JPH01175125A - Manufacture of multi-core oxide superconducting wire - Google Patents
Manufacture of multi-core oxide superconducting wireInfo
- Publication number
- JPH01175125A JPH01175125A JP33241187A JP33241187A JPH01175125A JP H01175125 A JPH01175125 A JP H01175125A JP 33241187 A JP33241187 A JP 33241187A JP 33241187 A JP33241187 A JP 33241187A JP H01175125 A JPH01175125 A JP H01175125A
- Authority
- JP
- Japan
- Prior art keywords
- superconducting
- metal
- wire
- core
- oxide
- 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 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 88
- 239000002184 metal Substances 0.000 claims abstract description 88
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000002887 superconductor Substances 0.000 claims abstract description 19
- 239000004020 conductor Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 31
- 239000000126 substance Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 description 34
- 239000000463 material Substances 0.000 description 24
- 239000011812 mixed powder Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 11
- 230000000737 periodic effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005056 compaction Methods 0.000 description 4
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- 238000003746 solid phase reaction Methods 0.000 description 4
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- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 239000000428 dust Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- -1 oxine ketone compounds Chemical class 0.000 description 1
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Landscapes
- 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、超電導マグネット等の超電導機器あるいは電
力輸送線などに用いられる多芯酸化物超電導線の製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a method for manufacturing a multi-core oxide superconducting wire used for superconducting equipment such as superconducting magnets or power transport lines.
「従来の技術」
最近に至り、常電導状態から超電導状態へ遷移する臨界
温度（Ｔｃ）が液体窒素温度以上の値を示す酸化物系の
超電導材料が種々発見されている。"Prior Art" Recently, various oxide-based superconducting materials have been discovered whose critical temperature (Tc) for transitioning from a normal conducting state to a superconducting state is higher than the temperature of liquid nitrogen.
この種の酸化物超電導材料として、例えば一般式Ａ −
Ｂ −Ｃｕ−０（ただし、ＡはＬａ、Ｃｅ、Ｙｂ、Ｓｃ
、Ｅｒ等の周期律表１１１ａ族元素の１種以上を示し、
ＢはＢａ、Ｓｒ等の周期律表■ａ族元素の１種以上を示
す）で示されるものがある。As this type of oxide superconducting material, for example, the general formula A -
B -Cu-0 (A is La, Ce, Yb, Sc
, represents one or more elements of group 111a of the periodic table such as Er,
B may be represented by one or more elements of Group A of the Periodic Table, such as Ba and Sr.
そして従来この種の酸化物超電導体を製造する方法の一
例として、前記［ａ族元素を含む粉末とＩｌａ族元素を
含む粉末と酸化銅粉末を混合して混合粉末を調製し、こ
の混合粉末を仮焼した後に所定の形状に圧粉成形し、得
られた圧粉成形体に熱処理を施し、各元素を固相反応さ
せて超電導物質を生成させることにより製造する方法が
知られている。As an example of a conventional method for manufacturing this type of oxide superconductor, a mixed powder is prepared by mixing a powder containing a group A element, a powder containing a group Ila element, and a copper oxide powder, and A manufacturing method is known in which the powder compact is calcined and then compacted into a predetermined shape, the obtained compact is subjected to heat treatment, and each element is subjected to a solid phase reaction to generate a superconducting material.
また、前記Ａ −Ｂ −Ｃｕ−０系の超電導線を製造す
る方法として、前記混合粉末を金属管に充填するか、あ
るいは混合粉末に熱処理を施して得た超電導前駆体粉末
を金属管に充填し、充填後にダイスなどを用いて金属管
を引抜加工して所望の直径の線材とし、次いでこの線材
に熱処理を施して線材内部で各元素を固相反応させ、線
材の芯線部分に超電導物質を生成させることにより超電
導線を製造する方法が知られている。In addition, as a method for producing the A-B-Cu-0 system superconducting wire, the mixed powder is filled into a metal tube, or the superconducting precursor powder obtained by heat-treating the mixed powder is filled into a metal tube. After filling, the metal tube is drawn using a die or the like to form a wire of the desired diameter.The wire is then heat-treated to cause a solid phase reaction of each element inside the wire, and a superconducting material is added to the core of the wire. A method of manufacturing superconducting wire by producing a superconducting wire is known.
「発明が解決しようとする問題点」
ところが、前述の製造方法にあっては、熱処理時の加熱
処理と冷却処理に際し、金属管と芯線の熱膨張率の差異
に起因して芯線部分に熱応力が作用するために、この熱
応力によって芯線に多数のクラックを生じる問題がある
。そして、このようなりラックが発生するために、従来
の製造方法では高臨界電流密度で機械強度の高い酸化物
超電導線を製造できない問題があった。 そこで前述の
問題点を解消する目的で本発明者らは先に、酸化物超電
導体を金属シースに充填して鍛造加工により縮径し、圧
密度の極めて高い線材を得、この線材から金属シースを
除去して芯線を露出させた後に熱処理を施すことにより
、臨界電流密度が１００００Ａ／ｃｍ”を超える高特性
の酸化物超電導線を製造するに至っている。"Problems to be Solved by the Invention" However, in the above manufacturing method, thermal stress is generated in the core wire portion due to the difference in thermal expansion coefficient between the metal tube and the core wire during the heat treatment and cooling treatment. There is a problem in that many cracks occur in the core wire due to this thermal stress. Due to the occurrence of such racks, there is a problem in that conventional manufacturing methods cannot produce oxide superconducting wires with high critical current density and high mechanical strength. Therefore, in order to solve the above-mentioned problems, the present inventors first filled a metal sheath with an oxide superconductor, reduced the diameter by forging, obtained a wire rod with extremely high consolidation density, and then made a metal sheath from this wire rod. By performing heat treatment after removing the core wire to expose the core wire, an oxide superconducting wire with high characteristics having a critical current density exceeding 10,000 A/cm'' has been manufactured.
