JPH01115015A - Manufacture of superconductor wire material - Google Patents
Manufacture of superconductor wire materialInfo
- Publication number
- JPH01115015A JPH01115015A JP62273955A JP27395587A JPH01115015A JP H01115015 A JPH01115015 A JP H01115015A JP 62273955 A JP62273955 A JP 62273955A JP 27395587 A JP27395587 A JP 27395587A JP H01115015 A JPH01115015 A JP H01115015A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- superconductor
- oxide superconductor
- tube
- 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.)
- Pending
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- 239000011812 mixed powder Substances 0.000 claims abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 230000007547 defect Effects 0.000 claims description 5
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 4
- 230000002950 deficient Effects 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 239000013590 bulk material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 238000012423 maintenance Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 7
- 238000005253 cladding Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000005491 wire drawing Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052706 scandium Inorganic materials 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
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 235000011499 Ferocactus hamatacanthus Nutrition 0.000 description 1
- 244000154165 Ferocactus hamatacanthus Species 0.000 description 1
- 229910052765 Lutetium 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- -1 Y2 03 Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 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、酸化物超電導体を使用した超電導体線材の製
造方法に関する。Detailed Description of the Invention [Object of the Invention] (Industrial Application Field) The present invention relates to a method for manufacturing a superconductor wire using an oxide superconductor.
（従来の技術）
近年、Ｂａ−Ｌａ−Ｃｕ−０系の屑状ペロプスカイト型
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ｉｔ！電導体の研究が行わ
れている（Ｚ、Ｐｈｙｓ、Ｂ Ｃｏｎｄｅｎｓｅｄ Ｍ
ａｔｔｅｒ６４、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 、
、型）（δは酸素欠陥を表し通常１以下、Ｌｎは、Ｙ
、Ｌａ、 Ｓｃ、 Ｎｄ、 Ｓｎ、 Ｅｕ、 Ｇｄ、Ｏ
ｖ、１１０、［「、■１、ｖｂおよび［Ｕから選ばれた
少なくとも １種の元素、Ｂａの一部はＳ「等で置換可
能））の酸化物超電導体は、臨界温度が９０に以上と液
体窒素の沸点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、 Ｌｅ
ｔｔ。(Prior Art) In recent years, since it was announced that Ba-La-Cu-0 based scrap perovskite oxides may have a high critical temperature, oxide IT! Research on electrical conductors is being conducted (Z, Phys, B Condensed M
atter64, 189-193 (1986)), among which defective perovskite type with oxygen defects represented by Y-Ba-Cu-0 system ((LnBa2Cu30,
, type) (δ represents oxygen defect and is usually 1 or less, Ln is Y
, La, Sc, Nd, Sn, Eu, Gd, O
The oxide superconductor of v, 110, [", ■1, vb and [at least one element selected from U, a part of Ba can be replaced with S", etc.) has a critical temperature of 90 or more. It is attracting attention as a very promising material because it exhibits a high temperature higher than the boiling point of liquid nitrogen (Phys, Rev, Le
tt.
Ｖｏｌ、５８ Ｎｏ、９，９０８−９１０）。Vol. 58 No. 9, 908-910).
ところで、このような酸化物超電導体は、結晶性の酸化
物の焼結体あるいはその粉末として得られるため、これ
らを例えば線材として利用する場合、銅や銀等の金属管
に酸化物超電導体粉末を充填した後、線引きする等して
長尺化して使用することが試みられている。また、上述
した酸素欠陥を有する欠陥ペロブスカイト型の酸化物超
電導体の場合には特に、結晶中の酸素空席の量によって
超電導特性が大きく影響を受け、この酸素空席の量が多
いと臨界電流密度等の超電導特性が低下してしまうため
、線引きを行った後にこの酸素空席へ酸素を導入するた
めに充分に酸素を供給することが可能な雰囲気中で熱処
理を行っている０通常、この熱処理は９００℃前後で行
われている。By the way, such oxide superconductors are obtained as sintered bodies of crystalline oxides or their powders, so when using them as wire rods, for example, oxide superconductor powder is placed in a metal tube such as copper or silver. Attempts have been made to fill the material and then draw it into a longer length for use. In addition, especially in the case of defective perovskite-type oxide superconductors having oxygen vacancies mentioned above, the superconducting properties are greatly affected by the amount of oxygen vacancies in the crystal, and if the amount of oxygen vacancies is large, the critical current density etc. Since the superconducting properties of the wire are reduced, heat treatment is performed in an atmosphere where sufficient oxygen can be supplied to introduce oxygen into the oxygen vacancies after wire drawing.Normally, this heat treatment is performed at a temperature of 900 It is carried out at around ℃.
