WO2017175711A1 - 超伝導安定化材、超伝導線及び超伝導コイル - Google Patents

超伝導安定化材、超伝導線及び超伝導コイル Download PDF

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WO2017175711A1
WO2017175711A1 PCT/JP2017/013926 JP2017013926W WO2017175711A1 WO 2017175711 A1 WO2017175711 A1 WO 2017175711A1 JP 2017013926 W JP2017013926 W JP 2017013926W WO 2017175711 A1 WO2017175711 A1 WO 2017175711A1
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Prior art keywords
superconducting
content
less
mass ppm
ppm
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English (en)
French (fr)
Japanese (ja)
Inventor
航世 福岡
優樹 伊藤
牧　一誠
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority to EP17779089.6A priority Critical patent/EP3441485B1/en
Priority to US16/090,775 priority patent/US20200002787A1/en
Priority to KR1020187025129A priority patent/KR102300981B1/ko
Priority to CN201780015156.9A priority patent/CN109072339B/zh
Publication of WO2017175711A1 publication Critical patent/WO2017175711A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/005—Continuous casting of metals, i.e. casting in indefinite lengths of wire
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • 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
    • H01B12/06—Films or wires on bases or cores
    • 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
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F6/00—Superconducting magnets; Superconducting coils
    • H01F6/06—Coils, e.g. winding, insulating, terminating or casing arrangements therefor
    • 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

  • the present invention relates to a superconducting stabilizer used for a superconducting wire, a superconducting wire provided with the superconducting stabilizer, and a superconducting coil comprising the superconducting wire.
  • the present application claims priority based on Japanese Patent Application No. 2016-076902 filed in Japan on April 6, 2016, the contents of which are incorporated herein by reference.
  • the above-mentioned superconducting wire is used in fields such as MRI, NMR, particle accelerator, linear motor car, and power storage device.
  • This superconducting wire has a multi-core structure in which a plurality of strands made of a superconductor such as Nb—Ti and Nb 3 Sn are bundled with a superconducting stabilizer interposed.
  • a tape-shaped superconducting wire in which a superconductor and a superconducting stabilizer are laminated is also provided.
  • a superconducting wire is also provided in which a channel member made of pure copper is provided with a strand.
  • a superconducting stabilizer having a relatively low resistance such as copper is disposed so as to be in contact with the superconductor (element wire). If the superconducting state is partially broken, the current flowing through the superconductor is temporarily diverted to the superconducting stabilizer, and the superconductor is cooled and returned to the superconducting state during that time. It has a structure that allows
  • the structure of the superconducting wire here refers to a superconducting wire that is processed so that a wire containing a superconductor represented by Nb—Ti, Nb 3 Sn and a superconducting stabilizer made of copper are in contact with each other. It is a wire that has been processed so that a plurality of strands including the body and the superconducting stabilizer become one structure. This processing includes extrusion, rolling, wire drawing, drawing, and twisting.
  • the above-described superconducting stabilizer is required to have a sufficiently low resistance at extremely low temperatures in order to efficiently bypass current.
  • Residual resistance ratio (RRR) is widely used as an index indicating electric resistance at extremely low temperatures.
  • the residual resistance ratio (RRR) is located ratio ⁇ 293K / ⁇ 4.2K with electrical resistivity [rho 4.2 K at room temperature electrical resistivity [rho 293 K and the liquid helium temperature at (293K) (4.2K)
  • Patent Documents 1-3 propose a Cu material having a high residual resistance ratio (RRR).
  • RRR residual resistance ratio
  • a copper material having a high residual resistance ratio (RRR) is obtained by heating a copper material having a purity of 99.999% or more in an inert gas atmosphere at a temperature of 650 to 800 ° C. for at least 30 minutes. It is described to obtain.
  • Patent Document 2 proposes high-purity copper in which the content of specific elements (Fe, P, Al, As, Sn, and S) is regulated and the impurity concentration is very low.
  • Patent Document 3 proposes a Cu alloy in which a small amount of Zr is added to high-purity copper having a low oxygen concentration.
  • Patent Document 1 shows a method of manufacturing pure copper or a copper alloy having a high residual resistance ratio (RRR) using pure copper having a purity of 99.999% or more, but 99.999% The use of pure copper having the above purity as a raw material has a problem in that the manufacturing cost is significantly increased.
