JPH025314A - Manufacture of oxide superconductive wire rod - Google Patents
Manufacture of oxide superconductive wire rodInfo
- Publication number
- JPH025314A JPH025314A JP63155692A JP15569288A JPH025314A JP H025314 A JPH025314 A JP H025314A JP 63155692 A JP63155692 A JP 63155692A JP 15569288 A JP15569288 A JP 15569288A JP H025314 A JPH025314 A JP H025314A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- oxide
- oxide superconductor
- heating
- atomized
- 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 abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000002887 superconductor Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 12
- 239000000470 constituent Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 22
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000006199 nebulizer Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012159 carrier gas Substances 0.000 abstract description 3
- 239000007921 spray Substances 0.000 abstract 2
- 239000010949 copper Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000001089 thermophoresis Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052727 yttrium 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
Abstract
Description
【発明の詳細な説明】 〔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する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing an oxide superconducting wire.
近年、アルカリ土金属、希土類元素、銅、ビスマス、タ
リウム等の元素及び酸素からなる酸化物超電導体が見出
されている。In recent years, oxide superconductors made of oxygen and elements such as alkaline earth metals, rare earth elements, copper, bismuth, and thallium have been discovered.
これらの酸化物超電導体は、液体Ｎ２温度以上で超電導
となるため従来の液体Ｈｅ温度で超電導を示す金属超電
導体に較べて格段に経済的であり、各分野での利用が検
討されている。These oxide superconductors are much more economical than conventional metal superconductors which exhibit superconductivity at liquid He temperatures because they become superconducting above the liquid N2 temperature, and their use in various fields is being considered.
ところで上記の酸化物超電導体は脆いため金属材料のよ
うに塑性加工ができず、これらを線材等に加工するには
、主に粉末冶金法が用いられ、例えば原料粉末の仮焼成
粉を基体上に被覆成形したり、又はＡｇ管等に充填して
伸延加工し、次いでこれを０□含を雰囲気中で加熱焼結
する方法がとられている。By the way, the above-mentioned oxide superconductors are brittle and cannot be plastically worked like metal materials, so powder metallurgy is mainly used to process them into wire rods, etc. A method is used in which the material is coated and molded into an Ag tube, or filled into an Ag tube or the like and stretched, and then heated and sintered in a 0□-containing atmosphere.
上記の粉末冶金法において、基体上に仮焼成粉を被覆成
形する方法には、プラズマ溶射法、ペースト塗布法、粉
体付着法等が用いられているが、プラズマ溶射法は付着
効率が悪く、又ペースト塗布法は乾燥に長時間を要する
上、付着体がポーラスになり、又粉体付着法は焼結時基
体と超電導体層との間で拡散反応が生じて超電導特性が
低下するという問題があった。又仮焼粉をＡｇ管等に充
填する方法は、仮焼粉を管内に連続して高密度に充填す
るのが難しく、特に線材等の長尺材において長手方向に
特性のバラツキを生し易いという問題があった。In the above powder metallurgy method, plasma spraying, paste coating, powder adhesion, etc. are used to coat and mold the pre-fired powder onto the substrate, but plasma spraying has poor adhesion efficiency; In addition, the paste coating method takes a long time to dry and the adhered body becomes porous, and the powder coating method has the problem that a diffusion reaction occurs between the substrate and the superconductor layer during sintering, resulting in a decrease in superconducting properties. was there. In addition, with the method of filling calcined powder into Ag pipes, etc., it is difficult to fill the tube with calcined powder continuously and at a high density, and it is easy to cause variations in properties in the longitudinal direction, especially in long materials such as wire rods. There was a problem.
本発明はかかる状況に鑑みなされたものでその目的とす
るところは特性に優れた酸化物超電導線材を効率よく製
造する方法を提供することにある。The present invention was devised in view of this situation, and its purpose is to provide a method for efficiently manufacturing an oxide superconducting wire with excellent properties.
