JPS63257125A - Manufacture of superconductive wire - Google Patents
Manufacture of superconductive wireInfo
- Publication number
- JPS63257125A JPS63257125A JP62090185A JP9018587A JPS63257125A JP S63257125 A JPS63257125 A JP S63257125A JP 62090185 A JP62090185 A JP 62090185A JP 9018587 A JP9018587 A JP 9018587A JP S63257125 A JPS63257125 A JP S63257125A
- Authority
- JP
- Japan
- Prior art keywords
- wire
- metals
- group
- alloy wire
- superconducting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 29
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 150000002739 metals Chemical class 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 4
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 239000002826 coolant Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052705 radium Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims 1
- 210000003608 fece Anatomy 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002887 superconductor Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、可とう性に富み、臨界電流密度が大きく、か
つ組成の均一性が高く、かつ作製工程の少ない超伝導線
材およびその作製方法に関するものであり、その超伝導
性は酸化物超伝導体により為されるものである。Detailed Description of the Invention (Industrial Field of Application) The present invention provides a superconducting wire material that is highly flexible, has a large critical current density, has a highly uniform composition, and requires few manufacturing steps, and a method for manufacturing the same. The superconductivity is achieved by an oxide superconductor.
（従来の技術）
Ｎｂ：＋Ｇｅ等の合金系の超伝導材料よりもＴｃ（超伝
導状態となる臨界温度）の高い酸化物系の超伝導材料が
見出されて以来、超伝導磁石や超伝導線材への′応用の
観点から、酸化物超伝導材料を線材化する試みが行われ
ている。しかしながら、合金と異なり酸化物は、塑性変
形能が乏しく線材にすることは困難である。すなわち、
超伝導電流は試料表面近傍しか流れないので応用の観点
からは表面積が大となるよう線径を細くしなければなら
ないが酸化物の線引化技術は金属や合金はど容易ではな
い。さらに高いＴｃを実現するためには、超伝導相の単
相のみを出現させる必要があるが、現実には状態図に示
されるような相分離をすることが多く、均一な超伝導相
の単相のみを出現させることは困難である。さらに、特
に可とう性が必要とされる場合、酸化物のみでは可とう
性が不足する場合がある。(Prior art) Since the discovery of oxide-based superconducting materials with a higher Tc (critical temperature for becoming superconducting) than alloy-based superconducting materials such as Nb:+Ge, superconducting magnets and superconducting From the viewpoint of application to wire rods, attempts are being made to turn oxide superconducting materials into wire rods. However, unlike alloys, oxides have poor plastic deformability and are difficult to make into wire rods. That is,
Superconducting current only flows near the surface of the sample, so from an application standpoint the wire diameter must be made small to increase the surface area, but wire drawing technology for oxides is not easy for metals and alloys. In order to achieve even higher Tc, it is necessary to make only a single superconducting phase appear, but in reality, phase separation as shown in the phase diagram often occurs, and a single homogeneous superconducting phase occurs. It is difficult to make only the phases appear. Furthermore, especially when flexibility is required, oxides alone may not provide sufficient flexibility.
このような技術的困難が存在するので、酸化物超伝導線
材が実現するには至っていない。Because of these technical difficulties, oxide superconducting wires have not yet been realized.
（発明が解決しようとする問題点）
本発明は、従来困難とされていた酸化物超伝導体の線材
を与え、その線材化、均一相化を実現するとともに可と
う性の向上をも実現する方法を与えようとするものであ
る。(Problems to be Solved by the Invention) The present invention provides a wire of an oxide superconductor, which has been considered difficult in the past, and realizes making the wire into a wire and having a uniform phase, as well as improving flexibility. It attempts to provide a method.
（問題点を解決するための手段） 本発明は、Ｓｃ、Ｙ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ。(Means for solving problems) The present invention applies to Sc, Y, La, Ce, Pr, and Nd.
Ｐｍ、Ｓｍ、Ｅｎ、Ｇｄ、 Ｔｂ、Ｄｙ、Ｈｏ。Pm, Sm, En, Gd, Tb, Dy, Ho.
Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ａｃ、Ａｌからなる群から選
ばれた一種または複数種の金属（１）と、Ｂｅ、Ｍｇ、
Ｃａ、Ｓｒ、Ｂａ、Ｒａからなる群から選ばれた一種ま
たば複数種の金属（ＩＩ）、Ｃｕ、Ａｇ、Ａｕからなる
群から選ばれた一種または複数種の金属（ＩＩＩ）を各
々原子％比で概略ｌ：２：３の割合で含む合金線材の少
なくとも表面全体が該合金線材の構成金属元素の酸化物
であることを特徴とする超伝導線材であり、上記金属を
各々原子％比で概略１：２：３の割合で混合し、この混
合物を加熱し、均一に溶融する工程と、溶融した合金を
ノズルより、冷却媒体中に噴出させ合金線材とする工程
と、該合金線材を酸素を含むふん囲気中で熱処理する工
程からなることを特徴とする超伝導線材の作製方法から
なる。この時、特に可とう性が要求される場合には、合
金線材の表面のみ超伝導酸化物層とし、中心部は合金層
のままとする。One or more metals (1) selected from the group consisting of Er, Tm, Yb, Lu, Ac, Al, Be, Mg,
atomic % of one or more metals (II) selected from the group consisting of Ca, Sr, Ba, and Ra, and one or more metals (III) selected from the group consisting of Cu, Ag, and Au. It is a superconducting wire characterized in that at least the entire surface of the alloy wire contains an oxide of the constituent metal elements of the alloy wire in a ratio of approximately 1:2:3, and each of the above metals is contained in an atomic % ratio. A process of mixing in a ratio of approximately 1:2:3, heating this mixture and melting it uniformly, a process of jetting the molten alloy from a nozzle into a cooling medium to make an alloy wire, and a process of making the alloy wire into an oxygen A method for producing a superconducting wire characterized by comprising a step of heat treatment in an atmosphere containing . At this time, if flexibility is particularly required, the superconducting oxide layer is formed only on the surface of the alloy wire, and the alloy layer remains in the center.
（実施例）
［実施例１］
Ｌａ、Ｂａ、Ｃｕを原子％比でｌ ：２：３の割合で混
合し、るつぼ中に入れ、１１００℃に加熱し均一な溶融
状態となった後、２０μｍφのノズルより、この溶融金
属を水中へ噴出させる。水中で冷却固化した合金線材を
１気圧酸素中９５０℃にて、５時間の酸化処理を施し、
酸化物線材とした。この酸化物線材の電気抵抗の温度変
化を測定したところ、４５°Ｋにて電気抵抗が零となり
、超伝導状態を確認した。(Example) [Example 1] La, Ba, and Cu were mixed in an atomic % ratio of l:2:3, placed in a crucible, and heated to 1100°C to become a uniform molten state. This molten metal is jetted into the water from a nozzle. The alloy wire rod cooled and solidified in water was subjected to oxidation treatment at 950°C in 1 atm oxygen for 5 hours.
It was made into an oxide wire. When the temperature change in the electrical resistance of this oxide wire was measured, the electrical resistance became zero at 45°K, confirming a superconducting state.
し実施例２コ
Ｙ、Ｈａ、Ｃｕを原子％比で１ ：２：３の割合で混合
し、るつぼ中に入れ、１５００℃に加熱し、均一な溶融
状態となった後、５０μｍφのノズルより、この溶融金
属を液体窒素中に噴出させる。Example 2 Y, Ha, and Cu were mixed in an atomic percent ratio of 1:2:3, placed in a crucible, heated to 1500°C, and after reaching a uniform molten state, the mixture was heated through a 50 μmφ nozzle. , the molten metal is jetted into liquid nitrogen.
液体窒素中で冷却固化した合金線材を０．２気圧酸素中
、１０００℃にて３時間の酸化処理を施し、この線材の
表面近傍のみ超伝導酸化物層とし、内部は合金線材のま
まとした。The alloy wire, which had been cooled and solidified in liquid nitrogen, was oxidized for 3 hours at 1000°C in 0.2 atmospheres of oxygen to form a superconducting oxide layer only near the surface of the wire, leaving the inside as the alloy wire. .
