JP3086237B2 - Manufacturing method of oxide superconducting wire - Google Patents
Manufacturing method of oxide superconducting wireInfo
- Publication number
- JP3086237B2 JP3086237B2 JP02216106A JP21610690A JP3086237B2 JP 3086237 B2 JP3086237 B2 JP 3086237B2 JP 02216106 A JP02216106 A JP 02216106A JP 21610690 A JP21610690 A JP 21610690A JP 3086237 B2 JP3086237 B2 JP 3086237B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconductor
- powder
- oxide
- wire
- superconducting wire
- 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.)
- Expired - Fee Related
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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、ピンニングセンター含有の酸化物超電導体
からなり、磁場下における臨界電流密度等の超電導特性
に優れる酸化物超電導線の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing an oxide superconducting wire comprising an oxide superconductor containing a pinning center and having excellent superconducting characteristics such as a critical current density under a magnetic field.
従来の技術及び課題 従来、固相反応方式で形成した酸化物超電導体の粉末
を銀チューブに充填したのち冷間加工して線やテープ等
の線材形態に成形し、その成形体を加熱処理して酸化物
超電導体の粉末を焼結させる酸化物超電導線の製造方法
が知られていた。Conventional technology and problems Conventionally, an oxide superconductor powder formed by a solid-phase reaction method is filled in a silver tube, and then cold-worked to form a wire or tape or the like, and the formed body is subjected to heat treatment. Thus, a method for producing an oxide superconducting wire in which oxide superconductor powder is sintered is known.
しかしながら、得られる酸化物超電導線が磁場下での
臨界電流密度に劣る問題点があった。However, there is a problem that the obtained oxide superconducting wire is inferior in critical current density under a magnetic field.
課題を解決するための手段 本発明者らは、前記問題点を克服すべく鋭意研究を重
ねた結果、ピンニングセンター含有の酸化物超電導体の
粉末を用いてこれを焼結する方法により、その超電導特
性を損なうことなく焼結処理できて前記の目的を達成で
きることを見出し、本発明をなすに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems, and as a result, have found that a method of sintering the oxide superconductor powder containing a pinning center to obtain a superconducting powder is used. The present inventors have found that the above objects can be achieved by sintering without impairing the characteristics, and the present invention has been accomplished.
すなわち本発明は、ピンニングセンターを含有する酸
化物超電導体の粉末を貴金属からなるチューブに充填し
て冷間加工し、それにより形成した線材を中間焼鈍なし
に前記の貴金属、ないし酸化物超電導体の融点未満の温
度で加熱処理して当該酸化物超電導体の粉末を焼結させ
ることを特徴とする酸化物超電導線の製造方法を提供す
るものである。That is, the present invention fills a tube made of a noble metal with a powder of an oxide superconductor containing a pinning center, cold-processes, and forms a wire formed thereby without the intermediate annealing of the noble metal or oxide superconductor. An object of the present invention is to provide a method for producing an oxide superconducting wire, which comprises sintering a powder of the oxide superconductor by heat treatment at a temperature lower than a melting point.
作用 ピンニングセンター含有の酸化物超電導体は、そのピ
ンニングセンターによる磁束のピン止め効果により高い
磁場下においても大きな臨界電流密度を示す。ピンニン
グセンターは酸化物超電導組成の超電導相中に、非酸化
物超電導組成の絶縁相を導入する方法などにより形成さ
れる。本発明では、かかるピンニングセンター含有の酸
化物超電導体の粉末を貴金属チューブを介した冷間加工
・焼結方式でその超電導特性を損なうことなくバルク化
して、酸化物超電導体からなる線材を形成するものであ
る。The oxide superconductor containing the pinning center exhibits a large critical current density even under a high magnetic field due to the pinning effect of the magnetic flux by the pinning center. The pinning center is formed by a method of introducing an insulating phase having a non-oxide superconducting composition into a superconducting phase having an oxide superconducting composition. In the present invention, such a pinning center-containing oxide superconductor powder is formed into a bulk by a cold working and sintering method using a noble metal tube without impairing its superconducting properties to form a wire made of an oxide superconductor. Things.
発明の構成要素の例示 本発明の製造方法においては先ず、第１図に例示の如
く、ピンニングセンターを含有する酸化物超電導体の粉
末１を貴金属からなるチューブ２に充填して冷間加工
（３）し、丸線やテープ状等の線材４を形成する。なお
図例では、ピンチロール３による冷間加工方式を示して
いる。Illustrative Elements of the Invention In the manufacturing method of the present invention, first, as shown in FIG. 1, a powder 1 of an oxide superconductor containing a pinning center is filled in a tube 2 made of a noble metal, and cold working (3) is performed. Then, a wire 4 such as a round wire or a tape is formed. In the example of the figure, a cold working method using the pinch roll 3 is shown.
