JPH03216917A - Manufacture of superconducting wire - Google Patents
Manufacture of superconducting wireInfo
- Publication number
- JPH03216917A JPH03216917A JP2009991A JP999190A JPH03216917A JP H03216917 A JPH03216917 A JP H03216917A JP 2009991 A JP2009991 A JP 2009991A JP 999190 A JP999190 A JP 999190A JP H03216917 A JPH03216917 A JP H03216917A
- Authority
- JP
- Japan
- Prior art keywords
- wire
- superconducting
- composition
- heat treatment
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 19
- 239000011812 mixed powder Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002887 superconductor Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229920006240 drawn fiber Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004804 winding 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、超電導線材の製造方法に関するものである。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing a superconducting wire.
従来、超電導セラミックスファイバなどの超電導線材は
、例えば「銀シースバイブ伸線法」により製造されてい
る。この方法では、まず原料としてＢｌ Ｏ 、Ｓ
ｒ ＣＯ 、Ｃａ Ｃｏ ＳＣｕ ０２ ３
３ ３
等が秤量、混合された後、予備焼結されて微粉末に粉砕
される。次いで、この原料混合粉末を銀（Ａｇ ）バイ
ブに充填した後、冷間加工を経て伸線され、細径化され
る。しかる後、その線材を熱処理することにより、超電
導現象を呈する線材とされている。Conventionally, superconducting wires such as superconducting ceramic fibers have been manufactured by, for example, the "silver sheath vibe wire drawing method." In this method, the raw materials are BlO, S
r CO , Ca Co SCu 02 3
3 3 etc. are weighed and mixed, pre-sintered and ground into fine powder. Next, this raw material mixed powder is filled into a silver (Ag) vibrator, and then cold-worked and wire-drawn to reduce the diameter. Thereafter, the wire is heat-treated to produce a wire exhibiting superconducting phenomena.
しかしながら、従来の製造方法ではバイブを冷間加工に
よって仲線しているため、長尺な線材を連続して得られ
ない。また、原料混合粉末をパイプに充填して伸線して
いるため、バイブの内部で原料混合粉末が途切れること
があり、従って十分？細径化ができない。However, in the conventional manufacturing method, the vibrator is formed into wires by cold working, so that it is not possible to continuously obtain long wire rods. Also, since the raw mixed powder is filled into the pipe for wire drawing, the raw mixed powder may be interrupted inside the vibrator. It is not possible to make the diameter smaller.
そこで本発明者らは、上記従来技術の欠点を解決すべく
、銀シース法とは全く異なる新規な超電導線材の製造方
法を完成し、先に特許出願した（特願昭６３−２９２２
１０号；未公開）。この先願の製造方法は、下記の３つ
の工程を備えて構成される。すなわち、超電導酸化物を
構成し得る原料として、例えばＢｌ■０３，ＰｂＯ，Ｓ
ｒＣ０３，ＣａＣＯ ，ＣｕＯからなる混合粉末を、
３
その融点以上の温度で加熱溶融した後、急速冷却によっ
て超電導組成のガラス母材とする第１工程と、このガラ
ス母材を加熱して、幅が１〜３ｌ■、厚さが５０〜５０
０μｍの超電導組成のテープ状ファイバに線引きする第
２工程と、このファイノく（予備線材）を熱処理によっ
て再結晶化させ、超電導セラミックスファイバとする第
３工程とを備えている。Therefore, in order to solve the above-mentioned drawbacks of the conventional technology, the present inventors completed a new method for manufacturing superconducting wires, which is completely different from the silver sheath method, and filed a patent application (Japanese Patent Application No. 63-2922
No. 10; unpublished). The manufacturing method of this prior application includes the following three steps. That is, as raw materials that can constitute the superconducting oxide, for example, BlO3, PbO, S
Mixed powder consisting of rC03, CaCO and CuO,
3 A first step of heating and melting at a temperature above the melting point and then rapid cooling to form a glass base material with a superconducting composition, and heating this glass base material to form a glass base material with a width of 1 to 3 liters and a thickness of 50 to 50 mm.
The method includes a second step of drawing a tape-shaped fiber having a superconducting composition of 0 μm, and a third step of recrystallizing this fiber (preliminary wire) through heat treatment to form a superconducting ceramic fiber.
