JP2003217370A - Magnesium diboride superconductive wire - Google Patents
Magnesium diboride superconductive wireInfo
- Publication number
- JP2003217370A JP2003217370A JP2002014718A JP2002014718A JP2003217370A JP 2003217370 A JP2003217370 A JP 2003217370A JP 2002014718 A JP2002014718 A JP 2002014718A JP 2002014718 A JP2002014718 A JP 2002014718A JP 2003217370 A JP2003217370 A JP 2003217370A
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- Japan
- Prior art keywords
- pipe
- alloy
- wire
- superconducting wire
- mgb
- 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.)
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Classifications
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- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高磁界を発生する
ための超電導マグネットや伝導冷却用マグネットに用い
られる二ホウ化マグネシウム超電導線材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnesium diboride superconducting wire used for a superconducting magnet for generating a high magnetic field or a conduction cooling magnet.
【０００２】[0002]
【従来の技術】ＭｇＢ2（二ホウ化マグネシウム）は、
Ｍｇ（マグネシウム）とＢ（ホウ素)の原子が交互に層
状に積み重なった結晶構造を持ち、超伝導特性を有する
ものであることが知られている。このＭｇＢ2は、金属
として電線などに加工して使いやすいものの中において
優れた超伝導転移温度を有している。 2. Description of the Related Art MgB 2 (magnesium diboride) is
It is known to have a crystal structure in which Mg (magnesium) and B (boron) atoms are alternately stacked in layers to have superconducting properties. This MgB 2 has an excellent superconducting transition temperature as a metal which is easy to be processed into an electric wire or the like.
【０００３】従来、ＭｇＢ2を利用したＭｇＢ2多芯構造
超電導線の作製方法として、例えば、次に記述すると
の製法が試みられている。Conventionally, as a method for manufacturing a MgB 2 multi-core structure superconducting wire using MgB 2, for example, then the method with the described have been attempted.
【０００４】ＭｇＢ2粉末を出発原料粉末とする方法
では、反応済みのＭｇＢ2超電導粉末をＴａ、Ｎｉ、Ｆ
ｅ等の金属パイプに充填し、その外側にＣｕパイプを被
覆したのち線引き加工してシングル六角線とし、それを
複数本パイプ内に組み込んで多芯構造としたのち伸線す
る。最後に、その多芯線を８００〜９００℃の範囲で熱
処理し、固相反応によってＭｇＢ2粉末同士を結合させ
て超電導線とする。In the method of using MgB 2 powder as the starting material powder, the reacted MgB 2 superconducting powder is Ta, Ni, F.
It is filled in a metal pipe such as e, coated with a Cu pipe on the outer side thereof, and then drawn to form a single hexagonal wire. A single hexagonal wire is incorporated into a plurality of pipes to form a multi-core structure and then drawn. Finally, the multifilamentary wire is heat-treated in the range of 800 to 900 ° C., and the MgB 2 powders are bonded to each other by a solid phase reaction to form a superconducting wire.
【０００５】ＭｇとＢの混合粉末を出発材料とし、Ｔ
ａパイプに充填する方法では、ＭｇとＢの微粒粉末をモ
ル比が約Ｍｇ：Ｂ＝１：２となるように混合した後、Ｍ
ｇと反応しないＴａパイプに充填し、その外周をＣｕパ
イプで被覆して押出し加工した後、線引き加工してシン
グル六角線とし、それを複数本パイプ内に組み込んで多
芯構造とする。この多芯構造のビレットを再度、押出し
加工して伸線し、最後に熱処理してＭｇＢ2多芯構造超
電導線を生成する。Starting from a mixed powder of Mg and B as a starting material, T
In the method of filling the a pipe, fine powders of Mg and B are mixed so that the molar ratio is about Mg: B = 1: 2, and then M
It is filled in a Ta pipe that does not react with g, the outer periphery thereof is covered with a Cu pipe and extruded, and then drawn to form a single hexagonal wire, which is incorporated into a plurality of pipes to form a multi-core structure. This multi-core structure billet is extruded again, drawn, and finally heat-treated to produce a MgB 2 multi-core structure superconducting wire.
【０００６】[0006]
【発明が解決しようとする課題】しかし、従来の方法に
おいては、次に記述するような問題があった。上記の
方法では、出発原料であるＭｇＢ2粉末の硬度が高く
（硬く）、延性が無いために加工性に難があり、加工で
きたとしても均一な断面の多芯線とすることが困難であ
った。加えて、断線防止のために、線材の引っ張り強度
を上げる必要性があり、線材全断面積に対するコア部分
のＭｇＢ2粉末比率（コア比）を高くできないため、結
果として被覆金属部分である非超電導部分の占積率が増
加し、線材オーバーオールの臨界電流密度が低下する傾
向にあった。However, the conventional method has the following problems. In the above method, since the starting material MgB 2 powder has high hardness (hardness) and lacks ductility, it has a difficulty in workability, and even if it can be processed, it is difficult to form a multifilamentary wire having a uniform cross section. It was In addition, in order to prevent disconnection, it is necessary to increase the tensile strength of the wire, and the MgB 2 powder ratio (core ratio) of the core part to the total cross-sectional area of the wire cannot be increased, resulting in the non-superconducting metal part of the coated metal part. The space factor of the part increased and the critical current density of the wire overall tended to decrease.
【０００７】これらの理由から、ＭｇＢ2超電導粉体を
出発材とした線材の断面構造は、単芯線あるいはフィラ
メント数が１０本以下と少なく、フィラメント径も１０
０μｍ以上ある多芯線構造しか作製することができな
い。これは、超電導線の交流損失低減や磁気的不安定性
低減（フラックスジャンプ防止）の観点から極細多芯構
造を有する実用超電導線の構造を満足するものではな
い。For these reasons, the cross-sectional structure of a wire starting from MgB 2 superconducting powder has a small number of single-core wires or 10 filaments or less, and a filament diameter of 10 or less.