ピンニングセンター含有の酸化物超電導体の粉末とし
ては適宜なものを用いてよい。例えば、YBa2 Cu3 OaやY
1-b Bab CuOcの如きＹ系酸化物超電導体、Ba1-d Kd BiO
3の如きBa系酸化物超電導体、Nd2-e Cee CuO4-fの如きN
d系酸化物超電導体、Bi2-g Pbg Sr2 Ca2 Cu3 OhやBi2 S
r2 Cai-1 Cui Ojの如きBi系酸化物超電導体、その他La
系酸化物超電導体、Tl系酸化物超電導体、Pb系酸化物超
電導体等、また前記のＹ等の成分を他の希土類元素で置
換したもの、ないしBa等の成分を他のアルカリ土類金属
で置換したもの、あるいはＯ成分をＦなどで置換したも
のなどの酸化物超電導体の粉末からなるもののいずれも
用いうる。粉末の粒径は、100μｍ以下、就中0.1〜10μ
ｍが適当であるが、これに限定されない。As the powder of the oxide superconductor containing the pinning center, an appropriate powder may be used. For example, YBa 2 Cu 3 O a or Y
Y-based oxide superconductor such as 1-b Ba b CuO c , Ba 1-d K d BiO
Ba-based oxide superconductor like 3 ; N like Nd 2-e Ce e CuO 4-f
d-based oxide superconductor, Bi 2-g Pb g Sr 2 Ca 2 Cu 3 O h or Bi 2 S
Bi-based oxide superconductors such as r 2 Ca i-1 Cu i O j and other La
-Based oxide superconductors, Tl-based oxide superconductors, Pb-based oxide superconductors, etc., wherein the above-mentioned component such as Y is replaced by another rare earth element, or the component such as Ba is replaced with another alkaline earth metal Or a powder of an oxide superconductor, such as a powder in which the O component is substituted with F or the like. The particle size of the powder is 100μm or less, especially 0.1-10μ
m is suitable, but not limited thereto.
ピンニングセンターを含有する酸化物超電導体の形成
は、溶融方式例えば、酸化物超電導体を部分溶融させた
のち方向凝固させるMTG法（Melt−Textured−Growth）
や、酸化物超電導組成の原料粉末を溶融させたのち急冷
し、ついで半溶融温度に加熱して部分溶融させたのち徐
冷するQMG法（Quench−and−Melt−Growth）、あるいは
酸化物超電導体形成用の原料粉末を適当な組成で仮焼
後、加熱溶融させて急冷し、形成された凝固物を粉砕後
その粉末を成形体として半溶融温度で部分溶融させて徐
冷するMPMG法（Melt−Powdering−Melt−Growth）など
により行うことができる。前記のMPMG法においては酸化
物超電導体の粉末とピンニングセンターとなる非酸化物
超電導体の粉末を混合し、これを仮焼してなるものに加
熱溶融以下の措置を施す方式などによってもピンニング
センター含有の酸化物超電導体を形成することができ
る。本発明では、後者の方式を含むMPMG法などにより形
成した、ピンニングセンターが超電導相中に微細な状態
で均質に分散しているものが好ましく用いうる。The oxide superconductor containing the pinning center is formed by a melting method, for example, an MTG method (Melt-Textured-Growth) in which the oxide superconductor is partially melted and then directionally solidified.
QMG method (Quench-and-Melt-Growth) in which the raw material powder of the oxide superconducting composition is melted, rapidly cooled, then partially melted by heating to a half-melting temperature, and then gradually cooled. The MPMG method (Melt) in which the raw material powder for forming is calcined with an appropriate composition, melted by heating and quenched, and the formed solidified product is pulverized, and then the powder is partially melted as a compact at a half-melting temperature and gradually cooled. -Powdering-Melt-Growth). In the above-mentioned MPMG method, the powder of the oxide superconductor and the powder of the non-oxide superconductor to be the pinning center are mixed, and the resulting mixture is calcined. Containing oxide superconductor can be formed. In the present invention, a material in which the pinning centers are finely and homogeneously dispersed in the superconducting phase and formed by the MPMG method including the latter method can be preferably used.