ところで、超電導線は、より大きな電胤を安定状態で流
すことができる構造とすることが必要とされ、この要求
に応えるために従来の合金系あるいは金属間化合物系の
超電導線では銅などの良導電性金属からなる安定化母材
の内部に多数の極細超電導フィラメントを配した構造の
多芯型超電導線の構造を採用することが一般的である。By the way, superconducting wires are required to have a structure that allows a larger current to flow in a stable state, and in order to meet this requirement, conventional alloy-based or intermetallic compound-based superconducting wires have It is common to adopt a multicore superconducting wire structure in which a large number of ultrafine superconducting filaments are arranged inside a stabilizing base material made of conductive metal.
従って本発明者らが前述の如く製造した酸化物超電導線
にあっても、より大きな電流を安定状態で流すことがで
きる構造に対応することが要求される。Therefore, even the oxide superconducting wire manufactured by the present inventors as described above is required to have a structure that allows a larger current to flow in a stable state.
本発明は、前記背景に鑑みてなされたもので、高臨界電
流密度を示し、機械強度が高く、安定性に優れ、連続製
造が可能な多芯酸化物超電導線の製造方法の提供を目的
とする。The present invention was made in view of the above background, and an object of the present invention is to provide a method for manufacturing a multicore oxide superconducting wire that exhibits a high critical current density, has high mechanical strength, excellent stability, and is capable of continuous production. do.
「問題点を解決するための手段」
本発明は、前記問題点を解決するために、酸化物系の超
電導導体を金属被覆体の内部に複数配してなる多芯酸化
物超電導線の製造方法において、管状の金属シースに酸
化物超電導体あるいは酸化物超電導体の前駆体を挿入し
た後に縮径加工を施して芯線と金属シースからなる素線
を得、次に、この素線の金属シースを除去して芯線を露
出させ、この後に芯線に酸化物系の超電導物質を生成さ
せる熱処理を施して酸化物超電導導体を得るとともに、
前記熱処理温度よりも低い融点を有する金属の溶湯を用
い、前記超電導導体を複数本整列させた状態で溶融金属
中を通過させ、金属溶湯を複数本の超電導導体に付着凝
固させ、金属溶湯の凝固体からなる金属被覆体の内部に
複数の酸化物超電導導体を埋設するものである。"Means for Solving the Problems" In order to solve the above problems, the present invention provides a method for manufacturing a multicore oxide superconducting wire in which a plurality of oxide-based superconducting conductors are arranged inside a metal coating. In this process, an oxide superconductor or a precursor of an oxide superconductor is inserted into a tubular metal sheath, and then diameter-reduced to obtain a wire consisting of a core wire and a metal sheath. The core wire is removed to expose it, and then the core wire is subjected to heat treatment to generate an oxide-based superconducting substance to obtain an oxide superconducting conductor.
Using a molten metal having a melting point lower than the heat treatment temperature, a plurality of the superconducting conductors are passed through the molten metal in an aligned state, and the molten metal adheres to the plurality of superconducting conductors and solidifies, thereby solidifying the molten metal. In this method, a plurality of oxide superconducting conductors are buried inside a metal covering consisting of a metal body.
１作用」
素線の金属シースを除去した状態で芯線を熱処理するこ
とにより十分な量の酸素を供給して高臨界電流密度の酸
化物超電導導体を得る。そして、複数の超電導導体を並
列状態で溶融金属に浸漬して金属被覆体を形成し、多芯
構造の安定性の高い長尺の超電導線を連続製造する。ま
た、複数の超電導導体を金属被覆体で覆った構造のため
に、金属被覆体により超電導導体を補強することができ
、機械歪に強い多芯酸化物超電導線を得る。1 Effect" By heat-treating the core wire with the metal sheath removed, a sufficient amount of oxygen is supplied to obtain an oxide superconducting conductor with a high critical current density. Then, a plurality of superconducting conductors are immersed in molten metal in parallel to form a metal coating, and a long superconducting wire with a highly stable multicore structure is continuously manufactured. Moreover, since the structure includes a plurality of superconducting conductors covered with metal coverings, the superconducting conductors can be reinforced by the metal coverings, and a multicore oxide superconducting wire that is resistant to mechanical strain can be obtained.
「実施例」
本発明方法を実施して多芯酸化物超電導線を製造するに
は、まず、出発物を調製する。この出発物としては、酸
化物超電導体、酸化物超電導体を措成する元素を含む材
料あるいはこれらの混合物が用いられる。"Example" To manufacture a multicore oxide superconducting wire by carrying out the method of the present invention, first, starting materials are prepared. As the starting material, an oxide superconductor, a material containing an element constituting the oxide superconductor, or a mixture thereof is used.
前記の酸化物超電導体としては、Ａ −Ｂ −Ｃ−Ｄ系
（ただしＡは、Ｙ、Ｓｃ、Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐ
ｍ。The above-mentioned oxide superconductors include A-B-C-D system (where A is Y, Sc, La, Ce, Pr, Nd, P
m.
Ｓｍ、Ｅｕ、Ｇｄ、Ｔ、ｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、
Ｙｂ、Ｌｕなどの周期律表■ａ族元素のうち１種あるい
は２種以上を示し、ＢはＳｒ、Ｂａ、Ｃａ、Ｂｅ、Ｍｇ
、Ｒａなどの周期律表Ｕａ族元素のうち１種あるいは２
種以上を示し、ＣはＣｕ、Ａｇ、Ａｕの周期律表ｒｂ族
元素とＮｂのうちＣｕあるいはＣｕを含む２種以上を示
し、ＤはＯ、Ｓ 、Ｓｅ、Ｔｅ、Ｐｏなどの周期律表■
ｂ族元素およびＦ、ＣＩ、Ｂｒ等の周期律表■ｂ族元素
のうちＯあるいはＯを含む２種以上を示す）のものが用
いられる。Sm, Eu, Gd, T, b, Dy, Ho, Er, Tm,
Indicates one or more elements of Group A of the periodic table such as Yb and Lu, and B is Sr, Ba, Ca, Be, Mg
, one or two of the Ua group elements of the periodic table such as Ra
C indicates Cu or two or more of the rb group elements of the periodic table such as Cu, Ag, and Au and Nb, and D indicates elements of the periodic table such as O, S, Se, Te, and Po. ■
B-group elements and O or two or more of the b-group elements of the periodic table such as F, CI, Br, etc.) are used.
