The present disclosure relates to a connection structure, and in particular, to a connection structure of superconducting wires.
Recently, as oxide superconductors having critical temperature (Tc) that is higher than liquid nitrogen temperature (about 77 K), high temperature superconductors such as YBCO system (Yttrium-based) and BSCCO system (bismuth-based), for example, have attracted attention. As superconducting wires manufactured with use of such high temperature superconductors, superconducting wires having a superconductor layer, formed by depositing an oxide superconductor film on a metal substrate of a metal or the like that is long and flexible, or depositing an oxide superconductor film on a single crystal substrate, are known.
Superconducting wires are considered to be applied as coil windings for magnetic resonance imaging (MRI), nuclear magnetic resonance (NMR), and the like, for example, and a demand for long superconducting wires is increasing. However, the length of a single continuous superconducting wire has a limitation in manufacturing. In order to obtain a coil winding of a desired length, it is necessary to connect superconducting wires with each other.
As a connection structure in which superconducting wires are connected with each other, Japanese Patent Application Laid-Open No. 2011-165435 discloses a connection structure of superconducting wires in which end portions of two superconducting wires in which both surfaces are covered with a reinforcing material are overlapped and connected by soldering. However, in the connection structure of Japanese Patent Application Laid-Open No. 2011-165435, solder is used for connecting superconducting wires. Therefore, it is difficult to make electrical resistance in the connecting section of the superconducting wires zero due to intervention of the solder.
As another method of connecting superconducting wires with each other, Japanese Patent Application Laid-Open No. 2013-235699 discloses a method of arranging a superconductor layer exposed at a connecting end portion of one superconducting wire and a superconductor layer exposed at a connecting end portion of the other superconducting wire in an opposed state, and between them, forming a superconducting joint layer formed by the metal organic deposition (MOD) method.
However, in the connection structure disclosed in Japanese Patent Application Laid-Open No. 2013-235699, a superconducting joint layer formed by the MOD method, interposed between the superconductor layer of one superconducting wire and the superconductor layer of the other superconducting wire, connects the superconducting wires with each other, and the strength of the superconductor joint layer itself is low. Therefore, when an undesired force is applied to the superconducting wires, the superconducting wires may be separated from the superconducting joint layer.
The present disclosure is related to providing a connection structure of superconducting wires having high connection strength.
In accordance with one aspect of the present disclosure, a connection structure includes first and second superconducting wires that are two superconducting wires each having a substrate in a tape shape, an intermediate layer formed on the substrate, and a superconductor layer formed on the intermediate layer; a connecting superconductor layer that connects the first and second superconducting wires in a positional relationship in which surfaces of the superconductor layers face each other, and forms a superconducting connecting section together with the first and second superconducting wires; two protective members each having a width larger than a width of the first and second superconducting wires, and disposed on substrate sides of the first and second superconducting wires in a positional relationship of sandwiching the superconducting connecting section; and an a metal part that joins the two protective members to each other.
It is preferable that in the connecting structure, each of the first and second conducting wires further includes a metal protective layer that covers an entire surface of the superconductor layer except for the superconducting connection section.
In the connection structure, it is preferable that the metal parts are provided in at least four positions surrounding the superconducting connecting section.
In the connection structure, it is preferable that the metal part is metal or alloy including at least one of Ag, Au, and Cu.
In the connection structure, it is preferable that a difference between an elastic coefficient of the substrate and an elastic coefficient of the protective member is in a range of 80 GPa or less.
In the connection structure, it is preferable that the elastic coefficient of the protective member ranges from 150 GPa to 250 GPa.
In the connection structure, it is preferable that a melting point of the protective member is equal to or higher than 1000° C.
In the connection structure, it is preferable that a thickness of the protective member ranges from 30 μm to 300 μm.
It is also preferable that the protective member is Ni-based alloy, stainless steel, or carbon steel.
According to the present disclosure, it is possible to provide a connection structure of superconducting wires having high connection strength, and to improve the manufacturing yield of connection structures.
Hereinafter, a connection structure of the present disclosure will be described with reference to the accompanying drawings. In the following description, a numerical range represented by using “to” means a range including numerical values described before and after “to” as lower and upper limits.