ところで、上述した金属管に酸化物超電導体粉末を充填
して線材化する方法において、金属管として例えば銅の
ような酸素の透過性の悪い素材を使用した場合には、上
述した酸素導入のための熱処理の際に充分に酸素を供給
することができず、充分な超電導特性が得られないとい
う問題がある。By the way, in the above-mentioned method of filling a metal tube with oxide superconductor powder and making it into a wire, if a material with poor oxygen permeability, such as copper, is used as the metal tube, the above-mentioned oxygen introduction may occur. There is a problem in that sufficient oxygen cannot be supplied during the heat treatment, and sufficient superconducting properties cannot be obtained.
また、銅は結晶中への酸素導入のための熱処理時に激し
く酸化し、非常に脆くなり線材としての強度が得られな
くなってしまうという問題もある。Another problem is that copper is severely oxidized during heat treatment to introduce oxygen into the crystal, making it extremely brittle and unable to provide strength as a wire.
このため、高温においても酸素と反応せず、酸素が透過
し内部の酸化物超電導体粉末への酸素供給に優れた銀が
、被覆管として期待されている。For this reason, silver is expected to be used as a cladding tube because it does not react with oxygen even at high temperatures, allows oxygen to pass through it, and is excellent in supplying oxygen to the oxide superconductor powder inside.
（発明が解決しようとする問題点）
しかしながら、上述したように鎖管を被覆管として用い
たものは、他の金属を用いたものに比べて酸素供給能力
に優れているが、銀の酸素透過能力は肉厚に大きく依存
するため、熱処理時間が肉厚Ｃよっては長時間となり、
Ｖ造コストが高くなるといった問題がある。このため、
線引き加工の際に被覆管の肉厚を充分に薄くするために
加工時間を長くすると、肉厚の不均一等により破損の危
険性が高くなる。また、充分に肉厚を薄くすることがで
きたとしても、バルク等から比べると単位時間あたりの
酸素供給量は低く、充分な超電導特性を得るためには長
時間の熱処理が必要であったり、さらに長時間かけて熱
処理を行ってもバルクに比べると超電導特性が低いとい
う難点がある。(Problem to be solved by the invention) However, as mentioned above, those using chain tubes as cladding tubes have superior oxygen supply ability compared to those using other metals, but the oxygen permeability of silver is Since the capacity greatly depends on the wall thickness, the heat treatment time will be long depending on the wall thickness C.
There is a problem that V-building costs increase. For this reason,
If the processing time is prolonged in order to sufficiently reduce the wall thickness of the cladding during wire drawing, the risk of breakage increases due to uneven wall thickness, etc. Furthermore, even if the wall thickness could be made sufficiently thin, the amount of oxygen supplied per unit time would be low compared to bulk, etc., and long-term heat treatment would be required to obtain sufficient superconducting properties. Furthermore, even if heat treatment is performed over a long period of time, the superconducting properties are lower than that of the bulk material.
本発明はこのような従来の難点を解決するためになされ
たもので、被覆管の肉厚によらず充分仁酸素を供給する
ことが可能で、優れた超電導特性を有する超電導体線材
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 difficulties, and provides a method for manufacturing a superconductor wire that can supply sufficient oxygen regardless of the thickness of the cladding tube and has excellent superconducting properties. The purpose is to provide
〔発明の構成］
（問題点を解決するための手段）
本発明の超電導体線材の製造方法は、酸化物超電導体粉
末あるいは加熱により酸化物超電導体となる混合粉末を
銀または銀合金からなる管材内に充填する工程と、この
管材を線状に加工する工程と、この加工工程により得た
線状体の前記管材表面から内部充填物に達する複数の貫
通孔を形成する工程と、この貫通孔の形成された線状体
を酸素含有雰囲気中で熱処理する工程とを有することを
特徴としている。[Structure of the Invention] (Means for Solving the Problems) The method for producing a superconductor wire of the present invention is to prepare an oxide superconductor powder or a mixed powder that becomes an oxide superconductor by heating into a tube material made of silver or a silver alloy. a step of processing this tube material into a linear shape, a step of forming a plurality of through holes reaching the inner filling material from the surface of the tube material of the linear body obtained by this processing step, and a step of forming the through holes. The method is characterized by comprising a step of heat-treating the formed linear body in an oxygen-containing atmosphere.
