JPH01161626A - Oxide superconducting wire and its manufacture - Google Patents
Oxide superconducting wire and its manufactureInfo
- Publication number
- JPH01161626A JPH01161626A JP62320738A JP32073887A JPH01161626A JP H01161626 A JPH01161626 A JP H01161626A JP 62320738 A JP62320738 A JP 62320738A JP 32073887 A JP32073887 A JP 32073887A JP H01161626 A JPH01161626 A JP H01161626A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- superconducting wire
- oxide
- oxide superconductor
- oxide superconducting
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001301 oxygen Substances 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
- 239000002887 superconductor Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 5
- 238000011049 filling Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- 230000007547 defect Effects 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 230000002950 deficient Effects 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 15
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 238000005242 forging Methods 0.000 abstract 1
- 230000002093 peripheral effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010304 firing Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052693 Europium Inorganic materials 0.000 description 2
- 101100514056 Rhodobacter capsulatus modD gene Proteins 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052706 scandium Inorganic materials 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 210000004262 dental pulp cavity Anatomy 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、酸化物超電導線およびその製造方法に係り、
特に臨界電流密度の高い酸化物超電導線およびその製造
方法に関する。[Detailed description of the invention] [Object of the invention] (Industrial application field) The present invention relates to an oxide superconducting wire and a method for manufacturing the same,
In particular, the present invention relates to an oxide superconducting wire with a high critical current density and a method for manufacturing the same.
（従来の技術）
近年、Ｂａ−Ｌａ−Ｃｕ−Ｑ系の層状ペロブスカイト型
の酸化物が高い臨界温度を有する可能性のあることが発
表されて以来、各所で酸化物超電導体の研究が行われテ
ィる（Ｚ、Ｐｈｙｓ、Ｂ Ｃｏｎｄｅｎｓｅｄ Ｍａｔ
ｔｅｒ６４、１８９−１９３（１９８６））。その中で
もＹ−Ｂａ−Ｃｕ−０系で代表される酸素欠陥を有する
欠陥ペロブスカイト型（ＬｎＢａ２Ｃｕ３０アーδ型）
（δは酸素欠陥を表わし通常１以下、Ｌｎは、Ｙ、 Ｌ
ａ、 Ｓｃ、、Ｎｄ、 Ｓｎ＋、、Ｅｕ、 Ｇｄ、０■
、＋１０ＳＥｒ、 Ｔｍ、 ｙｂおよびＬｕから選ばれ
た少なくとも１種の元素、Ｂａの一部はＳｒ等で買換可
能）の酸化物超電導体は、臨界温度が９０に以上と液体
窒素以上の高い温度を示すため非常に有望な材料として
注目されている（Ｐｈｙｓ、Ｒｅｖ、Ｌｅｔｔ、Ｖｏｌ
、５８Ｎｏ、 ９．９０８−９１０ ）。(Prior Art) In recent years, since it was announced that Ba-La-Cu-Q layered perovskite oxides may have a high critical temperature, research on oxide superconductors has been carried out in various places. Tiru (Z, Phys, B Condensed Mat
ter64, 189-193 (1986)). Among them, defective perovskite type (LnBa2Cu30ar δ type) with oxygen defects represented by Y-Ba-Cu-0 system.
(δ represents oxygen defect and is usually 1 or less, Ln is Y, L
a, Sc, , Nd, Sn+, , Eu, Gd, 0■
, +10SEr, Tm, yb, and at least one element selected from Lu, a part of Ba can be replaced with Sr, etc.) The oxide superconductor has a critical temperature of 90 or higher, which is higher than liquid nitrogen. (Phys, Rev, Lett, Vol.
, 58 No. 9.908-910).