即ち本発明は、酸化物超電導体の構成元素を各々含有す
る化合物をそれぞれ所定量溶媒に溶解し、この溶液を霧
状化して所定温度に加熱した反応炉内に供給して反応さ
せて上記霧状体を酸化物超電導体粉末となすとともに、
上記反応炉内に配置した冷却された管体表面に付着させ
、次いで該付着体を加熱焼結しつつ、上記冷却管体から
連続的に引き離し、引続き上記付着体を酸素含有雰囲気
中で加熱焼結したのち、上記焼結した付着体に所定の加
熱処理を施すことを特徴とするものである。That is, in the present invention, a predetermined amount of a compound containing each of the constituent elements of an oxide superconductor is dissolved in a solvent, and this solution is atomized and supplied to a reactor heated to a predetermined temperature to cause a reaction. While converting the shaped body into oxide superconductor powder,
The adhered body is deposited on the surface of a cooled tube placed in the reactor, and then the adhered body is heated and sintered while being continuously separated from the cooling tube body, and the adhered body is then heated and sintered in an oxygen-containing atmosphere. After sintering, the sintered adhered body is subjected to a predetermined heat treatment.
本発明において、酸化物超電導体の構成元素を各々含有
する化合物としては、例えばＹＢａ、Ｃｕ３０７−δ（
δ″−ｉ ０．１〜０．３ ）の超電導体ニツイて例示
するとＹ、Ｂａ、Ｃｕのそれぞれ酢酸塩、硝酸塩、ハロ
ゲン化物或いは有機金属化合物等である。In the present invention, examples of compounds containing each of the constituent elements of the oxide superconductor include YBa, Cu307-δ(
Examples of superconductors with δ″-i 0.1 to 0.3 include acetates, nitrates, halides, and organometallic compounds of Y, Ba, and Cu, respectively.
本発明において上記化合物を霧状化する方法としては、
例えば上記化合物をそれぞれ水等の溶媒に溶解し、これ
を超音波ネプライザ等により霧状化する方法が用いられ
る。In the present invention, the method for atomizing the above compound is as follows:
For example, a method may be used in which each of the above compounds is dissolved in a solvent such as water and atomized using an ultrasonic nebulizer or the like.
上記の霧状体を反応炉に連続的に供給する方法としては
、これを空気、Ｏｔ等のキャリアガスにのせて搬送する
のが供給量のコントロールが容易にできて好ましいもの
である。As a method for continuously supplying the above-mentioned atomized material to the reactor, it is preferable to transport the atomized material in a carrier gas such as air or Ot, since the amount of the atomized material to be supplied can be easily controlled.
本発明において上記霧状体を酸化物超電導体粉末に加熱
反応させる加熱方法としては、電気抵抗加熱、高周波誘
導加熱、バーナ加熱等の方法が特に適している。In the present invention, methods such as electric resistance heating, high frequency induction heating, and burner heating are particularly suitable as heating methods for causing the atomized material to undergo a thermal reaction with the oxide superconductor powder.
本発明において反応炉により加熱されて生成する酸化物
超電導体粉末は、例えばＹ−Ｂａ−Ｃｕ−Ｏ系酸化物超
電導体について示すと、ＹＢａｚＣｕ、Ｏっの化学式で
示される複合酸化物であり、上記の酸化物超電導体中に
は酸素量が欠乏した組成からなる複合酸化物も含まれて
おり、この粉末に酸素含有雰囲気中で所定の加熱焼結並
びに加熱処理を施すと超電導特性が更に向りするもので
ある。In the present invention, the oxide superconductor powder produced by heating in a reaction furnace is a composite oxide represented by the chemical formula of YBazCu, O, for example, in the case of a Y-Ba-Cu-O-based oxide superconductor. The above oxide superconductor also contains a composite oxide with a composition deficient in oxygen, and when this powder is subjected to prescribed heat sintering and heat treatment in an oxygen-containing atmosphere, the superconducting properties are further improved. It is something to be used for.
本発明において、上記の生成する酸化物超電導体粉末を
冷却された管体に付着させるのは、高温状態にある浮遊
粉末は、冷却管体上に付着し易いという所謂サーモホレ
シス効果を利用したもので、冷却された管体の温度が低
い桟付＠量が増加する。In the present invention, the oxide superconductor powder produced above is attached to the cooled tube by utilizing the so-called thermophoresis effect, in which suspended powder in a high temperature state tends to adhere to the cooled tube. , the amount of crosspieces with low temperature of the cooled tube increases.
本発明において、冷却された管体には内部に冷媒が流さ
れるパイプ等が用いられ、その形状、材質は用途に応じ
て任意に選ぶことができる。In the present invention, a pipe or the like through which a refrigerant flows is used as the cooled tube, and its shape and material can be arbitrarily selected depending on the purpose.