酸化物超電導体としては、多数のものが知られているが
、臨界温度の高い、希土類元素含有のペロブスカイト型
の酸化物超電導体の使用が実用的効果が高い、ここでい
う希土類元素を含有しペロブスカイト型構造を有する酸
化物ｒＡ電導体は、超電導状態を実現できるものであれ
ばよく、例えばＬｎＢａ Ｃｕ Ｏ系（δは酸素欠
陥を表し通常１２３７−δ
以下の数、Ｌｎは、Ｙ、 Ｌａ、 Ｓｃ、 Ｎｄ、 Ｓ
ｉ、 Ｅｕ、 Ｇｄ、ａｙ、１１０、Ｅ「、■１、Ｙｂ
、 Ｌｕ等の希土類元素から選ばれた少なくとも １種
の元素、Ｂａの一部はＣａ等で置換可能、）等の酸素欠
陥を有する欠陥ペロブスカイト型、５ｒ−Ｌａ−ＣＵ−
０系等の層状ペロブ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。ｔた、希土類元素は
広義の定義とし、Ｓｃ、 ＹおよびＬａ系を含むものと
する。代表的な系としてＹ−Ｂａ−Ｃｕ−０系のほかに
、ＹをＥｕ、Ｏｙ、Ｈｏ、Ｅ「、Ｔｎ、 Ｙｂ、 Ｌｕ
等の希土類で置換した系、５ｃ−Ｂａ−Ｃｕ−０系、５
ｒ−Ｌａ−Ｃｕ−０系、さらにＳ「をＢａ、 Ｃａ’ｔ
’置換した系等が挙げられる。Many types of oxide superconductors are known, but the use of perovskite-type oxide superconductors containing rare earth elements, which have a high critical temperature, has a high practical effect. The oxide rA conductor having a perovskite structure may be one that can realize a superconducting state, for example, LnBa Cu O type (δ represents an oxygen defect and is usually a number of 1237-δ or less, Ln is Y, La, Sc, Nd, S
i, Eu, Gd, ay, 110, E", ■1, Yb
, at least one element selected from rare earth elements such as Lu, a part of Ba can be replaced with Ca etc.), 5r-La-CU-
Examples include oxides having a perovskite type in a broad sense, such as a layered perovskite type such as 0 type. Furthermore, rare earth elements are defined in a broad sense and include Sc, Y, and La elements. In addition to the Y-Ba-Cu-0 system, representative systems include Y as Eu, Oy, Ho, E'', Tn, Yb, Lu.
5c-Ba-Cu-0 system, 5
r-La-Cu-0 system, and further S'Ba, Ca't
Examples include 'substituted systems.
本発明に使用される酸化物超電導体粉末は、例えば以下
のようにして製造される。The oxide superconductor powder used in the present invention is produced, for example, as follows.
まず、Ｙ 、 Ｂａ、 Ｃｕ等のペロブスカイト型酸化
物超電導体の構成元素を十分混合する。混合の際には、
Ｙ２ ０３ 、ＢａＣＯ３、ＣｕＯ等の酸化物や炭酸塩
を原料として用いることができるほか、焼成後酸化物に
転化する硝酸塩、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。First, the constituent elements of the perovskite oxide superconductor, such as Y, Ba, and Cu, are sufficiently mixed. When mixing,
In addition to oxides and carbonates such as Y2 03 , BaCO3, and CuO, which can be used as raw materials, compounds such as nitrates and hydroxides that are converted to oxides after firing may also be used.
Furthermore, oxalate obtained by a coprecipitation method or the like may be used.