Only a multi-core wire structure having a thickness of 0 μm or more can be produced. This does not satisfy the structure of a practical superconducting wire having an ultrafine multicore structure from the viewpoint of reducing AC loss of the superconducting wire and reducing magnetic instability (prevention of flux jump).
【０００８】また、ＭｇＢ2の表面に酸化膜やＭｇＢ4等
の異相（絶縁相あるいは常電導相）が存在していると、
最終熱処理しても粒界部分に異相が析出するために、個
々の粒子は超電導状態を示しても、粒界部で電流が妨げ
られ臨界電流が向上しない可能性があった。If a different phase (insulating phase or normal conducting phase) such as an oxide film or MgB 4 exists on the surface of MgB 2 ,
Even after the final heat treatment, a heterogeneous phase is precipitated in the grain boundary portion, so even if each particle exhibits a superconducting state, the current may be obstructed at the grain boundary portion and the critical current may not be improved.
【０００９】上記の方法では、の方法に比較してＭ
ｇとＢの混合粉末を出発材料とすることで、ある程度延
性のあるＭｇの存在により加工性が向上する。しかし、
ＴａはＭｇと反応しないものの、伸線加工するに連れて
Ｔａ部分の断面が乱れ、Ｔａ被覆が破れて外皮のＣｕと
Ｍｇが部分的に直接接触してしまうことがあった。そう
なると、最終的なＭｇＢ2生成熱処理時に融点が６５０
℃と比較的低いＭｇがＣｕ側に拡散してＣｕ−Ｍｇ合金
が生成し、コア部分が化学量論組成（Ｍｇ：Ｂ＝１：
２）からずれてＢ過剰（ボロンリッチ）となり、超電導
特性が劣化してしまうことがある。特に、多芯線になっ
た場合、Ｔａ被覆厚さは数十μｍ以下まで低下するた
め、乱れによって部分的に被覆が破れてしまう可能性が
高く、多芯線の臨界電流低下の要因となっていた。In the above method, M
By using a mixed powder of g and B as a starting material, workability is improved due to the presence of Mg, which is ductile to some extent. But,
Although Ta does not react with Mg, the cross-section of the Ta portion is disturbed as the wire drawing process is performed, and the Ta coating may be broken and Cu and Mg of the outer skin may be partially in direct contact with each other. If so, the melting point is 650 during the final heat treatment for forming MgB 2.
Mg, which is relatively low at ℃, diffuses to the Cu side to form a Cu—Mg alloy, and the core portion has a stoichiometric composition (Mg: B = 1:
There is a case where it deviates from 2) and B becomes excessive (boron rich), and the superconducting property is deteriorated. In particular, in the case of a multifilamentary wire, the Ta coating thickness is reduced to several tens of μm or less, so that there is a high possibility that the coating partially breaks due to turbulence, which is a factor of a decrease in the critical current of the multifilamentary wire. .
【００１０】伸線加工に伴う断面の乱れの原因は、１つ
目には、Ｔａの結晶粒が大きいため、粒界部分が少な
く、加工に伴う粒界すべりが、あまり期待できないこ
と、２つ目には、外周に被覆したＣｕとの密着性が悪く
界面隔離しやすいこと、３つ目には、Ｃｕとの硬さの違
いが大きく、伸線加工時の変形抵抗に大きな差が生じる
こと、等であると推測される。The cause of the disorder of the cross section due to the wire drawing work is that, firstly, since the crystal grains of Ta are large, the grain boundary portion is small, and the grain boundary slip accompanying the work cannot be expected so much. Eyes have poor adhesion to Cu coated on the outer circumference and are likely to be isolated from the interface. Thirdly, there is a large difference in hardness from Cu and a large difference in deformation resistance during wire drawing. , And so on.
【００１１】本発明は、かかる点に鑑みてなされたもの
であり、臨界電流密度の高い多芯構造の超電導線を作製
することができる二ホウ化マグネシウム超電導線材を提
供することを目的とする。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a magnesium diboride superconducting wire capable of producing a superconducting wire having a multicore structure having a high critical current density.
【００１２】[0012]
【課題を解決するための手段】上記課題を解決するため
に、本発明の二ホウ化マグネシウム超電導線材は、Ｍｇ
とＢの混合粉末、またはＭｇ、Ｂおよび、その他の添加
元素または化合物粉末を混合した混合粉末を、Ｎｂパイ
プまたはＮｂ−Ｔａ合金パイプ内に充填し、このパイプ
をＣｕ（銅）パイプまたはＣｕ合金パイプで被覆するこ
とにより、（Ｍｇ＋Ｂ）／Ｎｂ／Ｃｕ（またはＣｕ合
金）、あるいは（Ｍｇ＋Ｂ）／Ｎｂ−Ｔａ／Ｃｕ（また
はＣｕ合金）構造としたことを特徴としている。In order to solve the above-mentioned problems, the magnesium diboride superconducting wire of the present invention is made of Mg
And a mixed powder of B and Mg, or a mixed powder of Mg, B, and other additive element or compound powder are filled in an Nb pipe or an Nb-Ta alloy pipe, and this pipe is Cu (copper) pipe or Cu alloy It is characterized by having a (Mg + B) / Nb / Cu (or Cu alloy) or (Mg + B) / Nb-Ta / Cu (or Cu alloy) structure by coating with a pipe.
