JPH03105809A - Manufacture of oxide superconductive wire material - Google Patents
Manufacture of oxide superconductive wire materialInfo
- Publication number
- JPH03105809A JPH03105809A JP1241838A JP24183889A JPH03105809A JP H03105809 A JPH03105809 A JP H03105809A JP 1241838 A JP1241838 A JP 1241838A JP 24183889 A JP24183889 A JP 24183889A JP H03105809 A JPH03105809 A JP H03105809A
- Authority
- JP
- Japan
- Prior art keywords
- sintering
- critical current
- current density
- compressive stress
- 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
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000013078 crystal Substances 0.000 abstract description 7
- 229910052709 silver Inorganic materials 0.000 abstract description 7
- 239000004332 silver Substances 0.000 abstract description 7
- 238000003825 pressing Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- 239000002887 superconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 101100194003 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) rco-3 gene Proteins 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005204 segregation 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
- Superconductors And Manufacturing Methods Therefor (AREA)
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、臨界電流密度の高い酸化物超電導線材の製造
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 producing an oxide superconducting wire having a high critical current density.
（従来の技術）
酸化物超電導体の線材化の方法としては、原料酸化物の
仮焼粉末を、銀あるいは銀合金などのパイプを用いた銀
シース法が一般的である。(Prior Art) As a method for producing wires from oxide superconductors, a common method is a silver sheath method in which calcined powder of a raw material oxide is passed through a pipe made of silver or a silver alloy.
第２図に従来の銀シース法の製造プロセスを示す。超電
導材料粉末を仮焼し、粉砕することを適当回数繰り返し
、原料粉末を調整する。この調整した粉末を銀ないしは
銀合金のパイプに充填する。Figure 2 shows the conventional silver sheath manufacturing process. The superconducting material powder is calcined and pulverized an appropriate number of times to prepare the raw material powder. This adjusted powder is filled into a silver or silver alloy pipe.
このパイプを塑性加工して所望の形状の線材とする。こ
の例では、まず、九線に加工した後、さらにテープ状に
加工する。塑性加工された線材は焼結処理を受け、テー
プ状の超電導線を形成する。This pipe is plastically worked into a wire rod of a desired shape. In this example, it is first processed into a nine-line shape, and then further processed into a tape shape. The plastically worked wire undergoes a sintering process to form a tape-shaped superconducting wire.
（発明が解決しようとする問題点）
上記のような従来方法により製作された超電導線材は、
超電導部分の密度が低く、また、配向性も不十分なため
、臨界電流密度の低い線材しか得られなかった。本発明
は、焼結後の線材に対して、適当な処理を施すことによ
り、超電導部分を高緻密化するとともに、圧縮面に垂直
な方向への結晶の配同性を向上させることによって、臨
界電流密度の高い超電導線材を得ることを目的とする。(Problems to be solved by the invention) The superconducting wire manufactured by the conventional method as described above is
Because the density of the superconducting portion was low and the orientation was insufficient, only a wire with a low critical current density could be obtained. The present invention applies appropriate treatment to the wire after sintering to make the superconducting part highly dense and to improve the orientation of crystals in the direction perpendicular to the compression plane, thereby increasing the critical current. The aim is to obtain a superconducting wire with high density.
［発明の構成コ
（問題点を解決するための手段）
本発明は、上記のように、金属シース材を用いて形成さ
れた線材に対して、圧力、５０ｋｇｆ／ｍｍ２以上の圧
縮応力を加えた後、焼結することにより、臨界電流密度
の向上した超電導線材を得る製造方法である。[Structure of the Invention (Means for Solving the Problems) As described above, the present invention provides a method in which a compressive stress of 50 kgf/mm2 or more is applied to a wire rod formed using a metal sheath material. This is a manufacturing method in which a superconducting wire with improved critical current density is obtained by sintering the superconducting wire.
（作用）
本発明の製造方法によれば、線材に施す圧縮応力、例え
ば、圧力、５ ０ ｋ ｇ ｆ ／ ｍ ｍ ２以上の
プレス加工により、超電導部分の板状の結晶はさらに層
状構造をとり易くなり、超電導体部分を高緻密化すると
ともに、圧縮面に垂直な方向に結晶のＣ軸を配向させる
ことによって、臨界電流密度を大幅に向上させることが
できる。そして、プレスと焼結の工程を繰り返すことに
より、さらに臨界電流密度を向上させることができる。(Function) According to the manufacturing method of the present invention, the plate-like crystals of the superconducting portion further take on a layered structure by applying compressive stress to the wire material, for example, pressing at a pressure of 50 kgf/mm2 or more. By making the superconductor part highly dense and orienting the C axis of the crystal in the direction perpendicular to the compression plane, the critical current density can be greatly improved. Then, by repeating the pressing and sintering steps, the critical current density can be further improved.
