(1-3) An Al2O3 layer having a thickness of 100 nm was formed as a diffusion prevention layer on the main surface of the substrate by an ion beam sputtering method.
(1-4) A Y2O3 layer having a thickness of 30 nm was formed as a bed layer on the surface of the Al2O3 layer by an ion beam sputtering method.
(1-5) An MgO layer having a thickness of 5 to 10 nm was formed as an alignment layer on the surface of the Y2O3 layer by an ion beam assisted deposition method.
(1-6) A CeO2 layer having a thickness of 500 nm was formed as a cap layer on the surface of the MgO layer by a pulse laser deposition method. An in-plane orientation degree (Δφ) of the CeO2 layer was 4.0°.
(1-7) A GdBa2Cu3O7-X layer having a thickness of 2 μm was formed as a superconducting layer on the surface of the CeO2 layer by a pulse laser deposition method.
(1-8) An Ag layer having a thickness of 2 μm was formed as a protection layer by a DC sputtering method.
(1-9) The oxygen annealing was performed at 500° C. for 10 hours, and after the furnace cooling for 26 hours, the wire was taken out from the furnace.
(1-10) The wire was cut along the longitudinal direction with an infrared laser to obtain three connection target wires having a width of 4 mm. When the current characteristics of two of the wires were measured, the energizing current value (critical current value) at which two wires could be energized while maintaining the superconducting state was 200 A.
(1-11) The Ag layer in a section of 7 cm in the longitudinal direction from one end of the two wires whose current characteristics were measured was dissolved to expose the superconducting layer, and then the ends were butted together.
(2-1) to (2-5) were carried out in the same manner as (1-1) to (1-5) except that the length of the substrate was 2 m.
(2-6) The MgO layer was scratched from above by an acicular material to form a plurality of scratches extending in the longitudinal direction substantially in parallel. The scratches had a depth of 3 to 5 μm, a width of 30 to 50 μm, a roughness of Ra of 10 to 30 nm, and a distance in the width direction between adjacent scratches of 760 μm.
(2-7) A CeO2 layer having a thickness of 500 nm was formed as a cap layer on the surface of the MgO layer by a pulse laser deposition method. The in-plane orientation degree (Δφ) of a portion of the CeO2 layer having no scratches was 4.0°.
(2-8) A GdBa2Cu3O7-X layer having a thickness of 3.3 μm was formed as a superconducting layer on the surface of the CeO2 layer by a pulse laser deposition method.
(2-9) An Ag layer having a thickness of 2 μm was formed as a protective layer by a DC sputtering method.
(2-10) Oxygen annealing was performed at 500° C. for 10 hours, and after furnace cooling for 26 hours, the wire was taken out from the furnace.
(2-11) The wire was cut along the longitudinal direction with an infrared laser to obtain three superconducting wires having a width of 4 mm. When the current characteristics of one of the wires was measured, the critical current value was 230 A.
(2-12) One wire whose current characteristics were measured was cut and divided into 5-cm length, the Ag layer was dissolved over the entire length, and the superconducting layer was exposed to obtain a connecting superconducting wire. As a result of observation with a scanning ion microscope (SIM) or a scanning electron microscope (SEM), the scratched portion was a non-orientation portion with more holes than the orientation portion.
(3-1) As shown in
(3-2) The facing portions of the connection target wire rods 10 and 20 and the connection superconducting wire rod 30 were arranged under a reduced pressure of 3×10−2 Torr, and the superconducting layers 13, 23, and 33 were diffusion-bonded by irradiating an infrared laser from a side of the substrates 11 and 21 of the respective connection target wire rods 10 and 20. The laser irradiation conditions were a wavelength of 1064 nm, an energy density of 3×105 W/cm2, and an irradiation time of 10 seconds.
(3-3) After taking out the wire from under reduced pressure, 1 μm of Ag was deposited on the connection portion where the superconducting layer was exposed and on the connection portion.
(3-4) Oxygen annealing of the wire including the connection portion was performed at 500° C. for 10 hours, and after furnace cooling for 26 hours, the wire was taken out from the furnace.
