JPS60235308A - Method of producing compound superconductive wire - Google Patents
Method of producing compound superconductive wireInfo
- Publication number
- JPS60235308A JPS60235308A JP59089513A JP8951384A JPS60235308A JP S60235308 A JPS60235308 A JP S60235308A JP 59089513 A JP59089513 A JP 59089513A JP 8951384 A JP8951384 A JP 8951384A JP S60235308 A JPS60235308 A JP S60235308A
- Authority
- JP
- Japan
- Prior art keywords
- manufacturing
- copper
- barrier layer
- alloy
- bronze
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
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- Superconductors And Manufacturing Methods Therefor (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔技術分野〕
本発明は、Ａ、Ｂ型化合物超電導体のＡ元素を主成分と
するコア部と、Ｂ元素を含有するブロンズ部とからなる
複合基材から化合物超電導線を製造する方法の改良に関
するものである。Detailed Description of the Invention [Technical Field] The present invention relates to compound superconducting material made of a composite base material consisting of a core part mainly composed of the A element of an A and B type compound superconductor and a bronze part containing the B element. This invention relates to improvements in the method of manufacturing wire.
Ａ、Ｂ型化合物超電導体としては、Ｎ ｂ ａ Ｓ ｎ
、Ｖ ３Ｇａ ＸＮｂ：＋Ｇａ 、Ｎｂ３Ａｌなどがあ
るが、これらの化合物超電導体は通常、へ元素を主成分
とするコア部とＢ元素を含有するブロンズ部とからなる
複合基材を、減面加工により最終寸法の線にした後、拡
散熱処理を行うことにより製造されている。−例として
Ｎｂ３Ｓｎ線の製造工程を説明すると次の止おりである
。As A and B type compound superconductors, N b a S n
, V 3Ga It is manufactured by performing a diffusion heat treatment after the wire has been cut to its final dimensions. - As an example, the manufacturing process of Nb3Sn wire is explained as follows.
（ａｌ まず、Ｎｂコアを１０〜１５％Ｓｎのブロンズ
中に埋め込み、複合基材をつくる。(Al First, a Nb core is embedded in 10-15% Sn bronze to create a composite base material.
（ｂｌ この複合基材を減面加工する。(bl This composite base material is subjected to surface reduction processing.
ＦＣ） ｉｄ面加工率２０〜５０％毎に、４００〜７ｏ
ｏ℃ノ温度で１０分〜１時間の中間焼鈍を繰り返し行う
。FC) 400~7o for every 20~50% of id surface processing rate
Intermediate annealing is repeatedly performed at a temperature of 0° C. for 10 minutes to 1 hour.
（ｄｌ 最終寸法の線に仕上げる。(dl Finish the line to the final dimensions.
（ｅ） 拡散熱処理によってＮｂコアとブロンズの界面
にＮｂ３Ｓｎ化合物を生成させる。(e) A Nb3Sn compound is generated at the interface between the Nb core and the bronze by diffusion heat treatment.
上記のような従来の製造方法には次のような問題点があ
る。The conventional manufacturing method as described above has the following problems.
１ 複合基材中ではＮｂコアとブロンズが直接接触して
いるため、中間焼鈍の際に１回毎に０．（１５〜０．１
μｍのＮｂ３Ｓｎが形成される。1. Because the Nb core and bronze are in direct contact in the composite base material, 0. (15~0.1
Nb3Sn of μm is formed.
ｉｌ 中間焼鈍で形成されたＮｂ３Ｓｎは、その後の減
面加工で破壊し、Ｎｂコアの断面形状の不整や断線を誘
発する。il The Nb3Sn formed in the intermediate annealing is destroyed in the subsequent area reduction process, causing irregularities in the cross-sectional shape of the Nb core and disconnection.
ｉｉｉ 最終の拡散熱処理前にＮｂコア表面に不連続な
Ｎｂ３Ｓｎが形成されているため、拡散反応に有効なＳ
ｎ濃度が低下するだけでなく、反応界面の質が低下する
。その結果、拡散熱処理により生成されるＮｂ：＋Ｓｎ
層の断面積の減少や結晶粒の異常成長などによる超電導
特性の低下が起こる。iii Because discontinuous Nb3Sn is formed on the Nb core surface before the final diffusion heat treatment, S
Not only the n concentration decreases, but also the quality of the reaction interface decreases. As a result, Nb:+Sn produced by diffusion heat treatment
Deterioration of superconducting properties occurs due to a decrease in the cross-sectional area of the layer and abnormal growth of crystal grains.