一般に、このようなベロアスカイト型の結晶構造を有す
る酸化物超電導体を用いた酸化物超電導線を製造する場
合には、銀や銀合金のような酸素透過性金属管内に酸化
物超電導体の粉末を充填し、これに減面加工を施して所
望の外径にまで成形した優、９００〜９８０℃の温度で
１０数時間熱処理し、次いで酸化物超電導体結晶の酸素
空席に酸素を導入するために４００〜６００℃程度の酸
素雰囲気中で１０数時間程度加熱することが行われてい
た。Generally, when manufacturing an oxide superconducting wire using an oxide superconductor having such a velorskite crystal structure, the oxide superconductor is placed in an oxygen permeable metal tube such as silver or silver alloy. The powder is filled with powder, subjected to area reduction processing, and molded to the desired outer diameter.The product is then heat treated at a temperature of 900 to 980°C for more than 10 hours, and then oxygen is introduced into the oxygen vacancies in the oxide superconductor crystal. For this reason, heating was performed in an oxygen atmosphere at a temperature of about 400 to 600° C. for about 10 hours.
（発明が解決しようとする問題点）
しかしながら、このような従来の方法では、酸化物超電
導体の外周に金属被覆した状態で酸素導入のための熱処
理が行われるため、長時間熱処理しても充分に金属被覆
内に酸素を供給することが困難で、このため酸化物超電
導体のペロブスカイト型結晶構造の酸素空席に充分に酸
素を導入することが困難で、臨界電流密度の不十分な酸
化物超電導線しか得られないという問題があった。(Problem to be solved by the invention) However, in such conventional methods, heat treatment for introducing oxygen is performed with the outer periphery of the oxide superconductor coated with metal, so even long-term heat treatment is not sufficient. It is difficult to supply oxygen into the metal coating in the oxide superconductor, which makes it difficult to introduce enough oxygen into the oxygen vacancies in the perovskite crystal structure of the oxide superconductor, and the critical current density is insufficient. There was a problem that only lines could be obtained.
本発明は、このような従来の難点を解消すべくなされた
もので、上記欠点のない酸化物超電導線およびその製造
方法を提供することを目的とする。The present invention has been made to solve these conventional problems, and an object of the present invention is to provide an oxide superconducting wire and a method for manufacturing the same that are free from the above-mentioned drawbacks.
［発明の構成］
（問題点を解決するための手段）
第１の発明は、酸素透過性金属からなり少なくとも一方
の面に凹凸加工が施されたテープ状中空体の前記中空部
に、酸化物超電導体が充填されてなることを特徴として
おり、また第２の発明は、ほぼ等厚の酸素透過性金属か
らなる中空管内に酸化物超電導体を充填し、これをテー
プ状に加工した後、少くともその一方の面に凹凸加工を
施し、しかる後酸素雰囲気中で熱処理することを特徴と
している。[Structure of the Invention] (Means for Solving the Problems) The first invention provides an oxide material in the hollow portion of a tape-shaped hollow body made of an oxygen-permeable metal and having a roughened surface on at least one surface. The second invention is characterized in that a hollow tube made of an oxygen-permeable metal of approximately the same thickness is filled with an oxide superconductor, and after processing this into a tape shape, It is characterized in that at least one surface thereof is textured and then heat treated in an oxygen atmosphere.
本発明には各種の酸化物超電導体を用いることができる
が、臨界温度の高い、希土類元素含有のペロブスカイト
型の酸化物超電導体を用いた場合に特に実用的効果が大
きい。Although various oxide superconductors can be used in the present invention, the use of a perovskite-type oxide superconductor containing a rare earth element, which has a high critical temperature, has a particularly large practical effect.