ペロブ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等でずれていても差支えない０例え
ば、Ｙ−Ｂａ−Ｃｕ−０系ではＹ １ ｎｏｌに対しＢ
ａ ２１１０＋、Ｃｕ ３ ｎｏｔが標準組成であるが
、実用上はＹ １１’ｌｏｌに対して、Ｂａ ２±０．
６ ｌ１ｏｌ、Ｃｕ ３±０．２ ｎｏｌ程度のずれは
問題ない。The elements constituting the perovskite-type oxide superconductor are basically mixed to have a stoichiometric composition, but there may be a slight deviation depending on the manufacturing conditions etc. For example, Y-Ba -In the Cu-0 system, B for Y 1 nol
a 2110+, Cu 3 not is the standard composition, but in practice it is Y 11'lol and Ba 2±0.
A deviation of approximately 6 l1ol and Cu 3±0.2 nol is not a problem.
そして、前述の原料を十分に混合した後、８５０〜９８
０℃程度の温度で焼成する。この焼成は充分に酸素の供
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
０次いで、必要に応じて酸素含有雰囲気中、好ましくは
酸素雰囲気中で熱処理するか、または同様な雰囲気中で
３００℃程度まで徐冷することにより、酸素欠陥δに酸
素を導入し超電導特性を向上させることができる。この
熱処理は、通常３００〜７００℃程度で行う。After thoroughly mixing the above-mentioned raw materials, 850 to 98
Fire at a temperature of about 0°C. This firing is preferably carried out in an oxygen-containing atmosphere where sufficient oxygen can be supplied. Next, if necessary, heat treatment is performed in an oxygen-containing atmosphere, preferably an oxygen atmosphere, or at 300°C in a similar atmosphere. By slow cooling to a certain degree, oxygen can be introduced into the oxygen defects δ and the superconducting properties can be improved. This heat treatment is usually performed at about 300 to 700°C.
次に、この焼成物をボールミル、サンドグラインダ、そ
の他公知の手段により粉砕する。このとき、ペロプスカ
イト型の酸化物超電導体は、へき開面から分割されて微
粉末となる。この粉砕は、平均粒径が０．１〜５μＩと
なるように行うことが好ましい。Next, this fired product is pulverized using a ball mill, a sand grinder, or other known means. At this time, the perovskite-type oxide superconductor is split from the cleavage plane and becomes fine powder. This pulverization is preferably performed so that the average particle size is 0.1 to 5 μI.
このようにして得られた酸化物超電導体粉末は、酸素欠
陥δを有する酸素欠陥型ペロプスカイト構造（ＬｎＢａ
２Ｃｕ３０７−、 （δは通常１以下の数））となる。The oxide superconductor powder thus obtained has an oxygen-deficient perovskite structure (LnBa
2Cu307-, (δ is usually a number of 1 or less)).
なお、ＢａをＳ「やＣａ等で置換することも可能であり
、さらにＣｕの一部をＴｉ、 Ｖ 、 Ｃｒ、Ｍｎ、
Ｆｅ、Ｃ０１Ｎ１、Ｚｎ等で置換することもできる。こ
の置換量は、′Ｍ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、あまり多量の置換は超電導特性
を低下させてしまうので８０ｉｏ １％以下とする。In addition, it is also possible to replace Ba with S'', Ca, etc., and further replace a part of Cu with Ti, V, Cr, Mn,
Substitution with Fe, C01N1, Zn, etc. is also possible. The amount of substitution can be set as appropriate within a range that does not reduce the 'M conductive properties, but too much substitution will reduce the superconducting properties, so it is set to 80io1% or less.
本発明の超電導体線材の製造方法についてさらに詳述す
ると、まず上述したような方法により作製した酸化物超
電導体粉末、あるいは上述しな酸化物超電導体の原料と
なる混合粉末を高温においても酸素と反応せず形状維持
能力に優れた銀からなる管材内に充填する。この管材の
材質としては、銀のみに限らず、本発明の効果を損わな
い範囲で銀合金を使用することも可能である。次いで、
スェージングマシン等により管材外から粉末をつき固め
た後、伸線加工を施す等して長尺化し、線状に加工する
。To explain in more detail the method for manufacturing the superconductor wire of the present invention, first, the oxide superconductor powder produced by the method described above or the mixed powder that is the raw material for the oxide superconductor described above is exposed to oxygen even at high temperatures. It is filled into a tube made of silver, which does not react and has excellent shape retention ability. The material of this tube material is not limited to silver, but it is also possible to use a silver alloy within a range that does not impair the effects of the present invention. Then,
After compacting the powder from the outside of the tube using a swaging machine or the like, it is made into a long length by wire drawing, etc., and processed into a linear shape.
