WO2023127856A1 - 化合物超電導線 - Google Patents

化合物超電導線 Download PDF

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Publication number
WO2023127856A1
WO2023127856A1 PCT/JP2022/048120 JP2022048120W WO2023127856A1 WO 2023127856 A1 WO2023127856 A1 WO 2023127856A1 JP 2022048120 W JP2022048120 W JP 2022048120W WO 2023127856 A1 WO2023127856 A1 WO 2023127856A1
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Prior art keywords
compound
compound superconducting
superconducting wire
area
ratio
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PCT/JP2022/048120
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English (en)
French (fr)
Japanese (ja)
Inventor
弘之 福島
秀樹 伊井
昌弘 杉本
清慈 廣瀬
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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Priority to JP2023571045A priority Critical patent/JPWO2023127856A1/ja
Publication of WO2023127856A1 publication Critical patent/WO2023127856A1/ja
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0184—Manufacture or treatment of devices comprising intermetallic compounds of type A-15, e.g. Nb3Sn
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
    • H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
    • H01B12/10—Multi-filaments embedded in normal conductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/20—Permanent superconducting devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

Definitions

  • This disclosure relates to compound superconducting wires.
  • Patent Document 1 the present applicant has a structure in which a plurality of NbTi filaments are embedded in an alloy matrix of Cu and Ni, which is used as a reinforcing member of a compound superconducting wire after being subjected to diffusion heat treatment, and NbTi
  • the filaments are reported to be Cu/NbTi-based reinforcements formed with a diameter of 10 ⁇ m to 40 ⁇ m.
  • Even a Cu/NbTi-based Nb 3 Sn wire using a conventional Cu/NbTi-based reinforcing material cannot obtain practically sufficient characteristics such as visible brittleness.
  • Ni in the reinforcing material, the tensile strength and breaking stress of the Nb 3 Sn wire are improved.
  • the purpose of the present disclosure is to provide a compound superconducting wire with excellent tensile strength.
  • a compound superconducting wire comprising: a columnar reinforcing material portion composed of a second matrix containing Then, in the cross section perpendicular to the longitudinal direction of the compound superconducting wire, Ni with respect to the maximum strength in the SEM-EDX elemental analysis, which occupies the measurement area of the SEM-EDX elemental analysis for all elements in the reinforcement part
  • a compound superconducting wire wherein the ratio of the area of the Ni-rich region to which the attributed strength ratio is 15% or more is 5.0% or less.
  • the ratio of the area of the Ti-rich region in which the ratio of the strength attributed to Ti to the maximum strength in the SEM-EDX elemental analysis is 60% or more in the measurement area is 30% or more.
  • FIG. 1 is a cross-sectional view showing an example of a compound superconducting wire of an embodiment.
  • FIG. 2 is a cross-sectional view showing another example of the compound superconducting wire of the embodiment.
  • FIG. 3 is a graph showing an example of line analysis results of all elements using SEM-EDX.
  • the inventors of the present invention have found that although the tensile strength of the compound superconducting wire increases by containing Ni in the reinforcing member as in Patent Document 1, the Ni content in the reinforcing member increases. It has been found that the tensile strength of the compound superconducting wire decreases when the amount of NiTi-based compound (hereinafter simply referred to as NiTi compound) produced in the reinforcement portion increases.
  • NiTi compound NiTi-based compound
  • a compound superconducting wire of an embodiment comprises a plurality of compound superconducting filaments containing a compound superconducting phase composed of Nb 3 Sn, and a first matrix in which the plurality of compound superconducting filaments are embedded and which contains a first stabilizer.
  • a compound superconductor portion composed of a compound superconductor portion, a plurality of reinforcing filaments made of NbTi disposed inside the compound superconductor portion, and a second reinforcing filament embedded with the plurality of reinforcing filaments and made of a Cu alloy a second matrix containing a bistable material; and a cylindrical stabilizer portion disposed on at least one of the inner peripheral side and the outer peripheral side of the compound superconductor portion.
  • Ni with respect to the maximum strength in the SEM-EDX elemental analysis which occupies the measurement area of the SEM-EDX elemental analysis targeting all elements in the reinforcement part
  • the ratio of the area of the Ni-rich region with the attributed intensity ratio of 15% or more is 5.0% or less.
  • FIG. 1 is a cross-sectional view showing an example of the compound superconducting wire of the embodiment.
  • FIG. 2 is a cross-sectional view showing another example of the compound superconducting wire of the embodiment.