上記の希土類元素を含有しベロアスカイト型構造を有す
る酸化物超電導体は、超電導状態を実現できるものであ
ればよく、ＬｎＢａ２Ｃｕ３０７−δ系！（δは酸素欠
陥を表し通常１以下の数、Ｌｎは、Ｙ、Ｌａ、 Ｓｃ、
Ｎｄ１５ｍ１Ｅｕ１Ｇｄ、 Ｄｙ、 ｔｌｏ、Ｅｒ、
Ｔｍ１Ｙｂおよび［Ｕから選ばれた少なくとも１種の
元素、ｅａの一部はＳｒ等で置換可能）等の酸素欠陥を
有する欠陥ベロアスカイト型、５ｒ−Ｌａ−Ｃｌ−０系
等の層状ベロアスカイト型等の広義にペロブスカイト型
を有する酸化物が例示される。また希土類元素も広義の
定義とし、Ｓｃ、 ＹおよＵＬａ系を含むものとする
。The above-mentioned oxide superconductor containing a rare earth element and having a velorskite structure may be one that can realize a superconducting state, such as the LnBa2Cu307-δ system! (δ represents an oxygen defect and is usually a number of 1 or less, Ln is Y, La, Sc,
Nd15m1Eu1Gd, Dy, tlo, Er,
Defect velorskite type having oxygen defects such as Tm1Yb and [at least one element selected from U, a part of ea can be replaced with Sr etc.), layered velorskite type such as 5r-La-Cl-0 system Examples include oxides having a perovskite type in a broad sense, such as a perovskite type. Rare earth elements are also broadly defined to include Sc, Y, and ULa.
代表的な系としてＹ−Ｂａ−Ｃｕ−０系のほかに、Ｙを
Ｅｕ。In addition to the Y-Ba-Cu-0 system, Y is replaced by Eu as a typical system.
Ｄｙ、 Ｎｏ、ＥｒｌＴｍ、 Ｙｂ、［Ｕ等の希土類テ
置換した系、５ｃ−Ｂａ−Ｃｕ−０系、５ｒ−Ｌａ−Ｃ
ｕ−０系、さらにＳ「をＢａ、 Ｃａで置換した系等が
挙げられる。Dy, No, ErlTm, Yb, rare earth te-substituted system such as [U, 5c-Ba-Cu-0 system, 5r-La-C
Examples include the u-0 system and systems in which S' is replaced with Ba or Ca.
本発明に用いる酸化物超電導体は、たとえば以下に示す
製造方法により得ることができる。The oxide superconductor used in the present invention can be obtained, for example, by the manufacturing method shown below.
まず１．ｙ、 ｅａＳｃｕ等のペロブスカイト型酸化物
超電導体の構成元素を充分混合する。混合の際には、Ｙ
２Ｏ３、ＣｕＯ等の酸化物を原料として用いることがで
きる。また、これらの酸化物のほかに、焼成後酸化物に
転化する炭酸塩、硝酸塩、水酸化物等の化合物を用いて
もよい。さらには、共沈法等で得たシュウ酸塩等を用い
てもよい。ベロアスカイト型酸化物超電導体を構成する
元素は、基本的に化学量論比の組成となるように混合す
るが、多少製造条件等との関係でずれていても差支えな
い。たとえば、Ｙ−Ｂａ−Ｃｕ−０系ではＹ １ ｍｏ
ｌに対しＢａ ２ ｌｌ１ｏｌ、Ｃｕ ３ ｍｏｌが標
準組成であるが、実用上はＹ １ ｍｏｌに対して、Ｂ
ａ ２十０．６１１０１、ＣＯ３±０．２ ｌｌ１ｏｌ
程度のずれは問題ない。First 1. The constituent elements of the perovskite oxide superconductor such as y, eaScu, etc. are thoroughly mixed. When mixing, Y
Oxides such as 2O3 and CuO can be used as raw materials. In addition to these oxides, compounds such as carbonates, nitrates, and hydroxides that are converted into oxides after firing may be used. Furthermore, oxalate obtained by a coprecipitation method or the like may be used. The elements constituting the velorskite-type oxide superconductor are basically mixed so as to have a stoichiometric composition, but there is no problem even if the composition deviates slightly depending on the manufacturing conditions. For example, in the Y-Ba-Cu-0 system, Y 1 mo
The standard composition is Ba 2 ll1 ol and Cu 3 mol for Y 1 mol, but in practice, B
a 20.61101, CO3±0.2 ll1ol
There is no problem with the difference in degree.
