JP4500901B2 - Composite sheathed magnesium diboride superconducting wire and its manufacturing method - Google Patents
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本発明は、ニホウ化マグネシウム（ＭｇＢ2）が、２種以上の金属管から形成される複合シース内に充填され、一体化された複合シースニホウ化マグネシウム超電導線材とその製造方法に関するものである。 The present invention relates to a composite sheath magnesium diboride superconducting wire material in which magnesium diboride (MgB 2 ) is filled and integrated in a composite sheath formed of two or more kinds of metal tubes, and a method for manufacturing the same.
従来、超電導材料として、ニオブチタン（ＮｂＴｉ）、ニオブ３錫（Ｎｂ3Ｓｎ）等の金属系のものが知られている。しかし、これらの金属系超電導材料には、臨界温度が最も高いニオブ３ゲルマニウム（Ｎｂ3Ｇｅ）でも２３Ｋ（ケルビン）であり、冷却に高価な液体ヘリウムを使用しなければならないという問題があった。 Conventionally, metallic materials such as niobium titanium (NbTi) and niobium 3 tin (Nb 3 Sn) are known as superconducting materials. However, these metal-based superconducting materials have a problem that niobium 3 germanium (Nb 3 Ge) having the highest critical temperature is 23 K (Kelvin), and expensive liquid helium must be used for cooling.
一方、高温超電導体として、１９８６年４月に臨界温度が３０Ｋのランタン（Ｌａ）酸化物系の超電導体が発見されて以降、臨界温度が液体窒素の沸点温度（７７Ｋ）を超えるイットリウム（Ｙ）系、ビスマス（Ｂｉ）系、タリウム（Ｔｌ）系、水銀（Ｈｇ）系の酸化物系超電導体が相次いで発見された。しかし、これらは、いわゆるセラミックスで構成されていることから、加工性が悪く、長尺均質性に優れる線材を得ることが困難であるという問題があった。また、酸化物系超電導体は、磁気異方性が大きいため、超電導相の結晶方位を揃える必要があった。つまり、基板またはシース材の上に結晶軸の１軸あるいは２軸が配向したものを用いることが高性能化のポイントであった。このことから、結晶方位を揃える制御が非常に難しく、歩留まりやコストの点で課題が山積していた。 On the other hand, since the discovery of a lanthanum (La) oxide-based superconductor with a critical temperature of 30 K in April 1986 as a high-temperature superconductor, yttrium (Y) whose critical temperature exceeds the boiling point temperature (77 K) of liquid nitrogen. Oxide-based superconductors such as bismuth (Bi), thallium (Tl), and mercury (Hg) have been discovered one after another. However, since these are composed of so-called ceramics, there has been a problem that it is difficult to obtain a wire having poor workability and excellent long homogeneity. In addition, since the oxide superconductor has a large magnetic anisotropy, it is necessary to align the crystal orientation of the superconducting phase. In other words, the use of a substrate or sheath material in which one or two crystal axes are oriented is the key to high performance. For this reason, it is very difficult to control the crystal orientation, and there are many problems in terms of yield and cost.
２１世紀に入って、ニホウ化マグネシウム（ＭｇＢ2）が３９Ｋで超電導を示すことが発見された。この材料は、主に以下の特徴が知られている。
（１）臨界温度が３９Ｋと、従来の金属系超電導体と比べて２０Ｋ以上高い。
（２）臨界磁界が２０Ｔ程度あるいはそれ以上と、従来の金属系超電導体より大きい。
（３）輸送臨界電流密度は、最大で１０００Ａ／ｍｍ2オーダーである。
（４）磁気異方性が小さく、結晶のａ軸、ｂ軸およびｃ軸のどの方向にも同様の電流を流すことができる。
In the 21st century, it was discovered that magnesium diboride (MgB 2 ) exhibits superconductivity at 39K. This material is known mainly for the following characteristics.
(1) The critical temperature is 39K, which is 20K or more higher than the conventional metal superconductor.
(2) The critical magnetic field is about 20T or more, which is larger than the conventional metal superconductor.
(3) The transport critical current density is on the order of 1000 A / mm 2 at the maximum.
(4) The magnetic anisotropy is small, and the same current can flow in any direction of the a-axis, b-axis, and c-axis of the crystal.
このように、ＭｇＢ2超電導体は、臨界温度、臨界磁界ともに金属系超電導体より高いため、超電導マグネットに適用すれば、クエンチ事故のない極めて安定したシステムを構築することができるという顕著なメリットが生じる。また、臨界温度が高いため、液体ヘリウムを冷媒として用いる必要がなく、液体水素などの冷媒が利用可能になる。 As described above, the MgB 2 superconductor is higher in both critical temperature and critical magnetic field than the metallic superconductor, and therefore, when applied to a superconducting magnet, there is a remarkable merit that an extremely stable system without a quench accident can be constructed. Arise. Further, since the critical temperature is high, it is not necessary to use liquid helium as a refrigerant, and a refrigerant such as liquid hydrogen can be used.
一方、これまでに開発されてきたＭｇＢ2超電導体を用いた超電導マグネットは、性能の最も高い液体ヘリウム温度においても、発生磁場は１Ｔ程度であって、金属系超電導体を用いた超電導マグネットが２０Ｔ程度であることと比較すると、一桁低いのが現状である。 On the other hand, the superconducting magnet using the MgB 2 superconductor developed so far has a generated magnetic field of about 1 T even at the highest performance liquid helium temperature, and a superconducting magnet using a metal superconductor is 20 T. The current situation is that it is an order of magnitude lower than that.
ＭｇＢ2長尺線材の高性能化のための基本的な線材作製プロセスとして、酸化物系超電導体で用いられているパウダー・イン・チューブ法をはじめとする各種の手法が検討されている（たとえば、特許文献１参照）。しかし、公知の手法では、まだ、長尺線材における性能向上や熱的安定性を十分に達成することは難しく、線材の断面構造や製造条件の詳細を検討する必要があった。 Various methods including the powder-in-tube method used in oxide superconductors have been studied as a basic wire production process for improving the performance of MgB 2 long wires (for example, , See Patent Document 1). However, with the known method, it is still difficult to achieve sufficient performance improvement and thermal stability in the long wire, and it is necessary to examine details of the cross-sectional structure and manufacturing conditions of the wire.
ところで、超電導線材の最終形状としては、丸や平角線材の方がテープ状線材に比べ汎用性がある。たとえば、超電導マグネットへの適用を考えた場合、マグネットの径方向や軸方向での磁場均一度が重要なファクターになるが、用いる線材の加工精度により大きく異なる。つまり、加工精度の良好な丸線や平角線を用いると、高い磁場均一度を有するマグネットが実現可能であるが、加工精度の向上に難があるテープ状線材では磁場均一度の向上には限界がある。 By the way, as a final shape of a superconducting wire, a round or flat wire is more versatile than a tape-like wire. For example, when considering application to a superconducting magnet, the magnetic field uniformity in the radial direction and the axial direction of the magnet is an important factor, but varies greatly depending on the processing accuracy of the wire used. In other words, if round wires or rectangular wires with good machining accuracy are used, magnets with high magnetic field uniformity can be realized. However, with tape-shaped wires that have difficulty in improving machining accuracy, there is a limit to improving magnetic field uniformity. There is.
超電導線材の製造に際しては、通常、金属パイプ中に線材を複数本組み込み、縮径加工（減面加工ともいう）を施すことで、丸あるいは平角形状の長尺線材を得ている。たとえば、外径２５ｍｍ、長さ１ｍのビレットは、減面加工によって外径１ｍｍにすると、約５００ｍの長尺の超電導線材となる。長尺線材を作製するためには、減面加工は必要不可欠であり、加工度の大きく取れる製造方法が望ましい。最適な加工度は、超電導線材によって変化すると考えられる。すなわち、加工度が低すぎても、高すぎても高い臨界電流密度は得られず、超電導線材によって許容加工度が存在すると予想される。減面加工前の初期外径をｄ１、加工後の外径をｄ２とすると、加工度は、以下のとおりに求められる。 When manufacturing a superconducting wire, a plurality of wires are usually incorporated into a metal pipe, and diameter reduction processing (also referred to as surface reduction processing) is performed to obtain a round or flat rectangular long wire. For example, a billet with an outer diameter of 25 mm and a length of 1 m becomes a long superconducting wire of about 500 m when the outer diameter is reduced to 1 mm by surface reduction. In order to produce a long wire rod, surface reduction processing is indispensable, and a manufacturing method capable of obtaining a large degree of processing is desirable. The optimum degree of processing is considered to vary depending on the superconducting wire. That is, even if the workability is too low or too high, a high critical current density cannot be obtained, and it is expected that an allowable workability exists depending on the superconducting wire. When the initial outer diameter before the surface-reduction processing is d1, and the outer diameter after the processing is d2, the degree of processing is obtained as follows.