臨界電流密度と焼結、プレスの繰り返し数との関係を模
式的に示したものを第１図に示す。線材の臨界電流密度
は従来の製造方法により作られたものに比べ、プレスと
焼結の工程を繰り返すことにより向上し、２〜４回の繰
り返しで最大値に達する。臨界電流密度が最大値に達し
た後は、第１図に模式的に示すようにプレスと焼結の工
程をさらに繰り返しても、臨界電流密度が横ばいの状態
（ａ）になるか、ないしは、プレスと焼結工程の繰り返
しにより結晶粒の粗大化や結晶粒界への不純物の偏析な
どにより、過剰焼結状態になり、臨界電流密度が減少す
る状態（ｂ）となる。FIG. 1 schematically shows the relationship between the critical current density and the number of repetitions of sintering and pressing. The critical current density of the wire is improved by repeating the pressing and sintering process compared to those made by conventional manufacturing methods, and reaches its maximum value after 2 to 4 repetitions. After the critical current density reaches the maximum value, even if the pressing and sintering steps are further repeated as schematically shown in FIG. 1, the critical current density remains unchanged (a) or, Repeated pressing and sintering steps result in coarsening of crystal grains and segregation of impurities at grain boundaries, leading to an oversintered state and a state (b) in which the critical current density decreases.
焼結した線材にプレスにより、２００ｋｇｆ／ｍｍ’の
圧縮応力を加えた後、再び焼結した後の超電導部の組織
を第３図の写真（ｂ）に示す。第３図（ａ）のプレスを
しないものに比べ、第３図（ｂ）の２００ｋｇｆ／ｍｍ
’のプレスをしたものでは、板状の結晶が層状に重なり
、緻密化されているのがわかる。The structure of the superconducting part after applying a compressive stress of 200 kgf/mm' to the sintered wire by pressing and sintering it again is shown in the photograph (b) of FIG. 200kgf/mm in Figure 3(b) compared to the one without pressing in Figure 3(a)
It can be seen that the plate-shaped crystals overlap in layers and become denser in the pressed one.
超電導材料として、ビスマス系超電導体を用いた超電導
線材に対して、本発明の製造方法を実施した結果は、以
下の実施例でも示すように、優れた結果を得ることがで
きた例の一つである。また、焼結後、線材に圧縮応力を
負荷する手段としては、前述したプレスが一般的である
が、ＣＩＰあるいはＨＩＰを用いることもできる。この
場合、とくにプレスができない形状のもの、たとえば、
塑性加工により、コイルや円筒状に形成した後、焼結処
理したような場合にも、圧縮応力を負荷することができ
る。The results of implementing the manufacturing method of the present invention on a superconducting wire using a bismuth-based superconductor as a superconducting material are one example in which excellent results could be obtained, as shown in the examples below. It is. Further, as a means for applying compressive stress to the wire after sintering, the above-mentioned press is generally used, but CIP or HIP can also be used. In this case, especially if the shape cannot be pressed, for example,
Compressive stress can be applied even when a coil or cylinder is formed by plastic working and then sintered.
（実施例）
本発明の実施例として、ビスマス、鉛、ストロンチウム
、カルシウム、銅、及び酸素を構成元素とする（鉛を含
まない場合もある）ビスマス系超電導材料を用いた例に
ついて説明する。Ｂｉ２０３、ＰｂＯ１Ｓ ｒｃＯ３、
ＣａＣＯ３、ＣｕＯなどの粉末を混合したものを、仮焼
、粉砕を数回繰り返して、超電導原材料粉末として調整
する。この超電導原材料粉末を銀または銀合金のパイプ
に充填する。超電導材料粉末を充填した銀パイプを線状
に塑性加工する。その後、焼結処理を施し、圧力２００
ｋｇｆ／ｍｍ’でプレスした後、焼成する処理を繰り返
した。以下の表１にその結果を示す。(Example) As an example of the present invention, an example using a bismuth-based superconducting material containing bismuth, lead, strontium, calcium, copper, and oxygen as constituent elements (lead may not be included in some cases) will be described. Bi203, PbO1S rcO3,
A mixture of powders such as CaCO3 and CuO is repeatedly calcined and pulverized several times to prepare a superconducting raw material powder. This superconducting raw material powder is filled into a silver or silver alloy pipe. A silver pipe filled with superconducting material powder is plastically processed into a linear shape. After that, sintering treatment is performed and the pressure is 200
After pressing at kgf/mm', the process of firing was repeated. The results are shown in Table 1 below.
臨界電流密度の値については、複数の試料について測定
した値の分布領域を示したものである。The value of critical current density shows the distribution area of values measured for a plurality of samples.