また、酸化物超電導体を構成する元素を含む材料として
は、周期律表１１ａ族元素を含む粉末と周期律表ｌｌ１
ａ族元素を含む粉末と酸化銅粉末などからなる混合粉末
あるいはこの混合粉末を仮焼した粉末、または、前記混
合粉末と仮焼粉末の混合粉末などが用いられる。ここで
用いられる周期律表［Ｊ ａ族元素粉末としては、Ｂｅ
、Ｓ ｒ、Ｍｇ、Ｂａ、Ｒａの各元素の炭酸塩粉末、酸
化物粉末、塩化物粉末、硫化物粉末、フッ化物粉末など
の化合物粉末あるいは合金粉末などである。また、周期
律表ＩＩＩａ族元素粉末としては、Ｓｃ、Ｙ、Ｌａ、Ｃ
ｅ、Ｐｒ、Ｎｄ、Ｐｍ。In addition, materials containing elements constituting the oxide superconductor include powders containing elements of group 11a of the periodic table and ll1 of the periodic table.
A mixed powder consisting of a powder containing a group A element and a copper oxide powder, a calcined powder of this mixed powder, a mixed powder of the above mixed powder and calcined powder, etc. are used. The periodic table [J a group element powder used here includes Be
, Sr, Mg, Ba, and Ra, compound powders or alloy powders such as carbonate powders, oxide powders, chloride powders, sulfide powders, and fluoride powders. In addition, powders of Group IIIa elements in the periodic table include Sc, Y, La, and C.
e, Pr, Nd, Pm.
Ｓ ｍ、Ｅ ｕ、Ｇ ｄ、Ｔ ｂ、Ｄ Ｙ、Ｈｏ、Ｅ
ｒ、Ｔ ｍ、Ｙ ｂ、Ｌ ｕの各元素の酸化物粉末、炭
酸塩粉末、塩化物粉末、硫化物粉末、フッ化物粉末など
の化合物粉末あるいは合金粉末などが用いられる。更に
、酸化銅粉末としては、ＣｕＯ，ＣｕｚＯ，Ｃｕ３０ｔ
、Ｃｕ４０３などが用いられる。S m, E u, G d, T b, D Y, Ho, E
Compound powders or alloy powders such as oxide powders, carbonate powders, chloride powders, sulfide powders, and fluoride powders of the elements r, Tm, Yb, and Lu are used. Furthermore, as copper oxide powder, CuO, CuzO, Cu30t
, Cu403, etc. are used.
ところで首記混合粉末を調製するには、通常、前述の粉
末法が用いられるが、この方法に限定されるものではな
く、各元素を含む水溶液から塩として共沈させ、その沈
澱物を乾燥させて粉末状の混合粉末として得る共沈法を
適用させることら自由である。また、前記必要な元素の
アルコキッド化合物、オキンケトン化合物、シクロペン
タジェニル化合物などの塩を所定の比率で混合して混合
液とし、この混合液をゾル状にするとともに、このゾル
状の物質を加熱してゲル化し、このゲルを更に加熱して
固相とした上で粉砕して混合粉末を得るゾルゲル法を適
用して混合粉末を得ても良い。By the way, to prepare the above-mentioned mixed powder, the above-mentioned powder method is usually used, but it is not limited to this method, and it is possible to coprecipitate each element as a salt from an aqueous solution and dry the precipitate. There is no need to apply the coprecipitation method to obtain a mixed powder. In addition, salts of the above-mentioned necessary elements such as alkoxyd compounds, oxine ketone compounds, cyclopentadienyl compounds, etc. are mixed in a predetermined ratio to form a mixed solution, and this mixed solution is made into a sol, and this sol-like substance is The mixed powder may be obtained by applying a sol-gel method in which the gel is heated to form a gel, and the gel is further heated to form a solid phase, and then pulverized to obtain a mixed powder.
次に前記混合粉末を大気中において、５００〜１０００
℃の温度で１−１００時間加熱して予備焼結する。この
予備焼結処理によって混合粉末中の水分や炭酸基を飛ば
して除去することができる。Next, the mixed powder was placed in the atmosphere at a temperature of 500 to 1000
Pre-sintering is carried out by heating at a temperature of 1-100 hours. This preliminary sintering process allows moisture and carbonate groups in the mixed powder to be blown off and removed.
なお予備焼結処理は純酸素雰囲気中で行っても良い。Note that the preliminary sintering treatment may be performed in a pure oxygen atmosphere.
予備焼結処理が終了したならば、予備焼結物を更に粉砕
して焼結し粉砕する処理を数回繰り返して粒径を揃え、
ラバープレス法などの圧粉法により圧粉して棒状の成形
体を得る。ここで行う粉砕物の圧粉法は、ラバープレス
法に限るものではなく、而記粉砕物を所望の圧密度の圧
粉成形体に加圧成形できる方法であれば、いかなる方法
でも使用可能である。そして、成形圧力は、仮焼物の種
類、目的の圧密度などに応じて定められるか、通常は１
．５〜ＩＯｔ／ｃｍ”程度の範囲で定められる。 。Once the preliminary sintering process is completed, the preliminary sintered material is further crushed, sintered, and crushed several times to make the particle size uniform.
The powder is compacted by a powder compaction method such as a rubber press method to obtain a rod-shaped compact. The method for compacting the pulverized material here is not limited to the rubber press method; any method can be used as long as the pulverized material can be pressure-formed into a powder compact with the desired degree of compaction. be. The molding pressure is determined depending on the type of calcined product, the desired degree of compaction, etc., or is usually 1
．． It is determined in the range of approximately 5 to IOt/cm.
次いで前記成形体を酸素雰囲気中において８００〜１０
００℃に１〜１００時間加熱するとともに加熱後に徐冷
する中間熱処理を行って棒状の中間焼結体を得る。この
焼結処理によって気孔率０％の理論密度に対して７５％
程度の圧密度の中間焼結体を得ることができる。Next, the molded body was placed in an oxygen atmosphere at a temperature of 800 to 10
A rod-shaped intermediate sintered body is obtained by heating to 00° C. for 1 to 100 hours and performing an intermediate heat treatment of slowly cooling after heating. This sintering process reduces the theoretical density to 75% with a porosity of 0%.
It is possible to obtain an intermediate sintered body with a degree of consolidation.