前述の原料を混合した模、仮焼、粉砕し所望の形状にし
た後、８５０〜９８０℃程度で焼成する。仮焼は必ずし
も必要ではない。仮焼および焼成は充分な酸素が供給で
きるような酸素含有雰囲気中で行うことが好ましい。所
望の形状に焼成した後、酸素含有雰囲気中で熱処理して
超電導特性を付与する。上記熱処理は、通常６００℃以
下で徐冷しながら行うようにする。The mixture of the above-mentioned raw materials is calcined and crushed into a desired shape, and then fired at about 850 to 980°C. Calcining is not necessarily necessary. Preferably, calcination and firing are performed in an oxygen-containing atmosphere where sufficient oxygen can be supplied. After firing into a desired shape, it is heat-treated in an oxygen-containing atmosphere to impart superconducting properties. The above heat treatment is usually performed at 600° C. or lower while slowly cooling.
このようにして得られた酸化物超電導体は、酸素欠陥δ
を有する酸素欠陥型ペロブスカイト構造（ＬｎＢａ
Ｃｕ Ｏ（δは通常１以下））とな２３７−δ
る。なお、ＢａをＳｒ、 Ｃａの少なくとも１種で置換
することもでき、ざらにＣｕの一部をＴｉ、 ＶｌＣ
ｒ、 Ｈｎ。The oxide superconductor thus obtained has oxygen defects δ
Oxygen-deficient perovskite structure (LnBa
CuO (δ is usually 1 or less)) is 237-δ. Incidentally, Ba can also be replaced with at least one of Sr and Ca, and roughly a part of Cu can be replaced with Ti, VlC.
r, Hn.
Ｆｅ１ｃｏ、Ｎ１、Ｚｎ等で置換することもできる。Substitution with Fe1co, N1, Zn, etc. is also possible.
この置換置は、超電導特性を低下させない程度の範囲で
適宜設定可能であるが、あまりに多聞の置換は超電導特
性を低下させてしまうので８０ｍｏｌＸ以下、さらに実
用上は２０ｍｏ１％以下程度までとする。This substitution position can be set as appropriate within a range that does not deteriorate the superconducting properties, but too many substitutions will deteriorate the superconducting properties, so it is set at 80 molX or less, and in practical terms, 20 molX or less.
本発明の酸化物超電導体線材を得るには、まず、酸化物
超電導体の焼成し結晶化した焼成物をボールミル等の公
知の手段により粉砕する。このとき、酸化物超電導体粉
末はへき開面から分割されて微粉末となる。粉砕は、平
均粒径（結晶の０面の最大の長さ）が１〜５μｍ程度、
直径対厚さの比が３〜５となるまで行なうことが望まし
い。なお、必要に応じて、粉砕した粉末を上記の範囲と
なるように分級して用いてもよい。To obtain the oxide superconductor wire of the present invention, first, a fired and crystallized oxide superconductor is pulverized by a known means such as a ball mill. At this time, the oxide superconductor powder is divided from the cleavage plane and becomes fine powder. For pulverization, the average particle size (maximum length of the zero face of the crystal) is about 1 to 5 μm,
It is desirable to proceed until the diameter to thickness ratio is between 3 and 5. Note that, if necessary, the pulverized powder may be classified and used so as to fall within the above range.
次に、この酸化物超電導体粉末を銀または銀合金のよう
な酸素を透過する性質を有する金属管内に充填し、両端
を同質材により封止する。Next, this oxide superconductor powder is filled into a metal tube that is permeable to oxygen, such as silver or silver alloy, and both ends are sealed with a homogeneous material.
この侵、この酸化物超電導体粉末を充填した酸素透過性
の金属管を温間でスェージングマシン等により鍛造した
後、冷間で線引きして前記金属管の外径を元の外径の１
７１０以下、好ましくは１７２０以下程度となるまで縮
径加工して、ロールを用いて偏平に圧縮するとともに、
少なくともその一方の而に凹凸加工を施す。After this corrosion, an oxygen-permeable metal tube filled with this oxide superconductor powder is warmly forged using a swaging machine, etc., and then cold drawn to reduce the outer diameter of the metal tube to 1% of the original outer diameter.