次に、この酸化物超電導体粉末または加熱により酸化物
超電導体となる混合粉末を充填した管材の表面から内部
充填物に達する複数の貫通孔を形成する。この貫通孔の
形成は、ドリルやレーザ加工により容易に行うことが可
能である。また、貫通孔の大きさは、あまり大きいと線
材として使用する際に不便であり、また逆に小さすぎる
と酸素供給量が不充分となるため、直径０．１ｇｍ −
０，５ｉｉ程度が適当である。また、均一に酸化物超電
導体に酸素を供給するために等間隔で設けることが好ま
しい。Next, a plurality of through holes reaching the inner filling are formed from the surface of the tube filled with the oxide superconductor powder or the mixed powder that becomes an oxide superconductor by heating. This through hole can be easily formed by drilling or laser processing. In addition, if the size of the through hole is too large, it will be inconvenient to use it as a wire rod, and if it is too small, the amount of oxygen supplied will be insufficient, so the diameter is 0.1 g -
Approximately 0.5ii is appropriate. Further, in order to uniformly supply oxygen to the oxide superconductor, it is preferable to provide them at equal intervals.
この後、この貫通孔を形成した線状体に酸素含有雰囲気
中で熱処理を施す。この熱処理は、８５０℃〜９８０℃
程度の温度条件で行うことが適当であり、この熱処理は
０．５〜２時間程度で充分である。Thereafter, the linear body with the through holes formed therein is subjected to heat treatment in an oxygen-containing atmosphere. This heat treatment is carried out at 850°C to 980°C.
It is appropriate to carry out the heat treatment under a temperature condition of approximately 0.5 to 2 hours.
次いでこの熱処理温度から３００℃程度まで酸素を充分
に供給しながら徐冷することにより超電導特性が向上す
る。また、酸素を充分に供給しながら３００℃〜７００
℃程度の温度で数時間程度保持することも効果的である
。Next, the superconducting properties are improved by slowly cooling from this heat treatment temperature to about 300° C. while supplying sufficient oxygen. Also, while supplying sufficient oxygen,
It is also effective to maintain the temperature at a temperature of about °C for several hours.
なお、この超電導体線材を実際に使用する場合には、例
えば表面にメツキを施したり、また使用温度によっては
熱硬化樹脂等によって貫通孔を塞いだ後に使用する。When this superconductor wire is actually used, the surface is plated, or depending on the operating temperature, the through holes are closed with a thermosetting resin or the like before use.
（作 用）
本発明の超電導体線材の製造方法において、銀または銀
合金からなる管材内に酸化物超電導体を充填してなる線
状体に酸素供給用の貫通孔を形成した後に熱処理を施し
ているので、管材の肉厚によらず充分に酸素を供給する
ことが可能となり、よって短時間の熱処理で優れたａ電
導特性を有する超電導体線材を容易に得ることが可能と
なる。(Function) In the method for manufacturing a superconductor wire of the present invention, a wire body made of a tube made of silver or a silver alloy filled with an oxide superconductor is heat-treated after a through hole for oxygen supply is formed in the wire body. Therefore, it is possible to supply sufficient oxygen regardless of the wall thickness of the tube material, and it is therefore possible to easily obtain a superconductor wire having excellent a-conductivity characteristics with a short heat treatment.
（実施例） 次に、本発明の実施例について説明する。(Example) Next, examples of the present invention will be described.
実施例
粒径１〜５μＩＩのＢａＣ０３粉末２１１０１％、Ｙ２
Ｏ３粉末０．５ｍｏ１％、 ＣｕＯ粉末３ｉｏＨを、充
分混合して大気中９００℃で４８時間焼成して反応させ
た後、この焼成物をさらに酸素雰囲気中で８００℃で２
４時間焼成して反応させ、酸素空席に酸素を導入した後
、ボールミルを用いて粉砕し、平均粒径０．５μｍのペ
ロブスカイト型の酸化物超電導体粉末を得た。Example BaC03 powder 21101% with a particle size of 1 to 5μII, Y2
After thoroughly mixing 0.5 mo1% of O3 powder and 3ioH of CuO powder and firing in the atmosphere at 900°C for 48 hours to react, this fired product was further heated at 800°C in an oxygen atmosphere for 2 hours.