次に前述のように製造された中間焼結体１を第１図に示
す金属製の管体２に充填して複合体３を作成する。前記
管体２は、Ｃｕ、Ａｇ、ＡＩあるいはこれらの合金、ま
たはステンレスなどの金属材料から形成されている。な
お、管体２の構成材料は塑性加工可能なものであれば金
属材料に限らないが、熱処理時に中間焼結体１から酸素
を奪わないような非酸化性の材料を選択する必要がある
。Next, the intermediate sintered body 1 produced as described above is filled into a metal tube 2 shown in FIG. 1 to create a composite body 3. The tube body 2 is made of a metal material such as Cu, Ag, AI, an alloy thereof, or stainless steel. Note that the constituent material of the tube body 2 is not limited to a metal material as long as it can be plastically worked, but it is necessary to select a non-oxidizing material that does not deprive the intermediate sintered body 1 of oxygen during heat treatment.
従って貴金属あるいは貴金属を含有する合金などを用い
ることが好ましいが、管体の内周面に非酸化性の材料か
らなる被覆層を形成したものでら差し支えない。Therefore, it is preferable to use a noble metal or an alloy containing a noble metal, but it is also possible to use a coating layer made of a non-oxidizing material formed on the inner peripheral surface of the tube.
次に第１図に示すロータリースウェージング装置Ａによ
って前記複合体３に縮径加工を施す。このロータリース
ウェージング装置Ａは、図示路の駆動装置によって移動
自在に設けられた複数のダイス６を備えてなるものであ
る。これらダイス６は、棒状の複合体３をその長さ方向
に移動させる際の移動空間の周囲に、この移動空間を囲
むように設けられたもので、前記移動空間と直角な方向
（第１図に示す矢印ａ方向）に移動自在に、かつ、移動
空間の周回り（第１図に示す矢印す方向）に回転自在に
保持されている。また、各ダイス６の内面には、前記複
合体３を縮径加工するためのテーパ面６ａが形成されて
いて、各ダイス６のテーパ面６ａで囲む間隙が先窄まり
状となるようになっている。Next, the composite body 3 is subjected to a diameter reduction process using a rotary swaging device A shown in FIG. This rotary swaging device A includes a plurality of dies 6 that are movably provided by a drive device along the path shown in the figure. These dice 6 are provided around a movement space when the rod-shaped composite body 3 is moved in its length direction, so as to surround this movement space, and are arranged in a direction perpendicular to the movement space (see Fig. 1). It is held movably in the direction of the arrow a shown in FIG. 1) and rotatably around the movement space (in the direction of the arrow shown in FIG. 1). Further, a tapered surface 6a for reducing the diameter of the composite body 3 is formed on the inner surface of each die 6, so that the gap surrounded by the tapered surface 6a of each die 6 becomes tapered. ing.
前記複合体３を縮径するには、前記ロータリースウエー
ジング装置Ａを作動させるとともに、第１図に示すよう
に複合体３の一端をダイス６・・・の間の間隙に押し込
む。ここで前記ダイス６・・・は第１図の矢印ａ方向に
所定間隔往復移動しつつ回転しているために、複合体３
は一端側から順次鍛造しつつ縮径されて第１図に示す線
径まで縮径され、芯線１３ａと金属シース１３ｂとから
なる素線１３が得られる。To reduce the diameter of the composite body 3, the rotary swaging device A is operated and one end of the composite body 3 is pushed into the gap between the dies 6, as shown in FIG. Here, since the dice 6 are rotating while reciprocating at a predetermined interval in the direction of the arrow a in FIG.
is sequentially forged starting from one end and is reduced in diameter to the wire diameter shown in FIG. 1 to obtain a wire 13 consisting of a core wire 13a and a metal sheath 13b.
この縮径加工においては、回転しつつ往復遅動する複数
のダイス６によって複合体３を鍛造しつつ縮径するため
に、縮径加工中の複合体３に断線を起こすことなく大き
な加工率で縮径加工することができる。このため８０％
以上の高い圧密度の芯線１３ａを得ることができる。な
お、複合体３を縮径する装置は第１図に示すロータリー
スウエージング装置に限るものではなく、その他の縮径
加工装置を用いても差し支えない。In this diameter reduction process, since the composite body 3 is forged and reduced in diameter by a plurality of rotating dies 6 that reciprocate slowly, a large processing rate can be achieved without causing wire breakage in the composite body 3 during the diameter reduction process. Can be reduced in diameter. For this reason 80%
The core wire 13a with the above-mentioned high degree of consolidation can be obtained. Note that the device for reducing the diameter of the composite body 3 is not limited to the rotary swaging device shown in FIG. 1, and other diameter reducing devices may be used.
前記のように複合体３を所望の線径（例えば直径１ 、
０ ｍｍ）まで縮径したならば、縮径後の素線１３に以
下に説明する処理を施して超電導導体を製造する。As mentioned above, the composite 3 is cut to a desired wire diameter (for example, diameter 1,
After the diameter has been reduced to 0 mm), the reduced diameter strand 13 is subjected to the treatment described below to produce a superconducting conductor.
まず、前記索線１３から金属シース１３ｂを除去し、こ
れにより圧粉成形体からなる芯線１３ａを露出させる。First, the metal sheath 13b is removed from the cable wire 13, thereby exposing the core wire 13a made of a powder compact.
ここでの金属シース１３ｂの除去には、例えば酸あるい
はアルカリの水溶液などの処理液中に素線１３を浸漬し
、金属シース１３ｂのみを上記処理液中に溶解させる化
学的な方法などが用いられる。To remove the metal sheath 13b, for example, a chemical method is used in which the wire 13 is immersed in a treatment liquid such as an acid or alkali aqueous solution, and only the metal sheath 13b is dissolved in the treatment liquid. .