The diameter is reduced to 710 or less, preferably about 1720 or less, and compressed into a flat shape using a roll,
At least one of them is textured.
凹凸加工は、偏平に圧縮するロールの表面に所定の凹凸
形状を形成しておき、圧縮と同時に行ってもよく、別工
程で専用の凹凸加工ロールあるいはダイスを用いて行う
ようにしてもよい。このとき、凹凸の谷部に対する山部
の高さは、金属被覆厚の０．３〜３．０倍程度が好まし
い。また、凹凸加工後の酸化物超電導線の任意の横断面
における周囲長は、同断面積の真円の周囲長の２０〜１
３０倍であることが好ましい。The uneven processing may be performed simultaneously with the compression by forming a predetermined uneven shape on the surface of a roll to be flattened, or may be performed in a separate process using a dedicated uneven processing roll or die. At this time, the height of the peaks relative to the valleys of the unevenness is preferably about 0.3 to 3.0 times the metal coating thickness. In addition, the circumference of the oxide superconducting wire in any cross section after roughening is 20 to 1 times the circumference of a perfect circle with the same cross section.
Preferably, it is 30 times larger.
第１図ないし第３図はこのようにして成形された本発明
の酸化物超′Ｆｉ導線の外形を示すもので、酸素透過性
金属被覆１の外径は、第１図に示すように長さ方向に連
続した断面鋸歯条の凹凸形状であってもよく、第２図に
示すように、長さ方向に連続した断面矩形の凹凸形状で
あってもよく、さらに第３図に示すように、独立した凹
凸形状であってもよい。なお、各図において２は酸化物
超電導体を示している。1 to 3 show the outer shape of the oxide super-Fi conductor of the present invention formed in this way, and the outer diameter of the oxygen-permeable metal coating 1 is long as shown in FIG. It may have an uneven shape with a sawtooth cross section continuous in the width direction, or it may have an uneven shape with a rectangular cross section continuous in the length direction, as shown in FIG. 3, or as shown in FIG. , may be an independent uneven shape. Note that in each figure, 2 indicates an oxide superconductor.
このようにして所望の断面寸法および外形となったとこ
ろで、酸素含有雰囲気中８５０〜９８０℃で８〜８０時
間、焼成のための熱処理を行なう。焼成侵、酸素含有雰
囲気中で６００℃以下を１℃／分程度の割合いで徐冷し
、酸化物超電導体の結晶構造中の酸素空席に酸素を導入
して超ｆｆｉ導特性を向上させる。なお、酸素導入は、
このような徐冷を行わずに、焼成のための熱処理からの
冷却工程または別工程において、３００〜６００℃で１
〜２４時間保持することにより行うようにしてもよい。When the desired cross-sectional dimensions and external shape are obtained in this manner, heat treatment for firing is performed at 850 to 980° C. for 8 to 80 hours in an oxygen-containing atmosphere. After firing, the material is slowly cooled to 600° C. or lower at a rate of about 1° C./min in an oxygen-containing atmosphere, and oxygen is introduced into the oxygen vacancies in the crystal structure of the oxide superconductor to improve the super-FFI conductivity. In addition, oxygen introduction is
Without such slow cooling, in the cooling step from heat treatment for firing or in a separate step, 1 at 300-600℃
This may be carried out by holding for ~24 hours.
（作 用）
本発明の酸化物超電導線は、任愚の断面における周囲長
が長いので、酸素導入のための熱処理時間を短縮するこ
とができ、また金属被覆内の酸化物超電導体に均一に酸
素が供給されるので、高い臨界電流密度が得られる。(Function) Since the oxide superconducting wire of the present invention has a long circumference in the cross section, it is possible to shorten the heat treatment time for introducing oxygen, and the oxide superconductor in the metal coating can be uniformly coated. Since oxygen is supplied, a high critical current density can be obtained.