  • the present invention has been made in view of the above-described circumstances, and is a superconducting stabilizer that can be manufactured at a relatively simple and inexpensive manufacturing process and has a sufficiently high residual resistance ratio (RRR). It is an object of the present invention to provide a superconducting wire provided with a material and a superconducting coil comprising the superconducting wire.
  • the superconducting stabilizer according to one aspect of the present invention is a superconducting stabilizer used for a superconducting wire, and includes one or more additional elements selected from Mg, Mn, Ti, Y, and Zr. And the balance is Cu and inevitable impurities, and the total concentration of the inevitable impurities excluding O, H, C, N, and S, which are gas elements, is 5 inclusive. It is made of a copper material having a mass of not less than 100 ppm and not more than 100 ppm, and a compound containing at least one selected from MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS exists in the matrix. It is characterized by.
  • the total concentration of unavoidable impurities excluding O, H, C, N, and S, which are gas components, is added to copper in which the total concentration is 5 mass ppm to 100 mass ppm.
  • RRR residual resistance ratio
  • the total concentration of inevitable impurities excluding O, H, C, N, and S, which are gas components is made of copper having a mass of 5 mass ppm or more and 100 mass ppm or less, excessively high purity of copper can be achieved. There is no need to make a plan, the manufacturing process is simplified, and the manufacturing cost can be reduced.
  • a compound containing one or more selected from MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS is present in the matrix phase.
  • S, Se, and Te existing in the are reliably fixed, and the residual resistance ratio (RRR) can be improved.
  • RRR residual resistance ratio
  • the above-mentioned compound is thermally stable, a high residual resistance ratio (RRR) can be stably maintained even when heat-treated in a wide temperature range.
  • the above compound includes a compound in which part of S in MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS is substituted with Te and Se.
  • the content of Fe as the inevitable impurities is 10 mass ppm or less, the Ni content is 10 mass ppm or less, and the As content is 5 mass. ppm or less, Ag content is 50 mass ppm or less, Sn content is 4 mass ppm or less, Sb content is 4 mass ppm or less, Pb content is 6 mass ppm or less, and Bi content is 2 mass. It is preferable that ppm or less and the P content be 3 mass ppm or less.
  • elements of specific impurities such as Fe, Ni, As, Ag, Sn, Sb, Pb, Bi, and P have an action of reducing the residual resistance ratio (RRR). Therefore, the residual resistance ratio (RRR) can be reliably improved by defining the contents of these elements as described above.
  • the total content (x mass ppm) of S, Se, and Te and one or more selected from Mg, Mn, Ti, Y, and Zr are used.
  • the ratio y / x to the total content (y mass ppm) of the additive elements is preferably in the range of 0.5 ⁇ y / x ⁇ 100.
  • RRR residual resistance ratio
  • the residual resistance ratio (RRR) is preferably 250 or more.
  • the resistance value at extremely low temperature is sufficiently low, and the current can be sufficiently bypassed when the superconducting state of the superconductor is broken. It is particularly excellent as a superconducting stabilizer.
  • a superconducting wire according to an aspect of the present invention is characterized by including a strand including a superconductor and the above-described superconducting stabilizer.
  • the superconducting stabilizer having a high residual resistance ratio (RRR) is provided, even if the superconducting state of the superconductor is broken, The current flowing through the superconductor can be reliably diverted to the superconductor stabilizer, and the normal state is propagated to the entire superconductor (the entire superconductor wire is transformed into the normal state) Can be suppressed. For this reason, a superconducting wire can be used stably.
  • the superconducting coil which concerns on 1 aspect of this invention has the structure provided with the coil
  • the superconducting wire provided with the superconducting stabilizer having a high residual resistance ratio (RRR) is used, so that it can be used stably. .