この化学的方法には、金属シース１３ｂに銅、銀あるい
はこれらの合金を用いた場合、処理液として希硝酸など
が用いられ、金属シース１３ｂにアルミニウムを用いた
場合、処理液として苛性ソーダなどが用いられ、金属シ
ース１３ｂにステンレスを用いた場合、処理液として王
水などが用いられるが、シース材料と処理液との組み合
わせはこれらに限定されるものではない。そして、この
ような除去操作の後には、速やかに芯線１３ａの表面に
水洗処理あるいは中和処理を行なって処理液の芯線１３
ａなどへの影響を排除することが望ましい。In this chemical method, when copper, silver, or an alloy thereof is used for the metal sheath 13b, dilute nitric acid is used as the treatment liquid, and when aluminum is used for the metal sheath 13b, caustic soda or the like is used as the treatment liquid. When stainless steel is used for the metal sheath 13b, aqua regia or the like is used as the treatment liquid, but the combination of the sheath material and the treatment liquid is not limited to these. After such a removal operation, the surface of the core wire 13a is immediately washed with water or neutralized to remove the treatment liquid from the core wire 13a.
It is desirable to eliminate the influence on a.
なお、金属シース１３ｂの除去方法には前述した化学的
除去方法の他に、切削加工などの機械的除去方法、ある
いは、金属シース１３ｂのみを高周波コイルにより加熱
溶解して除去する方法などの方法を採用しても差し支え
ないが、芯線１３ａに歪やクラックを与えない方法を採
用する必要があるので、前記化学的除去方法あるいは高
周波誘導加熱による加熱溶解法などが好ましい。In addition to the chemical removal method described above, methods for removing the metal sheath 13b include a mechanical removal method such as cutting, or a method in which only the metal sheath 13b is removed by heating and melting with a high-frequency coil. Although this method may be used, it is necessary to use a method that does not cause distortion or cracks to the core wire 13a, so the chemical removal method described above or the heating melting method using high-frequency induction heating is preferable.
次いで、このようにして露出せしめられた芯線１３ａに
対して熱処理を施す。この熱処理は好ましくは酸素雰囲
気中で８００〜１１００℃に１〜１００時間程度加熱し
た後に徐冷することによって行う。なおここで、徐冷処
理の途中に４００〜６００℃の温度範囲で所定時間保持
する処理を行って、酸化物超電導体の結晶構造が正方品
から斜方晶に変態することを促刈するようにしても良い
。Next, the core wire 13a exposed in this way is subjected to heat treatment. This heat treatment is preferably carried out by heating to 800 to 1100° C. for about 1 to 100 hours in an oxygen atmosphere and then slowly cooling. Here, during the slow cooling process, a process of holding the temperature in the temperature range of 400 to 600°C for a predetermined period of time is performed to accelerate the transformation of the crystal structure of the oxide superconductor from a tetragonal to an orthorhombic crystal. You can also do it.
前述の熱処理により、上記芯線１３ａの各構成元素どう
しが互いに十分に固相反応を起こすとともに、芯線１３
ａの表面が露出せしめられていることから、芯線１３ａ
の表面全体からその内部に酸素元素が効率よく拡散され
る。また、前記芯線１３ａを形成するために用いた予備
焼結物は、純酸素雰囲気において予備焼結された場合に
はその内部には十分な量の酸素が含まれ、しかもロータ
リースウェージング装置Ａによって高い圧密度にされて
いるために、熱処理時に十分な酸素のもとで固相反応が
活発になされて効率良く酸化物超電導物質が生成される
。By the heat treatment described above, the constituent elements of the core wire 13a sufficiently cause a solid phase reaction with each other, and the core wire 13a
Since the surface of the core wire 13a is exposed, the core wire 13a
Oxygen element is efficiently diffused from the entire surface into the interior. Further, the pre-sintered material used to form the core wire 13a contains a sufficient amount of oxygen when pre-sintered in a pure oxygen atmosphere, and is furthermore Because it is highly compacted, solid-phase reactions occur actively in the presence of sufficient oxygen during heat treatment, and oxide superconducting materials are efficiently produced.
したがって、上記芯線１３ａには、その全長に亙って高
い臨界電流密度を示すＡ −Ｂ −Ｃ−Ｄ系の酸化物系
の超電導物質が生成され、これにより良好な臨界電流密
度を示す酸化物系の超電導導体が得られる。なお、この
超電導導体は、ロータリースウェージング装置Ａにより
圧密され気孔が少なく、焼結後の圧密塵は９０％以上に
達するために、機械強度も高く、曲げに強い構造となっ
ている。Therefore, in the core wire 13a, an oxide-based superconducting material of the A-B-C-D system exhibiting a high critical current density is generated over its entire length, and as a result, an oxide-based superconducting material exhibiting a good critical current density is generated. A superconducting conductor of the system is obtained. Note that this superconducting conductor is compacted by the rotary swaging device A and has few pores, and since the compaction dust after sintering reaches 90% or more, it has a high mechanical strength and a structure that is resistant to bending.
このため前記超電導導体は長尺のものをロール巻きした
状態で保存しておくことができる。Therefore, the superconducting conductor can be stored in a long roll.
次に前記酸化物系の超電導導体を用いて多芯酸化物超電
導線を製造する。Next, a multicore oxide superconducting wire is manufactured using the oxide-based superconducting conductor.
多芯酸化物超電導線を製造するには、第２図に示すよう
に複数本（数十本程度）の超電導導体２０を用意すると
ともに、これら超電導導体２０の１本１本を第１セパレ
ータ２１の透孔２１ａに通す。In order to manufacture a multi-core oxide superconducting wire, as shown in FIG. through the through hole 21a.
この第１セパレータ２１は、板体２１ａに多数の透孔２
１ｂを等間隔で形成してなるもので、各透孔２１ｂは前
記超電導導体２０を通過可能な大きさに形成されている
。この第１セパレータ２１は、ロール巻き状態で保持さ
れている前記超電導導体２０の曲がりを矯正して複数本
の超電導導体２０を並列状態に整列させるものである。This first separator 21 has a large number of through holes 2 in a plate body 21a.
1b are formed at equal intervals, and each through hole 21b is formed in a size that allows the superconducting conductor 20 to pass through. This first separator 21 corrects the bending of the superconducting conductor 20 held in a rolled state and aligns the plurality of superconducting conductors 20 in parallel.
