JPH1050150A - Compound type superconductive wire and production thereof - Google Patents
Compound type superconductive wire and production thereofInfo
- Publication number
- JPH1050150A JPH1050150A JP9122804A JP12280497A JPH1050150A JP H1050150 A JPH1050150 A JP H1050150A JP 9122804 A JP9122804 A JP 9122804A JP 12280497 A JP12280497 A JP 12280497A JP H1050150 A JPH1050150 A JP H1050150A
- Authority
- JP
- Japan
- Prior art keywords
- superconducting wire
- oxide superconductor
- sheath material
- compound superconducting
- metal sheath
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、化合物超伝導線に
係り、特に酸化物超伝導体を用いた化合物超伝導線の製
造方法及び酸化物超伝導体を用いた場合に好適な化合物
超伝導線の構造に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound superconducting wire, and more particularly to a method for producing a compound superconducting wire using an oxide superconductor and a compound superconducting wire suitable for using an oxide superconductor. Regarding the structure of the line.
【０００２】[0002]
【従来の技術】化合物超伝導体としては金属系のＡ１５
型、Ｂ１型、シェブレル型、ラーベス型、また酸化物セ
ラミック系のペロブスカイト型、層状ペロブスカイト型
等の結晶構造に属するものが知られている。これらの中
でもＬａ−Ｂａ−Ｃｕ−Ｏ系に代表される層状ペロブス
カイト型等の酸化物超伝導体では臨界温度が３０Ｋ以
上、またＹ−Ｂａ−Ｃｕ−Ｏ系のようなペロブスカイ
ト，層状ペロブスカイト等の多相からなる酸化物超伝導
体では臨界温度９０Ｋを超えるものが得られるため非常
に有望な材料である。しかしながらこれらの酸化物超伝
導体は従来、焼結によるペレット状のものしかできなか
った。また超電導マグネット等の応用を考慮した場合は
超伝導体の線材化が必要である。2. Description of the Related Art As a compound superconductor, a metallic A15 is used.
A type belonging to a crystal structure such as a type, a B1 type, a Chevrel type, a Laves type, or an oxide ceramic type perovskite type or a layered perovskite type is known. Among these, a layered perovskite-type oxide superconductor represented by La-Ba-Cu-O system has a critical temperature of 30K or more, and a perovskite such as Y-Ba-Cu-O system, layered perovskite, etc. An oxide superconductor composed of multiple phases is a very promising material because a material having a critical temperature exceeding 90 K can be obtained. However, these oxide superconductors have heretofore been produced only in the form of pellets obtained by sintering. In addition, when the application of a superconducting magnet or the like is considered, it is necessary to use a superconductor as a wire.
【０００３】[0003]
【発明が解決しようとする課題】このように酸化物超伝
導体は非常に有望な材料であるが、線材への加工ができ
なかったために超電導マグネット等への応用が困難であ
った。As described above, the oxide superconductor is a very promising material, but it has been difficult to apply it to a superconducting magnet or the like because it cannot be processed into a wire.
【０００４】そこで本発明は、線材等への加工が容易な
酸化物超伝導体を用いて化合物超伝導線を提供すること
を目的とする。Accordingly, an object of the present invention is to provide a compound superconducting wire using an oxide superconductor that can be easily processed into a wire or the like.
【０００５】[0005]
【課題を解決するための手段】第１の発明の化合物超伝
導線の製造方法にあっては、酸化物超伝導体を形成する
ための原料を金属シース材内部に充填した部材を作成す
る第１の工程と、前記部材に酸素含有雰囲気中で加熱処
理を施し、前記金属シース材内部に酸化物超伝導体を生
成する第２の工程とを具備したことを特徴としている。According to a first aspect of the present invention, there is provided a method for manufacturing a compound superconducting wire, comprising forming a member in which a raw material for forming an oxide superconductor is filled in a metal sheath material. And a second step of subjecting the member to a heat treatment in an oxygen-containing atmosphere to produce an oxide superconductor inside the metal sheath material.
【０００６】第２の発明の化合物超伝導線にあっては、
酸化物超伝導体を形成するための原料を金属シース材内
部に充填した部材を作成する第１の工程と、前記部材に
酸素含有雰囲気中で加熱処理を施し、前記金属シース材
内部に酸化物超伝導体を生成する第２の工程とによって
製造されたことを特徴としている。In the compound superconducting wire of the second invention,
A first step of preparing a member in which a raw material for forming an oxide superconductor is filled in a metal sheath material; and performing a heat treatment on the member in an oxygen-containing atmosphere to form an oxide in the metal sheath material. And a second step of producing a superconductor.