  • RRR residual resistance ratio
  • FIG. 1 It is a cross-sectional schematic diagram of the superconducting wire provided with the superconducting stabilizer which is one Embodiment of this invention. It is a longitudinal cross-sectional schematic diagram of the filament used for the superconducting wire shown in FIG. It is a schematic diagram of the superconducting wire provided with the superconducting stabilizer which is other embodiment of this invention. It is a schematic diagram of the superconducting wire provided with the superconducting stabilizer and channel member which are other embodiments of the present invention. It is a figure which shows the SEM observation result of the superconducting stabilization material of this invention example 2 in an Example, the analysis result of a compound, and an electron beam diffraction result. It is a figure which shows the SEM observation result of the superconducting stabilization material of this invention example 15 in an Example, the analysis result of a compound, and an electron beam diffraction result.
  • the superconducting wire 10 in the present embodiment is disposed on a core portion 11, a plurality of filaments 12 disposed on the outer peripheral side of the core portion 11, and an outer peripheral side of the plurality of filaments 12. And an outer shell portion 13.
  • the filament 12 described above has a structure in which a strand 15 made of a superconductor is covered with a superconducting stabilizer 20 as shown in FIGS. 1 and 2. That is, the filament 12 includes a strand 15 and a superconducting stabilizer 20 that covers the strand 15.
  • the superconducting stabilizer 20 is formed from a superconductor when the superconducting state is broken and a normal conduction region A is generated in a part of the strand 15 made of a superconductor. The current I flowing through the element wire 15 is temporarily bypassed.
  • the superconducting stabilizer 20 contains one or more additive elements selected from Mg, Mn, Ti, Y, and Zr within a total range of 3 mass ppm to 100 mass ppm,
  • the balance is made of Cu and inevitable impurities, and the total concentration of inevitable impurities excluding O, H, C, N, and S, which are gas components, is made of a copper material having a mass concentration of 5 ppm to 100 ppm. Yes.
  • a compound containing at least one selected from MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS exists in the matrix phase. is doing.
  • MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS a part of S may be replaced with Te or Se. Since Te and Se are contained in a small amount compared to S, Te and Se rarely form a compound with Mg, Mn, Ti, Y, Zr and the like. The compound is formed with the part replaced.
  • the content of Fe, which is an inevitable impurity is 10 mass ppm or less
  • the Ni content is 10 mass ppm or less
  • the As content is 5 mass ppm or less
  • Ag content is 50 mass ppm or less
  • Sn content is 4 mass ppm or less
  • Sb content is 4 mass ppm or less
  • Pb content is 6 mass ppm or less
  • Bi content is 2 mass ppm or less
  • the P content is 3 ppm by mass or less.
  • the ratio y / x to the total element content (y mass ppm) is in the range of 0.5 ⁇ y / x ⁇ 100.
  • the residual resistance ratio (RRR) is 250 or more.
  • One or more additive elements selected from Mg, Mn, Ti, Y, Zr Of the inevitable impurities contained in copper, S, Se, and Te are elements that greatly reduce the residual resistance ratio (RRR) by being dissolved in copper. For this reason, in order to improve the residual resistance ratio (RRR), it is necessary to eliminate the influence of these S, Se, and Te.
  • the one or more additive elements selected from Mg, Mn, Ti, Y, and Zr are elements that are highly reactive with S, Se, and Te. When the additive element generates a compound with S, Se, Te, it is possible to suppress the solid solution of these S, Se, Te in copper. Thereby, the residual resistance ratio (RRR) can be sufficiently improved.
  • the content of one or more additional elements selected from Mg, Mn, Ti, Y, and Zr is less than 3 ppm by mass, the effect of fixing S, Se, and Te cannot be sufficiently achieved. There is a fear.
  • the content of one or more additive elements selected from Mg, Mn, Ti, Y, and Zr exceeds 100 ppm by mass, the residual resistance ratio (RRR) may be greatly reduced.
  • the content of one or more additive elements selected from Mg, Mn, Ti, Y, and Zr is defined within a range of 3 mass ppm to 100 mass ppm.
  • the lower limit of the content of one or more additive elements selected from Mg, Mn, Ti, Y, and Zr should be 3.5 ppm by mass or more. Is preferable, and it is more preferable to set it as 4.0 mass ppm or more.
  • the upper limit of the content of one or more additive elements selected from Mg, Mn, Ti, Y, Zr is set to 50 ppm by mass or less. It is preferably 20 ppm by mass or less, more preferably 15 ppm by mass or less.
  • the concentration of inevitable impurities excluding gas components is set in a range of 5 mass ppm to 100 mass ppm in total.