また本発明の酸化物足Ｔｉ導線の製造方法によれば、榎
られる酸化物超電導線の外形が異形であるにもかかわら
ず、酸素透過性金属被覆の厚さを全体的にほぼ均一にす
ることができ、したがって酸素の供給が均一に行われる
。Further, according to the method for manufacturing an oxide-based Ti conductor wire of the present invention, the thickness of the oxygen-permeable metal coating can be made substantially uniform throughout, even though the outer shape of the oxide superconducting wire to be extracted is irregular. Therefore, the oxygen supply is uniform.
またさらに、本発明の酸化物超電導線の表面の凹凸は、
これを直接液化ガス中に浸漬して冷却する場合熱交換を
容易にし、システムの安全性を向上させる効果もある。Furthermore, the unevenness on the surface of the oxide superconducting wire of the present invention is
When this is directly immersed in liquefied gas to cool it, it facilitates heat exchange and has the effect of improving the safety of the system.
（実施例） 以下、本発明の実施例について説明する。(Example) Examples of the present invention will be described below.
実施例
まず、ＢａＣＯ３粉末２ｍｏｌＬ Ｙ２Ｏ３粉末ｏ、
ｓｍｏ１％、ＣＵＯ粉末３ｍｏ １％を充分混合し、混
合物を９００℃で４８時間焼成した後粉砕した。次いで
、この粉末原料を大気中７００ｖで２４時間熱処理して
酸素空席に酸素を導入した侵、ボールミルを用いて粉砕
し、分級して平均粒径２μＩ、直径対厚さの比が３〜５
のペロプスカイト型の酸化物超電導体粉末を得た。Example First, BaCO3 powder 2 molL Y2O3 powder o,
1% smo and 3mo 1% CUO powder were thoroughly mixed, the mixture was fired at 900° C. for 48 hours, and then pulverized. Next, this powder raw material was heat treated in the atmosphere at 700V for 24 hours to introduce oxygen into the oxygen vacancies, crushed using a ball mill, and classified to have an average particle size of 2 μI and a diameter-to-thickness ratio of 3 to 5.
A perovskite-type oxide superconductor powder was obtained.
次に、得られた酸化物超電導体粉末を、外径２０ｍｍ、
内径１５■１、長さ１００ｎの、一端を銀材により封止
した鎖管中に充填し、他端に銀材の栓をした後、常温で
スェージングマシンにより根管外から酸化物足７１１導
体粉末をつき固め、この後外径５■にまで冷間で線引き
した後厚さ２ｎにまで偏平に圧縮した。さらに、この偏
平に圧縮した線材を一方の表面に断面鋸歯条の凹溝を周
方向に形成した圧縮ロールを用いてさらに圧縮し、厚さ
０．３＋ｎ、幅８１１ｍ溝の深さ０．１Ｎの酸化物超電
導線を製造した。Next, the obtained oxide superconductor powder was heated to an outer diameter of 20 mm,
After filling a chain canal with an inner diameter of 15cm and a length of 100n, one end of which was sealed with a silver material, and the other end sealed with a silver material, an oxide foot 711 was inserted from outside the root canal using a swaging machine at room temperature. The conductor powder was compacted, then cold drawn to an outer diameter of 5 cm, and then flattened to a thickness of 2 nm. Furthermore, this flattened wire rod was further compressed using a compression roll in which a concave groove with a serrated cross section was formed in the circumferential direction on one surface, and the thickness was 0.3+n, the width was 811m, and the depth of the groove was 0.1N. An oxide superconducting wire was manufactured.
しかる後、酸素中９５０℃で２４時間熱処理して焼成し
た後、６００℃からは１℃／分で徐冷して超電ＩＩ材を
得た。Thereafter, the material was heat-treated and fired in oxygen at 950°C for 24 hours, and then gradually cooled from 600°C at a rate of 1°C/min to obtain a superelectric II material.