本発明において、冷却管体上の付着体を加熱焼結する理
由は、付着体に強度をもたせ付着体が冷却管体から引き
離される時破断するのを防止する為で、この加熱焼結は
、付着体が冷却管体」：を移動し易くする為、付着体の
内層が粉末状である程度にとどめるのが望ましい。In the present invention, the reason why the adhered body on the cooling pipe body is heated and sintered is to give strength to the adhered body and prevent the adhered body from breaking when it is separated from the cooling pipe body. In order to make it easier for the adhered body to move around the cooling pipe body, it is desirable that the inner layer of the adhered body be kept to a certain extent in powder form.
本発明において冷却された管体から引き離された付着体
は、酸素含有雰囲気中で内部まで加熱焼結され、粉末間
の結合並びに酸素の補給がなされ、引続き酸素含有雰囲
気中で所定の加熱処理が施されて更に酸素の補給と結晶
構造の調整がなされる。In the present invention, the adhered body separated from the cooled tube is heated and sintered to the inside in an oxygen-containing atmosphere to bond the powders and replenish oxygen, and then undergo a predetermined heat treatment in an oxygen-containing atmosphere. Furthermore, oxygen is supplied and the crystal structure is adjusted.
酸化物超電導体原料を溶媒に溶かして溶液となし、この
溶液を霧状化して加熱反応させるので微細な酸化物超電
導体粉末が生成され、更に生成させた粉末をサーモホレ
シス効果を利用して冷却された管体上に付着させるので
高い付着効率が得られるとともに、付着した酸化物超電
導体粉末は冷却管体と接するので拡散反応を起こして変
質するようなことがない。The oxide superconductor raw material is dissolved in a solvent to form a solution, and this solution is atomized and heated to generate a fine oxide superconductor powder, which is then cooled using the thermophoresis effect. Since the oxide superconductor powder is deposited on the cooling pipe body, high adhesion efficiency can be obtained, and since the deposited oxide superconductor powder comes into contact with the cooling pipe body, it will not undergo a diffusion reaction and change in quality.
又上記冷却管体上に付着した酸化物超電導体粉末は続け
て加熱焼結されるので冷却体からの引き離し時に破断す
ることなく容易に引き離しでき、引続き内部層の加熱焼
結並びに全体の加熱処理が連続してなされるので酸化物
超電導線材が効率よく製造される。In addition, since the oxide superconductor powder adhering to the cooling pipe body is continuously heated and sintered, it can be easily separated without breaking when removed from the cooling body, and the inner layer is subsequently heated and sintered and the entire heat treatment is performed. Since these steps are performed continuously, the oxide superconducting wire can be manufactured efficiently.
以下に本発明を実施例により詳細に説明する。 The present invention will be explained in detail below using examples.
第１図は本発明方法を実施する酸化物超電導線材製造装
置の一例を示す要部説明図である。FIG. 1 is an explanatory diagram of essential parts showing an example of an oxide superconducting wire manufacturing apparatus for carrying out the method of the present invention.
酸化物超電導線材製造装置は、原料？′？Ｉ液ｌを霧状
化する為の超音波式ネプライザ２、上記霧状体３を輸送
する為のキャリアガス制御用ＭＦＣ（Ｍａｓｓ−Ｆｌｏ
ｗ−Ｃｏｎｔｒｏｌｌｅｒ） ４、上記霧状体３の粒径
選別用ＤＭＡ （Ｄｉｆｆｅｒｅｎｔｉａｌ−Ｍｏｂｉ
ｌｉｔｙ−Ａｎａｌｙｚｅｒ）５、上記の選別された霧
状体３を酸化物超電導体粉末に加熱反応させる為の反応
炉６、反応炉６を内外から加熱する為の２基の反応用電
気炉７．８、上記酸化物超電導体粉末を付着させるため
の冷却された管９．上記の付着した粉末を加熱焼結する
ための表面焼結用電気炉１０、上記冷却管９から引き離
した酸化物超電導体粉末のパイプ状体１１を加熱焼結す
る為の内部焼結用電気炉１２、上記焼結されたパイプ状
体１１を加熱処理する為のアニール用電気炉１３から構
成されている。Is oxide superconducting wire production equipment used as raw material? ′? An ultrasonic nebulizer 2 for atomizing liquid I, a carrier gas control MFC (Mass-Flo
w-Controller) 4. DMA for particle size selection of the atomized material 3 (Differential-Mobi
5, a reactor 6 for heating and reacting the selected atomized material 3 into oxide superconductor powder, and two electric reaction furnaces 7 for heating the reactor 6 from the inside and outside. 8. Cooled tube for depositing the oxide superconductor powder 9. A surface sintering electric furnace 10 for heating and sintering the adhered powder, and an internal sintering electric furnace for heating and sintering the pipe-shaped body 11 of the oxide superconductor powder separated from the cooling tube 9. 12. It consists of an annealing electric furnace 13 for heat-treating the sintered pipe-shaped body 11.
