JP3181642B2 - Manufacturing method of oxide superconducting wire - Google Patents
Manufacturing method of oxide superconducting wireInfo
- Publication number
- JP3181642B2 JP3181642B2 JP29050491A JP29050491A JP3181642B2 JP 3181642 B2 JP3181642 B2 JP 3181642B2 JP 29050491 A JP29050491 A JP 29050491A JP 29050491 A JP29050491 A JP 29050491A JP 3181642 B2 JP3181642 B2 JP 3181642B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconducting
- wire
- sheath
- superconducting material
- crystal
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 28
- 238000010304 firing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000002887 superconductor Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 229910001316 Ag alloy Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 organic acid salts Chemical class 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910021521 yttrium barium copper oxide 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
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸化物超電導線材の製
造方法に関し、さらに詳しくは結晶粒界が少なく臨界電
流値の高い酸化物超電導線材を低コストで製造する方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an oxide superconducting wire, and more particularly to a method for producing an oxide superconducting wire having a small crystal grain boundary and a high critical current value at a low cost.
【０００２】[0002]
【従来の技術】従来公知の酸化物超電導線材の製造方法
としては、以下に示す方法がある。2. Description of the Related Art As a method of manufacturing a conventionally known oxide superconducting wire, there is the following method.
【０００３】（１）酸化物超電導原料粉の仮焼と焼結を
繰り返したのち粉砕してＡｇシース材に詰め、最終的に
ロール圧延してテープ状にするPowder-in-tube法。 （２）酸化物超電導原料粉をＡｇパイプに詰め、溝ロー
ル圧延機やロール圧延機を用いてテープ状に伸線加工す
る方法。 （３）エキシマレーザアプレーション法によるＹ−Ｂａ
−Ｃｕ−Ｏ膜を用いた超電導線材の製造法。 （４）耐熱合金ハステロイＣ−276 基材上にレーザー蒸
着法によって酸化物超電導体を連続的に作製し、テープ
化を図る方法。 （５）各構成元素の有機酸塩を秤量・混合して所定の有
機溶剤に溶解した均一溶液を、装置にセットされたＡｇ
テープ上にコーティングし、熱分解によりグリーンテー
ブルを作製した後、切断もしくはコイル状に成型する方
法。(1) A powder-in-tube method in which calcination and sintering of an oxide superconducting raw material powder are repeated, then crushed and packed into an Ag sheath material, and finally roll-rolled to form a tape. (2) A method in which an oxide superconducting raw material powder is packed into an Ag pipe and drawn into a tape shape using a groove roll rolling machine or a roll rolling mill. (3) Y-Ba by excimer laser application method
-A method for producing a superconducting wire using a Cu-O film. (4) A method in which an oxide superconductor is continuously produced on a heat-resistant alloy Hastelloy C-276 base material by a laser vapor deposition method to form a tape. (5) A uniform solution obtained by weighing and mixing the organic acid salts of the respective constituent elements and dissolving the same in a predetermined organic solvent is used for the Ag set in the apparatus.
A method of coating on tape, producing a green table by thermal decomposition, and then cutting or molding into a coil shape.
【０００４】これらの方法のうち（１）および（２）の
方法は、Ａｇシース材を用いた線材の製造方法である
が、これらの方法は、焼成炉内で温度勾配を掛けて結晶
を一軸成長させるものではないため、シース線内におい
て結晶成長がランダムになるか、または結晶粒間でラン
ダムに焼結し、臨界電流密度が低くなってしまってい
た。Among these methods, the methods (1) and (2) are methods for producing a wire rod using an Ag sheath material. In these methods, a crystal is uniaxially applied by applying a temperature gradient in a firing furnace. Since the crystal is not grown, the crystal growth is random in the sheath wire, or the crystal is sintered randomly between crystal grains, and the critical current density is low.
【０００５】また、（３）および（４）の方法は、エキ
シマレーザーによるＹＢＣＯ膜を長尺テープに成膜して
いくことで結晶配向に優れ、高い臨界電流密度のものを
作製することができるという利点はあるが、臨界電流値
が小さいため、膜厚を厚くしなければならず、処理時間
がかかるという欠点を有している。さらに、これらの方
法によると、銀合金の長尺線材では結晶配向膜を成膜す
ることができないため、現在ではＹＳＺの基板を用いる
か、ハステロイ基板上にＹＳＺを中間層として形成して
いる。In the methods (3) and (4), a YBCO film is formed on a long tape by using an excimer laser, whereby a crystal having excellent crystal orientation and a high critical current density can be manufactured. However, since the critical current value is small, the film thickness has to be increased, which has the disadvantage of requiring a long processing time. Further, according to these methods, since a crystal orientation film cannot be formed with a long wire of a silver alloy, a YSZ substrate is currently used, or YSZ is formed as an intermediate layer on a Hastelloy substrate.
