JPH02139808A - Manufacture of superconductive wire - Google Patents
Manufacture of superconductive wireInfo
- Publication number
- JPH02139808A JPH02139808A JP63292405A JP29240588A JPH02139808A JP H02139808 A JPH02139808 A JP H02139808A JP 63292405 A JP63292405 A JP 63292405A JP 29240588 A JP29240588 A JP 29240588A JP H02139808 A JPH02139808 A JP H02139808A
- Authority
- JP
- Japan
- Prior art keywords
- wire
- superconductor
- thallium
- orientation
- baking
- 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 7
- 239000002887 superconductor Substances 0.000 claims abstract description 25
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 17
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007906 compression Methods 0.000 claims abstract description 9
- 230000006835 compression Effects 0.000 claims abstract description 7
- 238000010304 firing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 7
- 229910052788 barium Inorganic materials 0.000 abstract description 3
- 229910052791 calcium Inorganic materials 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910003438 thallium oxide Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003475 thallium Chemical class 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】
［産業上の利用分野］
本発明はタリウムを含む酸化物超電導体（以下タリウム
系超電導体という）の線材の製造方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a wire of an oxide superconductor containing thallium (hereinafter referred to as thallium-based superconductor).
［従来の技術］
従来、タリウム系超電導体の線材は、タリウムの酸化物
と他の構成元素を含む酸化物の混合物、あるいは所望の
超電導体自体の粉末を被覆材に詰め線材成型した後、焼
成する方法で製造されていた。[Prior Art] Conventionally, wires of thallium-based superconductors have been produced by filling a coating material with a mixture of thallium oxide and oxides containing other constituent elements, or powder of the desired superconductor itself, forming the wire into a wire, and then firing. It was manufactured using a method that
［発明が解決しようとする課題］
タリウム系超電導体の超電導特性には異方性があり、高
い臨界電流密度を得るためには結晶粒を配向させる必要
があるが、上記の方法で製造した線材は配向度が低（、
液体窒素温度における臨界電流密度が４０００Ａ／ｃｍ
”程度と、高い臨界電流密度が得られないという問題点
を有していた。[Problem to be solved by the invention] The superconducting properties of thallium-based superconductors have anisotropy, and it is necessary to orient the crystal grains in order to obtain a high critical current density. has a low degree of orientation (,
Critical current density at liquid nitrogen temperature is 4000A/cm
``The problem was that a high critical current density could not be obtained.
［課題を解決するための手段］
本発明は前述の問題点を解決すべくなされたものであり
、タリウム系超電導体からなる線材を、長手方向に対し
て垂直に圧縮した後、焼成する超電導線材の製造方法を
提供するものである。[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and provides a superconducting wire material in which a wire material made of a thallium-based superconductor is compressed perpendicularly to the longitudinal direction and then fired. The present invention provides a method for manufacturing.
本発明においては、まずタリウム系超電導体を線材化す
る。線材化の方法は、特に限定されないが、従来法と同
様、原料粉末を金属管等の被覆材に充填した後、焼成す
る方法が好ましい。In the present invention, first, a thallium-based superconductor is made into a wire. The method of forming the wire into a wire rod is not particularly limited, but a method of filling a coating material such as a metal tube with raw material powder and then firing it is preferable, as in the conventional method.
本発明は、タリウム系超電導体であれば、特に限定され
ず適用できるが、ＴＱ、 Ｂａ、 Ｃａ、 Ｃｕを含む
複合酸化物からなるものは、臨界温度が高いので好まし
い。タリウム系超電導体の原料粉末としては、始めから
超電導体としての組成と、結晶構造を有する粉末をその
まま用いてもよいが、例えば酸化タリウムと銅、バリウ
ム、カルシウムの複合酸化物とを所定の組成になるよう
に混合した粉末を原料粉末とした時のほうが、反応性が
良く線材が緻密な焼結体として得られるので好ましい。The present invention can be applied to any thallium-based superconductor without particular limitation, but one made of a composite oxide containing TQ, Ba, Ca, and Cu is preferred because of its high critical temperature. As raw material powder for thallium-based superconductors, powders having a superconducting composition and a crystal structure may be used as they are, but for example, composite oxides of thallium oxide, copper, barium, and calcium may be used with a predetermined composition. It is preferable to use a powder mixed in such a manner as the raw material powder because the reactivity is good and the wire can be obtained as a dense sintered body.
原料粉末を焼成するに際しては、原料粉末どうしの焼結
性を向上させ、緻密な線材を得るために、焼成前に粉末
を緻密に圧縮しておくことが好ましい。このために粉末
を金属管に充填した後、金属管の長手方向に垂直上に圧
縮して、リボン状にしておくことが好ましい。その後、
この原料粉末成形体を、加熱焼成して、タリウム系超電
導体の線材を得る。When firing the raw material powder, it is preferable to compress the powder tightly before firing in order to improve the sinterability of the raw material powders and obtain a dense wire rod. For this purpose, it is preferable to fill the metal tube with the powder and then compress it vertically in the longitudinal direction of the metal tube to form a ribbon. after that,
This raw material powder compact is heated and fired to obtain a thallium-based superconductor wire.