  • the raw material has a purity of 99 to 99.999 mass%.
  • High-purity copper or oxygen-free copper (C10100, C10200) can be used.
  • the O concentration is preferably 20 mass ppm or less.
  • the O concentration is more preferably 10 ppm by mass or less, and most preferably 5 ppm by mass or less.
  • the lower limit of inevitable impurities not including O, H, C, N, and S as gas components is preferably 7 mass ppm or more, and more than 10 mass ppm. More preferably.
  • the total concentration of the inevitable impurities including the gas components O, H, C, N, and S is preferably 10 masses. More than 15 ppm, more preferably 15 ppm by mass or more, and most preferably 20 ppm by mass or more.
  • the upper limit of inevitable impurities not including gas components O, H, C, N, and S is preferably 90 ppm by mass or less, and 80% by mass. More preferably, it is at most ppm. Moreover, it is preferable that the upper limit of inevitable impurities containing O, H, C, N, and S as gas components is 110 mass ppm or less.
  • inevitable impurities excluding gas components in this embodiment are Fe, Ni, As, Ag, Sn, Sb, Pb, Bi, P, Li, Be, B, F, Na, Al, Si, Ca, Cl. , K, Sc, V, Cr, Nb, Co, Zn, Ga, Ge, Br, Rb, Sr, Mo, Ru, Pd, Cd, In, I, Cs, Ba, rare earth elements, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Th, U.
  • one or more additional elements selected from Mg, Mn, Ti, Y, and Zr are produced by forming a compound with an element such as S, Se, or Te, so that the element such as S, Se, or Te is copper. Suppresses solid solution inside. Therefore, a compound containing one or more selected from MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS in the matrix (including those in which a part of S is replaced by Te or Se) ), S, Se, and Te are fixed, and the residual resistance ratio (RRR) can be reliably improved.
  • RRR residual resistance ratio
  • a compound containing one or more selected from MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS has high thermal stability and can exist stably even at high temperatures. Although these compounds are produced during melt casting, they are stably present after processing and after heat treatment due to the above-mentioned properties. Therefore, even if heat treatment is performed in a wide temperature range, S, Se, and Te are fixed as compounds, and it is possible to stably have a high residual resistance ratio (RRR).
  • RRR residual resistance ratio
  • the presence of a compound containing one or more selected from MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS at a number density of 0.001 / ⁇ m 2 or more ensures the remaining.
  • the resistance ratio (RRR) can be improved.
  • the number density of the compounds is preferably 0.005 / ⁇ m 2 or more. More preferably, it is 0.007 pieces / ⁇ m 2 or more. In the present embodiment, the number density described above is intended for compounds having a particle size of 0.1 ⁇ m or more.
  • the upper limit of the number density of the above-described compound is 0.1 / ⁇ m 2. Or less, preferably 0.09 / ⁇ m 2 or less, more preferably 0.08 / ⁇ m 2 or less.
  • the total content of S, Se, and Te in the superconducting stabilizer 20 is preferably greater than 0 ppm by mass and preferably 25 ppm by mass or less, and more preferably 15 ppm by mass, but is not limited thereto.
  • the total content of S, Se, and Te in the superconducting stabilizer 20 is preferably as small as possible, but extremely reducing the total content of S, Se, and Te causes an increase in cost.
  • the total content of S, Se, and Te in the superconducting stabilizer 20 is more preferably 0.1 mass ppm or more, further preferably 0.5 mass ppm or more, and 1.0 Although it is still more preferable to set it as mass ppm or more, it is not limited to this.
  • the Fe content is 10 mass ppm or less
  • the Ni content is 10 mass ppm or less
  • the As content is 5 mass ppm or less
  • the Ag content is 50 mass ppm or less
  • the Sn content is The amount is 4 mass ppm or less
  • the Sb content is 4 mass ppm or less
  • the Pb content is 6 mass ppm or less
  • the Bi content is 2 mass ppm or less
  • the P content is 3 mass ppm or less.
  • the Fe content is 4.5 mass ppm or less
  • the Ni content is 3 mass ppm or less
  • the As content is 3 mass ppm.