しかしながら、上記の先願に係る製造方法は、可撓性に
優れて十分に臨界電流密度の高い超電導線材が得られる
点で有用であるものの、下記の点では未だ不十分な点を
有していた。すなわち、第３工程として再結晶化のため
の熱処理を行なうと、融点が低くて蒸気圧の高いビスマ
ス（Ｂ１）および鉛（Ｐｂ ）の多くが揮散し、特に線
材の表面付近で超電導相が良好に得られなかった。これ
は、線材としたときにはバルクに比べて表面積が極めて
大きく、特にテープ形状としたときには、表面積の大き
さ故にＢｌ，Ｐｂが益々揮散しやすくなったためと考え
られる。However, although the manufacturing method according to the above-mentioned prior application is useful in that a superconducting wire with excellent flexibility and a sufficiently high critical current density can be obtained, it still has the following disadvantages. Ta. In other words, when heat treatment is performed for recrystallization as the third step, much of bismuth (B1) and lead (Pb), which have low melting points and high vapor pressures, volatilizes, resulting in a good superconducting phase, especially near the surface of the wire. I couldn't get it. This is thought to be because when made into a wire, the surface area is extremely large compared to the bulk, and especially when made into a tape shape, Bl and Pb become more easily volatilized due to the large surface area.
本発明者は上記課題の解決のため、鋭意研究を重ねた結
果、長尺であって可撓牲が高く、しかもＢｌ，Ｐｂが所
要量含まれるが故に、高い臨界電流密度を実現できる超
電導線材の製造方法を見出した。In order to solve the above problems, the present inventor has conducted intensive research and found a superconducting wire that is long, highly flexible, and contains the required amounts of Bl and Pb, so that it can realize a high critical current density. discovered a manufacturing method.
この製造方法においては、まず第１工程として、超電導
酸化物を構成し得る原料混合粉末が用意され、例えばそ
の融点温度以上での加熱溶融の後に、急速冷却によって
超電導組成のガラス母材が形成される。ここで、原料混
合粉末の仕込みに際しては、ガラス母材に含まれる（Ｂ
ｌ十Ｐｂ）の量が、最終目的組成の１０１〜２００％と
なるようにする。このような過剰な仕込みをすれば、後
の熱処理でＢｌ，Ｐｂが揮散しても、これらが線材中に
必要量だけ残存する。なお、急冷処理は例えば原料融液
を鉄板上に流してプレスすればよい。In this manufacturing method, in the first step, a raw material mixed powder that can constitute a superconducting oxide is prepared, and after being heated and melted at a temperature higher than its melting point, a glass base material having a superconducting composition is formed by rapid cooling. Ru. Here, when preparing the raw material mixed powder, (B
The amount of Pb) is adjusted to be 101 to 200% of the final target composition. If such excessive preparation is performed, even if Bl and Pb are volatilized in the subsequent heat treatment, they will remain in the wire in the necessary amount. In addition, the rapid cooling process may be performed, for example, by pouring the raw material melt onto an iron plate and pressing it.
次に、第２工程として、超電導組成のガラス母材を第１
図のような紡糸装置にセットし、所望のサイズのファイ
バに線引きする。第１図に示すように、ガラス母材１は
石英製のダミー棒２に固着され、このガラス母材１は石
英管３に挿入される。Next, as a second step, a glass base material with a superconducting composition is
Set it in the spinning device as shown in the figure and draw it into a fiber of the desired size. As shown in FIG. 1, a glass base material 1 is fixed to a dummy rod 2 made of quartz, and this glass base material 1 is inserted into a quartz tube 3.
そして、石英管３の外側にはヒーター４が設けられてい
る。ダミー棒２が母材送り装置５によって下降されると
、そのダミー棒２の先端のガラス母材１はヒーター４で
加熱され、軟化して線引きが始められる。線引きされた
ファイバ６はキャブスタン７を経由して、巻取部８に巻
き取られる。A heater 4 is provided outside the quartz tube 3. When the dummy rod 2 is lowered by the base material feeding device 5, the glass base material 1 at the tip of the dummy rod 2 is heated by the heater 4, softens, and starts wire drawing. The drawn fiber 6 passes through a cab stan 7 and is wound into a winding section 8.