このような問題点はＮｂ３Ｓｎ線を製造する場合に限ら
ず、他のＡ３Ｂ型化合物超電導線を製造する場合にも存
在する。Such problems exist not only when manufacturing Nb3Sn wires but also when manufacturing other A3B type compound superconducting wires.
本発明は、上記のような従来技術の問題点を解決するも
ので、Ａ ３Ｂ型化合物超電導体のＡ元素を主成分とす
るコア部よ、Ｂ元素を含有するブロンズ部とからなる複
合基材を、中間焼鈍を含む減面加工により、最終寸法の
線にした後、拡散熱処理により内部にＡ ３Ｂ型化合物
超電導体を生成する化合物超電導体の製造方法において
、上記複合基材として、コア部とブロンズ部の間に上記
中間焼鈍時におけるＡ元素とＢ元素の反応を阻止するバ
リア層を介在させたものを用いることを特徴とするもの
である。上記のバリア層は中間焼鈍時には化合物超電導
体の生成をなくす働きをし、拡散熱処理時にはブロンズ
部上の拡散反応により消滅する。The present invention solves the problems of the prior art as described above, and provides a composite base material consisting of a core part mainly composed of element A of an A3B type compound superconductor and a bronze part containing element B. In the method for manufacturing a compound superconductor, in which the A3B type compound superconductor is produced inside by diffusion heat treatment after the wire is made into a line with the final dimension by surface reduction processing including intermediate annealing, the core part and This method is characterized by using a barrier layer interposed between the bronze parts to prevent the reaction between element A and element B during the intermediate annealing. The above-mentioned barrier layer serves to prevent the formation of compound superconductors during intermediate annealing, and disappears due to a diffusion reaction on the bronze portion during diffusion heat treatment.
上記バリア層は銅基希薄合金あるいは銅基希薄合金と純
銅の複合体で構成するとよい。いずれにしてもその厚さ
は０．０５〜１μｍの範囲にあることが好ましい。厚さ
の下限は複合基材の一部として均一に加工され、最終寸
法まで有効に作用する限界の薄さである。また厚さの上
限は拡散熱処理時のＢ元素の有効濃度を実用上低下させ
ない程度の値である。Ｂ元素の濃度の低下は化合物結晶
の粒径を大きくし、臨界電流密度の低下につながるから
である。The barrier layer is preferably composed of a copper-based diluted alloy or a composite of a copper-based diluted alloy and pure copper. In any case, the thickness is preferably in the range of 0.05 to 1 μm. The lower limit of the thickness is the thinnest limit that allows it to be uniformly processed as part of the composite substrate and to work effectively to its final dimensions. Further, the upper limit of the thickness is a value that does not practically reduce the effective concentration of B element during diffusion heat treatment. This is because a decrease in the concentration of element B increases the grain size of the compound crystal, leading to a decrease in critical current density.
銅基希薄合金の溶質元素は、Ａｇ 、Ｔｉ 、Ｚｒ、Ｈ
ｆ、Ｖ、Ｔａ、Ｐｄ、Ｍｇ、Ａｌ、Ｓｉ、Ｇｅ。The solute elements of the copper-based dilute alloy are Ag, Ti, Zr, and H.
f, V, Ta, Pd, Mg, Al, Si, Ge.
Ｉｎなどのいずれでもよく、また複数元素でもよいが、
溶質元素の合計の濃度は１原子％以下であることが好ま
しい。この範囲内であれば、冷間加工によっても実質的
に加工硬化せず、かつ純銅より高い硬さを有するため均
一に加工できると共に、拡散熱処理時に化合物超電導体
の生成に悪影響を及ぼすこともない。なお、銅基希薄合
金の代わりに銀基希薄合金を使用することも可能である
。It may be any element such as In, or it may be a plurality of elements,
The total concentration of solute elements is preferably 1 atomic % or less. Within this range, it will not substantially work harden even during cold working, and since it has higher hardness than pure copper, it can be processed uniformly, and it will not adversely affect the formation of compound superconductors during diffusion heat treatment. . Note that it is also possible to use a silver-based diluted alloy instead of the copper-based diluted alloy.
バリア層として純銅の如き極めて軟質なものを使用する
と、コア部とブロンズ部の加工性に整合できず、バリア
層の厚さが著しく変動したり、コア部とブロンズ部が直
接接触する部分ができたりする。If an extremely soft material such as pure copper is used as a barrier layer, the workability of the core and bronze parts cannot be matched, and the thickness of the barrier layer may vary significantly, or there may be areas where the core and bronze parts are in direct contact. or
なお、バリア層として銅基希薄合金と純銅の複合体を使
用するときは、銅基希薄合金が８０％以上を占めるよう
にすることが望ましい。これは、バリア層の強度を向上
させ、コア部の断面形状の不整を防止するためである。Note that when using a composite of a copper-based diluted alloy and pure copper as the barrier layer, it is desirable that the copper-based diluted alloy accounts for 80% or more. This is to improve the strength of the barrier layer and prevent irregularities in the cross-sectional shape of the core portion.