【０００７】各工程について第１図を用いて詳細に説明
する。第１図は各工程を示す線材の断面図である。Each step will be described in detail with reference to FIG. FIG. 1 is a cross-sectional view of a wire showing respective steps.
【０００８】第１の工程で用いる原料としては第３の工
程で、例えばＬａ−Ｓｒ−Ｃｕ−Ｏ，Ｌａ−Ｂａ−Ｃｕ
−Ｏ系に代表される層状ペロブスカイト型（Ｌａ
1-x Ｍ）2ＣｕＯ4 （Ｍ；Ｂａ，Ｓｒ，Ｃａ）の他、
Ｙ−Ｂａ−Ｃｕ−Ｏ系，Ｓｃ−Ｂａ−Ｃｕ−Ｏ系等の連
続した酸化物超伝導体が形成できればどのようなもので
も良い。例えば、Ｌａ、Ｙ，Ｓｃ、Ｍ、Ｃｕ単体若しく
は酸化物、さらには加熱により酸化物に転じる炭酸塩、
硝酸塩、水酸化物等を用い、これらを化学量論比に合う
ように混合したものを原料として用いることができる。
またこの混合物を仮焼し粉砕したものを原料として用い
ても良い。The raw materials used in the first step are, for example, La-Sr-Cu-O, La-Ba-Cu
-O-based layered perovskite type (La
1-x M) 2 CuO 4 (M; Ba, Sr, Ca)
Any material may be used as long as a continuous oxide superconductor such as Y-Ba-Cu-O or Sc-Ba-Cu-O can be formed. For example, La, Y, Sc, M, Cu alone or an oxide, further, a carbonate which is converted into an oxide by heating,
Nitrate, hydroxide, or the like may be used, and a mixture of these in a stoichiometric ratio may be used as a raw material.
A mixture obtained by calcining and pulverizing this mixture may be used as a raw material.
【０００９】この原料をシース材内部に埋め込む（第１
図）（ａ））。シース材としては、電気抵抗が低く、熱
伝導性に優れたものが好適であり、例えば銅、銀、金及
びこれらを主体とした合金があげられる。このシース材
は超伝導線を形成した場合の安定化材となる。また埋め
込む原料形態であるが、粉体でもよいし線状でも良い。
例えばＬａ，Ｂａ，Ｃｕの夫々の金属線を同時に埋め込
むこともできる。This raw material is embedded in the sheath material (first
Figure) (a)). As the sheath material, a material having low electric resistance and excellent heat conductivity is preferable, and examples thereof include copper, silver, gold, and alloys mainly containing these. This sheath material becomes a stabilizing material when a superconducting wire is formed. In addition, the form of the raw material to be embedded may be a powder or a linear form.
For example, respective metal lines of La, Ba, and Cu can be simultaneously buried.
【００１０】次に第２の工程である。この工程では第１
の工程で所望の加工が施された部材に酸素含有雰囲気中
で加熱処理を施し、シース材内部に充填された原料を連
続した化合物超伝導体とする（第１図（ｃ））。この加
熱処理温度は酸化物超伝導体が形成できるように適宜設
定できるが、シース材の融点が実質的な上限温度とな
る。また下限は特に設定しないが、酸化物超伝導体を形
成するためには、実用上５００℃以上が必要である。Next is a second step. In this step, the first
The member which has been subjected to the desired processing in the step is subjected to a heat treatment in an oxygen-containing atmosphere, and the raw material filled in the sheath material is made into a continuous compound superconductor (FIG. 1 (c)). This heat treatment temperature can be appropriately set so that an oxide superconductor can be formed, but the melting point of the sheath material becomes a substantial upper limit temperature. Although the lower limit is not particularly set, a temperature of 500 ° C. or higher is practically required to form an oxide superconductor.
【００１１】以上安定化材となるシース材内部に一つの
超伝導体を含む単芯線について説明したが、シース材内
部に複数の穴を設けて夫々に原料を埋め込んでも良い
し、単芯線を更に複数本束ねて再度安定化材に組み込ん
で多芯線を構成しても良い。Although the single core wire including one superconductor in the sheath material serving as the stabilizing material has been described above, a plurality of holes may be provided in the sheath material and the raw material may be embedded in each of the holes. A multi-core wire may be configured by bundling a plurality of them and reassembling them into the stabilizing material.