【０００６】（５）の方法は、超電導材料となる原料元
素の有機酸塩を有機溶剤に溶解させ、この有機溶媒をＡ
ｇテープ上に塗布して仮焼した後、これを巻きとって焼
成し、超電導テープを作製するというものであるが、こ
の方法によって得られる線材は多結晶体の超電導体であ
るため、結晶粒界によっては臨界電流密度が小さくな
り、高Ｊｃ化が難しいという欠点があった。In the method (5), an organic acid salt of a raw material element to be a superconducting material is dissolved in an organic solvent, and the organic solvent is dissolved in A
g is coated on a tape, calcined, wound and fired to produce a superconducting tape.Since the wire obtained by this method is a polycrystalline superconductor, In some fields, the critical current density is low, and it is difficult to increase the Jc.
【０００７】すなわち、上述従来の超電導線材の製造方
法の問題点をまとめると、エキシマレーザーを用いた成
膜方法では、良質な結晶配向をした膜を形成することが
できるという利点はあるものの、厚みがないために臨界
電流値が小さく、マグネット等に用いる臨界電流値より
も一桁小さかった。また、基本的に結晶核発生や結晶成
長が無制御であるため、結晶粒界が多く、臨界電流値を
著しく低下させる原因となっていた。That is, the problems of the above-mentioned conventional method for manufacturing a superconducting wire can be summarized as follows. The film forming method using an excimer laser has an advantage that a film having a good crystal orientation can be formed, but the thickness is high. The critical current value was small due to the absence of the magnetic flux, and was one order of magnitude smaller than the critical current value used for a magnet or the like. Further, since the generation of crystal nuclei and the crystal growth are basically uncontrolled, there are many crystal grain boundaries, causing a significant reduction in the critical current value.
【０００８】[0008]
【発明が解決しようとする課題】本発明は、上述従来の
技術の問題点を解決し、結晶粒界が少なく、臨界電流値
の高い酸化物超電導線材の製造方法を提供することを目
的とする。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a method for producing an oxide superconducting wire having a small crystal grain boundary and a high critical current value. .
【０００９】[0009]
【課題を解決するための手段】本発明者らは、斯る課題
を解決するため鋭意研究した結果、内部に酸化物超電導
材料粉末を充填した銀合金シース材を伸線してシース線
を作製し、内部の酸化物超電導材料粉末を部分溶融させ
た後、温度制御した焼成炉内において加熱処理すること
により、上記課題が解決されることを見い出し、本発明
を達成することができた。Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have drawn a silver alloy sheath material filled with an oxide superconducting material powder to prepare a sheath wire. After partially melting the oxide superconducting material powder inside, and then performing a heat treatment in a temperature controlled baking furnace, it was found that the above problem was solved, and the present invention could be achieved.
【００１０】 すなわち、本発明は、第１に、内部に酸
化物超電導材料粉末を充填したシース材に伸線処理を施
してシース線を作製し、このシース線表面にレーザー光
を局所的に照射して内部の酸化物超電導材料粉末を固相
と液相とが混在した部分溶融状態にし、このシース線を
焼成炉内において該酸化物超電導材料粉末の結晶化温度
以下に温度制御して加熱処理することにより該照射され
た位置との間に温度勾配を形成して、酸化物超電導材料
粉末の結晶成長を一軸的に制御することを特徴とする酸
化物超電導線材の製造方法；第２に、前記酸化物超電導
材料がＡｇＯ、ＢａＳｎＯ、ＰｔＯまたはＰｔのうちの
少なくとも１種を含有する、請求項１記載の製造方法；
第３に、前記シース線の巻き取り部または前記レーザー
光の照射位置を移動させることにより前記シース線に対
する前記レーザー光の照射位置を移動させる、請求項１
または２記載の製造方法、を提供するものである。That is, according to the present invention, first, a sheath material in which a sheath material filled with an oxide superconducting material powder is subjected to a drawing process to produce a sheath wire, and a laser beam is locally irradiated on the surface of the sheath wire The oxide superconducting material powder inside is partially melted in which a solid phase and a liquid phase are mixed, and the sheath wire is heat-treated in a firing furnace by controlling the temperature below the crystallization temperature of the oxide superconducting material powder. Forming a temperature gradient with the irradiated position to control the crystal growth of the oxide superconducting material powder uniaxially; second, a method for producing an oxide superconducting wire; The production method according to claim 1, wherein the oxide superconducting material contains at least one of AgO, BaSnO, PtO, and Pt;
Third, the irradiation position of the laser light with respect to the sheath wire is moved by moving the winding portion of the sheath wire or the irradiation position of the laser light.