加工度＝[１−（ｄ２／ｄ１）2]×１００ （％）
また、超電導線材の製造に際しては、交流損失対策として超電導フィラメントをツイストすることがある。交流で使用する場合は、通常、あるピッチでツイスト加工することでその目的が達せられている。
Further, when manufacturing a superconducting wire, a superconducting filament may be twisted as a measure against AC loss. When used in alternating current, the purpose is usually achieved by twisting at a certain pitch.
超電導マグネットとして使用する線材としては、高い臨界電流密度を有すること、長尺化が可能であること、電気的な安定性があることが最低限必要であり、形状は丸線あるいは平角線で、かつツイスト加工が施されていることが望ましい。 As a wire used as a superconducting magnet, it is necessary to have a high critical current density, to be long, and to have electrical stability as a minimum, and the shape is a round wire or a rectangular wire, In addition, it is desirable that twist processing is performed.
ＭｇＢ2超電導体の現状での第一の問題点は、４．２Ｋにおけるコイルの発生磁場が高々１Ｔ程度であって、実用に供するにはまだ小さすぎる点である。本格的な工業応用を考えるには、長尺線材で高い臨界電流密度を維持する技術を完成することが必要である。ここでの最大の課題は、すでに知られている短尺のＭｇＢ2超電導線の高い性能を、いかにしてコイルを構成可能なほど十分に長い線材において達成するかという工業的手段が確立していない点である。公知の短尺線の性能がそのまま長尺の線材で実現するならば、容易に工業材料として利用可能な５Ｔ〜７Ｔを超えるような磁界発生が実現しても何ら不思議なことではない。 The first problem with the present MgB 2 superconductor is that the magnetic field generated by the coil at 4.2 K is at most about 1 T, which is still too small for practical use. In order to consider full-scale industrial application, it is necessary to complete a technique for maintaining a high critical current density with a long wire rod. The biggest problem here is that the industrial means of how to achieve the high performance of the already known short MgB 2 superconducting wire in a sufficiently long wire that can constitute a coil has not been established. Is a point. If the performance of a known short wire is realized with a long wire as it is, it is no wonder that a magnetic field generation exceeding 5T to 7T that can be easily used as an industrial material is realized.
ところが、従来、ＭｇＢ2超伝導線を使用して作製したコイルを用いて、永久電流により磁気エネルギーを蓄積することができたという報告はない。その理由は、超電導部の臨界電流性能が永久電流を実現することができるほど十分に高くないからである。これは、長尺線材の製造プロセスにおいて、ＭｇＢ2超電導線材を高性能化する工程が最適化されていないことによると考えられる。ＭｇＢ2超電導体を工業的に広く適用可能とするためには、最低でも３Ｔの磁界発生を可能なレベルにし、さらに望ましくは、永久電流による運転を可能にする長尺線材の製造技術を確立する必要がある。 However, conventionally, there has been no report that magnetic energy can be accumulated by a permanent current using a coil manufactured using MgB 2 superconducting wire. The reason is that the critical current performance of the superconducting part is not high enough to achieve a permanent current. This is considered to be because the process of improving the performance of the MgB 2 superconducting wire is not optimized in the production process of the long wire. In order to make the MgB 2 superconductor widely applicable industrially, at least a level capable of generating a magnetic field of 3T is established, and more preferably, a manufacturing technique for a long wire material that enables operation with a permanent current is established. There is a need.
本発明は、このような事情に鑑みてなされたものであり、実用線材とするために必要な、高臨界電流密度化、長尺線材化、高安定化を同時に達成することのできるＭｇＢ2超電導線材とその製造方法を提供することを解決すべき課題としている。 The present invention has been made in view of such circumstances, and MgB 2 superconductivity capable of simultaneously achieving a high critical current density, a long wire, and a high stabilization necessary for a practical wire. Providing a wire and its manufacturing method is a problem to be solved.
本発明者らは、これまで、主に酸化物系超電導線材およびそのマグネットへの応用を目指した研究開発を進めてきた。この中で、高性能の超電導線材を作製するために必要不可欠な項目として、特に以下の４項目が重要であることを明らかにしてきた。すなわち、
（１）超電導体と熱的に反応しない金属被覆材の選定
（２）最終形状に加工した際の超電導体の充填密度
（３）結晶粒同士の接合性の向上
（４）量子化された磁束線をトラップして、侵入した磁束線を動かないようにするピンニングセンターの導入
である。以上の４項目を同時に実現することで、高い特性を有する超電導線材が得られる。
The inventors of the present invention have so far advanced research and development aimed mainly at oxide superconducting wires and their application to magnets. Among these, the following four items have been clarified as indispensable items for producing a high-performance superconducting wire. That is,
(1) Selection of a metal coating material that does not react thermally with the superconductor (2) Packing density of the superconductor when processed into a final shape (3) Improvement of bondability between crystal grains (4) Quantized magnetic flux It is the introduction of a pinning center that traps the wire and prevents the magnetic flux lines that have entered from moving. By realizing the above four items simultaneously, a superconducting wire having high characteristics can be obtained.
しかし、臨界電流密度は、物質固有の値ではなく、超電導線材の製造方法にも大きく依存する。このため、従来の酸化物系超電導線材および金属系超電導線材に適用してきた製造方法だけでは、ＭｇＢ2超電導線材の臨界電流密度はあまり向上しないことが分かった。したがって、超電導材料によってそれぞれ最適化を行う必要があり、ＭｇＢ2超電導体についても独自の検討が必要になった。 However, the critical current density is not a value specific to a substance, but greatly depends on a method for manufacturing a superconducting wire. For this reason, it has been found that the critical current density of the MgB 2 superconducting wire is not improved so much only by the manufacturing method applied to the conventional oxide superconducting wire and metal superconducting wire. Therefore, it is necessary to optimize each superconducting material, and the MgB 2 superconductor has to be independently studied.
そこで、本発明者らは、上記の課題を解決することに注力し、ＭｇＢ2超電導線材とその製造方法を鋭意検討した結果、課題を解決する手段を見出した。この手段を適用することにより、加工精度に優れる丸形状でも平角形状でも、高い臨界電流密度と高い安定性を持った長尺線材が容易に製造可能となる。 Therefore, the present inventors have focused on solving the above-mentioned problems, and as a result of intensive studies on the MgB 2 superconducting wire and its manufacturing method, have found means for solving the problems. By applying this means, it is possible to easily manufacture a long wire rod having a high critical current density and a high stability regardless of whether it is a round shape or a flat shape having excellent processing accuracy.
上記手段は、少なくとも２種の異なる種類の金属管を組み合わせた複合金属管から形成される複合シース中にニホウ化マグネシウムが内包された複合シースニホウ化マグネシウム超電導線材であって、最外周に銅あるいは銅合金が配置され、その内部にＦｅ、Ｎｂ、Ｔａ、Ｔｉ、炭素鋼あるいはステンレス鋼が配置され、最外周の銅あるいは銅合金の内面、または最外周の銅あるいは銅合金の内部に配置されるＦｅ、Ｎｂ、Ｔａ、Ｔｉ、炭素鋼あるいはステンレス鋼の外面に銅めっきが施され、加工度９９％以上になるまで減面加工され、最外周の銅あるいは銅合金の割合が、線材の全断面積の１５％以上であり、かつ最外周の銅あるいは銅合金および超電導コア部の合計の割合が線材の全断面積の８５％以下であり、温度５８０℃〜９００℃の真空中または不活性ガス中で熱処理されたものであることを特徴とする。 The above means is a composite sheath magnesium diboride superconducting wire in which magnesium diboride is encapsulated in a composite sheath formed of a composite metal tube in which at least two different types of metal tubes are combined, and copper or copper An alloy is disposed, Fe, Nb, Ta, Ti, carbon steel or stainless steel is disposed therein, and the innermost surface of the outermost copper or copper alloy, or the innermost surface of the copper or copper alloy is Fe. , Nb, Ta, Ti, carbon steel or stainless steel is plated on the outer surface, and the surface is reduced until the processing degree reaches 99% or more, and the ratio of the outermost copper or copper alloy is the total cross-sectional area of the wire. And the total ratio of the outermost copper or copper alloy and the superconducting core portion is 85% or less of the total cross-sectional area of the wire, and the temperature is 580 ° C to 900 ° C. Characterized in that it is one which is heat-treated in vacuum or in inert gas.