(3-5) The energizing current value, the connection resistance, and the adhesion by a stud pull test of the wire including the connection portion were measured. The energizing current value of the wire including the connection portion was 200 A, which was equivalent to 200 A which was the energizing current value of the connection target wire before the connection. The connection resistance was 1 nΩ or less, indicating a superconducting state. The adhesion (MPa) by a stud pull test using a stud pin having a diameter φ of 2.7 mm was 31 MPa, 33 MPa, 43 MPa, 48 MPa, and 55 MPa for five samples, respectively.
(4-1) Connection target wires were prepared in the same manner as (1-1) to (1-11) in Examples.
(4-2) In order to prepare the connection superconducting wire of the comparative example, after fabricating the wire in the same manner as (1-1) to (1-10) of the connection target wire of the Example, the wire was cut into 30 cm lengths. Then, the superconducting layer on the substrate was divided into four in the width direction in a section of 5 cm which was 12.5 to 17.5 cm in the longitudinal direction from the end portion. The four-section dividing processing was performed by fabricating three grooves so that the substrate was not cut by scribe processing under the conditions of the wavelength of 532 nm, the frequency of 500 kHz, the output of 12 W, the pulse width of 10 ps, the processing speed of 300 mm/s, and repeating laser irradiation three times per groove. Each groove width was 30 μm. The energizing current value of the wire after the groove processing was 190 A. After a scribe-processed 5-cm section was cut with an infrared CW laser, the Ag layer was dissolved to expose the superconducting layer to obtain a 5-cm long connection superconducting wire.
(4-3) Both ends of the connection superconducting wire scribe-processed with a length of 5 cm were opposed to the ends of the connection target wire, and were overlapped while being pressed in the thickness direction. Both opposing end portions were arranged under a reduced pressure of 3×10−2 Torr, and the superconducting layer was diffusion-bonded by irradiating an infrared laser from a side of the substrate of the connection target wire. The laser irradiation conditions were the wavelength of 1064 nm, the energy density of 3×105 W/cm2, and an irradiation time of 10 seconds.
(4-4) After taking out the wire from under reduced pressure, 1 μm of Ag was deposited on the connection portion where the superconducting layer was exposed and on the connection portion.
(4-5) Oxygen annealing of the wire including the connection portion was performed at 500° C. for 10 hours, and after furnace cooling for 26 hours, the wire was taken out from the furnace.
(4-6) The energizing current value, the connection resistance, and the adhesion by a stud pull test of the wire including the connection portion were measured. The energizing current value of the wire including the connection portion was 190 A, which was less than 200 A, which was the energizing current value of the connection target wire before the connection. The connection resistance was 1 nΩ or less, indicating a superconducting state. The adhesion (MPa) by a stud pull test using a stud pin having a diameter φ of 2.7 mm was 20 MPa, 25 MPa, 33 MPa, 38 MPa, and 50 MPa for five samples, respectively.
As mentioned above, the result of a stud pull test showed remarkable differences and it was confirmed that the adhesion in an Example is excellent.
Adhesion (MPa) in Example: 31, 33, 43, 48, and 55.
Adhesion (MPa) in Comparative Example: 20, 25, 33, 38, and 50.
In addition, if the current characteristics of the connection target superconducting wire were equal to or greater than the current characteristics of the connection target wire, the energization current value of the wire including the connection portion was equal to the energization current value of the connection target wire before connection. Moreover, if the current characteristics of the connection target superconducting wire was lower than the current characteristics of the connection target wire, the energization current value of the wire including the connection portion was lower than the energization current value of the connection target wire before connection.
Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present invention. Accordingly, the scope of the invention should be limited only by the attached claims.
Number | Date | Country | Kind |
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2017-198411 | Oct 2017 | JP | national |
This is a U.S. National Stage application of International Application No. PCT/JP2018/038093 filed Oct. 12, 2018, which claims priority from Japanese patent application No. 2017-198411 filed Oct. 12, 2017. These references are incorporated herein by reference in their entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/JP2018/038093 | 10/12/2018 | WO | 00 |