Or the production method according to 2.
【００１１】[0011]
【作用】酸化物超電導体にはコングリエント組成がない
ため、液相から目的とする結晶を直接形成することがで
きなかった。そこで、固相と液相とが混在した部分溶融
状態を形成し、その状態から包晶反応を進行させて目的
とする結晶を成長させるという部分溶融法などが用いら
れていた。このような部分溶融法により結晶を成長させ
ると、結晶中に不純物の形で包晶反応の残留物が残存
し、これがピンニングセンターとして働き、臨界電流値
向上の要因となる。また、部分溶融法で結晶化させた結
晶は結晶粒界が少ないため、そのバルクは焼結法で得た
焼結体よりも臨界電流値が二桁近く高くなることが知ら
れている。さらに、部分溶融法によると、温度勾配の掛
け方によっては50φ程度の単結晶状の結晶を作製するこ
ともできる。Since the oxide superconductor does not have a congruent composition, a desired crystal cannot be directly formed from a liquid phase. Therefore, a partial melting method has been used in which a partial melting state in which a solid phase and a liquid phase are mixed is formed, and a peritectic reaction proceeds from that state to grow a target crystal. When the crystal is grown by such a partial melting method, a residue of the peritectic reaction remains in the form of impurities in the crystal, which acts as a pinning center and causes an increase in the critical current value. Further, it is known that the crystal obtained by the partial melting method has a small number of crystal grain boundaries, and thus the bulk thereof has a critical current value nearly two orders of magnitude higher than that of the sintered body obtained by the sintering method. Further, according to the partial melting method, a single crystal of about 50φ can be produced depending on how to apply a temperature gradient.
【００１２】すなわち、本発明は、上記のような特性を
有する部分溶融法を酸化物超電導線材の製造技術に応用
することにより、結晶粒界が少なく、臨界電流値が高い
酸化物超電導線材の製造を可能にしたものである。That is, the present invention provides a method for producing an oxide superconducting wire having a small crystal grain boundary and a high critical current value by applying the partial melting method having the above-described characteristics to a technique for producing an oxide superconducting wire. Is made possible.
【００１３】本発明法によると、まず、シース用パイプ
に酸化物超電導材料粉末を充填し、これに伸線処理およ
び加熱処理を施してシース線を作製する。上記酸化物超
電導材料粉末の原料としては、Ｙ系ではＹ2 Ｏ3 ＋Ｂａ
x Ｃｕy Ｏz 、Ｙ2 Ｂａ1Ｃｕ1 Ｏ5 ＋Ｂａx Ｃｕy Ｏ
z 、Ｙ2 Ｏ3 ＋ＢａＯ＋ＣｕＯなどがあり、Ｂａx Ｃｕ
y Ｏz や酸化銅が液相成分となり易い性質を有してい
る。なお、酸化銅としてＣｕ2 Ｏを用いることもでき
る。また、これら主成分のほかにＡｇＯ、ＢａＳｎＯ、
ＰｔＯまたはＰｔなどを添加することにより、超電導線
材の特性は著しく向上する。一方、同じＹ系であって
も、Ｙ1 Ｂａz Ｃｕ3 Ｏ7-x などＹ系 123相の合成粉
は、 1,000℃以上に加熱しても簡単には 211相と液相成
分に分解しないため、Ａｇ合金のシース材の融点と上記
分解温度とが近似してしまい、Ａｇ系線材の原料粉とし
て用いることはできなくなってしまう。According to the method of the present invention, first, a sheath pipe is filled with an oxide superconducting material powder, and this is subjected to a drawing process and a heating process to prepare a sheath wire. As a raw material of the oxide superconducting material powder, Y 2 O 3 + Ba
x Cu y O z , Y 2 Ba 1 Cu 1 O 5 + Ba x Cu y O
z , Y 2 O 3 + BaO + CuO, etc., and Ba x Cu
y Oz and copper oxide have the property of easily becoming a liquid phase component. Note that Cu 2 O can also be used as copper oxide. In addition to these main components, AgO, BaSnO,
By adding PtO or Pt, the characteristics of the superconducting wire are significantly improved. On the other hand, even with the same Y-based, synthetic powder of Y 1 Ba z Cu 3 O 7 -x , etc. Y-123 phase, not decompose 211 and liquid phases component simplifies be heated to above 1,000 ° C. For this reason, the melting point of the Ag alloy sheath material and the above-mentioned decomposition temperature become close to each other, so that it cannot be used as a raw material powder for Ag-based wires.