最外周の銅あるいは銅合金の内面、または最外周の銅あるいは銅合金の内部に配置されるＦｅ、Ｎｂ、Ｔａ、Ｔｉ、炭素鋼あるいはステンレス鋼の外面に銅めっきを施すと、加工性が向上する。 Copper or inner surface of the copper alloy of the outermost, or outermost copper or Fe which is disposed inside the copper alloy, Nb, Ta, Ti, when copper plating is performed on the outer surface of the carbon steel or stainless steel, workability improvement Up.
５８０℃未満の熱処理温度ではＭｇＢ2の生成反応が進まず、臨界電流が向上しない。９００℃を超えた温度で熱処理を行うと、ＭｇＢ2の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）の析出が顕著となる。その結果、粒界部分で臨界電流が極端に低下するため、マクロ的に見た線材全体の臨界電流が低下する。 5 When the heat treatment temperature is less than 80 ° C., the formation reaction of MgB 2 does not proceed and the critical current does not improve. When heat treatment is performed at a temperature exceeding 900 ° C., coarsening of MgB 2 crystal grains is promoted, and precipitation of non-superconducting substances (MgB 4 , Mg and B oxides) that inhibit superconducting current at the grain boundary portion. Become prominent. As a result, the critical current drastically decreases at the grain boundary portion, so that the critical current of the whole wire as viewed macroscopically decreases.
また、上記手段は、ＭｇＢ2単芯線または多芯線が、ツイスト加工されて複合シース中に複数本組み込まれているものであることを特徴とする。ツイスト加工により、交流で使用する場合に問題となる各種交流損失を改善することができる。 Further , the above means is characterized in that a plurality of MgB 2 single core wires or multi-core wires are twisted and incorporated in the composite sheath. Twist processing can improve various AC losses that are problematic when used with AC.
さらに、上記手段は、最外周に配置される銅あるいは銅合金の外周管の内面、またはＦｅ、Ｎｂ、Ｔａ、Ｔｉ、炭素鋼あるいはステンレス鋼から選択され、外周管の内部に配置される内周管の外面に銅めっきを施す工程と、外周管と内周管が組み合わされた複合金属管から形成される複合シースの内周管にマグネシウム粉末およびホウ素粉末の混合粉末あるいはニホウ化マグネシウムの合成粉末を充填する工程と、粉末充填後の線材を９９％以上の加工度になるまで減面加工し、最外周に配置された銅あるいは銅合金の割合を線材の全断面積の１５％以上であり、かつ最外周の銅あるいは銅合金および超電導コア部の合計の割合を線材の全断面積の８５％以下とする工程と、５８０℃〜９００℃の真空中または不活性ガス中で熱処理する工程とを含むことを特徴とする。 Furthermore, the means, the inner surface of the outer tube of copper or a copper alloy is disposed in the outermost periphery or Fe, Nb, Ta,, Ti, selected from carbon steel or stainless steel, among which is disposed inside the external tube a step of performing copper plating on the outer surface of the peripheral tube, synthesis of the mixed powder or diboride magnesium external tube and magnesium powder and boron powder on the inner peripheral tube of the composite sheath the inner circumferential tube is formed from a composite metal tube in combination The step of filling the powder and the surface of the wire after powder filling is reduced until the degree of processing is 99% or more, and the ratio of copper or copper alloy disposed on the outermost periphery is 15% or more of the total cross-sectional area of the wire. There, and a step of 85% or less of the total cross-sectional area of the outermost copper or copper alloy and a total wire the ratio of the superconducting core part, a step of heat treatment in vacuum at 580 ° C. to 900 ° C. or in an inert gas Characterized in that it comprises a.
本発明によれば、実用線材とするために必要な、高臨界電流密度化、長尺線材化を同時に達成することができる。液体ヘリウムによる冷却はもちろんのこと、液体水素、液体ネオン、冷凍機伝導冷却等による冷却によっても機器の運転が可能となり、かつ磁場中においても高い臨界電流密度が得られる。 According to the present invention, it is possible to simultaneously achieve a high critical current density and a long wire necessary for a practical wire. Cooling with liquid helium, as well as cooling with liquid hydrogen, liquid neon, refrigerator cooling, etc., makes it possible to operate the apparatus and obtain a high critical current density even in a magnetic field.
粉末原料については、全てを一度に混合する方法や、一部を混合した後に残りを混合する方法がある。マグネシウム粉末には平均粒径５０μｍ以下のものを、ホウ素粉末には平均粒径５μｍ以下のものを用いることによって、高い臨界電流密度が得られる。平均粒径を細かくすることにより、結晶粒同士の反応性が良好になるためである。ナノメートルオーダーにまで粒径を細かくすると効果的である。両粉末については、機械的に混合し、さらに微粉化することで、粉末の表面に存在する酸化層等を除去することができる。 As for the powder raw material, there are a method of mixing all at once, and a method of mixing the remainder after mixing a part. High critical current density can be obtained by using magnesium powder having an average particle size of 50 μm or less and boron powder having an average particle size of 5 μm or less. This is because the reactivity between crystal grains is improved by reducing the average grain size. It is effective to reduce the particle size to the nanometer order. About both powders, the oxide layer etc. which exist on the surface of a powder can be removed by mixing mechanically and further pulverizing.
また、マグネシウム粉末およびホウ素粉末に、０．２原子％〜３０原子％の鉄、アルミニウム、マグネシウム、チタン、タングステン、酸化珪素、炭化珪素、窒化珪素等を単独あるいは複合して添加すると、臨界電流密度が向上する。 Moreover, when 0.2 atomic% to 30 atomic% of iron, aluminum, magnesium, titanium, tungsten, silicon oxide, silicon carbide, silicon nitride, or the like is added to magnesium powder and boron powder alone or in combination, the critical current density Will improve.
さらに、２００℃〜１２００℃の範囲内で窒素ガス、アルゴンガス、水素ガス、酸素ガスの単独あるいは複合した雰囲気中で、かつ大気圧以上の圧力下で熱処理を行うと、結晶粒同士の接合性が改善され、臨界電流密度が向上する。 Further, when heat treatment is performed in an atmosphere of nitrogen gas, argon gas, hydrogen gas, oxygen gas alone or in combination within a range of 200 ° C. to 1200 ° C. and under a pressure of atmospheric pressure or higher, the bonding property between crystal grains is obtained. And the critical current density is improved.
線材を作製する際には、混合粉末を成形し、焼結させた後、適当なサイズに粉砕したものをパイプ状の金属シース材に充填して塑性加工を施すパウダー・イン・チューブ法、混合粉末を成形した成形体をパイプ状の金属シース材に充填し、塑性加工を施すロッド・イン・チューブ法等を採用することができる。その場合、超電導体と金属シース材が熱的に反応し、臨界電流密度が低下するおそれがあるので、超電導体と直接接する金属シース材には、超電導体と反応しない材料を選択する。また、金属シース材の肉厚比があまり大きくない場合、高い加工度となると、超電導コア部がシースを突き破って表面から露出することがあるため、最終的な金属シース材の肉厚が、超電導コア部の厚みの１／２程度となるように設計しておくことが好ましい。さらに、超電導線材が、超電導状態から常電動状態に遷移する際に、一気に高い抵抗（電圧）が発生して線材が溶断しないように、電気抵抗の低い金属を線材の断面内に組み込む。このことにより、電気的な安定性が大きく改善される。特に電気抵抗が低い銅あるいは銅合金を使用し、これが最外周に配置されていれば、安定性のみならず、加工性も向上し、長尺線材化に有効となる。また、最外周に配置される銅あるいは銅合金の外周管の内面または外周管の内部に配置される内周管の外面に銅めっきを施すことにより、異種金属間の接合性が向上し、加工性がさらに良好となる。このため、加工途中の中間焼鈍の回数を大幅に減少させることができる。また、１パスあたりの加工度が向上し、最終径まで加工するパス回数が大幅に減少する。これらのことは、低コスト化に極めて有効である。 When producing wire, powder-in-tube method, in which mixed powder is molded, sintered, and then pulverized to an appropriate size into a pipe-shaped metal sheath material for plastic working, mixed A rod-in-tube method or the like in which a molded body obtained by molding powder is filled in a pipe-shaped metal sheath material and subjected to plastic working can be employed. In that case, the superconductor and the metallic sheath material reacts thermally, since the critical current density may be lowered, the metallic sheath material in direct contact with the superconductor, select a material which does not react with the superconductor. In addition, when the thickness ratio of the metal sheath material is not so large, the superconducting core part may break through the sheath and be exposed from the surface when the degree of processing is high. It is preferable to design it to be about ½ of the thickness of the core part. Furthermore, superconducting wire, when the transition from the superconducting state to the normal electric state, once a high resistance so that the wire (voltage) is generated not blow, write no set a low electrical resistance metal within the cross-section of the wire. This greatly improves the electrical stability. In particular, if copper or a copper alloy having a low electrical resistance is used and disposed on the outermost periphery, not only the stability but also the workability is improved, which is effective for making a long wire. Further, by performing copper plating on the outer surface of the inner tube is disposed within the inner surface or the outer peripheral tube of the outer tube of copper or a copper alloy is disposed in the outermost periphery, to improve the bonding property between dissimilar metals, working The property is further improved. For this reason, the frequency | count of the intermediate annealing in the middle of a process can be reduced significantly. In addition, the degree of processing per pass is improved, and the number of passes processed to the final diameter is greatly reduced. These are extremely effective for cost reduction.