【００１２】なお、第２の工程を行う前に、第１の工程
で得られた部材に、押し出し、スェージング、線引き等
の手法で減面加工を施し、所望の線径の線材を得る（第
１図（ｂ））ように、この減面加工された部材に熱処理
を施すようにしても良い。なお、超伝導線の形態として
は断面円形に限らず、リボン状等種々の形態が考えられ
る。Before performing the second step, the member obtained in the first step is subjected to surface reduction processing by a method such as extrusion, swaging, or drawing to obtain a wire having a desired wire diameter. As shown in FIG. 1 (b), a heat treatment may be applied to the member whose surface has been reduced. The form of the superconducting wire is not limited to a circular cross section, but various forms such as a ribbon shape can be considered.
【００１３】さて第２の工程の加熱処理による酸化物超
伝導体の生成であるが、シース材と原料との間に構成元
素、例えばＣｕ，Ｏ等、の拡散が生じると所定の化学量
論比からのズレが生じてしまい、超伝導特性を劣化させ
てしまう恐れがある。また、安定化材としての役割を果
たすシース材にしても原料側からの酸素等の拡散が顕著
となると、電気抵抗の上昇、熱伝導性の低下等の問題が
生じる。従ってこのような問題が生じる恐れがある場合
は、シース材と原料の間に拡散を防止するバリヤ材を介
在させることにより、この拡散による悪影響を防止する
ことができる。In the second step, the oxide superconductor is generated by the heat treatment. When the diffusion of constituent elements, for example, Cu and O, occurs between the sheath material and the raw material, a predetermined stoichiometry is obtained. A deviation from the ratio may occur, and the superconductivity may be degraded. Further, even if the diffusion of oxygen or the like from the raw material side becomes remarkable even in the case of the sheath material serving as a stabilizing material, problems such as an increase in electric resistance and a decrease in thermal conductivity occur. Therefore, when there is a possibility that such a problem may occur, a barrier material for preventing diffusion can be interposed between the sheath material and the raw material, so that adverse effects due to the diffusion can be prevented.
【００１４】このバリヤ材としては例えばステンレス、
銀、金、白金等があげられる。特にシース材として銅ま
たは銅合金を用いた場合、Ｌａ−Ｂａ−Ｃｕ−Ｏ系等の
銅含有酸化物超伝導体の酸素、銅の拡散による超伝導体
側の化学量論比からのズレ、及びシース材中への酸素の
拡散による熱伝導率の低下を防止する効果が顕著であ
る。As the barrier material, for example, stainless steel,
Silver, gold, platinum and the like. In particular, when copper or a copper alloy is used as the sheath material, oxygen of a copper-containing oxide superconductor such as a La-Ba-Cu-O system, deviation from the stoichiometric ratio of the superconductor due to diffusion of copper, and The effect of preventing a decrease in thermal conductivity due to diffusion of oxygen into the sheath material is remarkable.
【００１５】この様なバリヤ材を用いる場合は、第１の
工程で原料をバリヤ材で囲む。又は、シース材の内面を
バリヤ材で構成するなどの手法を取れば良い。この様子
を第２図に示す。When such a barrier material is used, the raw material is surrounded by the barrier material in the first step. Alternatively, a method of forming the inner surface of the sheath material with a barrier material may be employed. This is shown in FIG.
【００１６】また原料の調合具合、加熱処理条件等によ
っては酸化物超伝導体が所定の超伝導特性を発揮するの
に必要な化学量論比から、酸素が不足した形となる場合
がある。この様な場合は原料に十分な酸素を供給できる
ように、シース材の一部を線材の長手方向に沿って削除
し、原料が加熱処理時に外部の酸化性雰囲気と接触でき
るようにすることが好ましい（第３図（ａ））。また前
述の如くバリヤ材を設けた場合は、このバリヤ材の一部
も除去して加熱処理を行なう（第３図（ｂ））。Further, depending on the degree of preparation of the raw materials, the conditions of the heat treatment, etc., the oxide superconductor may have a form in which oxygen is insufficient due to the stoichiometric ratio necessary for the oxide superconductor to exhibit predetermined superconducting characteristics. In such a case, in order to supply sufficient oxygen to the raw material, a part of the sheath material is removed along the longitudinal direction of the wire so that the raw material can be brought into contact with an external oxidizing atmosphere during the heat treatment. Preferred (FIG. 3 (a)). When a barrier material is provided as described above, a part of the barrier material is also removed and heat treatment is performed (FIG. 3 (b)).