  • the Ag content is 38 mass ppm or less
  • the Sn content is 3 mass ppm or less
  • the Sb content is 1.5 mass ppm or less
  • the Pb content is 4.5 mass ppm or less
  • the Bi content Is preferably 1.5 mass ppm or less
  • the P content is preferably 1.5 mass ppm or less.
  • the Fe content is 3.3 mass ppm or less
  • the Ni content is 2.2 mass ppm or less
  • the As content is 2.2 mass ppm or less
  • the Ag content is 28 mass ppm or less
  • the lower limit of content of Fe, Ni, As, Ag, Sn, Sb, Pb, Bi, and P is 0 mass ppm.
  • the Fe content is 0.1 mass ppm or more
  • the Ni content is 0.1 mass ppm or more
  • the As content is 0.1 mass ppm or more
  • Ag content is 0.1 mass ppm or more
  • Sn content is 0.1 mass ppm or more
  • Sb content is 0.1 mass ppm or more
  • Pb content is 0.00. It is preferable that the content is 1 mass ppm or more, the Bi content is 0.1 mass ppm or more, and the P content is 0.1 mass ppm or more, but is not limited thereto.
  • one or more additive elements selected from Mg, Mn, Ti, Y, and Zr form compounds with elements such as S, Se, and Te.
  • the ratio y / x of the total content of S, Se, Te and the total content of the additive elements is less than 0.5, the content of the additive elements is insufficient, and elements such as S, Se, Te are sufficient. There is a risk that it will not be possible to fix it to.
  • the ratio y / x of the total content of S, Se, Te (x mass ppm) and the total content of the additive elements (y mass ppm) exceeds 100, surplus that does not react with S, Se, Te There will be many additive elements, and workability may be reduced. From the above, in this embodiment, the ratio y / x between the total content of S, Se, and Te (x mass ppm) and the total content of additive elements (y mass ppm) is 0.5 or more and 100 or less. It is prescribed within the range.
  • the lower limit of the ratio y / x between the total content of S, Se, and Te and the total content of additive elements is 0.75 or more. It is preferable to set it to 1.0 or more.
  • the upper limit of the ratio y / x between the total content of S, Se, and Te and the total content of additive elements is preferably 75 or less, and 50 or less. More preferably.
  • the residual resistance ratio (RRR) is 250 or more, the resistance value is low and the current can be well bypassed at an extremely low temperature.
  • the residual resistance ratio (RRR) is preferably 280 or more, more preferably 300 or more, and most preferably 400 or more.
  • the residual resistance ratio (RRR) is preferably 10,000 or less, more preferably 5000 or less, more preferably 3000 or less, and 2000 or less for surely suppressing an increase in manufacturing cost. Although it is most preferable, it is not limited to this.
  • the superconducting stabilizer 20 according to the present embodiment is manufactured by a manufacturing process including a melt casting process, a plastic working process, and a heat treatment process.
  • a manufacturing process including a melt casting process, a plastic working process, and a heat treatment process.
  • the rough drawn copper wire having the composition shown in the present embodiment is manufactured by a continuous casting and rolling method (for example, SCR method) or the like, and the superconducting stabilizing material 20 according to the present embodiment is manufactured using this as a raw material. Good.
  • the production efficiency of the superconducting stabilizer 20 according to the present embodiment is improved, and the manufacturing cost can be greatly reduced.
  • the continuous casting and rolling method used here refers to, for example, manufacturing copper roughing wire using a continuous casting and rolling facility equipped with a belt-wheel type continuous casting machine and a continuous rolling device, and using this copper roughing wire as a raw material, It is a process of manufacturing a wire.
  • the total concentration of inevitable impurities excluding O, H, C, N, and S, which are gas components is 5 mass ppm or more and 100. Since copper having a mass ppm or less contains one or more additive elements selected from Mg, Mn, Ti, Y, and Zr within a total range of 3 mass ppm to 100 mass ppm, copper S, Se, and Te inside are fixed as a compound, and it becomes possible to improve a residual resistance ratio (RRR).
  • RRR residual resistance ratio
  • the total concentration of inevitable impurities excluding O, H, C, N, and S, which are gas components is made of copper having a mass of 5 mass ppm or more and 100 mass ppm or less, excessively high purity of copper can be achieved. There is no need to make a plan, the manufacturing process is simplified, and the manufacturing cost can be reduced.