実際に、めっき処理を行わない場合は、９９．９％の加工度で断線し、それ以上の加工が困難となるが、めっき処理を行うことにより、９９．９８％の加工度まで断線することなく線材を作製することができる。めっき処理には、電気めっき、無電解めっき、溶融めっき、真空めっき等の一般的なめっき法が適用可能である。 Actually, when the plating treatment is not performed, the wire is disconnected at a work degree of 99.9%, and further processing becomes difficult. However, the wire is cut to a work degree of 99.98% by performing the plating treatment. It is possible to produce a wire rod without any problems. A general plating method such as electroplating, electroless plating, hot dipping, or vacuum plating can be applied to the plating treatment.
一方、銅をシース材として適用したニホウ化マグネシウム超電導線材の場合、ニホウ化マグネシウムを生成させるために必要な温度で熱処理を行うと、超電導コア部中のマグネシウムと銅が反応し、超電導特性が大きく低下する場合がある。そこで、超電導コア部と銅との間には超電導コア部と反応しないバリア層を設けることが好ましい。このバリア層には、Ｆｅ、Ｎｂ、Ｔａ、Ｔｉ、炭素鋼あるいはステンレス鋼を用いると、特性低下が起こらない。このようなバリア層についても、厚みが薄いと、加工度が増大した場合に破損するおそれがあるので注意を要する。 On the other hand, in the case of a magnesium diboride superconducting wire in which copper is used as a sheath material, if heat treatment is performed at a temperature necessary to produce magnesium diboride, magnesium in the superconducting core reacts with copper, resulting in large superconducting properties. May decrease. Therefore, it is preferable to provide a barrier layer that does not react with the superconducting core part between the superconducting core part and copper. When Fe, Nb, Ta, Ti, carbon steel, or stainless steel is used for this barrier layer, the characteristics do not deteriorate. For such a barrier layer, if the thickness is small, it may be damaged when the degree of processing increases.
線材の縮径加工には、ドローベンチ、静水圧押出、スエージャー、カセットローラーダイスあるいは溝ロールを用いることができ、１パス当たりの断面減少率が１％〜２０％程度の伸線加工を繰り返し行う。必要に応じて多芯化することができ、多芯化に際しては、一般に、丸断面形状あるいは六角断面形状に伸線加工した線材を多芯用の金属パイプの中に組み込み、１パス当たりの断面減少率を１％〜２０％程度として所定の線径まで伸線する方法が採られる。 A drawing bench, hydrostatic extrusion, a swager, a cassette roller die, or a grooved roll can be used for the diameter reduction processing of the wire, and the wire drawing processing in which the cross-sectional reduction rate per pass is about 1% to 20% is repeatedly performed. . Multi-cores can be used as needed, and when multi-cores are used, generally a wire rod drawn into a round or hexagonal cross-section is incorporated into a multi-core metal pipe, and the cross-section per pass A method of drawing to a predetermined wire diameter with a reduction rate of about 1% to 20% is adopted.
縮径加工は、線材を所望の形状にするとともに、金属シース材内に充填された超電導粉末を高密度化する作用がある。さらに緻密化を図るために、たとえば、冷間あるいは熱間圧延機で加工し、平角状あるいはテープ状の断面とし、必要に応じて適切な温度や雰囲気において熱処理することができ、高い臨界電流密度を有する線材を作製することができる。 The diameter reduction process has an effect of making the wire into a desired shape and increasing the density of the superconducting powder filled in the metal sheath material. For further densification, for example, it can be processed in a cold or hot rolling mill to have a flat or tape-shaped cross section, and heat treated at an appropriate temperature and atmosphere as necessary, and has a high critical current density. It is possible to produce a wire having
上記の方法以外にも、たとえば、溶射法、ドクターブレード法、ディップコート法、スプレーパイロシス法あるいはジェリーロール法等により作製した線材を用いても、同等の超電導特性を得ることが可能である。作製した線材は、目的に応じて２本以上複合させてスパイラル状に巻くことや、リード線状やケーブル線状に成形して利用することができる。 In addition to the above methods, for example, equivalent superconducting characteristics can be obtained by using a wire produced by a thermal spraying method, a doctor blade method, a dip coating method, a spray pyrolysis method, a jelly roll method, or the like. Two or more of the produced wires can be combined and wound in a spiral shape according to the purpose, or formed into a lead wire shape or a cable wire shape.
熱処理では、超電導体の特性を高めるため、熱処理雰囲気が適宜選択される。たとえば、酸素ガス、窒素ガス、アルゴンガスを単独あるいは混合したガスを適当な流量だけ気流または封入して熱処理する。ＭｇＢ2超電導体では、蒸気圧の高いマグネシウムが熱処理中に飛散して組成ずれを起こし、超電導特性が劣化することがあるため、たとえば、マグネシウム焼結体を同時に熱処理等して、擬マグネシウム雰囲気を作った状態で熱処理すると効果的である。また、金属シース材にマグネシウムを含有させることも同様な効果を奏する。 In the heat treatment, a heat treatment atmosphere is appropriately selected in order to improve the characteristics of the superconductor. For example, oxygen gas, nitrogen gas, and argon gas, alone or mixed, are air-flowed or sealed at an appropriate flow rate for heat treatment. In the MgB 2 superconductor, magnesium having a high vapor pressure is scattered during heat treatment, resulting in a composition shift, and superconducting characteristics may be deteriorated. It is effective to heat-treat in the prepared state. In addition, adding magnesium to the metal sheath material has the same effect.
本発明により製造される超電導線材を、たとえば、液体ヘリウム中で使用する場合、臨界磁場の高い金属系超電導体や酸化物系超電導体と組み合わせた構造とすることで、より強い磁場を発生する超電導マグネット等の実用導体を実現することができる。金属系超電導体としては、Ｎｂ3Ｓｎ系化合物、Ｎｂ3Ａｌ系化合物、Ｖ3Ｇａ系化合物、シェブレル系化合物を用いることができ、必要に応じて２種以上のマグネットを配置する。酸化物系超電導体としては、Ｙ系、Ｂｉ系、Ｔｌ系、Ｈｇ系、Ａｇ−Ｐｂ系が好ましく例示される。 When the superconducting wire manufactured according to the present invention is used in, for example, liquid helium, it is a superconductivity that generates a stronger magnetic field by combining it with a metal superconductor or oxide superconductor having a high critical magnetic field. Practical conductors such as magnets can be realized. As the metal-based superconductor, Nb 3 Sn-based compounds, Nb 3 Al-based compounds, V 3 Ga-based compounds, and Chevrel-based compounds can be used, and two or more kinds of magnets are arranged as necessary. Preferred examples of the oxide-based superconductor include Y-based, Bi-based, Tl-based, Hg-based, and Ag-Pb-based.
また、本発明により製造される超電導線材を、液体水素、液体ネオン中で使用する場合には、酸化物系超電導体と組み合わせることにより、より高性能の超電導マグネット等が実現される。 In addition, when the superconducting wire manufactured according to the present invention is used in liquid hydrogen or liquid neon, a higher performance superconducting magnet or the like is realized by combining it with an oxide superconductor.