次に、第３工程として、線引きされたファイバの熱処理
を行なう。熱処理条件については、ｐｂが揮散するのを
防止するために、酸素を含む雰囲気とするのが望ましく
、特に２５％以上の酸素雰囲気とすれば、良好にｐｂの
揮散を防止し得る。Next, as a third step, the drawn fiber is heat treated. Regarding the heat treatment conditions, in order to prevent PB from volatilizing, it is desirable to use an atmosphere containing oxygen, and in particular, an oxygen atmosphere of 25% or more can effectively prevent PB from volatilizing.
本発明によれば、ガラス母材には最終目的組成に対して
（ＢＩ＋Ｐｂ）が過剰に仕込まれているので、超電導特
性の優れた超電導線材を得ることができる。すなわち、
臨界温度Ｔ が７７Ｋ以上Ｃ
の結晶相としては、例えば、
８０Ｋ相
→（Ｂｌ，Ｐｂ） ２Ｓｒ２Ｃａ，Ｃｕ２０１１０Ｋ相
−”（Ｂｌ，Ｐｂ）２Ｓｒ２Ｃａ２Ｃｕ３０が知られて
いるが，（Ｂｌ ＋Ｐｂ） −２の組成比で仕込むと熱
処理での揮散によりＢｉ，Ｐｂが欠乏状態となり、他の
元素（Ｓｒ ， Ｃａ ， Ｃｕ ）が過剰になって不
純物として析出する。このため、体積分率が下がって、
臨界電流密度Ｊ が低くなＣ
る。本発明では、例えば１１０Ｋ相の（Ｂｌ，Ｐｂ）２
Ｓ『２Ｃａ２Ｃｕ３０において（Ｂ１，Ｐ ｂ ） ２
が１０１〜２００％仕込まれるので、熱処理によっても
（ＢＩ．Ｐｂ）が所要量残留し、Ｃａ．Ｃｕ，Ｓｒが不
純物として析出しない。According to the present invention, since the glass base material contains (BI+Pb) in excess of the final target composition, a superconducting wire with excellent superconducting properties can be obtained. That is,
As a crystal phase with a critical temperature T of 77K or higher, for example, 80K phase→(Bl,Pb)2Sr2Ca,Cu2010K phase-"(Bl,Pb)2Sr2Ca2Cu30 is known, but the composition of (Bl+Pb)-2 When charged at a specific ratio, Bi and Pb become deficient due to volatilization during heat treatment, and other elements (Sr, Ca, Cu) become excessive and precipitate as impurities.As a result, the volume fraction decreases,
The critical current density J becomes lower C. In the present invention, for example, 110K phase (Bl,Pb)2
S'2Ca2Cu30 (B1, P b ) 2
Since 101 to 200% of Ca. Cu and Sr do not precipitate as impurities.
なお、（Ｂｌ，Ｐｂ）を過剰に仕込みすぎたため、熱処
理後も（Ｂｉ，Ｐｂ）が過剰になることはありうるが、
上記１０１〜２００％の範囲ならば、Ｂｉサイト（Ｂｌ
＋Ｐｂ）が欠乏するよりは析出する不純物の体積分率
が非常に低く、臨界電流密度Ｊ に大きな影響は与えな
い。但し、Ｃ
２ ０ ０％以上にすると、（ＢＩ＋Ｐｂ）からなる不
純物析出により、臨界電流密度Ｊ が大きく低Ｃ
下していく。In addition, it is possible that (Bi, Pb) remains in excess even after heat treatment because (Bl, Pb) was prepared too much.
If it is in the range of 101 to 200% above, Bi site (Bl
The volume fraction of precipitated impurities is much lower than when Pb) is deficient, and the critical current density J2 is not significantly affected. However, when C 200% or more, the critical current density J decreases significantly due to impurity precipitation consisting of (BI+Pb).