【００１７】なおシース材としてＡｇ又はＡｇ合金を用
いた場合は、Ａｇが酸素を拡散し易く、かつＡｇ自体は
酸化しにくいため、加熱処理時に外部から原料に十分な
酸素を供給できるため上述のような問題が生じにくい。
このようにＡｇシースを用いた場合は、酸素雰囲気、大
気中等の酸化性雰囲気中、５００〜９４０℃程度で前記
加熱処理を行なうことが好ましい。あまり加熱処理温度
が低いと酸素の拡散が遅く、あまり高温の加熱処理では
素材が変形し易くなる。When Ag or an Ag alloy is used as the sheath material, since Ag easily diffuses oxygen and Ag itself is hardly oxidized, sufficient oxygen can be supplied to the raw material from the outside during the heat treatment. Such problems are unlikely to occur.
When the Ag sheath is used, the heat treatment is preferably performed at about 500 to 940 ° C. in an oxidizing atmosphere such as an oxygen atmosphere or the air. If the heat treatment temperature is too low, diffusion of oxygen is slow, and if the heat treatment is too high, the material is easily deformed.
【００１８】[0018]
【発明の実施の形態】以下に本発明の実施例を説明す
る。Embodiments of the present invention will be described below.
【００１９】実施の形態−１ Ｌａ2 Ｏ3 ，ＳｒＯ，ＣｕＯをＣｕＯ１モルに対してＬ
ａ2 Ｏ3 0.9モル、ＳｒＯ 0.2モルの割合でボールミル
を用いて混合した。この混合物を９００℃で仮焼した
後、再度粉砕・混合を行ない、化合物超伝導体の原料と
しての粉末を得た。この原料を銅製の管状のシース材の
内部に酸素ガス含有雰囲気中で詰め込む。その後シース
材の両端開口部を閉塞し、一体化する。この一体化され
た部材を断面減少比が約１００以上になるまで、押し出
し、スェージング，線引き等の減面加工を施して細線化
した後、９００℃、１５Ｈの加熱処理を施す。Embodiment 1 La 2 O 3 , SrO, and CuO were added to L per mole of CuO.
0.9 mol of a 2 O 3 and 0.2 mol of SrO were mixed using a ball mill. After calcining this mixture at 900 ° C., it was pulverized and mixed again to obtain a powder as a raw material of the compound superconductor. This raw material is packed inside a tubular sheath material made of copper in an atmosphere containing oxygen gas. Thereafter, both ends of the sheath material are closed and integrated. The integrated member is extruded until the cross-section reduction ratio becomes about 100 or more, subjected to surface reduction processing such as swaging and drawing, and then thinned, and then subjected to a heat treatment at 900 ° C. and 15H.
【００２０】この加熱処理によりシース材内部の原料が
反応して（Ｌａ0.9 Ｓｒ0.1 ）2ＣｕＯ4 の組成式で表
される層状ペロブスカイト型の酸化物超伝導体の連続体
が生成し、化合物超伝導線を得ることができる。この化
合物超伝導線を用いて超伝導特性を調べたところ、臨界
温度は３５Ｋ、臨界電流は１０Ａと良好な特性を示し
た。なお、銅製シース材の代わりにＣｕ−Ｎ１合金製シ
ース材を用いても同様の結果を得た。As a result of this heat treatment, the raw material inside the sheath material reacts to form a continuum of a layered perovskite-type oxide superconductor represented by a composition formula of (La 0.9 Sr 0.1 ) 2 CuO 4 , A conductive wire can be obtained. When the superconducting characteristics were examined using this compound superconducting wire, the critical temperature was 35 K and the critical current was 10 A, showing good characteristics. Similar results were obtained when a Cu-N1 alloy sheath material was used instead of the copper sheath material.
【００２１】実施の形態−２ Ｌａ2 Ｏ3 ，ＢａＯ，ＣｕＯを用い実施の形態−１と同
様に（Ｌａ0.925 Ｂａ0.075 ）2 ＣｕＯ4 の組成式で表
される層状ペロブスカイト型の酸化物超伝導体の化合物
超伝導線を得た。Embodiment 2 A layered perovskite-type oxide superconductor represented by a composition formula of (La 0.925 Ba 0.075 ) 2 CuO 4 in the same manner as in Embodiment 1 using La 2 O 3 , BaO, and CuO. A solid compound superconducting wire was obtained.
【００２２】臨界温度は３１Ｋ、臨界電流は８Ａと良好
な特性を示した。The critical temperature was 31 K and the critical current was 8 A, showing good characteristics.