線材の形状は、丸あるいはアスペクト比の小さい平角状であれば、マグネットにおける磁場均一度が大幅に向上し、たとえば、核磁気共鳴装置等では超高感度のイメージングを実現することが可能となる。 If the shape of the wire is a circle or a rectangular shape with a small aspect ratio, the magnetic field uniformity in the magnet is greatly improved. For example, in a nuclear magnetic resonance apparatus or the like, ultrasensitive imaging can be realized.
以下、本発明の実験例を示す。ただし、本発明は、以下の実験例に限定されるものではない。 Hereinafter, an experimental example of the present invention. However, the present invention is not limited to the following experimental examples.
平均粒径が３０μｍ以下のマグネシウム粉末（Ｍｇ純度：９９％）と平均粒径が２μｍ以下のアモルファス状ホウ素粉末（Ｂ純度：９９％）を用い、マグネシウムとホウ素が原子比で１：２となるように秤量し、アルゴン雰囲気中で１０分〜６０分間混合した。混合粉末を、外径１５ｍｍ、内径１１ｍｍ、長さ５００ｍｍの鉄（Ｆｅ）パイプに充填した。Ｆｅパイプの両端を封止した後、外径１８ｍｍ、内径１５．５ｍｍ、長さ５４０ｍｍの銅（Ｃｕ）パイプに組み込むことにより、Ｃｕ／Ｆｅの複合シースとした。 Magnesium powder (Mg purity: 99%) with an average particle size of 30 μm or less and amorphous boron powder (B purity: 99%) with an average particle size of 2 μm or less are used, and magnesium and boron have an atomic ratio of 1: 2. And weighed for 10-60 minutes in an argon atmosphere. The mixed powder was filled in an iron (Fe) pipe having an outer diameter of 15 mm, an inner diameter of 11 mm, and a length of 500 mm. After sealing both ends of the Fe pipe, a Cu / Fe composite sheath was obtained by incorporating it into a copper (Cu) pipe having an outer diameter of 18 mm, an inner diameter of 15.5 mm, and a length of 540 mm.
また、加工度の効果を確認するために、外径６．６７ｍｍ、内径４．８９ｍｍ、長さ５００ｍｍのＦｅパイプに上記混合粉末を充填し、両端を封止した後、外径８ｍｍ、内径６．８９ｍｍ、長さ５４０ｍｍのＣｕパイプに組み込んで、Ｃｕ／Ｆｅの複合シースとした。パイプ径の差はあるが、コア部の割合は両者で同じとした。 In order to confirm the effect of the processing degree, the mixed powder was filled in an Fe pipe having an outer diameter of 6.67 mm, an inner diameter of 4.89 mm, and a length of 500 mm, and both ends were sealed, and then an outer diameter of 8 mm and an inner diameter of 6 A Cu / Fe composite sheath was assembled into a Cu pipe having a length of .89 mm and a length of 540 mm. Although there is a difference in pipe diameter, the ratio of the core part is the same in both cases.
１パス当たりの断面積の減少率が３％〜２０％の範囲内となるように伸線加工を繰り返し、丸断面となるまで縮径した。種々の加工度で作製した線材をサンプリングして各々の臨界電流密度を測定し、加工度と臨界電流密度の関係について調べた。 The wire drawing process was repeated so that the reduction rate of the cross-sectional area per pass was in the range of 3% to 20%, and the diameter was reduced until a round cross-section was obtained. The wire rods produced at various working degrees were sampled and the respective critical current densities were measured, and the relationship between the working degree and the critical current density was investigated.
図１は、作製した超電導線材１の断面構造を示した模式図である。実験例１では、超電導線材１は、外周管２にＣｕパイプ、内周管３にＦｅパイプが配置され、内周管３の中に超電導コア部４が内包されている。外周管２および内周管３は、以上の例に限定されるものではなく、外周管２をＣｕ合金、内周管３をニオブ（Ｎｂ）、タンタル（Ｔａ）、チタン（Ｔｉ）、炭素鋼、ステンレス鋼等とすることができる。また、外周管２と内周管３との間に接合助剤を挿入し、加熱処理によって拡散接合すると、加工性が向上し、長尺線材化には一層効果的である。 FIG. 1 is a schematic diagram showing a cross-sectional structure of the produced superconducting wire 1. In Experiment Example 1, superconducting wire 1, Cu pipe external tube 2, Fe pipe inner circumferential tube 3 is arranged, superconducting core part 4 in the inner circumferential tube 3 is enclosed. The outer peripheral tube 2 and the inner peripheral tube 3 are not limited to the above examples. The outer peripheral tube 2 is a Cu alloy, the inner peripheral tube 3 is niobium (Nb), tantalum (Ta), titanium (Ti), carbon steel. , Stainless steel or the like. Further, when a bonding aid is inserted between the outer peripheral tube 2 and the inner peripheral tube 3 and diffusion bonding is performed by heat treatment, the workability is improved and it is more effective for making a long wire rod.
図２は、実験例１で作製したＣｕ／Ｆｅ複合シースＭｇＢ2単芯線材の製造工程である。 Figure 2 is a manufacturing process of the Cu / Fe compound sheath MgB 2 single-core wire material produced in Experiment Example 1.
実験例１では、１．６０ｍｍ〜０．５５ｍｍまでの線径を有する線材を作製した。外径１８ｍｍから伸線を開始した場合、線径０．５５ｍｍのときの加工度はおよそ９９．９％であるが、加工中に一度も焼鈍を入れなくても９９％という大きな加工度まで無断線で伸線することができた。 In Experiment Example 1 to prepare a wire having a wire diameter of up to 1.60Mm～0.55Mm. When wire drawing is started from an outer diameter of 18 mm, the processing degree when the wire diameter is 0.55 mm is approximately 99.9%, but without any annealing even during processing, the processing degree is as high as 99% without permission. I was able to draw with a wire.
このようにして作製した線材に、アルゴン雰囲気中で、６３０℃、１時間の熱処理を施し、ＭｇＢ2超電導線材を作製した。得られた線材のシースを剥がし、内部の粉末部分を微小部Ｘ線で回折分析を行った。その結果、ピーク強度比換算でＭｇＢ2超電導体が９８％以上含まれていることが分かった。ＭｇＢ2以外には、若干のＭｇＯ、ＭｇＢ4という非超電導相が含まれていた。 The wire thus produced was subjected to heat treatment at 630 ° C. for 1 hour in an argon atmosphere to produce a MgB 2 superconducting wire. The sheath of the obtained wire was peeled off, and the internal powder portion was subjected to diffraction analysis with a micro X-ray. As a result, it was found that 98% or more of MgB 2 superconductor was contained in terms of peak intensity ratio. In addition to MgB 2 , some non-superconducting phases of MgO and MgB 4 were included.
実験例１で作製した超電導線材１の臨界温度を直流四端子法で測定したところ、全て３８Ｋで超電導状態となることが分かった。次に、加工度を変えた線材の臨界電流密度を温度４．２Ｋ、磁場６Ｔ中で直流四端子法により測定した。その結果は、図３に示したとおりである。 Was the critical temperature of the superconducting wire 1 prepared in Experimental Example 1 were measured by a DC four-terminal method, it was found that the superconducting state at all 38K. Next, the critical current density of the wire material having a different degree of processing was measured by a direct current four-terminal method at a temperature of 4.2K and a magnetic field of 6T. The result is as shown in FIG.
加工度は、前述したとおり、以下のように算出した。 As described above, the degree of processing was calculated as follows.
加工度＝[１−（ｄ２／ｄ１）2]×１００ （％）
図３から明らかなように、加工度が９９％未満の場合、磁場６Ｔ中での臨界電流密度は約２００Ａ／ｍｍ2であまり差がなかった。しかし、加工度が９９％以上となると、臨界電流密度が加工度とともに向上し、加工度が９９．４６％のとき３００Ａ／ｍｍ2、９９．７５％のとき４００Ａ／ｍｍ2、９９．８７％のとき５００Ａ／ｍｍ2を超える臨界電流密度が得られた。
Degree of processing = [1- (d2 / d1) 2 ] × 100 (%)
As is clear from FIG. 3, when the degree of processing was less than 99%, the critical current density in the magnetic field 6T was about 200 A / mm 2 and there was not much difference. However, when the working degree is 99% or more, the critical current density is improved with the working degree. When the working degree is 99.46%, 300 A / mm 2 , and when 99.75%, 400 A / mm 2 , 99.87%. In this case, a critical current density exceeding 500 A / mm 2 was obtained.