また、酸素雰囲気で熱処理したときには、ｐｂの揮散を
有効に防止し得る。すなわち、アモルファス状態となっ
た予備線材は、熱処理によって再結晶化されるが、結晶
化時には各元素が再配列し、ｐｂが金属として存在する
ことがある。このような金属状態のｐｂは、融点が３２
７℃と低く、８００〜８５０℃前後の熱処理では蒸気圧
が高くて揮散しやすい。そこで、過剰な酸素雰囲気とし
ておけば、金属状態のｐｂは酸化してＰｂＯとなり、こ
れは融点が８８８℃であるので蒸気圧が低く、結果とし
てｐｂの揮散が防止される。Moreover, when heat-treated in an oxygen atmosphere, volatilization of PB can be effectively prevented. That is, the preliminary wire in an amorphous state is recrystallized by heat treatment, but during crystallization, each element is rearranged and PB may exist as a metal. PB in such a metallic state has a melting point of 32
Heat treatment at temperatures as low as 7°C and around 800 to 850°C results in high vapor pressure and easy volatilization. Therefore, if an excess oxygen atmosphere is provided, Pb in a metallic state is oxidized to become PbO, which has a melting point of 888° C., so its vapor pressure is low, and as a result, volatilization of Pb is prevented.
以下、本発明の好適な実施例を説明する。 Hereinafter, preferred embodiments of the present invention will be described.
（実施例１）
まず、ＢＩ Ｏ 、Ｐｂ ＯＳＳｒ Ｃｏ ．
．Ｃａ２ ３ ３
ＣＯ３およびＣｕＯを
Ｂｉ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−２．
１：０． ９：２：２：３となる仕込み組成で秤
量し、混合した。この混合された粉末を８００℃、１２
時間の仮焼の後に、再度、粉砕して混合した。この混合
粉末を白金るつぼに入れて、電気炉中で１２５０℃で２
０分間溶融した後、冷却された鉄板上に融液を流して板
状のガラス母材を得た。このガラス母材を石英製のダミ
ー棒の先端に取付けた後、４５０℃に加熱、軟化させて
線引し、幅１．５龍、厚さ１００μｍのテープ状ファイ
バを得た。(Example 1) First, BIO, Pb OSSr Co.
．． Ca233CO3 and CuO in Bi:Pb:Sr:Ca:Cu-2.
1:0. The ingredients were weighed and mixed at a charging composition of 9:2:2:3. This mixed powder was heated at 800℃ for 12
After calcination for an hour, it was ground and mixed again. This mixed powder was placed in a platinum crucible and heated at 1250℃ for 2 hours in an electric furnace.
After melting for 0 minutes, the melt was poured onto a cooled iron plate to obtain a plate-shaped glass base material. This glass base material was attached to the tip of a dummy rod made of quartz, heated to 450° C. to soften it, and drawn to obtain a tape-shaped fiber having a width of 1.5 mm and a thickness of 100 μm.
次に、このテープ状ファイバを熱処理炉に入れて、大気
中で８４０℃、１００時間の熱処理をし、結晶を析出さ
せて超電導線材を得た。このようにして得られた超電導
線材の特性（臨界温度Ｔ ，Ｃ
臨界電流密度Ｊ ）を、液体窒素中に入れて公知Ｃ
の４端子法で測定したところ、Ｊ −３６６Ａ／Ｃ
Ｃシ（７７゜Ｋ、零磁場下）の超電導特性を得た。また
、超電導線材の組成は、
Ｂｉ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１．
６：屹２＋２：２：３
であった。Next, this tape-shaped fiber was placed in a heat treatment furnace and heat treated in the atmosphere at 840° C. for 100 hours to precipitate crystals and obtain a superconducting wire. The characteristics (critical temperature T, C critical current density J) of the superconducting wire obtained in this way were measured by the four-terminal method of the known C in liquid nitrogen. We obtained superconducting properties at a temperature of 0.2 °K (under zero magnetic field). The composition of the superconducting wire is Bi:Pb:Sr:Ca:Cu-1.
6: 屹2+2:2:3.
（実施例２）
原料の仕込み組成を
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１． ６
ｇｏ． ４：２：２：３として、実施例１と同様に
超電導線材を作製した。(Example 2) The charging composition of the raw materials was Bl:Pb:Sr:Ca:Cu-1. 6
go. A superconducting wire was produced in the same manner as in Example 1, with the ratio of 4:2:2:3.
その結果、臨界電流Ｊ として
Ｃ
Ｊ ＝２Ａ／ｃシ（零磁場、７７Ｋ）Ｃ
を得た。また、最終組成は
Ｂｆ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ一 １
、 ｏ：ｏ． ０：２：２：３となっていた。As a result, C J =2 A/c (zero magnetic field, 77 K) C was obtained as the critical current J. Also, the final composition is Bf:Pb:Sr:Ca:Cu1
, o:o. The ratio was 0:2:2:3.