【００２３】実施の形態−３ Ｌａ2 Ｏ3 ，ＣａＯ，ＣｕＯを用い実施の形態−１と同
様に（Ｌａ0.9 Ｃａ0.1 ）2 ＣｕＯ4 の組成式で表され
る層状ペロブスカイト型の酸化物超伝導体の化合物超伝
導線を得た。Embodiment 3 A layered perovskite-type oxide superconductor represented by a composition formula of (La 0.9 Ca 0.1 ) 2 CuO 4 in the same manner as in Embodiment 1 using La 2 O 3 , CaO, and CuO. A solid compound superconducting wire was obtained.
【００２４】臨界温度は２９Ｋ、臨界電流は５Ａと良好
な特性を示した。The critical temperature was 29 K and the critical current was 5 A, showing good characteristics.
【００２５】実施の形態−４ Ｙ2 Ｏ3 ，ＣａＯ，ＣｕＯを用い実施の形態−１と同様
に（Ｙ0.7 Ｂａ0.3 ）2 ＣｕＯ4 の組成式で表される多
相の酸化物超伝導体の化合物超伝導線を得た。Embodiment 4 A multiphase oxide superconductor represented by a composition formula of (Y 0.7 Ba 0.3 ) 2 CuO 4 similarly to Embodiment 1, using Y 2 O 3 , CaO, and CuO. Was obtained.
【００２６】臨界温度は９０Ｋ、臨界電流は１０Ａと良
好な特性を示した。The critical temperature was 90 K and the critical current was 10 A, showing good characteristics.
【００２７】なおＹをＳｃに代えてもほぼ同様の結果を
得た。It should be noted that substantially the same results were obtained when Y was replaced with Sc.
【００２８】実施の形態−５ 実施の形態−１〜４の加熱処理前の部材にシース材の一
部を長手方向にＨＮＯ3 で除去した後（第３図）、各実
施例と同様の加熱処理を施したところ、各実施の形態の
臨界温度は約５Ｋ上昇し、臨界電流は約倍増した。Embodiment-5 After removing a part of the sheath material with HNO 3 in the longitudinal direction of the member before the heat treatment in Embodiments 1 to 4 (FIG. 3), the same heating as in each embodiment is performed. As a result of the treatment, the critical temperature of each embodiment increased by about 5K, and the critical current increased about twice.
【００２９】実施の形態−６ Ａｇ製のシース材に、Ｌａ，Ｓｒ，Ｃｕを（Ｌａ0.9 Ｓ
ｒ0.1 ）2 ＣｕＯ4 の組成式で表される層状ペロブスカ
イト型の酸化物超伝導体となるよう比率で混合した原料
を充填して、シース材の量端を閉塞した。その後、減面
加工により細線化した後、７００℃大気中７日間の酸化
熱処理を行った結果（Ｌａ0.9 Ｓｒ0.1）2 ＣｕＯ4 の
組成式で表される層状ペロブスカイト型の酸化物超伝導
体の連続体がシース材の内部に生成された。Embodiment 6 La, Sr, and Cu were added to a sheath material made of Ag (La 0.9 S
Raw materials mixed at a ratio so as to become a layered perovskite-type oxide superconductor represented by a composition formula of r 0.1 ) 2 CuO 4 were filled, and the end of the sheath material was closed. Then, after thinning by surface reduction processing, the resultant was subjected to an oxidizing heat treatment in the atmosphere at 700 ° C. for 7 days. As a result, a lamellar perovskite-type oxide superconductor represented by a composition formula of (La 0.9 Sr 0.1 ) 2 CuO 4 was obtained. A continuum was created inside the sheath material.
【００３０】臨界温度は３５Ｋ、臨界電流は１０Ａと良
好な特性を示した。The critical temperature was 35 K and the critical current was 10 A, showing good characteristics.
【００３１】実施の形態−７ 実施の形態−６におけるＳｒの代わりにＢａを用いて同
様に超伝導線を製造した。Embodiment-7 A superconducting wire was similarly manufactured by using Ba instead of Sr in the embodiment-6.
【００３２】臨界温度は２９Ｋ、臨界電流は５Ａと良好
な特性を示した。The critical temperature was 29 K and the critical current was 5 A, showing good characteristics.
【００３３】実施の形態−８ 実施の形態−６におけるＳｒの代わりにＣａを用いて同
様に超伝導線を製造した。Embodiment-8 A superconducting wire was similarly manufactured using Ca instead of Sr in the embodiment-6.
【００３４】臨界温度は２９Ｋ、臨界電流は５Ａと良好
な特性を示した。The critical temperature was 29 K and the critical current was 5 A, showing good characteristics.