第１図は本発明の製造方法に用いられる複合基材の一例
を示す。符号１はＮｂコア、２はブロンズ、３は銅基希
薄合金のバリア層、４は拡散障壁、５は安定化銅である
。FIG. 1 shows an example of a composite base material used in the manufacturing method of the present invention. 1 is a Nb core, 2 is bronze, 3 is a barrier layer of a copper-based dilute alloy, 4 is a diffusion barrier, and 5 is stabilized copper.
第２図は上記複合基材から製造された化合物超電導線を
示す。Ｎｂコア１とブロンズ２の間に、Ｎｂ、、Ｓｎ化
合物６が形成されている。FIG. 2 shows a compound superconducting wire manufactured from the above composite base material. A Nb, Sn compound 6 is formed between the Nb core 1 and the bronze 2.
第３図ないし第５図はそれぞれ本発明の製造方法に用い
られる複合基材の他の例を示す。第３図の複合基材は、
Ｎｂコア１とブロンズ２の間に銅基希薄合金７と純銅８
とを周方向に交互に配置してなるバリア層９を設けたも
のである。第４図の複合基材は、同様なバリア層９を有
するが、銅基希薄合金７と純銅８の厚さを異ならせであ
る。第５図の複合基材は、銅基希薄合金７と純銅８を同
軸状に複合してなるバリア層９を設けたものである。FIGS. 3 to 5 each show other examples of composite substrates used in the manufacturing method of the present invention. The composite base material in Figure 3 is
Copper-based dilute alloy 7 and pure copper 8 between Nb core 1 and bronze 2
A barrier layer 9 is provided in which these are alternately arranged in the circumferential direction. The composite substrate of FIG. 4 has a similar barrier layer 9, but with different thicknesses of copper-based dilute alloy 7 and pure copper 8. The composite base material shown in FIG. 5 is provided with a barrier layer 9 made of a coaxial composite of a copper-based diluted alloy 7 and pure copper 8.
ここにおけるＮｂコア１は主成分がＮｂであればよく、
Ｔｉ 、Ｈｆ 、Ｚｒ 、Ｓｎ 、、Ｃｕが含まれてい
ても総量として１５原子％以下ならばかまわない。また
、ブロンズ２中のＳｎの濃度は２〜９原子％の範囲が望
ましいが、そのほかにＭｇ 、 Ｇａなどの添加元素を
加えた三元あるいは四元合金ブロンズでもよい。The Nb core 1 here only needs to have a main component of Nb,
Even if Ti, Hf, Zr, Sn, and Cu are contained, there is no problem as long as the total amount is 15 at % or less. Further, the concentration of Sn in the bronze 2 is preferably in the range of 2 to 9 atomic %, but a ternary or quaternary alloy bronze containing additional elements such as Mg and Ga may also be used.
実施例１ （第１図相当）
Ｓｎ濃度１４重量％、Ｔｉ濃度０．５重量％、残部Ｃｕ
のブロンズに、予め０．１ｍｍ厚のＣｕ−０，２重量％
Ｔｉ希薄合金を被覆したＮｂ−２重量％Ｈｆ合金棒を複
合し、さらにその外側に拡散障壁としてＴａを、安定化
金属として純銅を順次設けて複合基材を形成した。次に
この複合基材を減面加工した。途中、減面加工率４０％
毎に５５０℃の温度で３０分間の中間焼鈍を行った。拡
散熱処理前の銅基希薄合金の厚さは０．５ μｍ、Ｎｂ
合金フィラメント径は７μｍであった。これを拡散熱処
理して化合物超電導線を得た結果は第１表のとおりであ
る。Example 1 (corresponding to Figure 1) Sn concentration 14% by weight, Ti concentration 0.5% by weight, balance Cu
0.1 mm thick Cu-0.2% by weight on the bronze.
A Nb-2% by weight Hf alloy rod coated with a Ti dilute alloy was composited, and Ta was sequentially provided on the outside as a diffusion barrier and pure copper as a stabilizing metal to form a composite base material. Next, this composite base material was subjected to surface reduction processing. During the process, surface reduction processing rate is 40%
Intermediate annealing was performed at a temperature of 550° C. for 30 minutes each time. The thickness of the copper-based dilute alloy before diffusion heat treatment is 0.5 μm, Nb
The alloy filament diameter was 7 μm. This was subjected to diffusion heat treatment to obtain a compound superconducting wire. The results are shown in Table 1.