貴金属チューブとしては、銀、金、白金などからなる
もの、就中、銀チューブが用いられる。As the noble metal tube, a tube made of silver, gold, platinum or the like, particularly, a silver tube is used.
冷間加工には、例えばピンチロールによる圧延方式
や、ダイス孔を介した引き伸ばし方式など、適宜な方式
を採用してよい。その際、ピンニングセンター含有の酸
化物超電導体の粉末がバルク化しない程度の加熱は許容
される。For the cold working, an appropriate method such as a rolling method using a pinch roll or a stretching method through a die hole may be adopted. At this time, heating to such an extent that the powder of the oxide superconductor containing the pinning center does not become bulky is allowed.
本発明において冷間加工により形成した線材は次に、
中間焼鈍なしにチューブを形成する貴金属、ないしチュ
ーブ内に充填した酸化物超電導体の融点未満の温度に加
熱処理して、その酸化物超電導体の粉末を焼結させる。
これにより、酸化物超電導体の粉末がバルク化して一体
化し、酸化物超電導線が形成される。前記の加熱温度
は、チューブを形成する貴金属の融点、又はチューブ内
に充填した酸化物超電導体の融点のいずれか低い方に基
づいて決定される。なお、焼結に際しては、第２図に例
示の如く、線材４を例えばコイルなどの二次形態に予め
成形しておいてもよい。The wire formed by cold working in the present invention is then:
A heat treatment is performed at a temperature lower than the melting point of the noble metal forming the tube or the oxide superconductor filled in the tube without intermediate annealing to sinter the powder of the oxide superconductor.
As a result, the powder of the oxide superconductor is bulked and integrated to form an oxide superconducting wire. The heating temperature is determined based on the lower of the melting point of the noble metal forming the tube and the melting point of the oxide superconductor filled in the tube. At the time of sintering, as illustrated in FIG. 2, the wire 4 may be formed in advance into a secondary form such as a coil.
発明の効果 本発明によれば、ピンニングセンター含有の酸化物超
電導体の粉末を用いて、その超電導特性を損なうことな
く線材に加工でき、かつ貴金属層内に焼結一体化するこ
とができて、超電導特性、就中、磁場下における臨界電
流密度に優れる酸化物超電導体の線材を安定に、かつ効
率的に製造することができる。Effects of the Invention According to the present invention, using a powder of an oxide superconductor containing a pinning center, it can be processed into a wire without impairing its superconducting properties, and can be sintered and integrated into a noble metal layer, It is possible to stably and efficiently manufacture a wire of an oxide superconductor having excellent superconducting properties, particularly, a critical current density under a magnetic field.
実施例 YBa2 Cu3 Oxの粉末100部（重量部、以下同じ）とY2 B
aCuOyの粉末30部を混合し、これを仮焼後、その粉砕物
を1200〜1400℃に加熱して溶融させたのち銅製金型（常
温）にて急冷し、形成された凝固物を粉砕してその粉末
を1100℃で加熱処理したのち徐冷してピンニングセンタ
ー含有の酸化物超電導体からなるバルク体を得た。Example 100 parts (parts by weight, hereinafter the same) of YBa 2 Cu 3 O x powder and Y 2 B
After mixing 30 parts of aCuO y powder, calcining the mixture, heating and melting the pulverized material at 1200-1400 ° C., quenching in a copper mold (normal temperature), and pulverizing the formed coagulated material Then, the powder was heat-treated at 1100 ° C., and then gradually cooled to obtain a bulk body composed of an oxide superconductor containing a pinning center.
前記のバルク体を粉砕して得た粒径0.1〜10μｍの粉
末を肉厚0.2mm、直径5mmの銀チューブに充填し（充填体
の重さ:3〜4g/cm3）、その両端部を圧着して閉塞したの
ちピンチロールを介し冷間加工して圧延し、幅30mm、厚
さ0.8mm（被覆銀層の厚さ150μｍ）のテープ形態とし
た。A powder having a particle diameter of 0.1 to 10 μm obtained by pulverizing the bulk body is filled in a silver tube having a thickness of 0.2 mm and a diameter of 5 mm (weight of the filled body: 3 to 4 g / cm 3 ). After being closed by pressing, it was cold-worked and rolled through a pinch roll to form a tape having a width of 30 mm and a thickness of 0.8 mm (the thickness of the coated silver layer was 150 μm).
次に、前記のテープ状線材を870〜930℃で12時間焼結
したのち、500℃で酸素アニールして酸化物超電導線を
得た。Next, after sintering the tape-shaped wire at 870 to 930 ° C. for 12 hours, oxygen annealing was performed at 500 ° C. to obtain an oxide superconducting wire.