第１セパレータ２１を通過させた超電導導体２０は、続
いて第２セパレータ２２に通す。この第２セパレータ２
２は、板体２２ａの中央部に、透孔２２ａを密集状態で
形成したもので、各透孔２２ｂは超電導導体２０を通過
可能な大きさに形成され、透孔２２ｂ・・・は相互に所
定間隔離間して円形状に密集している。これら透孔２２
ｂを通過することによって超電導導体２０・・・は相互
に所定間隔離間した状態で並列される。The superconducting conductor 20 that has passed through the first separator 21 is then passed through a second separator 22. This second separator 2
2 has through holes 22a densely formed in the center of a plate 22a, each through hole 22b is formed in a size that allows the superconducting conductor 20 to pass through, and the through holes 22b... They are clustered in a circular shape with a predetermined distance between them. These through holes 22
By passing through b, the superconducting conductors 20 are arranged in parallel with a predetermined distance from each other.
次に、第２セパレータ２２によって並列された超電導導
体２０・・・をＡ１などの金属の溶？Ｉｓ Ｍを収納し
た浴槽２３に送る。この浴槽２３は、一方の側部に引込
孔２４を他方の側部に取出孔を形成してなるもので、前
記第２セパレータ２２によって集合された超電導導体２
０・・・を引込孔２４から浴槽２３の内部に引き込み、
取出孔から取り出すことができるようになっている。な
お、引込孔２４の開口部には、第２セパレータ２２によ
って集合された超電導導体２０・・・を１本１本並列状
態であるいはツイストした状態で通過させるとともに、
溶融金属Ｍの漏洩を阻止するブツシュ部材が嵌入され、
取出孔には、溶２ＪＪ Ｍの漏洩防止用のダイスが組み
込まれている。なお、このダイスは超電導導体２０の取
出時に超電導導体２０に負荷をかけないような構成が好
ましいのでローラダイスなどを用いる。Next, the superconducting conductors 20 paralleled by the second separator 22 are melted with metal such as A1. Send it to the bathtub 23 containing Is M. This bathtub 23 has a lead-in hole 24 formed on one side and an extraction hole formed on the other side, and includes superconducting conductors 2 assembled by the second separator 22.
0... is drawn into the bathtub 23 from the drawing hole 24,
It can be taken out from the extraction hole. Note that the superconducting conductors 20 collected by the second separator 22 are passed through the opening of the lead-in hole 24 one by one in a parallel state or in a twisted state, and
A bushing member that prevents leakage of molten metal M is inserted,
A die for preventing leakage of Molten 2JJM is incorporated in the extraction hole. Note that this die preferably has a configuration that does not apply a load to the superconducting conductor 20 when taking out the superconducting conductor 20, so a roller die or the like is used.
更に、浴槽２３の内底部には超音波振動子２６が設置さ
れ、浴槽２３の下方にはヒータ２７が設置されていて、
前記超音波振動子２６の振動を金属溶？ａ Ｍに伝達さ
せることができるとともに、ヒータ２７により金属溶湯
Ｍを加熱できるようになっている。Furthermore, an ultrasonic vibrator 26 is installed at the inner bottom of the bathtub 23, and a heater 27 is installed below the bathtub 23.
Does the vibration of the ultrasonic vibrator 26 cause metal melting? aM, and the molten metal M can be heated by the heater 27.
浴槽２３に引き込まれた超電導導体２０・・・を浴槽２
３の取出孔から引き出すと、浴槽２３の金属溶’／Ｑ
Ｍが超電導導体２０・・・の周囲に付着して凝固するこ
とにより金属被覆体２５が形成され、第３図に示すよう
に金属被覆体２５の内部に多数の超電導導体２０を配し
た構造の多芯酸化物超電導線Ｔを得ることができる。The superconducting conductor 20 drawn into the bathtub 23 is called the bathtub 2
When pulled out from the extraction hole 3, the metal molten '/Q' in the bathtub 23 will be removed.
When M adheres to and solidifies around the superconducting conductors 20..., a metal covering 25 is formed, and as shown in FIG. A multicore oxide superconducting wire T can be obtained.
なお、超音波振動子２６による振動を金属溶湯Ｍに加え
ておき、この状態の金属溶？ｎ Ｍに超電導導体２０・
・・を浸漬すると、金属溶７８ Ｍか超電導導体２０・
・・になじみ良く付着し、金属被覆体２５が超電導導体
２０・・・に対して強く接着する。また、浴槽２３に引
き込んだ超電導導体２０・・・に金属溶７８ Ｍ内でね
じりを加えて超電導導体２０・・・をツイスト加工する
こともできる。このように超電導導体２０・・・をツイ
スト加工することによって多芯酸化物超電導線Ｔの磁気
的安定性を向上させることができる。ここで、第１図に
示す装置によって超電導導体２０・・・にツイスト加工
する場合には、送り出し機構と第１セパレータ２１と第
２セパレータ２２を低速で回転させ、第２セパレータ２
２と浴槽２３の取出孔の間でツイストすれば良い。In addition, vibration by the ultrasonic vibrator 26 is applied to the molten metal M, and the molten metal in this state? n M superconducting conductor 20.
When immersed in molten metal 78M or superconducting conductor 20.
..., and the metal covering 25 adheres strongly to the superconducting conductor 20. It is also possible to twist the superconducting conductors 20 drawn into the bathtub 23 by twisting them in the metal melt 78M. By twisting the superconducting conductors 20 in this manner, the magnetic stability of the multicore oxide superconducting wire T can be improved. Here, when twisting the superconducting conductor 20 using the apparatus shown in FIG.
2 and the outlet hole of the bathtub 23.
一方、前記金属溶？Ａ Ｍは、芯線１３ａに酸化物超電
導物質を生成させる際の熱処理温度よりも低い融点の金
属の溶湯、例えば、はんだ、アルミニウム、スズ、亜鉛
１．インジウム、ガリウム、鉛、ビスマス、あるいはそ
の他の合金の溶湯を用いる。On the other hand, the metal melt? A M is a molten metal having a melting point lower than the heat treatment temperature at which the oxide superconducting material is produced in the core wire 13a, such as solder, aluminum, tin, zinc, etc. Uses molten metal of indium, gallium, lead, bismuth, or other alloys.