【００３５】実施の形態−９ 実施の形態−６のＬａ，Ｓｒ，Ｃｕの代わりにＹ，Ｂ
ａ，Ｃｕを用いて（Ｙ0.4 Ｂａ0.6 ）ＣｕＯ3 の比率と
なるように混合し、同様に超伝導線を製造した。Embodiment-9 Instead of La, Sr, and Cu in Embodiment-6, Y, B
a and Cu were mixed at a ratio of (Y 0.4 Ba 0.6 ) CuO 3 to produce a superconducting wire in the same manner.
【００３６】臨界温度は９６Ｋ、臨界電流は１０Ａと良
好な特性を示した。The critical temperature was 96 K and the critical current was 10 A, showing good characteristics.
【００３７】実施の形態−１０ 実施の形態−６のＬａ，Ｓｒ，Ｃｕの代わりに（Ｙ0.9
Ｂａ0.1 ）ＣｕＯ3 の比率となるようにＹ2 Ｏ3 ，Ｂａ
Ｏ，ＣｕＯを用い混合し、同様に超伝導線を製造した。Embodiment 10 Instead of La, Sr, and Cu of Embodiment 6, (Y 0.9
Ba 0.1) such that the ratio of CuO 3 Y 2 O 3, Ba
O and CuO were mixed and a superconducting wire was similarly manufactured.
【００３８】臨界温度は８０Ｋ、臨界電流は１２Ａと良
好な特性を示した。The critical temperature was 80 K and the critical current was 12 A, showing good characteristics.
【００３９】実施の形態−１１ Ｌａ2 Ｏ3 ，ＳｒＯ，ＣｕＯをＣｕＯ１モルに対してＬ
ａ2 Ｏ3 0.92 モル、ＳｒＯ 0.2モルの割合でボールミ
ルを用いて混合した。この混合物を９００℃、２Ｈの条
件で仮焼した後、再度粉砕・混合を行ない、化合物超伝
導体の原料としての粉末を得た。この原料を銀製のシー
ト（バリヤ材）で棒状に包み込んだ。このバリヤ材で包
まれた複合体を直径１０ｍｍ，内径８ｍｍの銅製の管状
のシース材の内部に挿入した。その後シース材の両端開
口部を閉塞し、一体化した。次いでこの一体化された部
材を断面減少比が約１００以上になるまで、押し出し、
スェージング、線引き等の減面加工を施して直径１ｍｍ
の線材を得た。その後、真空中９００℃，１５Ｈの加熱
処理を施す。この加熱処理によりシース材内部に（Ｌａ
0.9 Ｓｒ0.1 ）2 ＣｕＯ4 の組成式で表される層状ペロ
ブスカイト型の酸化物超伝導体の連続体が生成している
ことがＸ線回析で確認された。Embodiment 11 La 2 O 3 , SrO, and CuO were mixed with L per mole of CuO.
a 2 O 3 0.92 mole, were mixed using a ball mill at a ratio of SrO 0.2 mol. This mixture was calcined under the conditions of 900 ° C. and 2H, and then pulverized and mixed again to obtain a powder as a raw material of the compound superconductor. This raw material was wrapped in a bar shape with a silver sheet (barrier material). The composite wrapped with the barrier material was inserted into a copper tubular sheath material having a diameter of 10 mm and an inner diameter of 8 mm. Thereafter, both ends of the sheath material were closed and integrated. Next, extrude the integrated member until the cross-sectional reduction ratio becomes about 100 or more,
1mm in diameter with surface reduction such as swaging and wire drawing
Was obtained. Thereafter, a heat treatment is performed in a vacuum at 900 ° C. for 15 hours. By this heat treatment, (La)
X-ray diffraction confirmed that a continuum of a layered perovskite-type oxide superconductor represented by a composition formula of 0.9 Sr 0.1 ) 2 CuO 4 was formed.
【００４０】このようにして製造された超伝導線を用い
て実測した結果、臨界温度４０Ｋ、臨界電流１０Ａの良
好な超伝導特性を示すことが確認された。また安定化材
であるシース材の銅の熱伝導率を見るために、ＲＲＲ
（室温抵抗を臨界温度直上の抵抗で割った値：ＲＲＲが
大きいほど熱伝導率大）を測定したところ、約５０であ
った。この値は従来一般に使用されているＮｂ3 Ｓｎ超
伝導線のＲＲＲに比べても充分大きな値であり、本実施
例の方法により安定化材としての銅が原料の酸素により
汚染（酸化）されていないことが明らかとなった。As a result of actual measurement using the superconducting wire thus manufactured, it was confirmed that the superconducting wire exhibited good superconducting characteristics at a critical temperature of 40K and a critical current of 10A. In order to check the thermal conductivity of copper of the sheath material, which is a stabilizing material, RRR was used.