（実施例３）
絵料の仕込み組成を
Ｂｌ ：Ｐｌ＋ ： Ｓｒ ：Ｃａ ：Ｃｕ−３．５
：１．５：２：２：３
として、実施例１と同様に超電導線材を作製した。(Example 3) The preparation composition of the paint was Bl:Pl+:Sr:Ca:Cu-3.5
:1.5:2:2:3, and a superconducting wire was produced in the same manner as in Example 1.
その結果、臨界電流Ｊ として
Ｃ
Ｊ ＝１ＯＡ／ｃｄ（零磁場、７７Ｋ）Ｃ
を得た。また、最終組成は
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−２． ｓ
：ｏ． ４：２：２：３となっていた。As a result, C J =1OA/cd (zero magnetic field, 77 K) C was obtained as the critical current J. The final composition is Bl:Pb:Sr:Ca:Cu-2. s
:o. The ratio was 4:2:2:3.
（実施例４）
原料の仕込み組成を
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−２． ２
８：１， ２２：２：２：３として、実施例１と同様
に超電導線材を作製した。(Example 4) The charging composition of the raw materials was Bl:Pb:Sr:Ca:Cu-2. 2
A superconducting wire was produced in the same manner as in Example 1, with the ratios of 8:1 and 22:2:2:3.
その結果、臨界電流Ｊ として
Ｃ
Ｊ ｃ −４ ０ ０ Ａ ／ ｃｄ （零磁場、７７
Ｋ）を得た。また、最終組成は
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１．
７：０． ３７２：２：３となっていた。As a result, the critical current J is C J c -400 A/cd (zero magnetic field, 77
K) was obtained. The final composition is Bl:Pb:Sr:Ca:Cu-1.
7:0. The ratio was 372:2:3.
（実施例５）
原料の仕込み組成を
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１．
８２：０．７８：２＋２：３
として、実施例１と同様に超電導線材を作製した。(Example 5) The composition of the raw materials was Bl:Pb:Sr:Ca:Cu-1.
82:0.78:2+2:3, and a superconducting wire was produced in the same manner as in Example 1.
その結果、臨界電流Ｊ として
Ｃ
Ｊ −６ＯＡ／ｃｊ（零磁場、７７Ｋ）Ｃ
を得た。また、最終組成は
Ｂ１ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ一 １
、 ２：０． ０５：２：２：３となっていた。As a result, C J -6OA/cj (zero magnetic field, 77 K) C was obtained as the critical current J. Also, the final composition is B1:Pb:Sr:Ca:Cu1
, 2:0. It was 05:2:2:3.
（実施例６）
原料の仕込み組成を
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−２．
ｏ：ｏ． ９：２：２：３として、実施例１と同
様に超電導線材を作製した。(Example 6) The composition of the raw materials was Bl:Pb:Sr:Ca:Cu-2.
o: o. A superconducting wire was produced in the same manner as in Example 1, with the ratio of 9:2:2:3.
その結果、臨界電流Ｊ として
Ｃ
Ｊ −３０ＯＡ／ｅシ（零磁場、７７Ｋ）Ｃ
を得た。また、最終組成は
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１．５：０
．１５：２：２：３
となっていた。As a result, a critical current J of C J -30OA/e (zero magnetic field, 77 K) was obtained. Also, the final composition is Bl:Pb:Sr:Ca:Cu-1.5:0
．． The ratio was 15:2:2:3.
（実施例７）
原料の仕込み組成を
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１．９６：
０．８４：２：２：３
として、実施例１と同様に超電導線材を作製した。(Example 7) The charging composition of raw materials was Bl:Pb:Sr:Ca:Cu-1.96:
A superconducting wire was produced in the same manner as in Example 1 with the ratio of 0.84:2:2:3.
その結果、臨界電流Ｊ として
Ｃ
Ｊ −１７５Ａ／ｃシ（零磁場、７７Ｋ）Ｃ
を得た。また、最終組成は
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１．３：０
．１０＋２：２：３
となっていた。As a result, C J -175 A/c (zero magnetic field, 77 K) C was obtained as the critical current J. Also, the final composition is Bl:Pb:Sr:Ca:Cu-1.3:0
．． The ratio was 10+2:2:3.