この理由は、金属溶湯Ｍの温度が酸化物超電導物質生成
時の加熱温度より高い場合、金属溶湯Ｍを通過する間に
芯線１３ａが加熱されてその超電導特性が劣化するおそ
れがあるためである。更に、前記浴槽２３に収納する金
属溶湯Ｍは、液体窒素温度などの低温における電気抵抗
が低い金属（例えばアルミニウム）の溶湯を用いること
がより好ましい。これは、低温において電気抵抗が低い
金属材料で金属被覆体２５を形成し、金属被覆体２５を
超電導導体２０・・の安定化材にするためである。The reason for this is that if the temperature of the molten metal M is higher than the heating temperature during the generation of the oxide superconducting material, the core wire 13a may be heated while passing through the molten metal M, and its superconducting properties may deteriorate. Further, as the molten metal M stored in the bathtub 23, it is more preferable to use a molten metal (for example, aluminum) that has low electrical resistance at low temperatures such as liquid nitrogen temperature. This is because the metal covering 25 is formed of a metal material that has low electrical resistance at low temperatures, and the metal covering 25 is used as a stabilizing material for the superconducting conductors 20 .
続いて前記多芯酸化物超電導線Ｔを第２図に示す水洗装
置２８によって水洗して冷却する。Subsequently, the multicore oxide superconducting wire T is washed with water and cooled using a water washing device 28 shown in FIG.
以上説明したように製造された多芯酸化物超電導線Ｔは
、ＡＩからなる金属被覆体２５の内部に複数の超電導導
体２０を配してなる構造であるために、電力容量が大き
く、安定性にも優れている。The multicore oxide superconducting wire T manufactured as described above has a structure in which a plurality of superconducting conductors 20 are arranged inside a metal covering 25 made of AI, so it has a large power capacity and is stable. It is also excellent.
また、超電導導体２０の周囲に設けた金属被覆層２５は
、超電導導体２０・・・の超電導状態が破れた場合のｒ
ｉ流通路となる安定化材の役目をなす。なお、超電導導
体２０を囲む金属被覆層２５は、超電導導体２０の補強
材としての機能も奏するので超電導線Ａは機械的歪にも
強く、超電導マグネット用の巻線ボビンなどに巻回した
場合でも臨界電流特性の低下を生じない。更に、複数の
超電導導体２０を金属溶７８ Ｍに浸漬して金属被覆層
２５を形成するので、長尺の多芯超電導線Ａの連続製造
が可能である。Further, the metal coating layer 25 provided around the superconducting conductor 20 is designed to prevent r
It serves as a stabilizing material that serves as a flow path. The metal coating layer 25 surrounding the superconducting conductor 20 also functions as a reinforcing material for the superconducting conductor 20, so the superconducting wire A is resistant to mechanical strain, even when wound around a winding bobbin for a superconducting magnet. No deterioration of critical current characteristics occurs. Furthermore, since the metal coating layer 25 is formed by immersing a plurality of superconducting conductors 20 in the metal melt 78M, continuous production of long multicore superconducting wires A is possible.
「製造例」
Ｙ、０３粉末とＢ ａ ＣＯ３粉末とＣｕＯ扮末粉末；
Ｂａ：Ｃｕ＝ １ ：２ ：３の割合になるように混合
ｉ、て得た混合粉末を９００°Ｃで２４時間加熱して仮
焼する。ついでこの仮焼粉末を粉砕して粒径を揃えた後
にラバープレスで圧粉成形して棒状の成形体を得た。"Production Example" Y, 03 powder, B a CO3 powder, and CuO powder powder;
The mixed powder obtained by mixing i so that the ratio of Ba:Cu=1:2:3 is heated and calcined at 900° C. for 24 hours. Next, this calcined powder was pulverized to have a uniform particle size, and then compacted using a rubber press to obtain a rod-shaped compact.
次に前記圧粉成形体を酸素雰囲気中で８９０°Ｃに１４
時間加熱する熱処理を行って中間焼結体を得た。次いで
前記中間焼結体を外径１０ｍｍ、肉厚１．５ｍｍのＡｇ
製のチューブに挿入し、ロータリースウェージング装置
による鍛造加工を行って直径１．０ｍｍの素線を得た。Next, the compact was heated to 890°C for 14 hours in an oxygen atmosphere.
An intermediate sintered body was obtained by heat treatment of heating for a certain period of time. Next, the intermediate sintered body was made of Ag having an outer diameter of 10 mm and a wall thickness of 1.5 mm.
The wire was inserted into a manufactured tube, and forged using a rotary swaging device to obtain a wire with a diameter of 1.0 mm.
次にこの素線・を５０％に希釈した硝酸水溶液に浸漬し
、硝酸によってＡｇ製のシース部分を溶解して除去し、
芯線を露出させた。Next, this wire was immersed in a nitric acid aqueous solution diluted to 50%, and the Ag sheath was dissolved and removed by the nitric acid.
The core wire is exposed.
更にこの芯線に対し、酸素ガス雰囲気中において８９０
°Ｃに１２時間加熱した後に徐冷する熱処理を施して芯
線の内部に超電導物質を生成させ、超電導導体を得た。Furthermore, this core wire is subjected to 890% in an oxygen gas atmosphere.
A heat treatment was performed in which the core wire was heated to 12 hours and then slowly cooled to generate a superconducting substance inside the core wire, thereby obtaining a superconducting conductor.
続いて首記超電導導体を５０本集合し、第２図に示す構
造の第１セパレータと第２セパレータを通過させながら
送り出し機構と第１セパレータと第２セパレータを低速
で回転させて超電導導体をツイスト加工し、更にＡ１の
金属溶湯を満たした超音波振動子骨の浴槽に引き込み、
続いて浴槽から引き出し、金属溶湯を超電導索線の周囲
に付着凝固させて金属被覆層を形成することにより多芯
酸化物超電導線を得ることができた。 この多芯酸化物
超電導線において、各超電導導体の臨界温度は９１Ｋを
示すとともに臨界電流密度は７７Ｋにおいて１１０００
Ａ／ａｍ”を示し、良好な臨界電流特性を示した。Next, 50 of the above superconducting conductors were assembled, and the superconducting conductors were twisted by rotating the feeding mechanism, the first separator, and the second separator at low speed while passing through the first separator and second separator having the structure shown in Fig. 2. After processing, the ultrasonic vibrator is drawn into a bone bath filled with A1 molten metal.