The value (the value obtained by dividing the room temperature resistance by the resistance immediately above the critical temperature: the larger the RRR, the higher the thermal conductivity) was measured and found to be about 50. This value is sufficiently larger than the RRR of a conventionally used Nb 3 Sn superconducting wire, and copper as a stabilizer is contaminated (oxidized) by oxygen as a raw material according to the method of this embodiment. It became clear that there was none.
【００４１】従ってこの様な方法によって得られた超伝
導線は良好な超伝導特性を有し、かつ、安定化材の熱伝
導率も高いため、超電導マグネットへ応用した場合に有
効である。Accordingly, the superconducting wire obtained by such a method has good superconducting properties and the thermal conductivity of the stabilizing material is high, so that it is effective when applied to a superconducting magnet.
【００４２】実施の形態−１２ Ｌａ2 Ｏ3 ，ＢａＯ，ＣｕＯを用い実施の形態−１１と
同様に（Ｌａ0.925 Ｃａ0.75）2 ＣｕＯ4 の組成式で表
される層状ペロブスカイト型の酸化物超伝導体の化合物
超伝導線を得た。Embodiment 12 A layered perovskite-type oxide superconductor represented by a composition formula of (La 0.925 Ca 0.75 ) 2 CuO 4 in the same manner as in Embodiment 11 using La 2 O 3 , BaO, and CuO. A solid compound superconducting wire was obtained.
【００４３】臨界温度は３５Ｋ、臨界電流は８Ａと良好
な特性を示した。The critical temperature was 35 K and the critical current was 8 A, showing good characteristics.
【００４４】実施の形態−１３ Ｌａ2 Ｏ3 ，ＣａＯ，ＣｕＯを用い実施の形態−１１と
同様に（Ｌａ0.9 Ｃａ0.1 ）2 ＣｕＯ4 の組成式で表さ
れる層状ペロブスカイト型の酸化物超伝導体の化合物超
伝導線を得た。Embodiment 13 A layered perovskite-type oxide superconductivity represented by a composition formula of (La 0.9 Ca 0.1 ) 2 CuO 4 in the same manner as in Embodiment 11 using La 2 O 3 , CaO and CuO. A solid compound superconducting wire was obtained.
【００４５】臨界温度は１８Ｋ、臨界電流は３Ａと良好
な特性を示した。The critical temperature was 18 K and the critical current was 3 A, showing good characteristics.
【００４６】実施の形態−１４ Ｙ2 Ｏ3 ，ＢａＯ，ＣｕＯを用い実施の形態−１１と同
様にＹ0.4 Ｂａ0.6 ＣｕＯ3 の組成比の酸化物超伝導体
の化合物超伝導線を得た。Embodiment 14 A compound superconducting wire of an oxide superconductor having a composition ratio of Y 0.4 Ba 0.6 CuO 3 was obtained in the same manner as in Embodiment 11 using Y 2 O 3 , BaO and CuO.
【００４７】臨界温度は９６Ｋ、臨界電流は１０Ａと良
好な特性を示した。The critical temperature was 96 K, and the critical current was 10 A, showing good characteristics.
【００４８】[0048]
【発明の効果】以上説明したように本発明によれば、臨
界温度が高い層状ペロブスカイト型等の酸化物超伝導体
を用いた化合物超伝導線を安定して得ることができ、超
電導マグネット等への応用に寄与するところ大である。As described above, according to the present invention, a compound superconducting wire using a layered perovskite type oxide superconductor having a high critical temperature can be stably obtained, and a superconducting magnet or the like can be obtained. It greatly contributes to the application of.
【図１】第１図は、本発明超伝導線の断面図。FIG. 1 is a sectional view of a superconducting wire of the present invention.
【図２】第２図は、本発明超伝導線の断面図。FIG. 2 is a cross-sectional view of the superconducting wire of the present invention.
【図３】第３図は、本発明超伝導線の断面図。FIG. 3 is a sectional view of the superconducting wire of the present invention.
１……超伝導体 ２……原料 ３……シース材 ４……バリヤ材 1 ... superconductor 2 ... raw material 3 ... sheath material 4 ... barrier material
Claims (15)
属シース材内部に充填した部材を作成する第１の工程
と、 前記部材に酸素含有雰囲気中で加熱処理を施し、前記金
属シース材内部に酸化物超伝導体を生成する第２の工程
とを具備したことを特徴とする化合物超伝導線の製造方
法。A first step of forming a member in which a raw material for forming an oxide superconductor is filled in a metal sheath material; and a step of subjecting the member to heat treatment in an oxygen-containing atmosphere. A second step of forming an oxide superconductor inside the material.