（実施例８）
原料の仕込み組成を
Ｂ１ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−２．８：１
．２：２：２：３
として、実施例１と同様に超電導線材を作製した。(Example 8) The charging composition of raw materials was B1:Pb:Sr:Ca:Cu-2.8:1
．． 2:2:2:3, a superconducting wire was produced in the same manner as in Example 1.
その結果、臨界電流Ｊ として
Ｃ
Ｊ −３００Ａ／ｃｄ（零磁場、７７Ｋ）Ｃ
を得た。また、最終組成は
Ｂｉ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−２． ｏ
：ｏ． ３５：２：２：３となっていた。As a result, a critical current J of C J -300 A/cd (zero magnetic field, 77 K) was obtained. The final composition is Bi:Pb:Sr:Ca:Cu-2. o
:o. The ratio was 35:2:2:3.
（実施例９）
原料の仕込み組成を実施例１と同様に
Ｂｌ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−２．ｉ：ｏ
．９：２：２：３
として、８４０℃、１００時間の熱処理を酸素気流中で
する点のみを変えて、他は実施例１と同様の工程で超電
導線材を作製した。その結果、臨界電流Ｊ として
Ｃ
Ｊ −５５３Ａ／ｃｄ（零磁場、７７Ｋ）Ｃ
を得た。また、鹸終組或は
Ｂｌ 二 Ｐｂ ：Ｓｒ ：Ｃａ ：
Ｃｕ− １ ． ７ 二 〇．３：２：２：３となっ
ていた。(Example 9) The charging composition of the raw materials was the same as in Example 1: Bl:Pb:Sr:Ca:Cu-2. i:o
．． 9:2:2:3, and a superconducting wire was produced in the same process as in Example 1, except that the heat treatment was performed at 840° C. for 100 hours in an oxygen stream. As a result, C J -553 A/cd (zero magnetic field, 77 K) C was obtained as the critical current J. In addition, the final group or Bl2 Pb:Sr:Ca:
Cu-1. 7 20. The ratio was 3:2:2:3.
以上の実施例１〜９の結果を第２図に（１）〜（９）と
して示す。本発明により、特性を大幅に向上できること
がわかる。なお、超電導体に対する熱処理として、例え
ば薄膜超電導体にアニールを加えることが知られている
。しかし、これは厚さ０，０１〜１０μｍ前後の薄膜を
基板上にスバッタ等で形成したときに、その組成がター
ゲットの組成からズレることに主として着目し、その対
策を主目的として後に施されるものであり、本発明の熱
処理とはその主たる目的、構成、作用および結果がいず
れも異なる。The results of Examples 1 to 9 above are shown in FIG. 2 as (1) to (9). It can be seen that the characteristics can be significantly improved by the present invention. Note that, as a heat treatment for a superconductor, for example, applying annealing to a thin film superconductor is known. However, this method focuses mainly on the fact that when a thin film with a thickness of around 0.01 to 10 μm is formed on a substrate by sputtering, etc., the composition deviates from the composition of the target, and this method is applied later with the main purpose of countering this. The heat treatment of the present invention is different from the heat treatment of the present invention in its main purpose, structure, action, and results.
すなわち、本発明の工程では、原料の仕込み段階から予
備線材の作製までの過程では、超電導体の組成は殆ど変
わることがなく、従って線材作製までに、あるいは熱処
理までに組成がズレたことへの対策を主目的として施さ
れる熱処理ではない。In other words, in the process of the present invention, the composition of the superconductor hardly changes during the process from the raw material preparation stage to the preparation of the preliminary wire, and therefore, there is no possibility that the composition may change before the wire is prepared or before the heat treatment. Heat treatment is not performed primarily as a countermeasure.
本発明では、熱処理における組成変動自体が問題となっ
ているのである。従って、本発明においては、テープ状
の線材では厚さが４０〜２００μｍのものを対象として
、８００〜８４０℃前後の温度条件で、５０〜３００時
間の長時間にわたって熱処理がされる。超電導薄膜の熱
処理条件が、本発明の実施例と比べてより高温で短時間
となっているのは、両名が本質的に異なるものだからで
ある。In the present invention, compositional fluctuation itself during heat treatment poses a problem. Therefore, in the present invention, tape-shaped wire rods having a thickness of 40 to 200 μm are heat-treated at a temperature of about 800 to 840° C. for a long time of 50 to 300 hours. The reason why the heat treatment conditions for the superconducting thin film are higher and for a shorter time than in the examples of the present invention is that the two are essentially different.