【００１３】即ち、ＭｇとＢの混合粉末を、Ｍｇと固溶
せず（反応せず）、かつＢとは高温でしか反応しないＮ
ｂパイプまたはＮｂ−Ｔａ合金パイプ内に充填し、加え
て伸線加工性を向上させるためＮｂパイプまたはＮｂ−
Ｔａ合金パイプの外周にＣｕパイプを被覆した構造とな
る。この構造によれば、Ｎｂは、Ｔａに比較してＣｕと
の接合性が良好で、加工時の変形抵抗の差も小さい。ま
た、Ｔａを数ａｔ％添加したＮｂ−Ｔａ合金は結晶粒が
微細化され、伸線あるいは圧延等の塑性加工時の割れや
乱れを防ぐことができる。ただし、Ｔａは、Ｎｂに比較
してＢとの反応温度が高く、約８００℃以上の高温でＭ
ｇＢ2生成熱処理をする場合は、混合粉末との接触部分
をＴａにしたほうが被覆パイプとＢの反応を防止するこ
とができる。That is, the mixed powder of Mg and B does not form a solid solution with Mg (does not react) and reacts with B only at high temperatures.
Bb pipe or Nb-Ta alloy pipe is filled with Nb pipe or Nb-
The outer periphery of the Ta alloy pipe is covered with a Cu pipe. According to this structure, Nb has a better bondability with Cu than Ta and has a small difference in deformation resistance during processing. In addition, the crystal grains of the Nb-Ta alloy containing Ta at a few at% are made finer, and cracking and disorder during plastic working such as wire drawing or rolling can be prevented. However, Ta has a higher reaction temperature with B than Nb, and Ta has a high reaction temperature of about 800 ° C. or higher.
When the heat treatment for generating gB 2 is performed, it is possible to prevent the reaction between the coated pipe and B by making the contact portion with the mixed powder Ta.
【００１４】また、前記ＮｂまたはＮｂ−Ｔａ合金パイ
プの内側にＴａパイプを配置することにより、（Ｍｇ＋
Ｂ）／Ｔａ／Ｎｂ／Ｃｕ（またはＣｕ合金）、あるいは
（Ｍｇ＋Ｂ）／Ｔａ／Ｎｂ−Ｔａ／Ｃｕ（またはＣｕ合
金）構造としたことを特徴としている。By arranging the Ta pipe inside the Nb or Nb-Ta alloy pipe, (Mg +
B) / Ta / Nb / Cu (or Cu alloy) or (Mg + B) / Ta / Nb-Ta / Cu (or Cu alloy) structure.
【００１５】即ち、ＭｇとＢの混合粉末を、Ｍｇと固溶
せず（反応せず）、かつＢとは高温でしか反応しないＴ
ａとＮｂの複合構造パイプ（Ｔａ／Ｎｂ構造）、または
ＴａとＮｂ−Ｔａの複合構造パイプ（Ｔａ／Ｎｂ・Ｔａ
構造）内に充填し、加えて伸線加工性を向上させるため
ＮｂパイプまたはＮｂ−Ｔａ合金パイプの外周にＣｕパ
イプを被覆した構造となる。この構造によれば、上記同
様に、Ｔａを数ａｔ％添加したＮｂ−Ｔａ合金は結晶粒
が微細化され、伸線あるいは圧延等の塑性加工時の割れ
や乱れを防ぐことができる。ただし、Ｔａは、Ｎｂに比
較してＢとの反応温度が高く、約８００℃以上の高温で
ＭｇＢ2生成熱処理をする場合は、混合粉末との接触部
分をＴａにしたほうが被覆パイプとＢの反応を防止する
ことができる。また、前記（Ｍｇ＋Ｂ）／Ｎｂ／Ｃｕ
（またはＣｕ合金）、（Ｍｇ＋Ｂ）／Ｎｂ−Ｔａ／Ｃｕ
（またはＣｕ合金）、（Ｍｇ＋Ｂ）／Ｔａ／Ｎｂ／Ｃｕ
（またはＣｕ合金）、あるいは（Ｍｇ＋Ｂ）／Ｔａ／Ｎ
ｂ−Ｔａ／Ｃｕ（またはＣｕ合金）の構造を有する線材
の複数が集合されたものであることを特徴としている。That is, the mixed powder of Mg and B does not form a solid solution with Mg (does not react) and reacts with B only at a high temperature.
Composite structure pipe of a and Nb (Ta / Nb structure) or composite structure pipe of Ta and Nb-Ta (Ta / Nb · Ta)
In order to improve the wire drawing workability, the Nb pipe or the Nb-Ta alloy pipe is covered with a Cu pipe on the outer periphery thereof. According to this structure, similarly to the above, in the Nb-Ta alloy to which Ta is added at a few at%, the crystal grains are made finer, and it is possible to prevent cracking and disorder during plastic working such as wire drawing or rolling. However, Ta has a higher reaction temperature with B than Nb, and when the MgB 2 production heat treatment is performed at a high temperature of about 800 ° C. or higher, Ta is better for the contact portion with the mixed powder than for the coated pipe and B. The reaction can be prevented. In addition, (Mg + B) / Nb / Cu
(Or Cu alloy), (Mg + B) / Nb-Ta / Cu
(Or Cu alloy), (Mg + B) / Ta / Nb / Cu
(Or Cu alloy), or (Mg + B) / Ta / N
It is characterized in that a plurality of wire rods having a structure of b-Ta / Cu (or Cu alloy) are aggregated.
【００１６】また、前記線材の全断面積に対する混合粉
末部の占積率（混合粉末部断面積／単芯線全断面積＝コ
ア比）が０．５５以下であることを特徴としている。Further, the space factor of the mixed powder portion with respect to the total sectional area of the wire (mixed powder portion sectional area / single-core wire total sectional area = core ratio) is 0.55 or less.