することを特徴とする請求項１記載の化合物超伝導線の
製造方法。2. The method of manufacturing a compound superconducting wire according to claim 1, wherein the surface of said member is reduced before said second step.
の少なくとも一種と、Ｂａ、Ｓｒ及びＣａの少なくとも
一種と、Ｃｕ及びＯとを構成元素とすることを特徴とす
る請求項１記載の化合物超伝導線の製造方法。3. The oxide superconductor comprises La, Y and Sc.
2. The method for producing a compound superconducting wire according to claim 1, wherein at least one of Ba, Sr and Ca, and Cu and O are constituent elements.
ト型の結晶構造を有することを特徴とする請求項１記載
の化合物超伝導線の製造方法。4. The method according to claim 1, wherein the oxide superconductor has a layered perovskite crystal structure.
はこれらの少なくともいずれか一種を主成分とする合金
から構成されることを特徴とする請求項１記載の化合物
超伝導線の製造方法。5. The method for manufacturing a compound superconducting wire according to claim 1, wherein said metal sheath material is made of silver or gold, or an alloy mainly containing at least one of them.
上でかつ前記金属シース材の融点未満の温度で行うこと
を特徴とする請求項１記載の化合物超伝導線の製造方
法。6. The method for producing a compound superconducting wire according to claim 1, wherein the heat treatment in the second step is performed at a temperature of 500 ° C. or higher and lower than the melting point of the metal sheath material.
分とした合金を用い、前記第２の工程の加熱処理は、５
００℃乃至９００℃の温度範囲で行うことを特徴とする
請求項１記載の化合物超伝導線の製造方法。7. The heat treatment in the second step is performed by using silver or an alloy containing silver as a main component as the metal sheath material.
The method for producing a compound superconducting wire according to claim 1, wherein the method is carried out at a temperature in the range of 00 to 900 ° C.
シース材の一部を除去することを特徴とする請求項１記
載の化合物超伝導線の製造方法。8. The method for producing a compound superconducting wire according to claim 1, wherein a part of said metal sheath material is removed before said heat treatment in said second step.
以上となるように行うことを特徴とする請求項２記載の
化合物超伝導線の製造方法。9. The reduction in surface area has a reduction ratio of approximately 100%.
The method for producing a compound superconducting wire according to claim 2, wherein the method is performed as described above.
前記金属シース材との間に酸素拡散防止のためのバリヤ
材を介在せしめることを特徴とする請求項１記載の化合
物超伝導線の製造方法。10. The compound superconductor according to claim 1, wherein a barrier material for preventing oxygen diffusion is interposed between said raw material and said metal sheath material when said first step is performed. Wire manufacturing method.
金属シース材内部に充填した部材を作成する第１の工程
と、前記部材に酸素含有雰囲気中で加熱処理を施し、前
記金属シース材内部に酸化物超伝導体を生成する第２の
工程とにより製造されたことを特徴とする化合物超伝導
線。11. A first step of forming a member in which a raw material for forming an oxide superconductor is filled in a metal sheath material, and heating the member in an oxygen-containing atmosphere to form the metal sheath material. A compound superconducting wire manufactured by the second step of forming an oxide superconductor inside the material.
ｃの少なくとも一種と、Ｂａ、Ｓｒ及びＣａの少なくと
も一種と、Ｃｕ及びＯとを構成元素とすることを特徴と
する請求項１１記載の化合物超伝導線。12. The oxide superconductor comprises La, Y and S
The compound superconducting wire according to claim 11, wherein at least one of c, at least one of Ba, Sr, and Ca, and Cu and O are constituent elements.
イト型の結晶構造を有することを特徴とする請求項１１
記載の化合物超伝導線。13. The oxide superconductor according to claim 11, wherein said oxide superconductor has a layered perovskite crystal structure.
The compound superconducting wire as described.
たはこれらの少なくともいずれか一種を主成分とする合
金から構成されることを特徴とする請求項１１記載の化
合物超伝導線。14. The compound superconducting wire according to claim 11, wherein said metal sheath material is made of silver or gold, or an alloy containing at least one of them as a main component.
との間に酸素拡散防止のためのバリヤ材を介在せしめる
ことを特徴とする請求項１１記載の化合物超伝導線。15. The compound superconducting wire according to claim 11, wherein a barrier material for preventing oxygen diffusion is interposed between said oxide superconductor and said metal sheath material.
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