  • the compound superconducting wire 1 has a compound superconductor portion 10, a reinforcement portion 20, and a stabilizer portion 30.
  • FIG. 1 is a cross-sectional view showing an example of the compound superconducting wire of the embodiment.
  • FIG. 2 is a cross-sectional view showing another example of the compound superconducting wire of the embodiment.
  • the compound superconducting wire 1 has a compound superconductor portion 10, a reinforcement portion 20, and a stabilizer portion 30.
  • a compound superconducting portion 10 constituting a compound superconducting wire 1 is composed of a plurality of compound superconducting filaments 11 containing a compound superconducting phase composed of Nb 3 Sn and a first matrix 12 .
  • the compound superconductor portion 10 is cylindrical and extends along the longitudinal direction of the compound superconducting wire 1 .
  • the first matrix 12 embeds a plurality of compound superconducting filaments 11 and contains a first stabilizer.
  • the first matrix 12 containing the first stabilizing material can provide the effects of suppressing damage to the compound superconducting filaments 11 in the compound superconducting wire 1, magnetically stabilizing it, and thermally stabilizing it. These effects are further improved when the first stabilizer constituting the first matrix 12 is copper or a copper alloy. Since the compound superconducting phase is a metal compound superconducting phase formed of Nb 3 Sn, the first stabilizer is preferably made of a Cu—Sn alloy.
  • the first stabilizer in the first matrix 12 is a Cu—Sn alloy, and the Sn in the Cu—Sn alloy is used to generate Nb 3 Sn filaments as the compound superconducting filaments 11. As a result, Even if the Sn content ratio of is reduced to about 1.0% by mass or more and about 2.0% by mass, the first matrix 12 does not have a function as a stabilizer corresponding to Cu.
  • a compound superconductor portion 10 manufactured by the bronze method is shown.
  • a compound superconducting wire precursor (not shown) in which multiple Nb filaments, which are compound superconducting filament precursors, are embedded in a first matrix precursor of a Cu—Sn alloy, which is a first stabilizer.
  • Sn in the first matrix precursor diffuses and reacts with the surface of the Nb filament, thereby converting the Nb filament to the compound superconducting filament 11 Nb 3 Sn filaments can be produced.
  • the enlarged views of the compound superconductor portion 10 shown in FIGS. 1 and 2 show an example in which a core portion 13 of unreacted Nb remaining without reacting with Sn exists.
  • the unreacted core portion 13 may become compound superconducting. It may not exist in the compound superconducting filament 11 of the body 10 .
  • the reinforcing member 20 that constitutes the compound superconducting wire 1 is columnar and is arranged inside the compound superconducting portion 10 .
  • the reinforcement part 20 is composed of a plurality of reinforcement filaments 21 and a second matrix 22 .
  • a second matrix 22 embeds a plurality of reinforcing filaments 21 and includes a second stabilizer.
  • the multiple reinforcing filaments 21 are made of NbTi.
  • the second stabilizer forming the second matrix 22 is made of a Cu alloy. Cu alloys contain Ni.
  • the stabilizer section 30 that constitutes the compound superconducting wire 1 is tubular and is arranged on at least one of the inner peripheral side and the outer peripheral side of the compound superconducting section 10 .
  • the stabilizing material portion 30 is made of a third stabilizing material. 1 shows an example in which the stabilizer portion 30 is arranged on the inner peripheral side and the outer peripheral side of the compound superconductor portion 10, and in FIG. 2, the stabilizer portion 30 is arranged on the outer peripheral side of the compound superconductor portion 10. example is shown.
  • the stabilizing material portion 30 can suppress abnormal deformation during processing of the compound superconductor portion 10 and have the effect of providing a stabilizing function.
  • the third stabilizer that constitutes the stabilizer part 30 is preferably copper or a copper alloy, more preferably oxygen-free copper.
  • the stabilizer ensures thermal contact with the refrigerant and/or provides an electrical and/or thermal effect to the superconductor so as to act as an electrical shunt circuit.
  • a normally-conducting metallic material generally metallic, which is compounded into a superconductor to increase the stability of the superconductor.
  • normal-conducting metals such as copper and aluminum have low resistivity at extremely low temperatures and good thermal conductivity. Also, current bypasses these normal-conducting metals.
  • the compound superconducting wire 1 includes Nb or It is preferable to further have a Sn diffusion preventing portion 40 made of Ta or an alloy or composite material thereof.