【００１７】この０．５５以下とする理由は、単芯線作
製工程（二ホウ化マグネシウム超電導線材作製工程）に
おいてコア比を高くする、つまり混合粉末部面積の単芯
線全断面積に対する比率を０．５５以上に高くすると、
ＮｂやＣｕ等の金属被覆パイプに比較して延性の低いコ
ア部の影響で伸線中に断線する可能性が高くなるからで
ある。特にコア周囲の被覆厚さが数十μｍ以下まで薄く
なる多芯線に、多数の本二ホウ化マグネシウム超電導線
材を適用した場合、伸線できてもＮｂやＴａ等の被覆が
部分的に破れ、最後のＭｇＢ2生成熱処理時にＭｇとＣ
ｕが反応して超電導特性の劣化が起きる可能性が非常に
高くなるからである。The reason for setting the ratio to 0.55 or less is to increase the core ratio in the single core wire manufacturing process (magnesium diboride superconducting wire manufacturing process), that is, the ratio of the mixed powder part area to the total single core wire cross-sectional area. If you raise it above 55,
This is because the possibility of disconnection during wire drawing increases due to the effect of the core portion having a low ductility as compared with a metal-coated pipe such as Nb or Cu. In particular, when a large number of main magnesium diboride superconducting wire rods are applied to a multifilamentary wire whose coating thickness around the core is reduced to several tens of μm or less, even if wire drawing is possible, the coating such as Nb or Ta partially breaks, Mg and C during the final MgB 2 formation heat treatment
This is because there is a very high possibility that u will react to cause deterioration of superconducting properties.
【００１８】また、前記線材における混合粉末部以外の
被覆厚さ（ｔ）と、混合粉末部分の半径（＝コア半径：
ｒ）との比率（ｔ／ｒ）が０．１２以上であることを特
徴としている。Further, the coating thickness (t) of the wire other than the mixed powder portion and the radius of the mixed powder portion (= core radius:
The ratio (t / r) to r) is 0.12 or more.
【００１９】この０．１２以上とする理由は、Ｎｂ、Ｎ
ｂ−Ｔａ、Ｔａ／ＮｂあるいはＴａ／Ｎｂ・Ｔａ被覆パ
イプの厚さが薄すぎると、例え外側のＣｕパイプ厚さが
厚く、伸線できたとしても断面が乱れてＮｂ等の被覆が
破れ、最後のＭｇＢ2生成熱処理時にＭｇとＣｕが反応
して超電導特性の劣化が起きる可能性が非常に高くなる
からである。The reason why the value is 0.12 or more is that Nb, N
If the thickness of b-Ta, Ta / Nb or Ta / Nb / Ta coated pipe is too thin, the thickness of the outer Cu pipe is large, and even if wire drawing is possible, the cross section is disturbed and the coating such as Nb is broken, This is because there is a high possibility that the superconducting characteristics will deteriorate due to the reaction between Mg and Cu during the final heat treatment for forming MgB 2 .
【００２０】また、ＭｇＢ2を生成する本線材への熱処
理として、６００℃以上、９００℃以下の熱処理を施し
たことを特徴としている。Further, the present invention is characterized in that a heat treatment at 600 ° C. or higher and 900 ° C. or lower is performed as a heat treatment on the main wire which produces MgB 2 .
【００２１】この熱処理を６００℃以上、９００℃以下
とする理由は、６００℃以下の熱処理温度ではＭｇＢ2
の生成反応が進まず、臨界電流が向上しないからであ
る。一方、９００℃以上の熱処理を行うと、ＭｇＢ2結
晶粒の粗大化が促進され、粒界部分に超電導電流を阻害
する非超電導物質（ＭｇＢ4、ＭｇやＢの酸化物）の析
出が顕著となり、粒界部分で臨界電流が極端に低下する
ため、マクロ的に見た線全体の臨界電流が低下してしま
うからである。The reason why this heat treatment is performed at 600 ° C. or higher and 900 ° C. or lower is that MgB 2 is used at a heat treatment temperature of 600 ° C. or lower.
This is because the production reaction of does not proceed and the critical current does not improve. On the other hand, when heat treatment is performed at 900 ° C. or higher, coarsening of MgB 2 crystal grains is promoted, and precipitation of non-superconducting substances (MgB 4 , oxides of Mg and B) that obstructs superconducting current becomes remarkable at grain boundaries. The reason is that the critical current is extremely reduced at the grain boundary portion, so that the critical current of the entire line seen from a macro perspective is reduced.
【００２２】[0022]
【発明の実施の形態】以下、本発明の実施の形態につい
て、図面を参照して詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below in detail with reference to the drawings.
【００２３】（実施の形態）図１は、本発明の実施の形
態に係るＭｇＢ2超電導線材の構成を示す断面図であ
る。(Embodiment) FIG. 1 is a sectional view showing a structure of a MgB 2 superconducting wire according to an embodiment of the present invention.
【００２４】この図１に示すＭｇＢ2超電導線材１０
は、ＭｇとＢを約１：２のモル比で混合した粉末（混合
粉末）１１を、ＮｂやＮｂ−Ｔａ合金パイプ１２に充填
するか、または、Ｎｂ−Ｔａ合金パイプ１２の内側に配
置したＴａパイプ１３との複合パイプ内に充填して粉体
をプレスし、その外側をＣｕパイプ１４で被覆すること
によって形成したものである。The MgB 2 superconducting wire 10 shown in FIG.
Is filled with Nb or Nb-Ta alloy pipe 12 with a powder (mixed powder) 11 in which Mg and B are mixed in a molar ratio of about 1: 2, or is arranged inside Nb-Ta alloy pipe 12. It is formed by filling a composite pipe with the Ta pipe 13 and pressing the powder, and coating the outside with a Cu pipe 14.