溶融合金液体が液体窒素中へと噴出される過程で急冷さ
れるため、合金構成成分は相分離を起こすことなく強制
固溶状態の合金線材となり、その後の熱処理で均一組成
の超伝導酸化物皮膜の形成が可能となる。Since the molten alloy liquid is rapidly cooled during the process of being ejected into liquid nitrogen, the alloy constituents become an alloy wire in a forced solid solution state without phase separation, and the subsequent heat treatment creates a superconducting oxide film with a uniform composition. It becomes possible to form
このようにして得られた、超伝導線材の電気抵抗の温度
依存性を４端子法で測定したところ、９６°にで電気抵
抗が零となり超伝導状態となるのを確認した。さらに、
この線材の引張試験を行ったところ、５２ ｋｇ／ｍ＋
ａ”の強度が得られ、さらに、この線材を万力にはさみ
、最初の位置より左右に９０°ずつ１０回の繰り返し曲
げを行ったが、折れることなく可とう性に富む線材であ
ることが認められた。When the temperature dependence of the electrical resistance of the superconducting wire thus obtained was measured using a four-terminal method, it was confirmed that the electrical resistance became zero at 96°, resulting in a superconducting state. moreover,
When this wire was subjected to a tensile test, it was 52 kg/m+
The wire rod was held in a vise and bent 10 times 90 degrees left and right from the initial position, but it was found that the wire was highly flexible without breaking. Admitted.
［実施例３］
その他の金属の組み合わせにより、本発明の方法で超伝
導線材を作製し、超伝導状態となる臨界温度（Ｔｃ）を
測定した結果を次表に示す。[Example 3] Superconducting wires were fabricated by the method of the present invention using combinations of other metals, and the critical temperatures (Tc) at which the wires became superconducting were measured. The results are shown in the following table.
表 金属１（１−ＩＩＩ）と作製された超伝導線材の超
伝導臨界温度（’Ｉ’ｃ）
表に示さない組み合わせにおいても、４０〜１００にで
超伝導となる線材が得られた。組成比の（１：２：３）
からのずれは特性の多少の劣化をもたらすが、本質的な
効果においては変化がない。Table: Superconducting Critical Temperature ('I'c) of Metal 1 (1-III) and Superconducting Wire Fabricated Even in combinations not shown in the table, wires that became superconducting at temperatures of 40 to 100 were obtained. Composition ratio (1:2:3)
A deviation from this results in some deterioration of the characteristics, but there is no change in the essential effect.
原料の混合は各金属の特性を考慮して、行うことが好ま
しい。たとえば、溶融工程において、失われやすい蒸気
圧の高い金属は多めの混合比とする ゛等である
。線材化後に所定の組成比となることが目的だからであ
る。It is preferable to mix the raw materials in consideration of the characteristics of each metal. For example, metals with high vapor pressure that are easily lost during the melting process should be mixed at a higher mixing ratio. This is because the purpose is to have a predetermined composition ratio after being made into a wire.
（発明の効果）
以上述べたとおり、本発明は変形能の乏しい酸化物超伝
導体を線引き加工工程を大幅に省略して線材化を達成し
たのみならず、均一な超伝導酸化物相を実現し、さらに
、可とう性が要求される場合には、心線部を合金線、そ
の周囲を超伝導酸化物皮膜で覆い、可とう性に富んだ超
伝導線材かできる。(Effects of the Invention) As described above, the present invention not only achieves the production of wire rods by significantly omitting the wire drawing process for oxide superconductors with poor deformability, but also realizes a uniform superconducting oxide phase. However, if flexibility is required, a highly flexible superconducting wire can be obtained by covering the core with an alloy wire and surrounding it with a superconducting oxide film.
また、超伝導電流が線材の表面近傍のみを流れることに
着目すれば、線径を細くし、表面積を大とすることが効
率化につながるが、そのためには溶融合金噴出部のノズ
ル径を小さくするのみで良い。Also, if we focus on the fact that superconducting current flows only near the surface of the wire, reducing the wire diameter and increasing the surface area will lead to higher efficiency, but in order to do this, the nozzle diameter of the molten alloy spouting part must be reduced. Just do it.
このように、本発明は従来困難であった酸化物超伝導体
の線材化を加工工程を省略して実現したものであり、超
伝導体の超伝導ケーブル、超伝導磁石等への広範な応用
を一気に可能とするものである。In this way, the present invention realizes the production of wires from oxide superconductors, which was difficult in the past, by omitting the processing process, and allows for a wide range of applications of superconductors to superconducting cables, superconducting magnets, etc. This makes it possible all at once.