液化窒素温度における臨界電流密度は、焼結のままでは
、２０００ 〜３０００Ａ／ｃｒｎ２であったが、プレ
スと焼結を２回繰り返すと臨界電流密度は２０００ＯＡ
／ｃｍ２を越え、最大２３６００Ａ／ｃｍ２が得られた
。さらに、プレスと焼結を繰り返すと、臨界電流密度は
、６０００〜１００００Ａ／ｃｍ”に減少した。The critical current density at liquefied nitrogen temperature was 2000 to 3000 A/crn2 in the sintered state, but when pressing and sintering were repeated twice, the critical current density increased to 2000 OA/crn2.
/cm2, and a maximum of 23,600 A/cm2 was obtained. Furthermore, after repeated pressing and sintering, the critical current density decreased to 6000-10000 A/cm''.
［発明の効果］
本発明の製造方法により、超電導線材の超電導部分の密
度、配向性を向上させ、臨界電流密度の高い超電導線材
を得ることができる。また、超電導部分の組織が均一化
される傾向が強まり、臨界電流密度のばらつきが小さく
なり、安定した値が得られるようになったことである。[Effects of the Invention] According to the manufacturing method of the present invention, the density and orientation of the superconducting portion of a superconducting wire can be improved, and a superconducting wire with a high critical current density can be obtained. In addition, the structure of the superconducting portion tends to be more uniform, and the variation in critical current density becomes smaller, making it possible to obtain a stable value.
これは線材に不可欠な長尺化時の安定性に極めて大きな
寄与をするという効果がある。This has the effect of making an extremely large contribution to the stability when lengthening, which is essential for wire rods.
第１図は本発明の製造方法における臨界電流密度と焼結
、プレスの繰り返し回数との関係を模式的に示した図、
第２図は従来の超電導線材の製造方法の説明図、第３図
は超電導線材の超電導部分の電子顕微鏡写真である。
０１
（Ｉｍのまま）
２
３
６
５
焼結一ブレス繰り返し数（回）
第１図
第２図
手続補正書（方式）
平成 ２年 １月FIG. 1 is a diagram schematically showing the relationship between the critical current density and the number of repetitions of sintering and pressing in the manufacturing method of the present invention,
FIG. 2 is an explanatory diagram of a conventional method for manufacturing a superconducting wire, and FIG. 3 is an electron micrograph of a superconducting portion of the superconducting wire. 01 (as Im) 2 3 6 5 Number of sintering press repetitions (times) Figure 1 Figure 2 Procedure amendment (method) January 1990
Claims (3)
に充填する手段、前記酸化物超電導材料粉末を充填した
金属パイプを所定の形状に塑性加工する手段、前記所定
の形状に塑性加工された金属パイプを焼結処理する手段
により形成された超電導線材に対して、圧力５０ｋｇｆ
／ｍｍ＾２以上の圧縮応力を加えた後、焼結する手段を
含むことを特徴とする酸化物超電導線材の製造方法。(1) means for filling a metal pipe with the adjusted oxide superconducting material powder; means for plastically working the metal pipe filled with the oxide superconducting material powder into a predetermined shape; A pressure of 50 kgf is applied to a superconducting wire formed by sintering a metal pipe.
1. A method for producing an oxide superconducting wire, the method comprising: applying a compressive stress of /mm^2 or more and then sintering.
を加えた後、焼結する手段を複数回繰り返すことを特徴
とする請求項１記載の酸化物超電導線材の製造方法。(2) The method for manufacturing an oxide superconducting wire according to claim 1, characterized in that the step of applying compressive stress of 50 kgf/mm^2 or more and then sintering is repeated multiple times.
ロンチウム、カルシウム、銅、及び酸素から選択された
元素を構成元素とするビスマス系超電導材料であること
を特徴とする請求項１および２記載の酸化物超電導線材
の製造方法。(3) The oxide superconducting material is a bismuth-based superconducting material containing an element selected from bismuth, lead, strontium, calcium, copper, and oxygen. A method for manufacturing oxide superconducting wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1241838A JPH03105809A (en) | 1989-09-20 | 1989-09-20 | Manufacture of oxide superconductive wire material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1241838A JPH03105809A (en) | 1989-09-20 | 1989-09-20 | Manufacture of oxide superconductive wire material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03105809A true JPH03105809A (en) | 1991-05-02 |
Family
ID=17080253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1241838A Pending JPH03105809A (en) | 1989-09-20 | 1989-09-20 | Manufacture of oxide superconductive wire material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03105809A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02207420A (en) * | 1989-02-06 | 1990-08-17 | Sumitomo Metal Ind Ltd | Manufacture of superconducting wire rod |
-
1989
- 1989-09-20 JP JP1241838A patent/JPH03105809A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02207420A (en) * | 1989-02-06 | 1990-08-17 | Sumitomo Metal Ind Ltd | Manufacture of superconducting wire rod |
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