【００２５】このＭｇＢ2超電導線材１０を、さらに、
パイプの前端と後端に栓をして単芯ビレットとし、押出
し加工後に引き抜き伸線加工して細線化し、最後に六角
ダイスで六角断面のシングル線（単芯線）とする。この
単芯線である六角線を複数束ねてＣｕまたはＣｕ−Ｎｉ
パイプ等に組み込み、パイプの前端と後端に栓をして多
芯ビレットとし、押出し加工後に引き抜き伸線加工して
細線化し、最終熱処理をしてＭｇとＢを反応させること
によって、ＭｇＢ2多芯超電導線を形成することができ
る。This MgB 2 superconducting wire 10 is further
A single core billet is obtained by plugging the front and rear ends of the pipe, and after extrusion, drawing and drawing to make a fine wire, and finally using a hexagon die to make a single wire (single core wire) with a hexagonal cross section. Cu or Cu-Ni is formed by bundling a plurality of hexagonal wires that are single-core wires.
Assembled into a pipe, etc., plug the front and rear ends of the pipe to form a multi-core billet, and after extruding, draw wire drawing to make a fine wire, and finally heat-treat to react Mg and B, thereby increasing the MgB 2 content. A core superconducting wire can be formed.
【００２６】このようなＭｇＢ2超電導線材１０およ
び、ＭｇＢ2超電導線材１０を用いたＭｇＢ2多芯超電導
線の実際の作製方法を、図２の作製工程の説明図を参照
して説明する。An actual manufacturing method of such a MgB 2 superconducting wire 10 and a MgB 2 multi-core superconducting wire using the MgB 2 superconducting wire 10 will be described with reference to the explanatory views of the manufacturing process of FIG.
【００２７】まず、工程２０１において、平均粒子径
０．１μｍの非晶質（アモルファス）Ｂ粉末と、平均粒
径２０μｍのＭｇ粉末をモル比でＭｇ：Ｂ＝１：２とな
るように混合することによって、ＭｇとＢの混合粉末１
１を得た。First, in step 201, amorphous B powder having an average particle diameter of 0.1 μm and Mg powder having an average particle diameter of 20 μm are mixed in a molar ratio of Mg: B = 1: 2. By this, mixed powder of Mg and B 1
Got 1.
【００２８】工程２０２において、混合粉末１１を内径
１８ｍｍ、外径１９ｍｍのＴａパイプ１３に充填し、こ
れを工程２０３において、プレスして粉末充填率を６２
％とした。また、粉末を充填したＴａパイプ１３の外側
に、内径１９．１ｍｍ、外径２２ｍｍのＮｂ−１ａｔ％
Ｔａパイプ（以下、Ｎｂ−Ｔａ合金パイプという）１２
を被覆し、その外側に内径２２．１ｍｍ、外径２８ｍｍ
のＣｕパイプ１４を被覆した。これによって、ＭｇＢ2
超電導線材１０を得た。In step 202, the mixed powder 11 is filled in a Ta pipe 13 having an inner diameter of 18 mm and an outer diameter of 19 mm, and this is pressed in step 203 so that the powder filling rate is 62.
%. Also, on the outside of the Ta pipe 13 filled with powder, Nb-1 at% with an inner diameter of 19.1 mm and an outer diameter of 22 mm.
Ta pipe (hereinafter referred to as Nb-Ta alloy pipe) 12
The inner diameter is 22.1 mm and the outer diameter is 28 mm.
Of Cu pipe 14 was coated. As a result, MgB 2
Superconducting wire 10 was obtained.
【００２９】工程２０４において、そのパイプの後端に
Ｆｅプラグ、前端にＣｕプラグをセットして、単芯ビレ
ットとし、それを静水圧押出し加工により外径１５ｍｍ
に押出しした。In step 204, a Fe plug is set at the rear end of the pipe and a Cu plug is set at the front end to form a single core billet, which is hydrostatically extruded to have an outer diameter of 15 mm.
Extruded.
【００３０】工程２０５において、その押出し材を伸線
加工し、工程２０６において、六角ダイスで伸線して対
近距離が２．６５ｍｍの六角線とした。工程２０７にお
いて、その六角線を矯正して直線状にしたのち、長さ１
５０ｍｍに切り分けした。この切り分けられた六角線の
概略斜視図を符号２１で示す。In step 205, the extruded material was drawn, and in step 206, it was drawn with a hexagonal die to obtain a hexagonal wire having a close distance of 2.65 mm. In step 207, the hexagonal line is corrected to form a straight line, and then the length 1
It was cut into 50 mm. Reference numeral 21 is a schematic perspective view of the cut hexagonal line.
【００３１】工程２０８において、六角線２１を６１本
選択し、工程２０９において、その６１本の六角線２１
を、内径２５．５ｍｍ、外径２８ｍｍのＣｕパイプ２２
に組み込み（概略斜視図参照）、さらに工程２１０にお
いて、その組み込み後のパイプの後端にＦｅプラグ、前
端にＣｕプラグをセットして、外径２８ｍｍの多芯ビレ
ットを静水圧押出し加工により外径１５ｍｍに押出しし
た。In step 208, 61 hexagonal lines 21 are selected, and in step 209, the 61 hexagonal lines 21 are selected.
Is a Cu pipe 22 having an inner diameter of 25.5 mm and an outer diameter of 28 mm.
(See schematic perspective view), and in step 210, set the Fe plug at the rear end of the pipe and the Cu plug at the front end after the assembling, and then the multi-core billet with an outer diameter of 28 mm was subjected to hydrostatic extrusion to produce an outer diameter. Extruded to 15 mm.