【００１４】また、上記酸化物超電導材料粉末の原料と
してＢｉ系2212相の合成粉を用いることもできる。例え
ば、Ｂｉ2 Ｐｂx Ｓｒ2 Ｃａ1-y Ｙy Ｃｕ2 Ｏ2 などが
あり、これらＢｉ系の合成粉は結晶化温度が 850℃と低
い上、ＢｉＯ2 、ＰｂＯまたはＣｕＯが液相成分として
作用し、Ｔｃが向上する上、雰囲気の影響を受けないた
めＪｃを容易に向上させることができる。Further, as a raw material of the above-mentioned oxide superconducting material powder, a Bi-based 2212 phase synthetic powder can be used. For example, there are Bi 2 Pb x Sr 2 Ca 1-y Y y Cu 2 O 2 , and these Bi-based synthetic powders have a low crystallization temperature of 850 ° C., and BiO 2 , PbO or CuO is used as a liquid phase component. Tc is improved, and Jc can be easily improved because it is not affected by the atmosphere.
【００１５】さらに、酸化物超電導材料粉末の原料がＹ
系の場合には 1,000℃以下、特に 940〜980 ℃の結晶育
成温度で加熱処理し、また、Ｂｉ系の場合には 860℃以
下、特に 850℃で加熱処理すると良い。Further, the raw material of the oxide superconducting material powder is Y
In the case of a system, heat treatment is preferably performed at a crystal growth temperature of 1,000 ° C. or less, particularly 940 to 980 ° C., and in the case of a Bi system, heat treatment is preferably performed at 860 ° C. or less, particularly 850 ° C.
【００１６】次に、上記作製したシース線にレーザー光
を照射して局所加熱し、シース線内部の酸化物超電導材
料粉末を部分溶融状態にし、これを温度制御した焼成炉
内で加熱処理することにより結晶を成長させる。この
時、焼成炉内の温度は、超電導材料の結晶化温度と同程
度から低めに制御することにより、レーザーのスポット
位置との間に温度勾配が形成され、結晶成長が制御され
る。このように結晶成長を制御することにより、結晶粒
界の少ない酸化物超電導線材を容易に得ることができる
のである。なお、線材の巻き取り部またはレーザーのス
ポット位置を移動させることにより、上記局所加熱位置
は容易に移動させることができる。Next, the above-prepared sheath wire is irradiated with a laser beam and locally heated to partially melt the oxide superconducting material powder inside the sheath wire, and heat-treated in a temperature-controlled firing furnace. To grow a crystal. At this time, the temperature in the firing furnace is controlled to be lower than or equal to the crystallization temperature of the superconducting material, so that a temperature gradient is formed between the temperature and the laser spot position, and the crystal growth is controlled. By controlling the crystal growth in this manner, an oxide superconducting wire having few crystal grain boundaries can be easily obtained. The local heating position can be easily moved by moving the winding portion of the wire or the spot position of the laser.
【００１７】このように温度勾配を形成し、結晶成長を
制御しながら結晶化させる方法は、シース線用パイプに
超電導材料を充填・加圧し線材を製造する方法、テープ
基板上に超電導材料を塗布して線材を製造する方法、ま
たはドクターブレードで成形した超電導材料をテープ基
板上に載置して線材を製造する方法のいずれの方法に採
用しても上記同様の効果を得ることができる。As described above, the method of forming a temperature gradient and crystallizing while controlling the crystal growth includes a method of filling and pressing a superconducting material in a sheath wire pipe to produce a wire, and a method of applying a superconducting material on a tape substrate. The same effects as described above can be obtained by adopting any method of manufacturing a wire by using a superconducting material formed by a doctor blade or mounting a superconducting material on a tape substrate to manufacture a wire.