After firing for 4 hours to cause a reaction and introduce oxygen into the oxygen vacancies, the mixture was pulverized using a ball mill to obtain perovskite-type oxide superconductor powder with an average particle size of 0.5 μm.
次に、この酸化物超電導体粉末を外径２Ｇ１１＋１Ｘ内
径１６１１＋１Ｘ長さ７０ｍｍの一端を鋼材により封止
されなた鎖管中に入れ、プレス圧１ｔＯ１’ｌ／ｄでつ
きかためた後、他端に銀栓をして通気孔を残して溶接し
、次いでタークスヘッド機で一端を保持して外径２、０
ＩＩｎ ｘ長さ８璽まで冷間で伸線加工を施し、線状に
加工した。Next, one end of this oxide superconductor powder with an outer diameter of 2G11+1X, an inner diameter of 1611+1X, and a length of 70mm was put into a chain pipe sealed with a steel material, and after being hardened with a press pressure of 1tO1'l/d, the other end was Welded with a silver stopper, leaving a ventilation hole, and then held one end with a Turkshead machine to reduce the outer diameter to 2.0.
Cold wire drawing was performed to a length of IIn x 8 coils to form a wire.
次いで、この線状体の径方向に゛５ｎｉ間隔でドリルに
よって直径０，１１〜０，２１程度の貫通孔を形成した
。Next, through holes with a diameter of about 0.11 to 0.21 mm were formed by a drill at intervals of 5 ni in the radial direction of this linear body.
この後、この線状体を大気中で９３０℃、１０時間の条
件で熱処理し、続いて６００℃まで５℃／分で冷却し、
６００℃から３７０’Ｃまで０．２ｊＱ１分で酸素を供
給しながら１℃／分で徐冷して目的とする超電導体線材
を得た。After that, this linear body was heat-treated in the atmosphere at 930°C for 10 hours, and then cooled to 600°C at a rate of 5°C/min.
The superconductor wire was slowly cooled from 600°C to 370'C at 1°C/min while supplying oxygen at 0.2jQ1min to obtain the desired superconductor wire.
このようにして得た超電導体線材の超電導特性を測定し
た°ところ、臨界温度は９４にで、臨界電流密度は１１
１０＾／ｄと良好な結果が得られた。When the superconducting properties of the superconductor wire thus obtained were measured, the critical temperature was 94 degrees, and the critical current density was 11 degrees.
A good result of 10^/d was obtained.
また、本発明との比較のため、実施例における貫通孔を
形成しない以外は同一条件で超電導体線材を作製し、こ
の超電導体線材についてもその特性を調べたところ、臨
界電流密度５２０Ａ／ｄと低いものであった。In addition, for comparison with the present invention, a superconductor wire was produced under the same conditions as in the example except that the through holes were not formed, and the characteristics of this superconductor wire were also investigated. As a result, the critical current density was 520 A/d. It was low.
Ｃ発明の効果コ
以上の実施例からも明らかなように、本発明の超電導体
線材の製造方法によれば、酸素供給能力に優れた銀から
なる管材を被覆管として使用し、さらに内部の酸化物超
電導体に達する複数の貫通孔を設けた後に熱処理を施し
ているので、管材の肉厚によらず充分に酸素を供給する
ことができるなめ、バルク材と同様な超電導特性を有す
る超電導体線材を容易に得ることが可能となる。C. Effects of the Invention As is clear from the above examples, according to the method for manufacturing a superconductor wire of the present invention, a tube material made of silver with excellent oxygen supply ability is used as a cladding tube, and the internal oxidation Since heat treatment is applied after providing multiple through holes that reach the superconductor, sufficient oxygen can be supplied regardless of the thickness of the tube material, resulting in a superconductor wire material that has superconducting properties similar to those of bulk material. can be easily obtained.