【００３２】工程２１１において、その押出し材を線径
１ｍｍまで伸線加工したのち、最後に、工程２１２にお
いて、Ａｒ雰囲気中で７００℃×５０時間のＭｇＢ2生
成熱処理を行った。これによって、ＭｇＢ2超電導線材
１０を用いたＭｇＢ2多芯超電導線を得た。これを以
降、本実施の形態超電導線という。In step 211, the extruded material was drawn to a wire diameter of 1 mm, and finally, in step 212, a heat treatment for forming MgB 2 at 700 ° C. for 50 hours was performed in an Ar atmosphere. Thus, a MgB 2 multi-core superconducting wire using the MgB 2 superconducting wire 10 was obtained. Hereinafter, this is referred to as the superconducting wire of the present embodiment.
【００３３】次に、この本実施の形態超電導線の特性の
向上を検証するため、図３に示す従来のＭｇＢ2超電導
線材３０を用いてＭｇＢ2多芯超電導線を作製した。こ
の作製方法は、上記本実施の形態超電導線作製方法と同
じ混合粉末１１を上記工程２０２で、内径１８ｍｍ、外
径２２ｍｍのＴａパイプ１３ａに充填し、これを上記工
程２０３で、プレスして粉末充填率を６２％とした。さ
らに、粉末を充填したＴａパイプ１３ａの外側に、内径
２２．１ｍｍ、外径２８ｍｍのＣｕパイプ１４を被覆し
た。これによって、従来のＭｇＢ2超電導線材３０を得
た。以下、上記工程２０４〜２１２と同様に処理するこ
とによって、従来のＭｇＢ2超電導線材３０を用いたＭ
ｇＢ2多芯超電導線を得た。これを以降、従来超電導線
という。Next, in order to verify the improvement of the characteristics of the superconducting wire of this embodiment, a MgB 2 multi-core superconducting wire was produced using the conventional MgB 2 superconducting wire 30 shown in FIG. In this manufacturing method, the same mixed powder 11 as in the superconducting wire manufacturing method of the present embodiment is filled in a Ta pipe 13a having an inner diameter of 18 mm and an outer diameter of 22 mm in the step 202, and the Ta pipe 13a is pressed into a powder in the step 203. The filling rate was 62%. Further, the outside of the Ta pipe 13a filled with powder was covered with a Cu pipe 14 having an inner diameter of 22.1 mm and an outer diameter of 28 mm. Thereby, the conventional MgB 2 superconducting wire 30 was obtained. Thereafter, by performing the same processing as in the above steps 204 to 212, M using the conventional MgB 2 superconducting wire 30 is obtained.
A gB 2 multifilamentary superconducting wire was obtained. This is hereinafter referred to as a conventional superconducting wire.
【００３４】次に、本実施の形態超電導線と従来超電導
線の双方を比較した結果を述べる。線径１ｍｍの多芯線
の断面を観察した結果、Ｔａ／Ｃｕ構造である従来超電
導線のフィラメント形状は、不均一で６１本あるフィラ
メントのサイズもバラツキが大きかった。また、フィラ
メントの周囲を覆うＴａバリアの計算上の厚さ約１２μ
ｍに対して、厚さ分布が不均一で部分的にバリアが破
れ、この破れによって直接ＣｕとＭｇ＋Ｂ粉末が接触し
ている箇所が観察された。Next, the result of comparison between the superconducting wire of this embodiment and the conventional superconducting wire will be described. As a result of observing the cross section of the multifilamentary wire having a wire diameter of 1 mm, the filament shape of the conventional superconducting wire having the Ta / Cu structure was non-uniform and the size of the 61 filaments also varied greatly. Also, the calculated thickness of the Ta barrier covering the periphery of the filament is about 12μ.
With respect to m, the thickness distribution was non-uniform and the barrier was partially broken, and the breakage was observed at the location where Cu and Mg + B powder were in direct contact.
【００３５】一方、Ｔａ／Ｎｂ−Ｔａ／Ｃｕ構造である
本実施の形態超電導線のフィラメント形状は、従来超電
導線に比較して均一性が大幅に向上し、サイズのバラツ
キも小さく、Ｔａ／Ｎｂ・Ｔａバリアが破れている箇所
もなかった。On the other hand, the filament shape of the superconducting wire of the present embodiment having the Ta / Nb-Ta / Cu structure has significantly improved homogeneity as compared with the conventional superconducting wire, and the variation in size is small, and Ta / Nb.・ There were no places where the Ta barrier was broken.
【００３６】このような本実施の形態超電導線と従来超
電導線の各々の液体ヘリウム中における臨界電流密度Ｊ
ｃ（Ａ／ｍｍ2）と外部磁界Ｂ（Ｔ）との特性（Ｊｃ−
Ｂ特性）を、図４に示す。The critical current density J in the liquid helium of each of the superconducting wire of the present embodiment and the conventional superconducting wire.
c (A / mm 2 ) and external magnetic field B (T) characteristics (Jc-
B characteristic) is shown in FIG.
【００３７】５ＴにおけるＪｃは、従来超電導線４２の
４８０Ａ／ｍｍ2に対して、本実施の形態超電導線４１
が約２.５倍の１２２０Ａ／ｍｍ2となった。本実施の形
態超電導線４１は、従来超電導線４２に比較して全ての
磁界領域で約２倍以上のＪｃを示した。この理由は、本
実施の形態超電導線４１のほうが線材断面においてフィ
ラメントの均一性とバリアの健全性が優れていたためと
考えられる。The Jc at 5T is 480 A / mm 2 of the conventional superconducting wire 42, whereas the superconducting wire 41 of this embodiment has
Was about 2.5 times as high as 1220 A / mm 2 . The superconducting wire 41 of the present embodiment showed Jc about twice or more in all magnetic field regions as compared with the conventional superconducting wire 42. It is considered that this is because the superconducting wire 41 of the present embodiment is superior in the uniformity of the filament and the soundness of the barrier in the cross section of the wire.