以上の結果は、線材の加工度と臨界電流密度には相関関係があって、ニホウ化マグネシウム超電導線材の高臨界電流密度化には、９９％以上の加工度に減面加工することが重要であることを示している。 The above results show that there is a correlation between the degree of processing of the wire and the critical current density. To increase the critical current density of the magnesium diboride superconducting wire, it is important to reduce the surface to 99% or more. It shows that there is.
実験例１のようにして作製した混合粉末を、内周管３としての外径１５ｍｍ、内径１１ｍｍ、長さ２５０ｍｍの純鉄（Ｆｅ）パイプに充填した。Ｆｅパイプの両端を封止した後、外周管２としての外径１８ｍｍ、内径１５．５ｍｍ、長さ２９０ｍｍの（ａ）Ｃｕパイプ、（ｂ）Ｃｕ−Ａｇ合金パイプ、（ｃ）Ｃｕ−Ｎｉ合金パイプ、（ｄ）炭素鋼パイプ、（ｅ）ステンレス鋼パイプ、（ｆ）Ｎｂパイプの６種類に組み込み、複合シースとした。 The mixed powder was made as Experiment Example 1, the outer diameter 15mm as the inner circumferential tube 3, the inner diameter 11 mm, was packed in pure iron (Fe) Pipe length 250 mm. After sealing both ends of the Fe pipe, (a) Cu pipe, (b) Cu—Ag alloy pipe, (c) Cu—Ni alloy having an outer diameter of 18 mm, an inner diameter of 15.5 mm, and a length of 290 mm as the outer pipe 2 The composite sheath was assembled into six types of pipe, (d) carbon steel pipe, (e) stainless steel pipe, and (f) Nb pipe.
作製した線材の断面構造は、図１に示すとおりである。これら６種類の複合シース線材を伸線加工した。その結果、外周管２にＣｕパイプあるいはＣｕ合金パイプを配置した場合には、およそ９９．９％の加工度となるまで伸線することができた。一方、それ以外の複合シース材では、９０．０％〜９７．２％の加工度で線材が断線した。表１に断線したときの加工度と線材の臨界電流密度を示す。 The cross-sectional structure of the produced wire is as shown in FIG. These 6 kinds of composite sheath wires were drawn. As a result, when a Cu pipe or a Cu alloy pipe was disposed in the outer peripheral pipe 2, the wire could be drawn to a working degree of approximately 99.9%. On the other hand, in the other composite sheath materials, the wires were disconnected at a working degree of 90.0% to 97.2%. Table 1 shows the degree of processing when the wire is broken and the critical current density of the wire.
加工性が劣る炭素鋼、ステンレス鋼、Ｎｂパイプを外周管２に配置した場合、断線という問題に加え、温度４．２Ｋ、磁場６Ｔ中における線材の臨界電流密度が低下する。走査型顕微鏡により断線した線材の断面組織を観察した結果、いずれの線材も断線の１パス〜５パス前の伸線時に外周管２および内周管３に亀裂が生じていることが確認された。したがって、これらの線材では、伸線加工後の超電導化させる熱処理の際に、その亀裂部から蒸気圧の高いＭｇが大気中に蒸発し、線材内部の超電導コア部４が組成ずれ（ホウ素リッチ）することが分かった。 When carbon steel, stainless steel, and Nb pipe, which are inferior in workability, are arranged in the outer tube 2, in addition to the problem of disconnection, the critical current density of the wire in a temperature of 4.2K and a magnetic field of 6T decreases. As a result of observing the cross-sectional structure of the broken wire with a scanning microscope, it was confirmed that the outer tube 2 and the inner tube 3 were cracked when the wire was drawn 1 to 5 passes before the break. . Therefore, in these wires, during the heat treatment for superconducting after wire drawing, Mg having a high vapor pressure evaporates from the cracked portion into the atmosphere, and the superconducting core portion 4 inside the wire is out of composition (boron rich). I found out that
以上の結果は、線材の最外周に配置するシース材と、加工性あるいは臨界電流密度とは相関関係があり、両者を向上させるには、最外周にＣｕあるいはＣｕ合金を配置することが重要であることを示している。 The above results show that there is a correlation between the sheath material arranged on the outermost periphery of the wire and the workability or critical current density, and in order to improve both, it is important to arrange Cu or a Cu alloy on the outermost periphery. It shows that there is.
外周管２のＣｕパイプと内周管３のＮｂパイプの肉厚を変化させ、線材全体におけるＣｕの割合とＮｂの割合を変えた以外は、実験例１と同様のプロセスで、Ｃｕ／Ｎｂの複合シースＭｇＢ2超電導線材を作製した。実験例３では、Ｃｕが線材全体の０．５％〜２０％となるように調整した。 The thickness of the Nb pipe Cu pipe and the inner circumferential tube 3 of the outer tube 2 is changed, except for changing the ratio of proportion and Nb of Cu in the entire wire, in the same process as Experimental Example 1, Cu / Nb A composite sheath MgB 2 superconducting wire was prepared. In Experiment Example 3, were adjusted to Cu of 0.5% to 20% of the total wire.
仮にＣｕが安定化材としての効果を発揮するならば、臨界電流近傍で通電を終了すれば、ジュールの法則にしたがった発熱（電流×電流×抵抗）による温度上昇が生じても、線材は焼損しないはずである。このことを明らかにするため、Ｃｕの割合を変えた線材を温度４．２Ｋ、磁場４Ｔ中で臨界電流を直流四端子法により測定した。Ｃｕの割合を変化しても、超電導コア部４の割合は全て同等であるため、いずれも臨界電流は約４００Ａと一定である。臨界電流に換算すると、約８５０Ａ／ｍｍ2である。 If Cu exhibits its effect as a stabilizing material, the wire will burn out even if the temperature rises due to heat generation (current x current x resistance) according to Joule's law if energization is terminated near the critical current. Should not. In order to clarify this, the critical current was measured by the direct current four-terminal method in a wire having a changed Cu ratio in a temperature of 4.2K and a magnetic field of 4T. Even if the proportion of Cu is changed, the proportions of the superconducting core portions 4 are all the same, so that the critical current is constant at about 400 A in all cases. When converted to a critical current, it is about 850 A / mm 2 .
表２に、臨界電流の４００Ａに対して１０５％となる４２０Ａまで通電した場合の線材の外観状態を示した。 Table 2 shows the external appearance of the wire when energizing up to 420 A, which is 105% of the critical current of 400 A.
Ｃｕの割合が１５％以上では線材の焼損（溶断）は確認されなかったが、それよりも少ないと、通電時に線材の温度が上昇し、焼損することが分かった。 When the proportion of Cu was 15% or more, no burnout (melting) of the wire was confirmed, but when it was less than that, it was found that the temperature of the wire rose during energization and burnout.
外周管２をＣｕ−Ａｇ、Ｃｕ−Ｎｉに代表されるＣｕ合金パイプにした場合でも、同様の結果が得られた。 Similar results were obtained even when the outer pipe 2 was a Cu alloy pipe typified by Cu-Ag and Cu-Ni.
以上の結果から、最外周のＣｕあるいはＣｕ合金は、線材の全断面積の１５％以上は確保しておくことが重要であることが分かった。 From the above results, it was found that it is important to secure 15% or more of the total cross-sectional area of the wire in the outermost peripheral Cu or Cu alloy.
次に、最外周のＣｕを線材の全断面積の１５％に固定し、バリア層として機能する内周管３としてのＮｂパイプが、線材の全断面積の８％〜３０％となるように調整した。このことは、最外周のＣｕと超電導コア部４の合計の割合が線材の全断面積９２％〜７０％に相当する。 Next, the outermost peripheral Cu is fixed to 15% of the total cross-sectional area of the wire, and the Nb pipe as the inner peripheral tube 3 functioning as a barrier layer is 8% to 30% of the total cross-sectional area of the wire. It was adjusted. This corresponds to the total ratio of the outermost peripheral Cu and the superconducting core portion 4 being 92% to 70% of the total cross-sectional area of the wire.
そして、最外周のＣｕと超電導コア部４の合計の割合と臨界電流密度との関係について調べた。その結果が、表３である。 Then, the relationship between the total ratio of the outermost peripheral Cu and the superconducting core portion 4 and the critical current density was examined. The results are shown in Table 3.