The substrate 1 is configured of a metal substrate or a ceramic substrate having a low magnetism in a tape form. As a material of the metal substrate, a metal such as Co, Cu, Cr, Ni, Ti, Mo, Nb, Ta, W, Mn, Fe, Ag, or the like or an alloy of these metals that is excellent in strength and heat resistance may be used, for example. In particular, from a viewpoint of excellent corrosion resistance and heat resistance, it is preferable to use a Ni-based alloy such as Hastelloy (registered trademark) or Inconel (registered trademark), or a Fe-based alloy such as stainless steel. It is more preferable to use Hastelloy (registered trademark) that is a Ni—Fe—Mo-based alloy. The thickness of the substrate 1 is preferably 30 to 100 μm, and more preferably, 30 to 50 μm, although not limited particularly.
The intermediate layer 2 is formed on the substrate 1, and is a base layer formed so that the superconductor layer 3 realizes high biaxial orientation, for example. Such an intermediate layer 2 is made of a material in which physical property values such as a thermal expansion and a lattice constant show intermediate values of those of the substrate 1 and a superconductor constituting the superconductor layer 3. The intermediate layer 2 may have a single-layer structure or a multilayer structure. In the case where the intermediate layer 2 is formed to have a multilayer structure, it can be configured by sequentially laminating a bed layer containing non-crystalline Gd2Zr2O7-δ (δ represents the oxygen non-stoichiometric amount), Al2O3, Y2O3, or the like, a forced alignment layer containing crystalline MgO or the like and formed by the ion beam assisted deposition (IBAD) method, and an LMO layer containing LaMnO3+δ (δ represents the oxygen non-stoichiometric amount), for example, although the number of layers and the type are not limited. Moreover, a cap layer containing CeO2 or the like may be further provided on the LMO layer. While the thickness of each layer is not particularly limited, examples include that the Y2O3 layer of the bed layer is 7 nm, the Al2O3 layers is 80 nm, the MgO layer of the forced alignment layer is 40 nm, and the LMO layer is 30 nm.
The Superconductor layer 3 is formed on the intermediate layer 2. It is preferable that the superconductor layer 3 is formed of a high-temperature superconductor in which the transition temperature of the superconductor is higher than the boiling point (−196° C.: 77K) of liquid nitrogen. In particular, it is more preferable that the superconductor layer 3 contains a copper oxide superconductor. As a copper oxide superconductor, a high temperature superconductor such as REBa2Cu3O7-δ (RE-based superconductor) is preferred, for example. Note that RE in a RE-based superconductor is a single rare earth element or a plurality of rare earth elements such as Y, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Lu. Also, δ is an oxygen non-stoichiometric amount, and is equal to or greater than 0 and equal to or less than 1, for example. From the viewpoint that the superconducting transition temperature is high, it is preferable that δ is closer to 0. Note that when high-pressure oxygen annealing or the like is performed with use of a device such as an autoclave, the oxygen non-stoichiometric amount, represented by δ, may take a value less than 0, that is, a negative value. The thickness of the superconductor layer 3 is preferably 0.1 to 10 μm, and more preferably, 0.5 to 5 μm.
Furthermore, it is preferable that the superconducting wire 10 further includes a metal protective layer 4 that covers the entire surface of the superconductor layer 3 except for a superconducting connecting section C to be described below. In addition, the superconducting wire 10 may further include the metal protective layer 4 also on a surface 1b of the substrate 1, on the opposite side of the surface 1a on which the intermediate layer 2 is formed. The metal protective layer 4 is preferably a metal layer or an alloy layer including at least one of Ag, Au, and Cu, and more preferably, a metal layer of Ag. The material of the metal protective layer 4 may be the same as or different from the material of a metal part 9 to be described below. The thickness of the metal protective layer 4 is preferably 30 to 300 μm, and more preferably, 30 to 100 μm. When the metal protective layer 4 is formed on the surface of the superconductor layer 3, protection can be made effectively without exposing the surface of the superconductor layer 3. Further, when the metal protective layer 4 is provided on the surface 1b side of the substrate 1, in the connection structure 20 to be described below, the protective member 7 and the superconducting wire 10 can be joined via the metal protective layer 4 provided on the surface 1b side of the substrate 1. Thereby, it is possible to further strengthen the reinforcing effect of the superconducting connecting section C. Note that with respect to the lengthwise dimension of the metal protective layer 4, it is not particularly limited. The metal protective layer 4 may be formed to be longer or may be formed to be shorter than the protective member 7, or may be formed to have the same length as that of the protective member 7.
In
Such a connection structure 20 has a sandwich structure in which the superconducting wires 10a and 10b are interposed between the two protective members 7 and 7, and the protective members 7 and 7 are joined to each other by the metal parts 9. Therefore, as a result that the superconducting connecting section C is reinforced with two protective members 7 and 7, the connection state of the superconducting wires 10a and 10b can be firmly held.