【００３８】従って、本実施の形態超電導線によれば、
高い臨界電流密度を得ることができる。Therefore, according to the superconducting wire of this embodiment,
A high critical current density can be obtained.
【００３９】このような本実施の形態超電導線を巻線す
ることにより超電導マグネットを形成すれば、この超電
導マグネットは高磁界を安定して発生可能となる。ま
た、本実施の形態超電導線は、臨界温度が３９Ｋと高い
ため、従来の金属系超電導マグネットを用いた伝導冷却
式マグネット（約５Ｋまで冷却）に比較して、冷却温度
を１０Ｋ程度まで高くすることが可能となり、その結
果、上記超電導マグネットを用いた冷凍機においては、
その負荷を大幅に低減することが可能となる。If the superconducting magnet is formed by winding the superconducting wire of the present embodiment, the superconducting magnet can stably generate a high magnetic field. Further, since the superconducting wire of this embodiment has a high critical temperature of 39K, the cooling temperature is raised to about 10K as compared with the conduction cooling type magnet (cooling to about 5K) using the conventional metal-based superconducting magnet. As a result, in a refrigerator using the above superconducting magnet,
The load can be significantly reduced.
【００４０】[0040]
【発明の効果】以上説明したように、本発明によれば、
ＭｇとＢの混合粉末を、Ｍｇと固溶せず（反応せず）、
かつＢとは高温でしか反応しないＮｂパイプまたはＮｂ
−Ｔａ合金パイプ内に充填し、加えて伸線加工性を向上
させるためＮｂパイプまたはＮｂ−Ｔａ合金パイプの外
周にＣｕパイプを被覆した構造とした。この構造では、
Ｎｂは、Ｔａに比較してＣｕとの接合性が良好で、加工
時の変形抵抗の差も小さく、また、Ｔａを数Ａｔ％添加
したＮｂ−Ｔａ合金は、結晶粒が微細化され、伸線ある
いは圧延等の塑性加工時の割れや乱れを防ぐことができ
るので、高い臨界電流密度を得ることができる。従っ
て、臨界電流密度の高い多芯構造の超電導線を作製する
ことができるAs described above, according to the present invention,
The mixed powder of Mg and B does not form a solid solution with Mg (does not react),
And Nb pipe or Nb that reacts only with B at high temperature
In order to improve the wire drawing workability, the Nb pipe or the Nb-Ta alloy pipe was covered with a Cu pipe so as to be filled in the -Ta alloy pipe. In this structure,
Nb has a better bondability with Cu than Ta and a small difference in deformation resistance at the time of working. Further, Nb-Ta alloy containing Ta added by several At% has a finer crystal grain and has a better elongation. Since it is possible to prevent cracking and disturbance during plastic working such as wire or rolling, it is possible to obtain a high critical current density. Therefore, a superconducting wire having a multi-core structure with a high critical current density can be manufactured.
【図１】本発明の実施の形態に係るＭｇＢ2超電導線材
の構成を示す断面図である。FIG. 1 is a cross-sectional view showing the structure of a MgB 2 superconducting wire according to an embodiment of the present invention.
【図２】上記実施の形態に係るＭｇＢ2超電導線材およ
び、ＭｇＢ2超電導線材を用いたＭｇＢ2多芯超電導線の
作製工程の説明図である。[Figure 2] MgB 2 superconducting wire according to the above embodiment and is an explanatory view of a manufacturing process of MgB 2 multi-core superconducting wire using MgB 2 superconducting wire.
【図３】従来のＭｇＢ2超電導線材の構成を示す断面図
である。FIG. 3 is a sectional view showing a structure of a conventional MgB 2 superconducting wire.
【図４】本実施の形態および従来例双方のＭｇＢ2超電
導線材を用いたＭｇＢ2多芯超電導線超電導線の液体ヘ
リウム中における臨界電流密度Ｊｃ（Ａ／ｍｍ2）と外
部磁界Ｂ（Ｔ）との特性（Ｊｃ−Ｂ特性）を示す図であ
る。FIG. 4 shows a critical current density Jc (A / mm 2 ) and an external magnetic field B (T) in liquid helium of a MgB 2 multi-core superconducting wire using the MgB 2 superconducting wire of both the present embodiment and the conventional example. It is a figure which shows the characteristic (Jc-B characteristic) with.
１０ 本実施の形態のＭｇＢ2超電導線材 １１ ＭｇとＢの混合粉末 １２ Ｎｂ−Ｔａ合金パイプ １３，１３ａ Ｔａパイプ １４，２２ Ｃｕパイプ ２１ 六角線 ３０ 従来のＭｇＢ2超電導線材 ４１ 本実施の形態の多芯構造超電導線 ４２ 従来の多芯構造超電導線10 MgB 2 superconducting wire rod 11 of the present embodiment 11 Mixed powder of Mg and B 12 Nb-Ta alloy pipe 13, 13 a Ta pipe 14, 22 Cu pipe 21 Hexagonal wire 30 Conventional MgB 2 superconducting wire rod 41 Core structure superconducting wire 42 Conventional multi-core structure superconducting wire
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｆ 6/06 Ｈ０１Ｆ 5/08 Ｂ Ｆターム(参考） 4G047 JA05 JC16 KB02 KB04 KB17 LB01 5G321 AA98 BA03 CA32 CA42 DA03 DA04 DB18 DB47 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01F 6/06 H01F 5/08 BF term (reference) 4G047 JA05 JC16 KB02 KB04 KB17 LB01 5G321 AA98 BA03 CA32 CA42 DA03 DA04 DB18 DB47
Claims (6)
混合粉末、またはＭｇ、Ｂおよび、その他の添加元素ま
たは化合物粉末を混合した混合粉末を、Ｎｂ（ニオブ）
パイプまたはＮｂ−Ｔａ（タンタル）合金パイプ内に充
填し、このパイプをＣｕ（銅）パイプまたはＣｕ合金パ
イプで被覆することにより、（Ｍｇ＋Ｂ）／Ｎｂ／Ｃｕ
（またはＣｕ合金）、あるいは（Ｍｇ＋Ｂ）／Ｎｂ−Ｔ
ａ／Ｃｕ（またはＣｕ合金）構造としたことを特徴とす
る二ホウ化マグネシウム超電導線材。1. A mixed powder of Mg (magnesium) and B (boron) or a mixed powder of Mg, B, and other additive element or compound powder is mixed with Nb (niobium).