  • the Sn diffusion preventing portions 40 are provided on the inner peripheral side and the outer peripheral side of the compound superconductor portion 10 .
  • the Sn diffusion prevention part 40 is a first matrix precursor for forming Nb 3 Sn filaments in the compound superconductor part 10 when the compound superconducting wire precursor is subjected to the heat treatment for producing the compound superconductor part.
  • the amount of Sn necessary for reacting with the Nb filament of the compound superconducting filament precursor to generate Nb 3 Sn is retained in the Cu—Sn alloy. It has the function to
  • the compound superconducting wire 1 may further have an electrical insulation portion 50 on the outermost periphery.
  • the electrical insulation portion 50 is made of resin, glass, or the like having electrical insulation.
  • the ratio of the strength attributed to Ni to the maximum strength in the SEM-EDX elemental analysis for all elements in the reinforcement part 20, which occupies the measurement area of the EDX elemental analysis (hereinafter also simply referred to as SEM-EDX elemental analysis)
  • the area ratio of the Ni-rich region (hereinafter also simply referred to as the Ni-rich region) that is 15% or more is 5.0% or less.
  • a CuTi-based compound (hereinafter simply referred to as a CuTi compound), which is a reinforcing member, is generated in the reinforcing member 20, and the compound NiTi compounds that reduce the tensile strength of the superconducting wire 1 are also produced.
  • a NiTi compound exists in the Ni-rich region in the reinforcing member 20 .
  • the portion where the NiTi compound exists corresponds to the Ni-rich region.
  • the Ni-rich region is a region in which the ratio of the strength attributed to Ni to the maximum strength in SEM-EDX elemental analysis is 15% or more in the area measured by SEM-EDX elemental analysis, and is present in the reinforcement part 20. do.
  • the compound superconducting wire 1 has excellent tensile strength.
  • the ratio of the area of the Ni-rich region to the area measured by SEM-EDX elemental analysis is 5.0% or less and 4.1% or less. is preferable, and the decrease in the tensile strength of the compound superconducting wire 1 can be suppressed as the ratio of the area of the Ni-rich region is smaller.
  • the ratio of the intensity attributed to Ti to the maximum intensity in SEM-EDX elemental analysis in the measurement area of SEM-EDX elemental analysis is 60% or more.
  • the ratio of the area of the rich region (hereinafter also simply referred to as the Ti-rich region) is preferably 30% or more.
  • a CuTi compound which is a reinforcing member, exists in the Ti-rich region in the reinforcing member 20 .
  • the portion where the CuTi compound exists corresponds to the Ti-rich region.
  • the Ti-rich region is a region in which the ratio of the strength attributed to Ti to the maximum strength in SEM-EDX elemental analysis is 60% or more in the area measured by SEM-EDX elemental analysis, and is present in the reinforcement portion 20. do. Therefore, in the cross section of the compound superconducting wire 1, the tensile strength of the compound superconducting wire 1 can be further improved when the ratio of the area of the Ti-rich region to the area measured by the SEM-EDX elemental analysis is equal to or higher than the above ratio.
  • the SEM-EDX elemental analysis targeting all the elements in the reinforcement portion 20 is performed as follows.
  • the value of the X-ray intensity attributed to each element is defined with the maximum X-ray intensity (number of counts per second, unit cps) observed for all elements being 100(%).
  • the ratio of the X-ray intensity attributed to Ni to the maximum X-ray intensity observed for all elements is defined as 15% or more.
  • the ratio of the X-ray intensity attributed to Ti to the maximum X-ray intensity observed for all elements is defined as 60% or more.
  • FIG. 3 is an example of line analysis results and is outside the scope of this embodiment.
  • Ni, Ti, Cu, Nb, and Sn were detected as a result of line analysis of all elements using SEM-EDX.
  • the vertical axis is X-ray intensity (counts per second, unit cps).
  • the ratio of the X-ray intensity attributed to Ni (Ni15%) and the ratio of the X-ray intensity attributed to Ti (Ti60%) with respect to the maximum X-ray intensity observed for all elements are indicated respectively.
  • the area of the Ni-rich region and the area of the Ti-rich region can be obtained as follows.
  • Ni element and Ti element is performed on the measured area (3072 ⁇ m 2 ) of the reinforcing member 20 observed above.
  • the surface analysis result is represented by the X-ray intensity with respect to the scanning position of the electron beam.