  • a compound containing one or more selected from MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS is contained in the matrix.
  • the above-mentioned compound is thermally stable, it can stably have a high residual resistance ratio (RRR) even when heat-treated in a wide temperature range.
  • the number density of the above-mentioned compound having a particle diameter of 0.1 ⁇ m or more is 0.001 / ⁇ m 2 or more, S, Se, Te can be reliably fixed as a compound, and the residual resistance The ratio (RRR) can be sufficiently improved.
  • the Fe content is 10 mass ppm or less for the content of Fe, Ni, As, Ag, Sn, Sb, Pb, Bi, and P affecting the residual resistance ratio (RRR).
  • the content is 10 mass ppm or less, the As content is 5 mass ppm or less, the Ag content is 50 mass ppm or less, the Sn content is 4 mass ppm or less, the Sb content is 4 mass ppm or less, and Pb
  • the content is specified to be 6 mass ppm or less, the Bi content is 2 mass ppm or less, and the P content is 3 mass ppm or less. For this reason, it becomes possible to improve the residual resistance ratio (RRR) of the superconducting stabilizer 20 reliably.
  • the total content of S, Se, Te (x mass ppm) and the total content of one or more additive elements selected from Mg, Mn, Ti, Y, Zr (y mass ppm) ) Ratio y / x is in the range of 0.5 ⁇ y / x ⁇ 100.
  • the superconducting wire 10 which is this embodiment is equipped with the superconducting stabilizer 20 with a high residual resistance ratio (RRR) as mentioned above, the superconducting state is in the strand 15 which consists of a superconductor. Even when the torn normal conduction region A is generated, the current can be reliably bypassed to the superconducting stabilizer 20 and can be used stably.
  • the superconducting coil of this embodiment is provided with a winding frame and a winding part, and the winding part is the superconducting wire of this embodiment wound around the peripheral surface of the winding frame.
  • the core part 11 and the outer shell part 13 constituting the superconducting wire 10 may also be made of a copper material having the same composition as that of the superconducting stabilizer 20 according to the present embodiment.
  • the outer shell portion 13 is formed of a superconductor when a superconducting state is broken and a normal conduction region A is generated in a part of the strand 15 made of a superconductor. The current I flowing through the line 15 can be temporarily bypassed.
  • the superconducting wire 10 has been exemplified as the structure including the superconducting stabilizer 20 and the outer shell portion 13, but is limited to this. Instead, the superconducting stabilizer 20 and the outer shell portion 13 may be integrated into a product.
  • the superconducting wire 10 having a structure in which a plurality of filaments 12 are bundled is described as an example.
  • the present invention is not limited to this.
  • a superconducting wire 110 having a structure in which a superconductor 115 and a superconducting stabilizer 120 are stacked on a tape-like base material 113 may be used. That is, the superconducting wire 110 may include a tape-like base material 113, a superconductor 115 and a superconducting stabilizer 120 stacked on the base material 113.
  • a superconducting wire 210 having a structure in which a plurality of filaments 12 are bundled and then incorporated into a channel member 220 made of pure copper may be used. That is, the superconducting wire 210 may include a channel member 220 having a recess and a bundle of a plurality of filaments 12 incorporated in the recess. The bundle of the plurality of filaments 12 may be, for example, the superconducting wire 10 shown in FIG.
  • high-purity copper is melted using an electric furnace in a reducing gas atmosphere of N 2 + CO, and then a mother alloy of various additive elements and impurities is added to prepare a predetermined concentration and cast into a predetermined mold.
  • a mother alloy of various additive elements and impurities is added to prepare a predetermined concentration and cast into a predetermined mold.
  • an ingot having a diameter of 70 mm and a length of 150 mm was obtained.
  • a square bar having a cross-sectional dimension of 25 mm ⁇ 25 mm was cut out from the ingot, and hot rolled at 850 ° C. to obtain a hot rolled wire with a diameter of 8 mm.
  • a thin wire having a diameter of 2.0 mm was formed from the hot-rolled wire by cold drawing, and a heat treatment was performed by holding the wire at a temperature shown in Table 2 for 1 hour, thereby producing an evaluation wire.
  • contamination of impurity elements was also observed during the melt casting process. Using these evaluation wires, the following items were evaluated.