上記において、冷却された管９は、超電導体粉末が冷却
管９の先端部分にのみ付着し上部には付着しないような
構成になっている。即ち上記冷却管９は二重構造になっ
ていて中心管から冷媒が入れられ外周管を通って排出さ
れる構造のもので、冷却管９は先端部分に冷媒が流出す
るので先端部分がよく冷却され、冷却管９の上部程冷却
媒体は高温となり上部の冷却は弱まる。更に反応用電気
炉７は冷却管９の上部を加熱できるように配置されてい
る。In the above, the cooled tube 9 is configured such that the superconductor powder adheres only to the tip portion of the cooling tube 9 and does not adhere to the upper portion. That is, the cooling pipe 9 has a double structure, in which refrigerant is introduced from the center pipe and discharged through the outer peripheral pipe, and since the refrigerant flows out to the tip of the cooling pipe 9, the tip is well cooled. As a result, the higher the cooling pipe 9, the higher the temperature of the cooling medium becomes, and the cooling of the upper part becomes weaker. Further, the reaction electric furnace 7 is arranged so as to be able to heat the upper part of the cooling pipe 9.
実施例１
出発原料としてＹ （ＣＨｓ ＣＯＯ） ｘ・４ Ｈ□
○、Ｂａ （ＣＨ，Ｃｏｏ）、−Ｈ，Ｏ及びＣｕ （Ｃ
Ｈ２ＣＯ２）よ・Ｈ，Ｏを用い、上記の各々の出発原料
をＹ：Ｂａ：Ｃｕが原子比で１：２：３になるように秤
量し、これを水に熔解してＹＢａ、Ｃｕ３の組成で０．
０３モル／１２１１度の水溶液を用意した。Example 1 Y (CHs COO) x・4 H□ as a starting material
○, Ba (CH,Coo), -H,O and Cu (C
Using H2CO2), H, and O, weigh each of the above starting materials so that the atomic ratio of Y:Ba:Cu is 1:2:3, and dissolve it in water to obtain the composition of YBa and Cu3. So 0.
An aqueous solution of 0.03 mol/1211 degrees was prepared.
上記水溶液を第１図に示した酸化物超電導線材製造装置
の超音波式ネプライザ２内にセットして５０ｃｃ／ｗｉ
ｎの速度で霧状化し、次いでこの霧状体３をＭＦＣ４か
ら２３４！／５ｈｉｎの流量で流入する０２気流にのせ
てＤＭＡ５に輸送し、上記ＤＭＡ５により粒径４−以下
の霧状体３を選別してこれを反応炉６内に供給した。The above aqueous solution was set in the ultrasonic nebulizer 2 of the oxide superconducting wire manufacturing apparatus shown in Fig.
n at a speed of 234! The atomized material 3 having a particle size of 4 mm or less was selected by the DMA 5, and was supplied into the reactor 6.
反応炉６内に供給された上記霧状体３は反応用電気炉７
．８により加熱されて反応して酸化物超電導体粉末とな
し、この粉末を上記反応炉６内の中心部に配置した外径
６閤の銀製冷却管９の先端部分に付着させた。上記冷却
管９の先端部分の表面温度は、冷却水量の上記表面温度
に及ぼす影響を予備実験により求めておいて制御した。The atomized material 3 supplied into the reaction furnace 6 is transferred to the reaction electric furnace 7.
．． 8 to react and form an oxide superconductor powder, and this powder was attached to the tip of a silver cooling tube 9 with an outer diameter of 6 mm located at the center of the reactor 6. The surface temperature at the tip of the cooling pipe 9 was controlled by determining the influence of the amount of cooling water on the surface temperature through preliminary experiments.