Subsequently, the superconducting cable was pulled out from the bathtub, and the molten metal was adhered and solidified around the superconducting cable to form a metal coating layer, thereby producing a multicore oxide superconducting wire. In this multicore oxide superconducting wire, the critical temperature of each superconducting conductor is 91K, and the critical current density is 11000 at 77K.
A/am'' and showed good critical current characteristics.
「発明の効果」
以上説明したように本発明は、酸化物超電導体あるいは
酸化物超電導体の前駆体を金属ノースに充填して縮径加
工した後に、金属シースを除去して熱処理するために、
十分な酸素の元で熱応力を加えることなく超電導物質を
生成させることができ、臨界電流密度の高い優れた超電
導導体を得ることができる。そしてこの超電導導体を複
数本集合して並行状態であるいはツイスト加工状態で金
属溶湯に浸漬して金属被覆層を形成するので、多芯構造
で臨界電流密度が高く、安定性に富む多芯酸化物超電導
線を連続製造できる効果がある。また、本発明により製
造された多芯酸化物超電導線は金属被覆層の内部に多数
の超電導導体を配した構造てあり１、金属被覆体が超電
導導体を補強するために機械強度も高く、機械歪による
臨界電流特性の劣化ら少ない。更に、超電導物質を生成
させる熱処理温度よりも低い融点の金属の溶湯に浸漬し
て金属被覆体を形成するので、溶融金属に超電導導体を
浸漬する場合でも超電導特性を劣化させることなく多芯
構造とすることができる効果がある。"Effects of the Invention" As explained above, the present invention has the following advantages: After filling a metal north with an oxide superconductor or a precursor of an oxide superconductor and reducing its diameter, the metal sheath is removed and heat treated.
Superconducting materials can be produced in sufficient oxygen without applying thermal stress, and excellent superconducting conductors with high critical current density can be obtained. Then, a plurality of these superconducting conductors are assembled and immersed in molten metal in a parallel state or in a twisted state to form a metal coating layer, so a multi-core oxide with a multi-core structure has a high critical current density and is highly stable. This has the effect of allowing continuous production of superconducting wires. In addition, the multicore oxide superconducting wire manufactured according to the present invention has a structure in which a large number of superconducting conductors are arranged inside a metal coating layer 1, and since the metal coating reinforces the superconducting conductor, it has high mechanical strength and mechanical strength. There is little deterioration of critical current characteristics due to distortion. Furthermore, since the metal coating is formed by immersing the metal in a molten metal whose melting point is lower than the heat treatment temperature used to generate the superconducting material, even when the superconducting conductor is immersed in the molten metal, it is possible to create a multi-core structure without deteriorating the superconducting properties. There is an effect that can be done.
第１図ないし第２図は、本発明を説明するためのもので
、第１図は縮径加工状態を説明するための断面図、第２
図は超電導導体の集合状態を示す斜視図、第３図は多芯
酸化物超電導線の断面図である。
Ａ・・・ロータリースウエージング装置、１・・・中間
焼結体、 ２・・・管体、３・・・複合体、
２０・・・超電導導体、２１・・・第１セパレータ
、２２・・・第２セパレータ、２３・・浴槽、
Ｍ・・・金属溶湯、２５・・・金属被覆体、Ｔ・・・
多芯酸化物超電導線。Figures 1 and 2 are for explaining the present invention, and Figure 1 is a sectional view for explaining the diameter reduction processing state,
The figure is a perspective view showing an assembled state of superconducting conductors, and FIG. 3 is a cross-sectional view of a multicore oxide superconducting wire. A... Rotary swaging device, 1... Intermediate sintered body, 2... Tube body, 3... Composite body,
20... Superconducting conductor, 21... First separator, 22... Second separator, 23... Bathtub,
M...Metal molten metal, 25...Metal coating, T...
Multicore oxide superconducting wire.
Claims (1)
なる多芯酸化物超電導線の製造方法において、 管状の金属シースに酸化物超電導体あるいは酸化物超電
導体の前駆体を挿入した後に縮径加工を施して芯線と金
属シースからなる素線を得、次に、この素線の金属シー
スを除去して芯線を露出させ、この後に芯線に酸化物系
の超電導物質を生成させる熱処理を施して酸化物超電導
導体を得るとともに、前記熱処理温度よりも低い融点を
有する金属の溶湯を用い、前記超電導導体を複数本整列
させた状態で金属溶湯中を通過させ、金属溶湯を超電導
導体に付着凝固させて金属溶湯の凝固体からなる金属被
覆体の内部に複数の酸化物超電導導体を埋設することを
特徴とする多芯酸化物超電導線の製造方法。[Claims] A method for manufacturing a multi-core oxide superconducting wire in which a plurality of oxide superconducting conductors are arranged inside a metal sheath, comprising the steps of: After inserting the precursor, diameter reduction processing is performed to obtain a wire consisting of a core wire and a metal sheath.Then, the metal sheath of this wire is removed to expose the core wire, and then an oxide-based superconductor is applied to the core wire. An oxide superconducting conductor is obtained by performing heat treatment to generate a substance, and using a molten metal having a melting point lower than the heat treatment temperature, a plurality of the superconducting conductors are aligned and passed through the molten metal, A method for manufacturing a multi-core oxide superconducting wire, which comprises: adhering and solidifying a molten metal to a superconducting conductor, and embedding a plurality of oxide superconducting conductors inside a metal covering made of a solidified body of molten metal.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33241187A JPH01175125A (en) | 1987-12-28 | 1987-12-28 | Manufacture of multi-core oxide superconducting wire |
| US07/251,847 US5045527A (en) | 1987-10-02 | 1988-10-03 | Method of producing a superconductive oxide conductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33241187A JPH01175125A (en) | 1987-12-28 | 1987-12-28 | Manufacture of multi-core oxide superconducting wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01175125A true JPH01175125A (en) | 1989-07-11 |
Family
ID=18254668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33241187A Pending JPH01175125A (en) | 1987-10-02 | 1987-12-28 | Manufacture of multi-core oxide superconducting wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01175125A (en) |
-
1987
- 1987-12-28 JP JP33241187A patent/JPH01175125A/en active Pending
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