比較例 Y2 BaCuOyを含有しないYBa2 Cu3 Oxを用いてその粉末
（粒径0.1〜10μｍ）を銀チューブに充填し（充填体の
重さ:3〜4g/cm3）、それを実施例に準じてテープ形態と
し、焼結・酸素アニール処理して酸化物超電導線を得
た。Comparative Example The powder (particle diameter: 0.1 to 10 μm) was filled into a silver tube using YBa 2 Cu 3 O x containing no Y 2 BaCuO y (the weight of the filling: 3 to 4 g / cm 3 ), and A tape was formed according to the example, and sintering and oxygen annealing were performed to obtain an oxide superconducting wire.
評価試験 実施例、比較例で得た酸化物超電導線について下記の
超電導特性を調べた。Evaluation Test The oxide superconducting wires obtained in Examples and Comparative Examples were examined for the following superconducting properties.
［臨界温度］ 0.1A/cm2の電流密度下、液体ヘリウムで冷却しながら
４端子法により電気抵抗の温度による変化を測定し、電
圧端子間の発生電圧がＯとなる時の温度を調べた。[Critical temperature] Under a current density of 0.1 A / cm 2 , a change in electric resistance with temperature was measured by a four-terminal method while cooling with liquid helium, and the temperature when the generated voltage between the voltage terminals became O was determined. .
［臨界電流密度］ 種々の磁場の下で、パワーリードと共に液体窒素で冷
却しながら徐々に電流値をあげて４端子法により電圧端
子間の電圧の印加電流による変化を測定し、Ｘ−Ｙレコ
ーダーにおいて１μV/cmの電圧が出現したときの電流値
を測定し、それを酸化物超電導体の断面積で除して算出
した。[Critical current density] Under various magnetic fields, the current value is gradually increased while cooling with liquid nitrogen together with the power lead, and the change due to the applied current of the voltage between the voltage terminals is measured by the four-terminal method, and the XY recorder is used. , A current value when a voltage of 1 μV / cm appeared was measured and calculated by dividing the current value by the cross-sectional area of the oxide superconductor.
結果を表に示した。 The results are shown in the table.
第１図は本発明方法における冷間加工工程を例示した部
分断面説明図、第２図は焼結に供する際の線材の形態を
例示した斜視図である。 1:酸化物超電導体の粉末 2:貴金属チューブ 3:ピンチロール 4:線材FIG. 1 is a partial cross-sectional explanatory view illustrating a cold working step in the method of the present invention, and FIG. 2 is a perspective view illustrating the form of a wire rod used for sintering. 1: Oxide superconductor powder 2: Precious metal tube 3: Pinch roll 4: Wire rod
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−140520（ＪＰ，Ａ) 特開 平１−292506（ＪＰ，Ａ) 特開 平１−161612（ＪＰ，Ａ) 特開 平３−141512（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01B 12/00 - 13/00 C04B 35/00 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-1-140520 (JP, A) JP-A-1-292506 (JP, A) JP-A-1-161612 (JP, A) JP-A-3- 141512 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01B 12/00-13/00 C04B 35/00
Claims (1)
導体の粉末を貴金属からなるチューブに充填して冷間加
工し、それにより形成した線材を中間焼鈍なしに前記の
貴金属、ないし酸化物超電導体の融点未満の温度で加熱
処理して当該酸化物超電導体の粉末を焼結させることを
特徴とする酸化物超電導線の製造方法。An oxide superconductor powder containing a pinning center is filled in a tube made of a noble metal and cold-worked, and a wire formed thereby is formed without intermediate annealing by using the noble metal or oxide superconductor. A method for producing an oxide superconducting wire, comprising sintering the oxide superconductor powder by performing a heat treatment at a temperature lower than the melting point.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02216106A JP3086237B2 (en) | 1990-08-15 | 1990-08-15 | Manufacturing method of oxide superconducting wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02216106A JP3086237B2 (en) | 1990-08-15 | 1990-08-15 | Manufacturing method of oxide superconducting wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0498714A JPH0498714A (en) | 1992-03-31 |
| JP3086237B2 true JP3086237B2 (en) | 2000-09-11 |
Family
ID=16683337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02216106A Expired - Fee Related JP3086237B2 (en) | 1990-08-15 | 1990-08-15 | Manufacturing method of oxide superconducting wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3086237B2 (en) |
-
1990
- 1990-08-15 JP JP02216106A patent/JP3086237B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0498714A (en) | 1992-03-31 |
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