【００１８】以下、実施例により本発明をさらに詳細に
説明する。しかし本発明の範囲は以下の実施例により制
限されるものではない。Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by the following examples.
【００１９】[0019]
【実施例１】まず、酸化物超電導材料Ｙ1 Ｂａ2 Ｃｕ3
Ｏ7-x の原料粉として、Ｙ2 Ｏ3 とＢａＣｕＯ2 および
ＣｕＯを用意し、Ｙ：Ｂａ：Ｃｕ＝1.4 :2.2 : 3.2 の
組成比で混合したものにＰｔを 0.5wt％およびＡｇＯを
5wt％添加し、均一に混合した。次いで、この粉末をＡ
ｇにＰｔを 5wt％添加した肉厚 2mm、内径10φ、長さ50
の銀合金シース用パイプに充填し、このパイプをスウェ
ージング装置で伸線処理して直径 100μｍのシース線を
作製した。Example 1 First, an oxide superconducting material Y 1 Ba 2 Cu 3
As raw material powder of O 7-x , Y 2 O 3 , BaCuO 2 and CuO are prepared, and 0.5 wt% of Pt and AgO are mixed in a mixture of Y: Ba: Cu = 1.4: 2.2: 3.2.
5 wt% was added and mixed uniformly. Then, this powder is A
g with Pt added at 5wt%, wall thickness 2mm, inner diameter 10φ, length 50
Was filled in a silver alloy sheath pipe, and the pipe was drawn with a swaging apparatus to produce a sheath wire having a diameter of 100 μm.
【００２０】次に、作製したシース線に、光ファイバー
でガイドしながらＮｄ：ＹＡＧレーザーを局所的に照射
し、シース線内部の酸化物超電導材料粉末を部分溶融状
態にした。次いで、焼成炉内にセットしたシース線巻き
取り用ボビンにより、１cm/hr 程度の巻き取り速度で該
シース線を炉外から巻き取り、炉内において加熱処理を
施して酸化物超電導線材を得た。なお、焼成炉内の温度
は 940℃に設定した。Next, the produced sheath wire was locally irradiated with an Nd: YAG laser while being guided by an optical fiber to partially melt the oxide superconducting material powder inside the sheath wire. Next, the sheath wire was wound from the outside of the furnace at a winding speed of about 1 cm / hr by a bobbin for winding a sheath wire set in a firing furnace, and subjected to heat treatment in the furnace to obtain an oxide superconducting wire. . The temperature in the firing furnace was set at 940 ° C.
【００２１】このようにして得られた酸化物超電導線材
のＪｃ値は 2×103 A/cm2 であった。また、ＳＥＭ観察
の結果、緻密な組織が作製されており、粒界と見られる
部分が少ないることが確認された。The Jc value of the oxide superconducting wire thus obtained was 2 × 10 3 A / cm 2 . In addition, as a result of SEM observation, it was confirmed that a dense structure was produced, and that a portion regarded as a grain boundary was small.
【００２２】[0022]
【実施例２】まず、Ｂｉ系2212相酸化物超電導材料の原
料粉末として、Ｂｉ2 Ｏ、ＳｒＯ、ＣａＯ、ＣｕＯおよ
びＹ2 Ｏ3 の粉を用意し、Ｂｉ：Ｓｒ：Ｃａ：Ｃｕ：Ｙ
＝2: 2 : 0.8 : 2 : 0.2 の組成比で混合したものにＰ
ｔを 0.5wt％およびＡｇＯを5wt％添加し、均一に混合
した。次いで、この粉末をＡｇにＰｔを 5wt％添加した
肉厚 2mm、内径10φ、長さ50の銀合金シース用パイプに
充填し、このパイプをスウェージング装置で伸線処理し
て直径 100μｍのシース線を作製した。Example 2 First, powders of Bi 2 O, SrO, CaO, CuO and Y 2 O 3 were prepared as raw material powders of a Bi-based 2212 phase oxide superconducting material, and Bi: Sr: Ca: Cu: Y
= 2: 2: 0.8: 2: 0.2
0.5 wt% of t and 5 wt% of AgO were added and mixed uniformly. Next, the powder was filled into a silver alloy sheath pipe having a thickness of 2 mm, an inner diameter of 10 mm, and a length of 50 in which 5 wt% of Pt was added to Ag, and the pipe was drawn with a swaging apparatus to form a sheath wire having a diameter of 100 μm. Was prepared.