Note that the two protective members 7 and 7 are fixed by the metal parts 9 in a state where a mutually attractive force of a level not changing the thickness is acted in a direction of sandwiching the superconducting wires 10a and 10b. Therefore, in the connection structure 20, the superconducting wires 10a and 10b are connected with each other with high connection strength. As a result, in the superconducting connecting section C, occurrence of separation between the superconducting wires 10a and 10b can be suppressed effectively, and the manufacturing yield of the connection structures 20 can be improved. Further, since the superconducting connecting section C is covered with the two protective members 7 and 7, it is possible to effectively protect the superconducting connecting section C, and even if an external load such as an undesirable external force is applied to the connection structure 20, it is possible to effectively suppress braking of the superconducting connecting section C. Furthermore, since the metal parts 9 are provided at locations away from the superconducting connecting section C, it is possible to reduce a risk that the connecting superconductor layer 8 is burned due to an influence of joining (fusion) of the metal parts 9.
Furthermore, since a gap G is formed between the two protective members 7 and 7, at the time of manufacturing the connection structure 20, it is possible to secure a supply channel for oxygen, and consequently, crystallization of the connecting superconductor layer 8 can be promoted.
It is preferable that the connecting superconductor layer 8 is configured of composition of a superconductor that is the same as that of the superconductor layer 3. In particular, the connecting superconductor layer 8 can be formed with use of a composition (solution) containing a raw material necessary for forming an RE-based superconductor. As such a solution, it is possible to use an acetylacetonate or naphthenate MOD solution or the like containing RE (rare earth elements such as yttrium (Y), gadolinium (Gd), samarium (Sm), and holmium (Ho)), Ba, and Cu in a ratio of about 1:2:3, for example. The connecting superconductor layer 8 having crystallinity can be obtained by applying a MOD solution onto the superconducting wires 10a and 10b and performing firing under predetermined conditions.
Next, the protective member 7 will be described in detail. It is preferable that the protective member 7 has a material that can be pressurized and fired together with the superconducting wires 10a and 10b forming the superconductive connecting section C, and that the material is capable of withstanding the firing temperature of approximately 800° C. Accordingly, the melting point of the protective member 7 is preferably 1000° C. or higher, and more preferably, 1200° C. or higher. It is also preferable that a mutually attracting force to the extent that a force is applied to the superconducting connecting section C is applied between the two protective members 7 and 7. Therefore, it is preferable that the protective member 7 is configured of the same material as that of the substrate 1 of the superconducting wires 10a and 10b having such strength and heat resistance. However, the protective member 7 may be configured of a material different from that of the substrate 1. Such a protective member 7 includes a metal material such as Ni-based alloy, stainless steel, or carbon steel, for example.
Furthermore, in the protective member 7, it is preferable that a difference between the elastic coefficient of the substrate 1 and the elastic coefficient of the protective member 7 is within a range of 80 GPa or less, from the viewpoint of strength balance between the components constituting the connection structure 20. When the difference between the elastic coefficients is greater than 80 GPa, stress is not uniformly applied to the connecting section, so that good connection cannot be made.
The elastic coefficient of the protective member 7 may be determined in consideration of the difference between it and the elastic coefficient of the substrate, and it is not particularly limited. For example, the elastic coefficient is preferably 150 GPa to 250 GPa, and more preferably, 160 GPa to 230 GPa.
The thickness of the protective member 7 is preferably 30 to 300 μm, and more preferably, 30 to 100 μm. When the thickness of the protective member 7 is less than 30 μm, the protective member 7 itself may be broken by the pressure in the firing step to be described below. Moreover, sufficient reinforcing effect of the superconducting connecting section C by the protective member 7 cannot be achieved. Consequently, the superconducting connecting section C may not be sufficiently protected from external loads. On the other hand, if the thickness of the protective member 7 exceeds 300 μm, stress is not applied to the connecting section and connection is not sufficient. Consequently, a critical current value Ic may decrease significantly. Therefore, by setting the thickness of the protective member 7 to be in a range from 30 μm to 300 μm, it is possible to suppress a decrease in the critical current value Ic that is a limit current value of the current flowing through the superconductor layer 3, while reinforcing the superconducting connecting section C. Note that the critical current value Ic can be obtained by measuring a connection resistance of the superconducting connecting section C by a four-terminal method, for example.