  • the data obtained by SEM-EDX is analyzed by analysis software (a Python self-made program) to obtain a monochrome bitmap image in which X-ray intensities are assigned within the hierarchy of 0-255.
  • analysis software a Python self-made program
  • an X-ray intensity region in which the ratio of the X-ray intensity attributed to Ni in the measurement area is 15% or more is defined as a Ni-rich region, and the X-ray intensity in which the ratio of the X-ray intensity attributed to Ti is 60% or more. Let the region be a Ti-rich region.
  • the ratio of the area of reinforcing member 20 to the area of compound superconducting wire 1 is preferably 10% or more and 50% or less, and more preferably 10% or more and 30%. % or less.
  • the tensile strength of the compound superconducting wire 1 can be improved when the ratio of the area of the reinforcing member 20 to the area of the compound superconducting wire 1 in the cross section of the compound superconducting wire 1 is 10% or more.
  • the ratio of the area of the reinforcing material portion 20 to the area of the compound superconducting wire 1 is 50% or less, the area of the compound superconducting portion 10 occupying the area of the compound superconducting wire 1 is reduced. It is possible to suppress deterioration in the current-carrying properties of the compound superconducting wire 1 that accompanies this.
  • a Sn diffusion preventing portion is provided inside the stabilizer portion, and a plurality of compound superconducting filament precursor Nb filaments and a Cu-
  • a compound superconductor portion precursor composed of a first matrix precursor made of an Sn alloy, and a billet formed by sequentially arranging an Sn diffusion prevention portion and a reinforcement portion inside the compound superconductor portion precursor.
  • a compound superconducting wire precursor is obtained by extruding and then drawing.
  • a bronze method As a process for obtaining a compound superconducting wire precursor, a bronze method, an internal tin diffusion method, a powdery tube method, etc. can be applied.
  • the compound superconducting wire 1 can be manufactured by subjecting the compound superconducting wire precursor to a heat treatment that produces a compound superconducting portion.
  • the heat treatment of the compound superconducting wire precursor is performed in multiple stages.
  • the compound superconducting wire precursor is heat-treated in two stages.
  • the first step the condition of 530 ° C. or higher and 630 ° C. or lower for 70 hours or more and 120 hours or less
  • the second step the condition of 630 ° C. or higher and 700 ° C. or lower and 30 hours or more and 60 hours or less
  • the compound superconducting wire precursor It is preferable to heat-treat the body.
  • the compound superconducting wire precursor is heat treated at a high temperature, the formation of NiTi compounds tends to be promoted.
  • an electrical insulation portion is formed in the compound superconducting wire 1 as necessary.
  • the element distribution in the reinforcement portion by controlling the element distribution in the reinforcement portion and suppressing the amount of NiTi compound produced in the reinforcement portion, the decrease in the tensile strength of the compound superconducting wire caused by the NiTi compound is suppressed. It is possible to obtain a compound superconducting wire having excellent tensile strength.
  • the compound superconducting wire of the embodiment has the configuration shown in FIGS.
  • the compound superconductor portion, the reinforcing material portion, and the stabilizing material portion shown in (1) may be provided.
  • the compound superconducting wire has a wire diameter of 1.8 mm, and in the cross section of the compound superconducting wire, the ratio of the area of the reinforcing material portion to the area of the compound superconducting wire is 10%, and the compound In the cross section of the superconducting wire, Table 1 shows the ratio of the area of the Ni-rich region and the ratio of the area of the Ti-rich region to the area measured by SEM-EDX elemental analysis for all elements in the reinforcement part.
  • the first stage heat treatment is performed at 550° C. or more and 610° C. or less for 70 hours or more and 80 hours or less
  • the second stage heat treatment is performed at 630° C. or more and 680° C.
  • a compound superconducting wire was produced under the following conditions for 30 hours or more and 60 hours or less.
  • Example B-1 and B-2 A compound superconducting wire was produced in the same manner as in Example A-1, except that the ratio of the area of the reinforcement portion to the area of the compound superconducting wire in the cross section of the compound superconducting wire was set to 20%.
  • Examples C-1 to C-2) A compound superconducting wire was produced in the same manner as in Example A-1, except that the ratio of the area of the reinforcement portion to the area of the compound superconducting wire in the cross section of the compound superconducting wire was set to 30%.
  • Example D-1 to D-2 A compound superconducting wire was produced in the same manner as in Example A-1, except that in the cross section of the compound superconducting wire, the ratio of the area of the reinforcement portion to the area of the compound superconducting wire was set to 50%.