この酸化物超電導体線材の臨界温度は８７Ｋ、臨界電流
密度は１１００Ａ／ｃｊであった。The critical temperature of this oxide superconductor wire was 87 K, and the critical current density was 1100 A/cj.
一方、偏平に圧縮せずに外径５ｎの断面円形の状態で実
施例と同一条件で酸素中で熱処理して得た酸化物超電導
体の臨界電流密度は３００Ａ／ｃｊであった。On the other hand, the critical current density of the oxide superconductor obtained by heat-treating in oxygen under the same conditions as in the example in a circular cross-sectional state with an outer diameter of 5n without being flattened was 300 A/cj.
［発明の効果］
以上説明したように、本発明の酸化物超電導線は、任意
の断面積における周囲長が大きいので、酸素導入のため
の熱処理時間を短縮することができ、また金属被覆内の
酸化物超電導体に均一に酸素が供給されるので、高い臨
界電流密度が１ｑられる。[Effects of the Invention] As explained above, since the oxide superconducting wire of the present invention has a large circumference in any cross-sectional area, it is possible to shorten the heat treatment time for oxygen introduction, and to reduce the heat treatment time in the metal coating. Since oxygen is uniformly supplied to the oxide superconductor, a high critical current density of 1q is achieved.
さらに、本発明の酸化物超電導線の製造方法によれば、
得られる酸化物超電導線の外径が異形であるにもかかわ
らず、酸素透過性金属被覆の厚さを全体的にほぼ均一に
することができ、したがって酸素の供給を均一に行わせ
ることができる。Furthermore, according to the method for manufacturing an oxide superconducting wire of the present invention,
Even though the outer diameter of the resulting oxide superconducting wire is irregular, the thickness of the oxygen-permeable metal coating can be made almost uniform throughout, and therefore oxygen can be supplied uniformly. .
また酸化物超電導線の表面の凹凸は、これを直接液化ガ
ス中に浸漬して冷却する場合熱交換を容易にし、システ
ムの安全性を向上させる効果もある。Furthermore, the unevenness on the surface of the oxide superconducting wire facilitates heat exchange when it is directly immersed in liquefied gas to cool it, which also has the effect of improving the safety of the system.
第１図ないし第３図は、それぞれ本発明の酸化物超電導
線の表面の凹凸形状を示す斜視図である。
１・・・・・・・・・酸素透過性金属被覆２・・・・・
・・・・酸化物超′ｔｆｉ々体出願人 株式会
社 東芝
代理人弁理士 須 山 佐 −1 to 3 are perspective views showing the uneven shape of the surface of the oxide superconducting wire of the present invention, respectively. 1... Oxygen permeable metal coating 2...
...Oxide super'tfi body Applicant: Toshiba Corporation Patent Attorney Satoshi Suyama -
Claims (12)
凸加工が施されたテープ状中空体の前記中空部に、酸化
物超電導体が充填されてなることを特徴とする酸化物超
電導線。(1) An oxide superconducting wire characterized in that the hollow portion of a tape-shaped hollow body made of an oxygen-permeable metal and having a roughened surface on at least one surface is filled with an oxide superconductor.
を特徴とする特許請求の範囲第１項記載の酸化物超電導
線。(2) The oxide superconducting wire according to claim 1, wherein the oxygen permeable metal is made of silver or a silver alloy.
の周囲長の２０〜１３０倍であることを特徴とする特許
請求の範囲第１項または第２項記載の酸化物超電導線。(3) The oxide superconducting wire according to claim 1 or 2, wherein the circumference in any cross section is 20 to 130 times the circumference of a perfect circle having the same cross section.
スカイト型の酸化物超電導体であることを特徴とする特
許請求の範囲第１項ないし第３項記載の酸化物超電導線
。(4) The oxide superconducting wire according to any one of claims 1 to 3, wherein the oxide superconductor is a perovskite-type oxide superconductor containing a rare earth element.