Claims (2)
、Ｅｎ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、
Ｌｕ、Ａｃ、Ａｌからなる群から選ばれた一種または複
数種の金属（ I ）と、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ
、Ｒａからなる群から選ばれた一種または複数種の金属
（II）、Ｃｕ、Ａｇ、Ａｕからなる群から選ばれた一種
または複数種の金属（III）を各々原子％比で概略１：
２：３の割合で含む合金線材の少なくとも表面全体が該
合金線材の構成金属元素の酸化物であることを特徴とす
る超伝導線材。(1) Sc, Y, La, Ce, Pr, Nd, Pm, Sm
, En, Gd, Tb, Dy, Ho, Er, Tm, Yb,
One or more metals (I) selected from the group consisting of Lu, Ac, Al, Be, Mg, Ca, Sr, Ba
, one or more metals (II) selected from the group consisting of Ra, and one or more metals (III) selected from the group consisting of Cu, Ag, and Au, each in an atomic % ratio of approximately 1:
A superconducting wire comprising an alloy wire in a ratio of 2:3, at least the entire surface of which is an oxide of a metal element constituting the alloy wire.
、Ｅｎ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、
Ｌｕ、Ａｃ、Ａｌからなる群から選ばれた一種または複
数種の金属（ I ）と、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ
、Ｒａからなる群から選ばれた一種または複数種の金属
（II）、Ｃｕ、Ａｇ、Ａｕからなる群から選ばれた一種
または複数種の金属（III）を各々原子％比で概略１：
２：３の割合で混合し、この混合物を加熱し、均一に溶
融する工程と、溶融した合金をノズルより、冷却媒体中
に噴出させ合金線材とする工程と、該合金線材を酸素を
含むふん囲気中で熱処理する工程からなることを特徴と
する超伝導線材の作製方法。(2) Sc, Y, La, Ce, Pr, Nd, Pm, Sm
, En, Gd, Tb, Dy, Ho, Er, Tm, Yb,
One or more metals (I) selected from the group consisting of Lu, Ac, Al, Be, Mg, Ca, Sr, Ba
, one or more metals (II) selected from the group consisting of Ra, and one or more metals (III) selected from the group consisting of Cu, Ag, and Au, each in an atomic % ratio of approximately 1:
A step of mixing at a ratio of 2:3 and heating this mixture to uniformly melt it, a step of jetting the molten alloy into a cooling medium from a nozzle to make an alloy wire rod, and a step of blowing the alloy wire rod under oxygen-containing dung gas. A method for producing a superconducting wire, comprising a step of heat treatment in an ambient atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62090185A JPS63257125A (en) | 1987-04-13 | 1987-04-13 | Manufacture of superconductive wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62090185A JPS63257125A (en) | 1987-04-13 | 1987-04-13 | Manufacture of superconductive wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63257125A true JPS63257125A (en) | 1988-10-25 |
Family
ID=13991425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62090185A Pending JPS63257125A (en) | 1987-04-13 | 1987-04-13 | Manufacture of superconductive wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63257125A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277514A (en) * | 1987-05-08 | 1988-11-15 | Koujiyundo Kagaku Kenkyusho:Kk | Oxide superconductive material |
| JPH0226825A (en) * | 1988-07-16 | 1990-01-29 | Ngk Spark Plug Co Ltd | Superconducting ceramic material |
| US4968663A (en) * | 1989-02-27 | 1990-11-06 | Polytechnic University | Ductile, single phase-continuous super-conducting oxide conductors |
| JPH04198018A (en) * | 1990-11-28 | 1992-07-17 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Oxide superconductor and production thereof |
-
1987
- 1987-04-13 JP JP62090185A patent/JPS63257125A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277514A (en) * | 1987-05-08 | 1988-11-15 | Koujiyundo Kagaku Kenkyusho:Kk | Oxide superconductive material |
| JPH0226825A (en) * | 1988-07-16 | 1990-01-29 | Ngk Spark Plug Co Ltd | Superconducting ceramic material |
| US4968663A (en) * | 1989-02-27 | 1990-11-06 | Polytechnic University | Ductile, single phase-continuous super-conducting oxide conductors |
| JPH04198018A (en) * | 1990-11-28 | 1992-07-17 | Kokusai Chodendo Sangyo Gijutsu Kenkyu Center | Oxide superconductor and production thereof |
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