【００２３】次に、作製したシース線を用い、炉内温度
を840 ℃にセットしたこと以外は実施例１と同様にして
酸化物超電導線材を製造した。その結果、得られた線材
のＪｃ値は 3×103 A/cm2 であり、またＳＥＭによる断
面観察ではＢｉ系特有の板状結晶の配向組織が観察され
た。Next, an oxide superconducting wire was manufactured in the same manner as in Example 1 except that the furnace temperature was set to 840 ° C. using the prepared sheath wire. As a result, the Jc value of the obtained wire was 3 × 10 3 A / cm 2 , and in the cross-section observation by SEM, an oriented structure of plate-like crystal peculiar to Bi system was observed.
【００２４】[0024]
【発明の効果】本発明法の開発により、シース線内部の
酸化物超電導材料粉末の結晶成長を一軸的に制御するこ
とができようになったため、結晶粒界が少なく、臨界電
流値の高い酸化物超電導線材を製造することができるよ
うになった。According to the development of the method of the present invention, the crystal growth of the oxide superconducting material powder inside the sheath wire can be controlled uniaxially. Superconducting wires can be manufactured.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01B 12/00 - 13/00 C30B 29/22 Continuation of front page (58) Field surveyed (Int.Cl. 7 , DB name) H01B 12/00-13/00 C30B 29/22
Claims (3)
シース材に伸線処理を施してシース線を作製し、このシ
ース線表面にレーザー光を局所的に照射して内部の酸化
物超電導材料粉末を固相と液相とが混在した部分溶融状
態にし、このシース線を焼成炉内において該酸化物超電
導材料粉末の結晶化温度以下に温度制御して加熱処理す
ることにより該照射された位置との間に温度勾配を形成
して、酸化物超電導材料粉末の結晶成長を一軸的に制御
することを特徴とする酸化物超電導線材の製造方法。1. A sheath material in which a sheath material filled with an oxide superconducting material powder is drawn to form a sheath wire, and the surface of the sheath wire is locally irradiated with a laser beam to thereby form an inner oxide superconducting material. The powder is brought into a partially melted state in which a solid phase and a liquid phase are mixed , and this sheath wire is placed in a firing furnace with the oxide superconductor.
Heat treatment by controlling the temperature below the crystallization temperature of the conductive material powder
To form a temperature gradient with the irradiated position
And controlling the crystal growth of the oxide superconducting material powder uniaxially .
ｎＯ、ＰｔＯまたはＰｔのうちの少なくとも１種を含有
する、請求項１記載の製造方法。 2. The oxide superconducting material is AgO, BaS.
Contains at least one of nO, PtO or Pt
The method according to claim 1, wherein
ーザー光の照射位置を移動させることにより前記シース
線に対する前記レーザー光の照射位置を移動させる、請
求項１または２記載の製造方法。 3. A winding portion of the sheath wire or the laser wire.
The sheath is moved by moving the irradiation position of the laser light.
Moving the irradiation position of the laser beam with respect to the line;
3. The production method according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29050491A JP3181642B2 (en) | 1991-10-09 | 1991-10-09 | Manufacturing method of oxide superconducting wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29050491A JP3181642B2 (en) | 1991-10-09 | 1991-10-09 | Manufacturing method of oxide superconducting wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05101726A JPH05101726A (en) | 1993-04-23 |
| JP3181642B2 true JP3181642B2 (en) | 2001-07-03 |
Family
ID=17756878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29050491A Expired - Fee Related JP3181642B2 (en) | 1991-10-09 | 1991-10-09 | Manufacturing method of oxide superconducting wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3181642B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69529443T2 (en) * | 1994-09-30 | 2003-10-02 | Canon K.K., Tokio/Tokyo | Process for the production of a superconducting wire |
| JP3161938B2 (en) * | 1995-05-11 | 2001-04-25 | キヤノン株式会社 | Superconducting wire manufacturing method |
-
1991
- 1991-10-09 JP JP29050491A patent/JP3181642B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05101726A (en) | 1993-04-23 |
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