素から選ばれた少なくとも１種の元素）、ＢａおよびＣ
ｕを原子比で実質的に１：２：３の割合で含有すること
を特徴とする特許請求の範囲第１項ないし第４項のいず
れか１項記載の酸化物超電導線。(5) The oxide superconductor contains Ln element (Ln is at least one element selected from rare earth elements), Ba and C
The oxide superconducting wire according to any one of claims 1 to 4, characterized in that it contains u in an atomic ratio of substantially 1:2:3.
＿−＿δ（＿δは酸素欠陥を表わす）で表わされる酸素
欠陥型ペロブスカイト構造を有することを特徴とする特
許請求の範囲第１項ないし第４項のいずれか１項記載の
酸化物超電導線。(6) The oxide superconductor is LnBa_2Cu_3O_7
The oxide superconducting wire according to any one of claims 1 to 4, characterized in that it has an oxygen-deficient perovskite structure represented by _-_δ (_δ represents an oxygen defect).
化物超電導体を充填し、これをテープ状に加工した後、
少くともその一方の面に凹凸加工を施し、しかる後酸素
雰囲気中で熱処理することを特徴とする酸化物超電導線
の製造方法。(7) After filling an oxide superconductor into a hollow tube made of an oxygen-permeable metal of approximately equal thickness and processing it into a tape shape,
1. A method for producing an oxide superconducting wire, characterized in that at least one surface thereof is textured and then heat treated in an oxygen atmosphere.
を特徴とする特許請求の範囲第７項記載の酸化物超電導
線の製造方法。(8) The method for producing an oxide superconducting wire according to claim 7, wherein the oxygen-permeable metal is made of silver or a silver alloy.
断面積の真円の周囲長の２０〜１３０倍となるよう行わ
れることを特徴とする特許請求の範囲第７項または第８
項記載の酸化物超電導線の製造方法。(9) The uneven processing is performed so that the circumferential length of any cross section is 20 to 130 times the circumferential length of a perfect circle having the same cross-sectional area.
A method for manufacturing an oxide superconducting wire as described in .
ブスカイト型の酸化物超電導体であることを特徴とする
特許請求の範囲第７項ないし第９項のいずれか１項記載
の酸化物超電導線の製造方法。(10) The oxide superconductor wire according to any one of claims 7 to 9, wherein the oxide superconductor is a perovskite-type oxide superconductor containing a rare earth element. manufacturing method.
元素から選ばれた少なくとも１種の元素）、Ｂａおよび
Ｃｕを原子比で実質的に１：２：３の割合で含有するこ
とを特徴とする特許請求の範囲第７項ないし第１０項の
いずれか１項記載の酸化物超電導線の製造方法。(11) The oxide superconductor contains Ln element (Ln is at least one element selected from rare earth elements), Ba and Cu in an atomic ratio of substantially 1:2:3. A method for producing an oxide superconducting wire according to any one of claims 7 to 10.
７＿−＿δ（δは酸素欠陥を表わす）で表わされる酸素
欠陥型ペロブスカイト構造を有することを特徴とする特
許請求の範囲第７項ないし第１１項のいずれか１項記載
の酸化物超電導線の製造方法。(12) The oxide superconductor is LnBa_2Cu_3O_
Production of an oxide superconducting wire according to any one of claims 7 to 11, which has an oxygen-deficient perovskite structure represented by 7_-_δ (δ represents an oxygen defect). Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62320738A JPH01161626A (en) | 1987-12-18 | 1987-12-18 | Oxide superconducting wire and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62320738A JPH01161626A (en) | 1987-12-18 | 1987-12-18 | Oxide superconducting wire and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01161626A true JPH01161626A (en) | 1989-06-26 |
Family
ID=18124749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62320738A Pending JPH01161626A (en) | 1987-12-18 | 1987-12-18 | Oxide superconducting wire and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01161626A (en) |
-
1987
- 1987-12-18 JP JP62320738A patent/JPH01161626A/en active Pending
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