  • Examples A-3 to A-4, B-3 to B-4, C-3 to C-4, D-3 to D-4) The area ratio of the reinforcing material shown in Table 1 and the first stage heat treatment are performed at 570 ° C. or higher and 610 ° C. or lower for 80 hours or more and 90 hours or less, and the second stage heat treatment is performed at 660 ° C. or higher and 680 ° C. or lower for 40 hours.
  • a compound superconducting wire was produced in the same manner as in Example A-1, except that the conditions were 1 hour to 50 hours.
  • Examples A-5 to A-6, B-5 to B-6, C-5 to C-6, D-5 to D-6) The area ratio of the reinforcing material shown in Table 1 and the first stage heat treatment are performed at 530 ° C. or higher and 610 ° C. or lower for 90 hours or more and 100 hours or less, and the second stage heat treatment is performed at 660 ° C. or higher and 700 ° C. or lower for 50 hours.
  • a compound superconducting wire was produced in the same manner as in Example A-1, except that the conditions were 60 hours or longer.
  • Examples A-7, B-7, C-7, D-7) The area ratio of the reinforcing material shown in Table 1 and the first stage heat treatment are performed at 610 ° C. or higher and 630 ° C. or lower for 110 hours or more and 120 hours or less, and the second stage heat treatment is performed at 680 ° C. or higher and 700 ° C. or lower for 50 hours.
  • a compound superconducting wire was produced in the same manner as in Example A-1, except that the conditions were 60 hours or longer.
  • the ratio of the X-ray intensity attributed to Ni to the maximum X-ray intensity (counts per second, unit cps) observed for all elements was defined as 15% or more.
  • the Ti-rich region was defined as having a ratio of the X-ray intensity attributed to Ti to the maximum X-ray intensity observed for all elements to be 60% or more.
  • Ni element was surface analysis of Ni element was performed on the measured area (3072 ⁇ m 2 ) of the observed reinforcement portion.
  • the data obtained by the SEM-EDX was analyzed with analysis software (a Python self-made program) to obtain a monochrome bitmap image in which the X-ray intensities are assigned within the hierarchy of 0-255. Then, an X-ray intensity region in which the ratio of the X-ray intensity attributed to Ni to the measured area was 15% or more was defined as a Ni-rich region. Also, an X-ray intensity region in which the ratio of the X-ray intensity attributed to Ti to the measured area was 60% or more was defined as a Ti-rich region.
  • the area ratio of the Ni-rich region to the measurement area of SEM-EDX elemental analysis for all elements in the reinforcement part is 5.0% or less.
  • the example had higher tensile strength than the comparative example in which the area ratio of the Ni-rich region exceeded 5.0%.
  • the tensile strength increased as the ratio of the area of the reinforcement portion to the area of the compound superconducting wire increased.
  • the critical current of the compound superconducting wire of the example was equal to or higher than that of the comparative example.

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PCT/JP2022/048120 2021-12-28 2022-12-27 化合物超電導線 Ceased WO2023127856A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025232153A1 (zh) * 2024-05-06 2025-11-13 西安聚能超导线材科技有限公司 一种低损耗超导线材用CuNb复合棒及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09143597A (ja) * 1995-11-14 1997-06-03 Hitachi Cable Ltd リードフレーム用銅合金およびその製造法
JP2007509466A (ja) * 2003-10-17 2007-04-12 オックスフォード スーパーコンダクティング テクノロジー Ｔｉソース・ロッドを用いて（Ｎｂ，Ｔｉ）３Ｓｎワイヤを製造するための方法
JP2007305503A (ja) * 2006-05-15 2007-11-22 Furukawa Electric Co Ltd:The 強化材及び化合物超電導線材

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09143597A (ja) * 1995-11-14 1997-06-03 Hitachi Cable Ltd リードフレーム用銅合金およびその製造法
JP2007509466A (ja) * 2003-10-17 2007-04-12 オックスフォード スーパーコンダクティング テクノロジー Ｔｉソース・ロッドを用いて（Ｎｂ，Ｔｉ）３Ｓｎワイヤを製造するための方法
JP2007305503A (ja) * 2006-05-15 2007-11-22 Furukawa Electric Co Ltd:The 強化材及び化合物超電導線材

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025232153A1 (zh) * 2024-05-06 2025-11-13 西安聚能超导线材科技有限公司 一种低损耗超导线材用CuNb复合棒及其制备方法

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