Ｃｕと超電導コア部４の合計が、全断面積の８５％以下のときには、温度４．２Ｋ、磁場４Ｔ中で約８５０Ａ／ｍｍ2の臨界電流密度が得られた。一方、８５％を超えると、臨界電流密度は一気に低下し、８７％では１４０Ａ／ｍｍ2、９２％では１２０Ａ／ｍｍ2となった。このような臨界電流密度の低下の原因を走査型電子顕微鏡により調査した結果、バリア層である内周管３としてのＮｂパイプが一部破損し、最外周のＣｕと超電導コア部４が直接接触している箇所が存在した。その部分を組成分析すると、ＣｕとＭｇの反応層が生成しており、これが性能低下を引き起こした原因となっていることが分かった。 When the total of Cu and the superconducting core portion 4 was 85% or less of the total cross-sectional area, a critical current density of about 850 A / mm 2 was obtained at a temperature of 4.2 K and a magnetic field of 4 T. On the other hand, when it exceeded 85%, the critical current density decreased at a stretch, with 87% being 140 A / mm 2 and 92% being 120 A / mm 2 . As a result of investigating the cause of the decrease in the critical current density with a scanning electron microscope, the Nb pipe as the inner peripheral tube 3 serving as the barrier layer is partially broken, and the outermost peripheral Cu and the superconducting core portion 4 are in direct contact. There was a place to do. Analysis of the composition of the part showed that a reaction layer of Cu and Mg was formed, which caused the performance to be degraded.
なお、内周管３としてのＮｂパイプをＦｅやＴａパイプに替えても同様の結果になることが確認された。また、最外周のＣｕあるいはＣｕ合金は、最低でも線材の全断面積の１５％を確保しておかないと、電気的に極めて不安定となることが確認された。 It was confirmed that the same result was obtained even when the Nb pipe as the inner peripheral pipe 3 was replaced with an Fe or Ta pipe. Moreover, it was confirmed that Cu or Cu alloy at the outermost periphery becomes electrically unstable unless at least 15% of the total cross-sectional area of the wire is secured.
以上の結果から、高臨界電流密度化と高安定化を同時に達成するには、最外周のＣｕあるいはＣｕ合金の割合を線材の全断面積の１５％以上、かつＣｕあるいはＣｕ合金と超電導コア部４の合計の割合を線材の全断面積の８５％以下とすることが重要であることが分かった。 From the above results, in order to achieve high critical current density and high stabilization at the same time, the ratio of Cu or Cu alloy at the outermost periphery is 15% or more of the total cross-sectional area of the wire, and Cu or Cu alloy and the superconducting core part. It was found that it is important that the total ratio of 4 is 85% or less of the total cross-sectional area of the wire.
内周管３としてのＮｂパイプの外面に電気めっき法で厚さ０．５ｍｍ以下のＣｕめっきを施した以外は、同様のプロセスでＣｕ／Ｎｂ複合シースＭｇＢ2超電導線材を作製した。この線材を伸線加工した結果、外径０．２５ｍｍまで無断線で加工することができた。加工度に換算すると、９９．９８％である。 A Cu / Nb composite sheath MgB 2 superconducting wire was produced by the same process except that the outer surface of the Nb pipe as the inner peripheral tube 3 was subjected to Cu plating having a thickness of 0.5 mm or less by electroplating. As a result of drawing this wire, it was possible to process the wire up to an outer diameter of 0.25 mm without disconnection. When converted into the processing degree, it is 99.98%.
作製した線材の臨界電流密度を温度４．２Ｋ、磁場６Ｔ中で直流四端子法により測定した。その結果、実験例１と同様に、加工度が増加するにしたがって臨界電流密度が向上し、加工度が９９．９８％のとき、５７５Ａ／ｍｍ2の臨界電流密度が得られた。 The critical current density of the produced wire was measured by the direct current four-terminal method in a temperature of 4.2K and a magnetic field of 6T. As a result, as in Experiment Example 1, the critical current density is improved in accordance with the working ratio is increased, the working ratio is when 99.98%, the critical current density of 575A / mm 2 was obtained.
この結果は、内周管３として、Ｆｅ、Ｔａ、Ｔｉパイプを採用する場合にも同様であり、さらに、最外周のＣｕの内面にＣｕめっきを施しても同様であった。 This result was the same when the Fe, Ta, and Ti pipes were adopted as the inner peripheral tube 3, and the same result was obtained even when Cu plating was performed on the inner surface of the outermost peripheral Cu.
以上の結果は、最外周のＣｕあるいはＣｕ合金の内面、またはＣｕあるいはＣｕ合金の内部に配置される金属管の外面にＣｕめっきを施すことが、線材の長尺化と臨界電流密度の向上に有効であることを示している。 The above results show that Cu plating is applied to the inner surface of the outermost Cu or Cu alloy, or the outer surface of the metal tube disposed inside the Cu or Cu alloy, to increase the length of the wire and improve the critical current density. It shows that it is effective.
実験例１のようにして、Ｃｕ／Ｆｅ複合シース線材およびＣｕ／Ｎｂ複合シース線材を作製した。これらの線材を用いて熱処理条件を検討した。熱処理温度は、５００℃〜９５０℃の範囲で行った。このとき、電気炉内の雰囲気は、（１）真空中、（２）Ａｒフロー中、（３）Ｎ2フロー中、（４）大気中の４種類とした。 As described experimental example 1 was prepared Cu / Fe composite sheath wire and Cu / Nb composite sheath wire. The heat treatment conditions were examined using these wires. The heat treatment temperature was in the range of 500 ° C to 950 ° C. At this time, there were four atmospheres in the electric furnace: (1) vacuum, (2) Ar flow, (3) N2 flow, and (4) air.
表４に、各条件で熱処理した線材の温度４．２Ｋ、磁場６Ｔ中における臨界電流密度を示した。 Table 4 shows the critical current density in a temperature of 4.2K and a magnetic field of 6T of the wire heat-treated under each condition.
表４から明らかであるように、温度が５８０℃〜９００℃の範囲内で、かつ雰囲気が真空中、Ａｒ中、Ｎ2中で熱処理した場合に、高い臨界電流密度が得られることが分かった。線材内部をＸ線回折および走査型電子顕微鏡観察した結果、５８０℃未満の温度ではＭｇＢ2が生成していないことが分かった。９００℃を超える温度で熱処理をした場合には、ＭｇＢ2相以外の非超電導相が粗大化し、電流パスを妨げていることが確認された。また、大気中で熱処理を行うと、結晶粒の表面に絶縁体である酸化膜が形成され、臨界電流密度の低下を引き起こすことも分かった。 As is apparent from Table 4, it was found that a high critical current density was obtained when the temperature was in the range of 580 ° C. to 900 ° C. and the atmosphere was heat-treated in vacuum, Ar, or N 2 . . As a result of X-ray diffraction and scanning electron microscope observation of the inside of the wire, it was found that MgB 2 was not generated at a temperature lower than 580 ° C. When heat treatment was performed at a temperature exceeding 900 ° C., it was confirmed that the non-superconducting phase other than the MgB 2 phase was coarsened and hindered the current path. It was also found that when heat treatment is performed in the atmosphere, an oxide film as an insulator is formed on the surface of the crystal grains, causing a decrease in critical current density.
以上の結果は、複合シースＭｇＢ2超電導線材の臨界電流密度と熱処理条件には相関関係があり、臨界電流密度を向上させるためには、温度５８０℃〜９００℃の真空中または不活性ガス中で熱処理することが有効であることを示している。 The above results show that there is a correlation between the critical current density of the composite sheath MgB 2 superconducting wire and the heat treatment conditions. In order to improve the critical current density, in a vacuum of 580 ° C. to 900 ° C. or in an inert gas It shows that heat treatment is effective.
実験例１と同様のプロセスで作製したＭｇＢ2超電導線材１を、７本１組としてツイスト加工し、図６に示したような７本撚り線材５とした。ツイストピッチは３０ｍｍとした。そして、ツイスト加工した７本撚り線材５を多芯用金属シース材６に組み込んだ。多芯用金属シース材６にはＣｕパイプを用いた。７本撚り線材５を多芯用金属シース材６に組み込む際には若干の隙間が生じるが、加工を行うことで両者は密着してほぼ一体化する。 The MgB 2 superconducting wire 1 was prepared by the same process as Experimental Example 1, and twisted as seven one set, and a 7-ply wire 5 as shown in FIG. The twist pitch was 30 mm. Then, the twisted seven-strand wire 5 was incorporated into a multi-core metal sheath material 6. A Cu pipe was used for the multi-core metal sheath material 6. When the seven-strand wire 5 is incorporated into the multi-core metal sheath material 6, a slight gap is produced, but the two are in close contact with each other by processing.