タリウム系超電導体は、層状の結晶構造を有し、板状に
粒成長する。原料粉末を焼成した段階では、この結晶粒
は配向していない。本発明では次に、このタリウム系超
電導体線材を長手方向に対して垂直に圧縮する。この際
、金属で被覆して焼成した線材については、このまま被
覆した状態で圧縮するほうが、線材が傷つきあるいは切
断することを防ぐことができるので好ましい。ここで、
圧縮することにより、板状の超電導体結晶が結晶層の面
が圧縮方向に対して垂直になるように配向する。また、
線材の密度が増加する。タリウム系超電導体は、結晶の
１面方向に電流が流れやすいことが知られており、この
配向け、線材の長手方向に電流が流れやすくなることを
意味する。A thallium-based superconductor has a layered crystal structure, and grains grow in a plate shape. At the stage when the raw material powder is fired, the crystal grains are not oriented. In the present invention, next, this thallium-based superconductor wire is compressed perpendicularly to the longitudinal direction. At this time, it is preferable to compress the wire rod coated with metal and fired while it is coated as it is, since this can prevent the wire rod from being damaged or cut. here,
By compressing, the plate-shaped superconductor crystals are oriented such that the plane of the crystal layer is perpendicular to the direction of compression. Also,
The density of the wire increases. It is known that in thallium-based superconductors, current flows easily in one plane of the crystal, and this orientation means that current flows easily in the longitudinal direction of the wire.
圧縮過程においては、線材は必ずしも太き（変形させる
必要はない。逆に大きく変形させる場合は、切断等のお
それがある。焼成前に圧縮したリボン状の線材について
は、焼成前の同じ方向に圧縮することが好ましい。During the compression process, the wire does not necessarily need to be thick (deformed).On the other hand, if it is greatly deformed, there is a risk of breakage, etc.For ribbon-shaped wire rods that are compressed before firing, Compression is preferred.
線材を圧縮する方法は、特に限定されないが、平板には
さみ込んで圧縮する方法あるいはツインローラーにより
圧縮する方法が好ましい。圧縮の圧力は、超電導体にか
かる圧縮応力にして、２〜ＬＯｔ／ｃｍ’程度が好まし
い。２ｔ／Ｃｍ”以下では、本発明の効果が充分に発現
しないおそれがあり、Ｌｏｔ／ａｍ”以上では、配向性
向上の効果が、それ以上あまり大きくならず逆に、被覆
材がやぶれる等の問題点が発生するおそれがあるので、
それぞれ好ましくない。The method of compressing the wire is not particularly limited, but a method of compressing it by inserting it between flat plates or a method of compressing it with twin rollers is preferable. The compression pressure is preferably about 2 to LOt/cm' in terms of compressive stress applied to the superconductor. If it is less than 2t/Cm", the effect of the present invention may not be fully expressed, and if it is more than Lot/am", the effect of improving orientation will not be much greater, and conversely, there will be problems such as the coating material being torn. There is a possibility that spots may occur.
Each is undesirable.
線材は、原線直後では、配向性が向上し、密度も増加し
ているが、線材には微細なりラックが生じ結晶粒どうし
の結合が不十分であるので、その後焼成する必要がある
。この焼成により、結晶粒の結合性が向上する。焼成は
、 ８９０〜９１０℃の温度で、１〜２０時間行なうこ
とが好ましい。Immediately after the wire is made from raw material, its orientation is improved and its density is increased, but fine racks are formed in the wire and the bonds between the crystal grains are insufficient, so it is necessary to bake it afterwards. This firing improves the cohesion of crystal grains. The firing is preferably carried out at a temperature of 890 to 910°C for 1 to 20 hours.
その後同様の、圧縮焼成の工程を繰り返すことも可能で
、結晶の配向性を更に向上させることができる。超電導
体に対する圧縮焼成工程が３回以上の場合は、新たな圧
縮工程における配向性向上の効果が小さくなる。Thereafter, it is also possible to repeat the same compression firing process, and the crystal orientation can be further improved. If the compression firing process for the superconductor is performed three or more times, the effect of improving orientation in the new compression process becomes small.