以上、詳細に説明したように、原料の仕込み組成におい
て、（Ｂｉ＋Ｐｂ）を最終目的組成に対して過剰に仕込
んだので、熱処理中にｆ３１，Ｐｂが揮散しても、良好
に超電導相を線材中に生成させることができる。このた
め、臨界電流密度Ｊ のＣ
大幅な向上が可能になる。また、原料を溶融、急冷する
ことによって超電導組成のガラス母材を作製し、このガ
ラス母材を電気炉で線引することによってファイバ（予
備線材）が得られるので、このファイバを熱処理した超
電導線材は、長尺かつ可撓性に優れたものとすることが
できる。As explained in detail above, in the charging composition of raw materials, (Bi+Pb) was charged in excess of the final target composition, so even if f31 and Pb volatilized during heat treatment, the superconducting phase could be well incorporated into the wire. can be generated. Therefore, it becomes possible to significantly improve the critical current density J. In addition, a glass base material with a superconducting composition is produced by melting and rapidly cooling raw materials, and a fiber (preliminary wire) is obtained by drawing this glass base material in an electric furnace. can be long and have excellent flexibility.
第１図は超電導予備線材（ファイバ）を線引きするため
の紡糸装置を示す図、
第２図は実施例の
結果を示すグラフである。
１・・・ガラス母材、
２・・・ダミー棒、
４・・・ヒーターFIG. 1 is a diagram showing a spinning device for drawing a superconducting preliminary wire (fiber), and FIG. 2 is a graph showing the results of Examples. 1...Glass base material, 2...Dummy rod, 4...Heater
Claims (1)
化物の原料混合粉末を加熱溶融した後、急速冷却するこ
とにより、（ビスマス＋鉛）の含有量が最終目的組成の
１０１〜２００％となったガラス母材を形成する第１工
程と、 前記ガラス母材を加熱して超電導組成の予備線材に線引
きする第２工程と、 前記予備線材を熱処理によって超電導線材とする第３工
程とを備えることを特徴とする超電導線材の製造方法。 ２、前記第３工程は、酸素を２５％以上含む雰囲気で熱
処理する工程である請求項１記載の超電導線材の製造方
法。[Claims] 1. By heating and melting a raw material mixed powder of superconducting oxide containing at least bismuth, lead, and oxygen, and then rapidly cooling it, the content of (bismuth + lead) is reduced to 101 to 100% of the final target composition. a first step of forming a glass base material with a 200% strength, a second step of heating the glass base material and drawing it into a preliminary wire having a superconducting composition, and a third step of heating the preliminary wire to form a superconducting wire. A method for manufacturing a superconducting wire, comprising: 2. The method for manufacturing a superconducting wire according to claim 1, wherein the third step is a step of heat treatment in an atmosphere containing 25% or more of oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009991A JPH03216917A (en) | 1990-01-19 | 1990-01-19 | Manufacture of superconducting wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009991A JPH03216917A (en) | 1990-01-19 | 1990-01-19 | Manufacture of superconducting wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03216917A true JPH03216917A (en) | 1991-09-24 |
Family
ID=11735332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009991A Pending JPH03216917A (en) | 1990-01-19 | 1990-01-19 | Manufacture of superconducting wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03216917A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993002460A1 (en) * | 1991-07-24 | 1993-02-04 | Sumitomo Electric Industries, Ltd. | Method for manufacturing superconductive wire material of bismuth based oxide |
| CN114203354A (en) * | 2021-12-20 | 2022-03-18 | 中国科学院电工研究所 | Multi-core iron-based superconducting strip and preparation method thereof |
-
1990
- 1990-01-19 JP JP2009991A patent/JPH03216917A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993002460A1 (en) * | 1991-07-24 | 1993-02-04 | Sumitomo Electric Industries, Ltd. | Method for manufacturing superconductive wire material of bismuth based oxide |
| CN114203354A (en) * | 2021-12-20 | 2022-03-18 | 中国科学院电工研究所 | Multi-core iron-based superconducting strip and preparation method thereof |
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