伸線加工を行い、最終的に外径０．７５ｍｍ〜１．２ｍｍの超電導多芯線材を得た。実験例６では７芯としたが、芯数は適宜変更することができる。 Drawing was performed to finally obtain a superconducting multi-core wire having an outer diameter of 0.75 mm to 1.2 mm. Although the experimental example 6, 7 a core that number may be appropriately changed.
なお、各超電導線材１の金属シース材にはＣｕ／Ｆｅ複合シースを用いた。 A Cu / Fe composite sheath was used as the metal sheath material of each superconducting wire 1.
伸線加工した結果、ツイスト加工した線材が充填されていても、断線することなく所定の径まで加工することができた。 As a result of the wire drawing, even when the twisted wire was filled, the wire could be processed to a predetermined diameter without disconnection.
作製した外径１．２ｍｍのＭｇＢ2超電導多芯線材を温度６００℃、Ａｒ雰囲気で熱処理し、臨界温度を直流四端子法で測定した。３８Ｋで超電導状態になった。臨界電流密度は、温度４．２Ｋ、磁場６Ｔ中で測定した結果、２９０Ａ／ｍｍ2であった。 The produced MgB 2 superconducting multifilamentary wire having an outer diameter of 1.2 mm was heat-treated in an Ar atmosphere at a temperature of 600 ° C., and the critical temperature was measured by a DC four-terminal method. It became superconducting at 38K. The critical current density was 290 A / mm 2 as a result of measurement at a temperature of 4.2 K and a magnetic field of 6 T.
また、作製したＭｇＢ2超電導多芯線材の交流損失を磁場中で測定した。比較のため、ツイスト加工していない多芯線材についても同様に測定した。印加磁場は０．００５Ｔ〜０．５Ｔ、周波数は５０Ｈｚとした。その結果、ツイスト加工したＭｇＢ2超電導多芯線材は、ツイスト加工していないものに比べ、交流損失がおよそ１／１０に低減することが分かった。 Moreover, the alternating current loss of the produced MgB 2 superconducting multi-core wire was measured in a magnetic field. For comparison, the same measurement was performed for a multi-core wire that was not twisted. The applied magnetic field was 0.005 T to 0.5 T, and the frequency was 50 Hz. As a result, it was found that the twisted MgB 2 superconducting multi-core wire has an AC loss reduced to about 1/10 compared to that of the non-twisted one.
したがって、交流応用の場合には、線材の長手方向にツイスト加工された超電導多芯線材を使用することにより、トータルの交流損失を大幅に低減することができることが明らかとなった。 Therefore, in the case of AC application, it has become clear that the total AC loss can be significantly reduced by using a superconducting multi-core wire twisted in the longitudinal direction of the wire.
本発明のＭｇＢ2超電導線材は、広く超電導機器に適用することが可能で、たとえば、大型マグネット、核磁気共鳴分析装置、医療用磁気共鳴診断装置、超電導電力貯蔵装置、磁気分離装置、磁場中単結晶引上装置、冷凍機冷却超電導マグネット装置、磁気浮上列車等に利用することができる。また、各機器の高効率化が達成される。 The MgB 2 superconducting wire of the present invention can be widely applied to superconducting equipment. For example, a large magnet, a nuclear magnetic resonance analyzer, a medical magnetic resonance diagnostic device, a superconducting power storage device, a magnetic separation device, a single magnetic field It can be used for crystal pulling devices, refrigerator-cooled superconducting magnet devices, magnetic levitation trains, and the like. Moreover, high efficiency of each device is achieved.
１ ＭｇＢ2超電導線材
２ 外周管
３ 内周管
４ 超電導コア部
５ ７本撚り線材
６ 多芯用金属シース材
DESCRIPTION OF SYMBOLS 1 MgB 2 Superconducting wire 2 Outer tube 3 Inner tube 4 Superconducting core part 5 Seven strand wire 6 Multi-core metal sheath material
Claims (3)
最外周に銅あるいは銅合金が配置され、その内部にＦｅ、Ｎｂ、Ｔａ、Ｔｉ、炭素鋼あるいはステンレス鋼が配置され、最外周の銅あるいは銅合金の内面、または最外周の銅あるいは銅合金の内部に配置されるＦｅ、Ｎｂ、Ｔａ、Ｔｉ、炭素鋼あるいはステンレス鋼の外面に銅めっきが施され、
加工度９９％以上になるまで減面加工され、
最外周の銅あるいは銅合金の割合が、線材の全断面積の１５％以上であり、かつ最外周の銅あるいは銅合金および超電導コア部の合計の割合が線材の全断面積の８５％以下であり、
温度５８０℃〜９００℃の真空中または不活性ガス中で熱処理されたものである
ことを特徴とする複合シース二ホウ化マグネシウム超電導線材。 A composite sheath magnesium diboride superconducting wire in which magnesium diboride is encapsulated in a composite sheath formed of a composite metal tube in which at least two different types of metal tubes are combined,
Copper or copper alloy is disposed on the outermost periphery, Fe, Nb, Ta, Ti, carbon steel or stainless steel is disposed on the inside thereof, the innermost surface of the outermost copper or copper alloy, or the outermost copper or copper alloy. Copper plating is applied to the outer surface of Fe, Nb, Ta, Ti, carbon steel or stainless steel disposed inside,
The surface is reduced until the degree of processing reaches 99% ,
The ratio of the outermost copper or copper alloy is 15% or more of the total cross-sectional area of the wire, and the total ratio of the outermost copper or copper alloy and the superconducting core is 85% or less of the total cross-sectional area of the wire. Yes,
A composite sheath magnesium diboride superconducting wire characterized by being heat-treated in a vacuum at 580C to 900C or in an inert gas .
外周管と内周管が組み合わされた複合金属管から形成される複合シースの内周管にマグネシウム粉末およびホウ素粉末の混合粉末あるいはニホウ化マグネシウムの合成粉末を充填する工程と、
粉末充填後の線材を９９％以上の加工度になるまで減面加工し、最外周に配置された銅あるいは銅合金の割合を線材の全断面積の１５％以上であり、かつ最外周の銅あるいは銅合金および超電導コア部の合計の割合を線材の全断面積の８５％以下とする工程と、
５８０℃〜９００℃の真空中または不活性ガス中で熱処理する工程
とを含むことを特徴とする複合シースニホウ化マグネシウム超電導線材の製造方法。 Copper plating on the inner surface of the outer peripheral tube of copper or copper alloy disposed on the outermost periphery, or on the outer surface of the inner peripheral tube selected from Fe, Nb, Ta, Ti, carbon steel or stainless steel and disposed inside the outer peripheral tube A process of applying
Filling an inner tube of a composite sheath formed of a composite metal tube in which an outer tube and an inner tube are combined with a mixed powder of magnesium powder and boron powder or a synthetic powder of magnesium diboride;
The wire rod after powder filling is surface-reduced until it has a working degree of 99% or more, and the ratio of copper or copper alloy disposed on the outermost periphery is 15% or more of the total cross-sectional area of the wire, and the outermost copper Or the process which makes the ratio of the sum total of a copper alloy and a superconducting core part 85% or less of the total cross-sectional area of a wire,
The method of producing a composite sheath diboride magnesium superconducting wire which comprises a step <br/> a heat treatment in vacuum at 580 ° C. to 900 ° C. or in an inert gas.
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| JP2011076821A (en) * | 2009-09-30 | 2011-04-14 | Hitachi Ltd | Magnesium diboride wire, and manufacturing method thereof |
| JP5602588B2 (en) * | 2010-10-29 | 2014-10-08 | 公益財団法人鉄道総合技術研究所 | Manufacturing method of MgB2 superconducting bulk magnet and MgB2 superconducting bulk magnet |
| WO2014162379A1 (en) * | 2013-04-01 | 2014-10-09 | 株式会社 日立製作所 | Superconducting wire and manufacturing method for same, as well as superconducting coil |
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| JP6941599B2 (en) * | 2016-04-14 | 2021-09-29 | 株式会社日立製作所 | Manufacturing method of MgB2 superconducting wire, superconducting coil and MRI |
| JP7072162B2 (en) * | 2018-03-02 | 2022-05-20 | 株式会社日立製作所 | Superconducting power transmission pipe |
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