［実施例］
実施例
純度９９．９９％のＢａＣＯ５，ＣａＣＯ５，（：ｕＯ
をＢａ ： Ｃａ ： Ｃｕのモル比が１：３：３にな
るように秤量し、メノウ製の遊星ミルで２０分間混合し
た。これを電気炉で空気中で８７０℃、１０時間焼成し
た。このＢａ： Ｃａ ： Ｃｕを含む酸化物にＴＱｚ
ＯｓをＴＱ：Ｂａ：Ｃａ：Ｃｕのモル比が１：ｌ：３：
３になるように秤量しメノウ製の乳鉢で２０分間混合し
た。この粉末を外径３ｍｍ、内径２ｍｍの金管に詰め両
端を封じた後５ ｔ／ａｍ”の圧力でプレスしテープ状
線材としだ後８９０℃で３００分焼成した。（線材Ａ）
線材Ａを再び５ ｔ／ｃｍ”の圧力でプレスし８９０℃
で３００分焼成した。（線材Ｂ）
線材Ｂについて金を剥し電気抵抗測定を行なったところ
ゼロ抵抗は１１７Ｋ、液体窒素温度における臨界電流密
度は６２５０Ａ／ｃｍ”であった。また、金を剥した線
材表面についてＸ線回折を調べたところ（Ｏ，Ｏ，Ｑ）
方向に強（配向していることがわかった。[Example] Example purity 99.99% BaCO5, CaCO5, (:uO
were weighed so that the molar ratio of Ba:Ca:Cu was 1:3:3, and mixed for 20 minutes in an agate planetary mill. This was fired in air at 870° C. for 10 hours in an electric furnace. TQz is added to this Ba:Ca:Cu-containing oxide.
The molar ratio of Os to TQ:Ba:Ca:Cu is 1:l:3:
The mixture was weighed so as to have a volume of 3, and mixed in an agate mortar for 20 minutes. This powder was packed into a brass tube with an outer diameter of 3 mm and an inner diameter of 2 mm, both ends of which were sealed, and then pressed at a pressure of 5 t/am'' to form a tape-shaped wire rod, which was then fired at 890°C for 300 minutes. (Wire A)
Wire A was pressed again at a pressure of 5 t/cm" and heated to 890°C.
It was baked for 300 minutes. (Wire B) When wire B was stripped of gold and electrical resistance was measured, the zero resistance was 117 K, and the critical current density at liquid nitrogen temperature was 6250 A/cm. When I investigated (O, O, Q)
It was found that there was a strong orientation in the direction.
［比較例］
上記実施例中の線材Ａについて金を剥し電気測定測定を
行なったところゼロ抵抗は１１７Ｋ、液体窒素温度にお
ける臨界電流密度は３６５０Ａ／ｃｍ”であった。また
、金を剥した線材表面についてＸ線回折を調べたところ
特に配向していないことがわかった。[Comparative Example] Wire A in the above example was stripped of gold and subjected to electrical measurement, and the zero resistance was 117 K, and the critical current density at liquid nitrogen temperature was 3650 A/cm''. When the surface was examined by X-ray diffraction, it was found that there was no particular orientation.
［発明の効果］
本発明により、結晶の配向性の良好なタリウム系超電導
体が得られるので、臨界電流密度の高い超電導線材が得
られる。[Effects of the Invention] According to the present invention, a thallium-based superconductor with good crystal orientation can be obtained, so a superconducting wire with a high critical current density can be obtained.
Claims (4)
方向に垂直に圧縮した後、焼成することを特徴とする超
電導線材の製造方法。(1) A method for producing a superconducting wire, which comprises compressing a wire made of a thallium-based superconductor perpendicularly to the direction of extension of the wire and then firing it.
材の製造方法。(2) A method for manufacturing a superconducting wire in which the compression and firing of claim 1 are repeated multiple times.
２の超電導線材の製造方法。(3) The method for producing a superconducting wire according to claim 1 or 2, wherein the wire coated with metal is compressed.
金属管に充填し、圧縮した後焼成して得た線材を、再び
圧縮、焼成する超電導体の製造方法。(4) Powder that can be heated to become a thallium-based superconductor,
A method for manufacturing superconductors in which the wire obtained by filling a metal tube, compressing it, and firing it is then compressed and fired again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63292405A JPH02139808A (en) | 1988-11-21 | 1988-11-21 | Manufacture of superconductive wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63292405A JPH02139808A (en) | 1988-11-21 | 1988-11-21 | Manufacture of superconductive wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02139808A true JPH02139808A (en) | 1990-05-29 |
Family
ID=17781359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63292405A Pending JPH02139808A (en) | 1988-11-21 | 1988-11-21 | Manufacture of superconductive wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02139808A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02183918A (en) * | 1989-01-06 | 1990-07-18 | Furukawa Electric Co Ltd:The | Manufacture of oxide superconductor |
| US5646097A (en) * | 1994-12-27 | 1997-07-08 | General Electric Company | Method of fabricating a (1223) Tl-Ba-Ca-Cu-O superconductor |
-
1988
- 1988-11-21 JP JP63292405A patent/JPH02139808A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02183918A (en) * | 1989-01-06 | 1990-07-18 | Furukawa Electric Co Ltd:The | Manufacture of oxide superconductor |
| US5646097A (en) * | 1994-12-27 | 1997-07-08 | General Electric Company | Method of fabricating a (1223) Tl-Ba-Ca-Cu-O superconductor |
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