(Mg + B) / Nb / Cu by filling a pipe or a Nb-Ta (tantalum) alloy pipe and coating this pipe with a Cu (copper) pipe or a Cu alloy pipe.
(Or Cu alloy), or (Mg + B) / Nb-T
A magnesium diboride superconducting wire having an a / Cu (or Cu alloy) structure.
内側にＴａパイプを配置することにより、（Ｍｇ＋Ｂ）
／Ｔａ／Ｎｂ／Ｃｕ（またはＣｕ合金）、あるいは（Ｍ
ｇ＋Ｂ）／Ｔａ／Ｎｂ−Ｔａ／Ｃｕ（またはＣｕ合金）
構造としたことを特徴とする請求項１記載の二ホウ化マ
グネシウム超電導線材。2. By arranging a Ta pipe inside the Nb or Nb-Ta alloy pipe, (Mg + B)
/ Ta / Nb / Cu (or Cu alloy) or (M
g + B) / Ta / Nb-Ta / Cu (or Cu alloy)
2. The magnesium diboride superconducting wire according to claim 1, which has a structure.
Ｃｕ合金）、（Ｍｇ＋Ｂ）／Ｎｂ−Ｔａ／Ｃｕ（または
Ｃｕ合金）、（Ｍｇ＋Ｂ）／Ｔａ／Ｎｂ／Ｃｕ（または
Ｃｕ合金）、あるいは（Ｍｇ＋Ｂ）／Ｔａ／Ｎｂ−Ｔａ
／Ｃｕ（またはＣｕ合金）の構造を有する線材の複数が
集合されたものであることを特徴とする請求項１または
２に記載の二ホウ化マグネシウム超電導線材。3. The (Mg + B) / Nb / Cu (or Cu alloy), (Mg + B) / Nb-Ta / Cu (or Cu alloy), (Mg + B) / Ta / Nb / Cu (or Cu alloy), or (Mg + B) / Ta / Nb-Ta
The magnesium diboride superconducting wire according to claim 1 or 2, wherein a plurality of wires having a structure of / Cu (or Cu alloy) are aggregated.
の占積率（混合粉末部断面積／単芯線全断面積＝コア
比）が０．５５以下であることを特徴とする請求項１〜
３のいずれかに記載の二ホウ化マグネシウム超電導線
材。4. The space factor of the mixed powder portion with respect to the total sectional area of the wire (mixed powder portion sectional area / single core total sectional area = core ratio) is 0.55 or less. ~
3. The magnesium diboride superconducting wire according to any one of 3 above.
厚さ（ｔ）と、混合粉末部分の半径（＝コア半径：ｒ）
との比率（ｔ／ｒ）が０．１２以上であることを特徴と
する請求項１〜４のいずれかに記載の二ホウ化マグネシ
ウム超電導線材。5. The coating thickness (t) of the wire other than the mixed powder portion and the radius of the mixed powder portion (= core radius: r).
And a ratio (t / r) of 0.12 or more is 0.12 or more, and the magnesium diboride superconducting wire according to any one of claims 1 to 4.
成する本線材への熱処理として、６００℃以上、９００
℃以下の熱処理を施したことを特徴とする請求項１〜５
のいずれかに記載の二ホウ化マグネシウム超電導線材。6. The heat treatment for the main wire which produces MgB 2 (magnesium diboride) is 600 ° C. or higher, 900 ° C.
A heat treatment at a temperature of less than or equal to 0 ° C. is performed.
2. A magnesium diboride superconducting wire according to any one of 1.
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| JP2002014718A JP4058951B2 (en) | 2002-01-23 | 2002-01-23 | Magnesium diboride superconducting wire precursor and magnesium diboride superconducting wire |
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| WO2005104144A1 (en) * | 2004-04-22 | 2005-11-03 | Tokyo Wire Works, Ltd. | Process for producing mgb2 superconductive wire excelling in critical current performance |
| JP2006107841A (en) * | 2004-10-01 | 2006-04-20 | National Institute For Materials Science | Magnesium diboride compound sheath superconducting wire and manufacturing method of the same |
| JP2007221013A (en) * | 2006-02-20 | 2007-08-30 | Hitachi Ltd | Persistent current switch |
| JP2008508677A (en) * | 2004-07-30 | 2008-03-21 | コロンブス・スーパーコンダクターズ・ソシエタ・ア・レスポンサビリタ・リミタータ | Superconducting composite wire made from magnesium diboride |
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| KR101212111B1 (en) * | 2010-06-10 | 2012-12-13 | 한국기계연구원 | Preparing method of MgB2 superconducting conductor and MgB2 superconducting conductor prepared thereby |
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