而して上記冷却管９に付着した酸化物超電導体粉末の表
面層を表面焼結用電気炉ｌＯにより加熱焼結し、この表
面層が焼結した付着体を図示していないピンチロールに
より冷却管９から連続的に引き離し、酸化物超電導パイ
プ状体１１となし、引続きこのパイプ状体１１を上記冷
却管９の下方に配置した内部焼結用電気炉１３により内
部迄焼結し、次いで上記内部焼結用電気炉１２の下方に
配置したアニール用電気炉１３により大気中で加熱処理
を施した。Then, the surface layer of the oxide superconductor powder adhering to the cooling tube 9 is heated and sintered in an electric furnace for surface sintering IO, and the adhered body with this sintered surface layer is cooled by pinch rolls (not shown). It is continuously separated from the tube 9 to form an oxide superconducting pipe-like body 11, and then this pipe-like body 11 is sintered to the inside in an internal sintering electric furnace 13 disposed below the cooling pipe 9, and then the above-mentioned Heat treatment was performed in the atmosphere using an annealing electric furnace 13 placed below the internal sintering electric furnace 12.
アニール用電気炉１３は上部から下部にかけて９００°
Ｃから室温迄直線的温度勾配がつけられており、上記パ
イプ状体１１は２°（：／ｇ＋ｉｎの速度で徐冷した。The annealing electric furnace 13 has an angle of 90° from the top to the bottom.
A linear temperature gradient was established from C to room temperature, and the pipe-shaped body 11 was gradually cooled at a rate of 2° (:/g+in).
このようにして得られたＹ Ｂ ａ ｔ Ｃｕ ３０
ｑ−δ（δζ０．１〜０．３）の酸化物超電導線材は図
示していないコイラーに連続して巻き取った。Y B a t Cu 30 thus obtained
The q-δ (δζ0.1 to 0.3) oxide superconducting wire was continuously wound around a coiler (not shown).
実施例２
冷却管の先端部分の表面温度を６０゛Ｃとした他は実施
例１と同じ方法により酸化物超電導線材を製造した。Example 2 An oxide superconducting wire was produced in the same manner as in Example 1, except that the surface temperature of the tip of the cooling tube was 60°C.
実施例３
霧状化のための水溶液に、Ｂ ｉ （ＣａＨｗＯ，）
・７Ｈ，ＯｌＳ ｒ （ＣｈＨ＊ＯＪｚ ・３８ｚＯ
，Ｃａ（Ｃ−Ｈ９０ｈ ） ｔ ・５ Ｈｔ ＯとＣｕ
（ＣｈＨｗｏｉ）２・２Ｈ，ＯをＢｉ：Ｓｒ：Ｃａ：
Ｃｕが１：１：ｌ：２になるように配合し混合した混合
粉末を、エタノール５０％十水５０％の溶媒に？容かし
てＢ１５ｒｃａｃｕｚの組成で０．０１５モル／ｌ濃度
となしたものを用いた他は実施例１と同様の方法により
Ｂ１５ｒＣａＣｕ、Ｏｌ−δ（δ−０，１〜０．３）の
酸化物超電導線材を製造した。Example 3 B i (CaHwO,) was added to the aqueous solution for atomization.
・7H,OlS r (ChH*OJz ・38zO
, Ca(C-H90h) t ・5 Ht O and Cu
(ChHwoi)2.2H,O Bi:Sr:Ca:
Mixed powder mixed so that Cu ratio is 1:1:1:2 is mixed in a solvent of 50% ethanol and 50% water? Oxidation of B15rCaCu, Ol-δ (δ-0,1 to 0.3) was carried out in the same manner as in Example 1, except that B15rcacuz was used at a concentration of 0.015 mol/l. A superconducting wire was manufactured.
従来例１
２■φのＳＵＳ線上にＹ Ｂ ａ ２ Ｃｕ ３０ ｘ
組成のペースト状仮焼成粉をｌ１１１ｆｆｉ厚さに塗布
し、これを乾燥後酸素気流中で９００ ’Ｃ２０時間加
熱焼結したのち、９００″Ｃから室温迄２°（：／ｗｉ
ｎの速度で徐冷して酸化物超電導線材を製造した。Conventional example 1 Y B a 2 Cu 30 x on 2■φ SUS wire
A paste-like calcined powder of the composition was applied to a thickness of 111ffi, and after drying, it was heated and sintered at 900'C in an oxygen stream for 20 hours, and then heated at 2° from 900'C to room temperature (:/wi
An oxide superconducting wire was produced by slow cooling at a rate of n.
斯くの如くして得られた各々の酸化物超電導線材につい
て、寸法、相対密度及びＪ、を測定した。The dimensions, relative density and J of each of the oxide superconducting wires thus obtained were measured.
結果は製造条件を併記して第１表に示した。The results are shown in Table 1 along with the manufacturing conditions.