実施例２（第３図相当）
実施例１と同じブロンズに、厚さ０．１ｍｍのＣｕ−０
，２重量％Ｔ１希薄合金および純銅を被覆したＮｂ−２
重量％Ｈｆ合金棒を複合し、さらに実施例１と同様にし
て複合基材を形成した。その後の工程は実施例１と同じ
とした。結果は第１表のとおりである。Example 2 (corresponding to Figure 3) The same bronze as in Example 1 was coated with Cu-0 with a thickness of 0.1 mm.
, 2 wt% T1 dilute alloy and pure copper coated Nb-2
Weight % Hf alloy rods were composited, and a composite base material was further formed in the same manner as in Example 1. The subsequent steps were the same as in Example 1. The results are shown in Table 1.
比較例
実施例１と同じブロンズとＮｂ合金コアの界面に高純度
無酸素銅層を有するもの１と有しないもの２を用意し、
同様の減面加工および拡散熱処理を経て、化合物超電導
線を製造した。結果は第１表のとおりである。Comparative Example Samples 1 and 2 without a high-purity oxygen-free copper layer were prepared at the interface between the bronze and Nb alloy cores as in Example 1.
A compound superconducting wire was manufactured through similar area reduction processing and diffusion heat treatment. The results are shown in Table 1.
第１表から明らかなように、実施例ではＮｂフィラメン
トが均一な径に加工され、すぐれた超電導特性を示すが
、比較例ではフィラメント径の不揃いが大きい。比較例
１では軟質のＣｕが、２では中間焼鈍で出来るＮｂ、Ｓ
ｎ層が大きく影響してフィラメント径を大きく変動させ
ている。また比較例ではＮｂ３Ｓｎ層の厚さの変動も大
きく、超電導特性を悪くしている。As is clear from Table 1, in the Examples, the Nb filaments were processed to have a uniform diameter and exhibited excellent superconducting properties, but in the Comparative Examples, the filament diameters were largely uneven. In Comparative Example 1, soft Cu was used, and in Comparative Example 2, Nb and S produced by intermediate annealing were used.
The n-layer has a large influence and causes the filament diameter to vary greatly. Furthermore, in the comparative example, the variation in the thickness of the Nb3Sn layer was large, which worsened the superconducting properties.
第１表
〔発明の効果〕
以上説明したように本発明によれば、複合基材として、
コア部とブロンズ部の間にバリア層を介在させたものを
用いたので、減面加工中の中間焼鈍でコア部とブロンズ
部の間に化合物超電導体が生成されることがなくなり、
最終寸法に加工した状態でのへ元素を主成分とするフィ
ラメントの径を高度に均一化できる。このため拡散熱処
理で形成される化合物超電導体の結晶粒径や層厚さも均
一になり、臨界電流密度のみならず、許容曲げ歪率など
機械的特性も改善することができる。Table 1 [Effects of the Invention] As explained above, according to the present invention, as a composite base material,
Since a barrier layer was used between the core part and the bronze part, compound superconductors were not generated between the core part and the bronze part during intermediate annealing during surface reduction processing.
It is possible to make the diameter of the filament whose main component is helium element highly uniform after it has been processed to its final size. Therefore, the crystal grain size and layer thickness of the compound superconductor formed by diffusion heat treatment become uniform, and not only the critical current density but also mechanical properties such as allowable bending strain rate can be improved.