  • Composition analysis Using the sample whose residual resistance ratio (RRR) was measured, component analysis was performed as follows. For elements other than gas components, glow discharge mass spectrometry was used when the content was less than 10 ppm by mass, and inductively coupled plasma emission spectroscopy was used when the content was 10 ppm by mass or more. Moreover, the infrared absorption method was used for the analysis of S. The concentration of O was all 10 ppm by mass or less. For the analysis of O, an infrared absorption method was used.
  • the major axis of the intermetallic compound (the length of the straight line that can be drawn the longest in the grain without contact with the grain boundary in the middle) and the minor axis (in the direction perpendicular to the major axis, the grain in the middle The average value of the length of the straight line that can be drawn the longest under conditions that do not contact the boundary).
  • the composition was analyzed using EDX (energy dispersive X-ray spectroscopy), and it was confirmed that it is a compound containing Mg, Mn, Ti, Y, Zr and S. .
  • MgS, MgSO 4 , MnS, TiS, YS, Y 2 SO 2 , and ZrS compounds were identified. Among these compounds, it was confirmed that MgS, MnS, and YS have a NaCl type, TiS has a NiAs type, MgSO 4 has a CuSO 4 type, and Y 2 SO 2 has a Ce 2 SO 2 type crystal structure.
  • Evaluation results are shown in Table 2. Moreover, the SEM observation result, analysis result, and electron diffraction result of the compound of Invention Example 2 are shown in FIG. 5, and the SEM observation result, analysis result, and electron diffraction result of the compound of Invention Example 15 are shown in FIG.
  • Comparative Example 1 one or more additive elements selected from Mg, Mn, Ti, Y, Zr were not added, and MgS, MgSO 4 , MnS, TiS, YS, Y were added inside the matrix. There was no compound containing one or more selected from 2 SO 2 and ZrS, and the residual resistance ratio (RRR) was as low as 167. In Comparative Example 2, one or more additive elements selected from Mg, Mn, Ti, Y, and Zr were 518 ppm by mass, exceeding the range of the present invention, and the residual resistance ratio (RRR) was as low as 30.
  • the residual resistance ratio (RRR) is 250 or more, which is confirmed to be particularly suitable as a superconducting stabilizer. It was.
  • FIG. 5 when Zr was added, a compound containing ZrS having a NaCl-type crystal structure was observed.
  • FIG. 6 when Mg was added, a compound containing MgS having a NaCl-type crystal structure was observed. From the above, according to the present invention, it was confirmed that the superconducting stabilizer can be provided with a relatively simple and inexpensive manufacturing process and a sufficiently high residual resistance ratio (RRR).
  • the superconducting stabilizer of the present invention has a relatively simple manufacturing process, can be manufactured at low cost, and has a sufficiently high residual resistance ratio (RRR). For this reason, the superconducting stabilizer of the present invention can be suitably applied to superconducting wires and superconducting coils used in MRI, NMR, particle accelerators, linear motor cars, power storage devices and the like.

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KR1020187025129A KR102300981B1 (ko) 2016-04-06 2017-04-03 초전도 안정화재, 초전도선 및 초전도 코일
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US20230243020A1 (en) * 2020-06-30 2023-08-03 Mitsubishi Materials Corporation Plastic copper alloy working material, copper alloy wire material, component for electronic and electrical equipment, and terminal
JP7604935B2 (ja) 2021-02-16 2024-12-24 三菱マテリアル株式会社 銅合金、銅合金塑性加工材、電子・電気機器用部品、端子、バスバー、リードフレーム、放熱基板

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JP2021022505A (ja) * 2019-07-29 2021-02-18 三菱マテリアル株式会社 絶縁性超電導線材、絶縁性超電導線材の製造方法、超電導コイルおよび絶縁性超電導線材用のチャネル
CN111549254A (zh) * 2020-04-29 2020-08-18 铜陵有色金属集团股份有限公司金威铜业分公司 一种无氧铜基微合金及其制备方法和应用
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JP7136157B2 (ja) * 2020-06-30 2022-09-13 三菱マテリアル株式会社 銅合金、銅合金塑性加工材、電子・電気機器用部品、端子
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EP3441485B1 (en) 2022-06-01
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