出願人 株式会社 東芝 代理人 弁理士 須 山 佐 −Applicant: Toshiba Corporation Agent Patent Attorney Suyama Sa
Claims (4)
電導体となる混合粉末を銀または銀合金からなる管材内
に充填する工程と、この管材を線状に加工する工程と、
この加工工程により得た線状体の前記管材表面から内部
充填物に達する複数の貫通孔を形成する工程と、この貫
通孔の形成された線状体を酸素含有雰囲気中で熱処理す
る工程とを有することを特徴とする超電導体線材の製造
方法。(1) A step of filling an oxide superconductor powder or a mixed powder that becomes an oxide superconductor by heating into a tube material made of silver or a silver alloy, and a step of processing this tube material into a linear shape.
A step of forming a plurality of through holes reaching the internal filling material from the tube material surface of the linear body obtained by this processing step, and a step of heat treating the linear body with the through holes formed therein in an oxygen-containing atmosphere. A method for manufacturing a superconductor wire, comprising:
ロブスカイト型の超電導体であることを特徴とする特許
請求の範囲第１項記載の超電導体線材の製造方法。(2) The method for manufacturing a superconductor wire according to claim 1, wherein the oxide superconductor is a perovskite-type superconductor containing a rare earth element.
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１項または第２項記載
の超電導体線材の製造方法。(3) The oxide superconductor contains rare earth elements, Ba and Cu in an atomic ratio of substantially 1:2:3. A method for manufacturing superconductor wire.
＿７＿−＿δ（Ｌｎは希土類元素から選ばれた少なくと
も１種、δは酸素欠陥を表す。）で示される酸素欠陥型
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３項のいずれか１項記載の超電導
体線材の製造方法。(4) The oxide superconductor is LnBa_2Cu_3O
Claims 1 to 3 are characterized by having an oxygen-deficient perovskite structure represented by _7_-_δ (Ln is at least one selected from rare earth elements, and δ represents an oxygen defect). A method for producing a superconductor wire according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62273955A JPH01115015A (en) | 1987-10-29 | 1987-10-29 | Manufacture of superconductor wire material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62273955A JPH01115015A (en) | 1987-10-29 | 1987-10-29 | Manufacture of superconductor wire material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01115015A true JPH01115015A (en) | 1989-05-08 |
Family
ID=17534898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62273955A Pending JPH01115015A (en) | 1987-10-29 | 1987-10-29 | Manufacture of superconductor wire material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01115015A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09185914A (en) * | 1987-02-05 | 1997-07-15 | Sumitomo Electric Ind Ltd | Manufacture of composite oxide ceramic superconducting wire |
| JP2008232249A (en) * | 2007-03-20 | 2008-10-02 | Nok Corp | Dust cover fixing structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63291311A (en) * | 1987-05-22 | 1988-11-29 | Fujikura Ltd | Superconducting wire |
| JPS6471005A (en) * | 1987-05-02 | 1989-03-16 | Sumitomo Electric Industries | Superconductive composite and its manufacture |
| JPH01140520A (en) * | 1987-02-05 | 1989-06-01 | Sumitomo Electric Ind Ltd | Manufacture of composite oxide ceramic superconductive wire |
| JPH01163910A (en) * | 1987-05-01 | 1989-06-28 | Sumitomo Electric Ind Ltd | Superconductive composite and its manufacture |
| JPH01251514A (en) * | 1987-05-25 | 1989-10-06 | Hitachi Ltd | Superconductive wire and manufacture thereof |
-
1987
- 1987-10-29 JP JP62273955A patent/JPH01115015A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01140520A (en) * | 1987-02-05 | 1989-06-01 | Sumitomo Electric Ind Ltd | Manufacture of composite oxide ceramic superconductive wire |
| JPH01163910A (en) * | 1987-05-01 | 1989-06-28 | Sumitomo Electric Ind Ltd | Superconductive composite and its manufacture |
| JPS6471005A (en) * | 1987-05-02 | 1989-03-16 | Sumitomo Electric Industries | Superconductive composite and its manufacture |
| JPS63291311A (en) * | 1987-05-22 | 1988-11-29 | Fujikura Ltd | Superconducting wire |
| JPH01251514A (en) * | 1987-05-25 | 1989-10-06 | Hitachi Ltd | Superconductive wire and manufacture thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09185914A (en) * | 1987-02-05 | 1997-07-15 | Sumitomo Electric Ind Ltd | Manufacture of composite oxide ceramic superconducting wire |
| JP2008232249A (en) * | 2007-03-20 | 2008-10-02 | Nok Corp | Dust cover fixing structure |
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