第１図は本発明の製造方法に使用される複合基材の一例
を示す断面図、第２図は同複合基材から製造した化合物
超電導線を示す拡大断面図、第３図ないし第５図はそれ
ぞれ本発明の製造方法に使用される複合基材の他の例を
示す要部断面図である。
１〜ココア、２〜ブロンズ部、３〜バリア層、６〜化合
物超電導体、７〜銅基希薄合金、８〜純第１図
第２図FIG. 1 is a sectional view showing an example of a composite base material used in the manufacturing method of the present invention, FIG. 2 is an enlarged sectional view showing a compound superconducting wire manufactured from the same composite base material, and FIGS. 3 to 5 2A and 2B are cross-sectional views of main parts showing other examples of composite base materials used in the manufacturing method of the present invention. 1 - Cocoa, 2 - Bronze part, 3 - Barrier layer, 6 - Compound superconductor, 7 - Copper-based dilute alloy, 8 - Pure Figure 1 Figure 2
Claims (1)
るコア部と、Ｂ元素を含有するブロンズ部とからなる複
合基材を、中間焼鈍を含む減面加工により、最終寸法の
線にした後、拡散熱処理により内部にＡ３Ｂ型化合物超
電導体を生成する方法において、上記複合基材として、
コア部とブロンズ部の間に上記中間焼鈍時におけるＡ元
素とＢ元素の反応を阻止するバリア層を介在させたもの
を用いることを特徴とする化合物超電導線の製造方法。 （２、特許請求の範囲第１項記載の製造方法であって、
上記バリア層は銅基希薄合金からなるもの。 （３）特許請求の範囲第２項記載の製造方法であって、
上記バリア層の厚さは０．０５〜１μｍであるもの。 （４） 特許請求の範囲第２項または第３項記載の製造
方法であって、上記銅基希薄合金は、溶質元素の濃度が
１原子％以下であるもの。 （５）特許請求の範囲第１項記載の製造方法であって、
上記バリア層は、銅基希薄合金と純銅との複合体からな
るもの。 （６）特許請求の範囲第５項記載の製造方法であって、
上記バリア層の厚さは０．０５〜１μｍであるもの。 （７）特許請求の範囲第５項または第６項記載の製造方
法であって、上記銅基希薄合金は、溶質元素の濃度が１
原子％以下であるもの。 （８）特許請求の範囲第５項ないし第７項のいずれかに
記載の製造方法であって、上記複合体は銅基希薄合金が
８０％以上を占めるもの。[Scope of Claims] (1) A composite base material consisting of a core part mainly composed of element A of an A3B type compound superconductor and a bronze part containing element B is subjected to surface reduction processing including intermediate annealing, In the method of producing an A3B type compound superconductor inside by diffusion heat treatment after forming the wire into the final dimension, as the composite base material,
A method for manufacturing a compound superconducting wire, characterized in that a barrier layer is interposed between the core part and the bronze part to prevent the reaction of elements A and B during the intermediate annealing. (2. The manufacturing method according to claim 1,
The barrier layer is made of a copper-based diluted alloy. (3) The manufacturing method according to claim 2, comprising:
The thickness of the barrier layer is 0.05 to 1 μm. (4) The manufacturing method according to claim 2 or 3, wherein the copper-based dilute alloy has a solute element concentration of 1 atomic % or less. (5) The manufacturing method according to claim 1, comprising:
The barrier layer is made of a composite of a copper-based diluted alloy and pure copper. (6) The manufacturing method according to claim 5, comprising:
The thickness of the barrier layer is 0.05 to 1 μm. (7) The manufacturing method according to claim 5 or 6, wherein the copper-based dilute alloy has a solute element concentration of 1.
Atomic % or less. (8) The manufacturing method according to any one of claims 5 to 7, wherein the composite comprises 80% or more of the copper-based dilute alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59089513A JPS60235308A (en) | 1984-05-07 | 1984-05-07 | Method of producing compound superconductive wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59089513A JPS60235308A (en) | 1984-05-07 | 1984-05-07 | Method of producing compound superconductive wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60235308A true JPS60235308A (en) | 1985-11-22 |
| JPH0464124B2 JPH0464124B2 (en) | 1992-10-14 |
Family
ID=13972862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59089513A Granted JPS60235308A (en) | 1984-05-07 | 1984-05-07 | Method of producing compound superconductive wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60235308A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62177809A (en) * | 1986-01-31 | 1987-08-04 | 古河電気工業株式会社 | Compound superconductor wire |
| JPH0317247A (en) * | 1989-03-31 | 1991-01-25 | General Electric Co <Ge> | Niobium-tin wire stable in length and annealing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5734607A (en) * | 1980-08-11 | 1982-02-25 | Yazaki Corp | Composition for semiconductor layer for power cable |
| JPS609012A (en) * | 1983-06-27 | 1985-01-18 | 日立電線株式会社 | Method of producing extrafine multicore compound superconductive conductor |
-
1984
- 1984-05-07 JP JP59089513A patent/JPS60235308A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5734607A (en) * | 1980-08-11 | 1982-02-25 | Yazaki Corp | Composition for semiconductor layer for power cable |
| JPS609012A (en) * | 1983-06-27 | 1985-01-18 | 日立電線株式会社 | Method of producing extrafine multicore compound superconductive conductor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62177809A (en) * | 1986-01-31 | 1987-08-04 | 古河電気工業株式会社 | Compound superconductor wire |
| JPH0317247A (en) * | 1989-03-31 | 1991-01-25 | General Electric Co <Ge> | Niobium-tin wire stable in length and annealing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0464124B2 (en) | 1992-10-14 |
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