The width of the protective member 7 varies according to the width of the superconducting wires 10a and 10b. The width of the protective member 7 may be larger than the width of the superconducting wires 10a and 10b, and is not particularly limited. The width of the protective member 7 is preferably wider by 2 to 10 mm than the width of the superconducting wires 10a and 10b, and more preferably wider by 2 to 5 mm than the width of the superconducting wires 10a and 10b.
The metal parts 9 are provided to opposing inner surfaces of the two protective members 7 and 7, respectively, and join the two protective members 7 and 7 to each other. It is preferable that the metal parts 9 are formed on the inner surfaces of the two protective members 7 and 7 at positions where the superconducting connecting section C is not located, for example. Further, when the superconducting wires 10a and 10b are pressurized and fired via the connecting superconductor layer 8 to form the superconducting connecting section C, it is preferable that the protective member 7 is made of a material capable of withstanding the firing temperature of about 800° C. Meanwhile, it is preferable that the metal part 9 is made of a material to be fused. Therefore, it is preferable that the material of the metal part 9 is different from that of the protective member 7. The metal part 9 may be made of metal that the metal parts 9 and 9 provided on the inner surfaces of the two protective members 7 and 7 respectively can be joined, and is not limited particularly. It is preferable that the metal part 9 is made of metal or alloy including at least one of Ag, Au, and Cu, and Ag is more preferable. The thickness of the metal part 9 is preferably 10 nm to 10 μm, and more preferably 10 nm to 2 μm. Formation of the metal part 9 is not particularly limited. For example, any publicly known method that enables formation of the metal part 9, such as sputtering, vacuum deposition, pasting, or the like, may be used.
Next, a method of manufacturing a connection structure according to the present disclosure will be described with reference to
Then, as illustrated in
The composition base that is the same as that of the superconductor layer 3 means that in the case where a RE-based superconductor is used as a high-temperature superconductor constituting the superconductor layer 3, a composition (solution) for forming the connecting superconductor layers 8 is also composed of a composition (solution) that is required for forming the RE-based superconductor. That is, a raw material required for forming a RE-based superconductor is included in the composition (solution), and both the superconductor layer 3 and the connecting superconductor layer 8 are configured of a superconducting composition of the same RE-based superconductor. The solvent contained in the composition (solution) is not limited particularly, as long as it can dissolve a desired superconducting base and the connecting superconductor layer 8 having good crystallinity can be obtained after the main calcination step. For example, an acetylacetonate-based or naphthenate-based MOD solution containing RE (rare earth element such as yttrium (Y), gadolinium (Gd), samarium (Sm), holmium (Ho), or the like), Ba, and Cu in a ratio of about 1:2:3 may be used.
Next, as illustrated in
Thereafter, as illustrated in
Further, after the main calcination step, an oxygen annealing step of doping oxygen with respect to the connecting superconductor layer 8 is performed. In the oxygen annealing process, the connection end portions of the superconducting wires 10a and 10b are accommodated in an oxygen atmosphere, and are heated at a predetermined temperature. As a specific example, a portion subjected to oxygen annealing is placed under an oxygen atmosphere in a temperature range from 350° C. to 500° C. and oxygen doping is performed under this condition. Note that the connecting superconductor layer 8 is formed over the entire width of the superconducting wires 10a and 10b. Therefore, on both side faces in the width direction of the superconducting wires 10a and 10b, an end surface of the connecting superconductor layer 8 is in an exposed state, and oxygen doping can be performed effectively from the exposed end face. In this way, the connection structure 20 as illustrated in
As described above, the connection structure obtained by the manufacturing method of the present disclosure has high connection strength, and the yield of the connection structure 20 can be improved.
While the connection structures according to the embodiments have been described above, the present disclosure is not limited to the embodiments described above. Various variants and changes can be made based on the technical concept of the present disclosure.
In the connection structure 20 according to the present disclosure, a space portion may be filled with resin such as epoxy resin in order to prevent oxidation of metal due to air contact.
Number | Date | Country | Kind |
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2017-066709 | Mar 2017 | JP | national |
The present application is a continuation application of International Patent Application No. PCT/JP2018/012947 filed on Mar. 28, 2018, which claims the benefit of Japanese Patent Application No. 2017-066709, filed on Mar. 30, 2017. The contents of these applications are incorporated herein by reference in their entirety.
Number | Date | Country | |
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Parent | PCT/JP2018/012947 | Mar 2018 | US |
Child | 16586313 | US |