第１表より明らかなように本発明方法品（実施例１〜３
）は従来方法品（従来例１）に較べて相対密度、ＪＣと
も高い値を示している。As is clear from Table 1, the method of the present invention (Examples 1 to 3)
) shows higher values for both relative density and JC than the conventional method product (Conventional Example 1).
本発明方法品において、酸化物超電導体粉末は溶液加熱
分解法により生成するので微細であり、上記粉末の付着
体の密度が高く、又冷却管との界面は温度が低いので拡
散反応を起こすことがなくＪ、が高い値となった。又本
発明方法品において冷却管の温度が低い程上記粉末が厚
く付着する。In the product produced by the method of the present invention, the oxide superconductor powder is produced by a solution thermal decomposition method, so it is fine, the density of the powder adhered to it is high, and the temperature at the interface with the cooling tube is low, so that no diffusion reaction occurs. There was no J, and the value was high. In addition, in the method of the present invention, the lower the temperature of the cooling pipe, the thicker the powder adheres.
本発明方法において、酸化物超電導体粉末の冷却管から
の引き離しは、いずれの場合も−Ｆ記粉末のパイプ状体
が破断することなくスムーズになされた。製出したパイ
プ状線材の外内径はともに冷却管の外径より細くなって
いるが、これは引き離し直後自重により伸延し、更に加
熱焼結により縮小した為である。In the method of the present invention, the oxide superconductor powder was smoothly separated from the cooling tube without breaking the pipe-shaped body of the -F powder in all cases. Both the outer and inner diameters of the produced pipe-shaped wire rod are smaller than the outer diameter of the cooling tube, but this is because it was elongated due to its own weight immediately after being separated, and was further reduced by heating and sintering.
従来方法品のＪ、が低いのはペースト状の仮焼成粉をＳ
ＵＳ基体上に塗布して加熱焼結した為、酸化物超電導体
層がポーラスとなり、又基体から不純物元素が拡散侵入
した為である。The J of the conventional method product is low because of the paste-like pre-calcined powder S.
This is because the oxide superconductor layer became porous because it was coated on a US substrate and heated and sintered, and impurity elements diffused into the substrate.
本発明方法において、細径の円形冷却管又は平角状の冷
却管を用い、酸化物超電導体粉末を厚めに付着させて上
記付着体を冷却管から引き離したのち、適度の圧下を施
すことにより中実線材を製造することも可能である。In the method of the present invention, a small-diameter circular cooling tube or a rectangular cooling tube is used, oxide superconductor powder is deposited thickly, the adhered body is separated from the cooling tube, and then moderate pressure is applied to reduce the temperature. It is also possible to produce solid wire.
以上述べたように本発明方法によれば、密度及び純度が
高く、超電導特性に優れた長尺の酸化物超電導線材が連
続して効率よく製造し得るので、工業上顕著な効果を奏
する。As described above, according to the method of the present invention, a long oxide superconducting wire having high density and purity and excellent superconducting properties can be continuously and efficiently manufactured, and therefore it has a significant industrial effect.
第１図は本発明方法を実施する酸化物超電導線材製造装
置の一例を示す要部説明図である。
■・・・溶液、 ３・・・霧状体、 ６・・・反応炉、
９・・冷却管、 １１・・・酸化物超電導パイプ状
体。FIG. 1 is an explanatory diagram of essential parts showing an example of an oxide superconducting wire manufacturing apparatus for carrying out the method of the present invention. ■...Solution, 3...Atomized body, 6...Reactor,
9... Cooling pipe, 11... Oxide superconducting pipe-shaped body.
Claims (1)
ぞれ所定量溶媒に溶解し、この溶液を霧状化して所定温
度に加熱した反応炉内に供給して反応させて上記霧状体
を酸化物超電導体粉末となすとともに、上記反応炉内に
配置した冷却された管体の表面に付着させ、次いで該付
着体を加熱焼結しつつ、上記冷却管体から連続的に引き
離し、引続き上記付着体を酸素含有雰囲気中で加熱焼結
したのち、上記焼結した付着体に所定の加熱処理を施す
ことを特徴とする酸化物超電導線材の製造方法。A predetermined amount of a compound containing each of the constituent elements of an oxide superconductor is dissolved in a solvent, and this solution is atomized and supplied to a reactor heated to a predetermined temperature to react, and the atomized material is converted into an oxide. The superconductor powder is formed into superconductor powder, and is adhered to the surface of a cooled tube placed in the reactor, and then the adhered body is heated and sintered while being continuously separated from the cooling tube, and then the adhered body is A method for producing an oxide superconducting wire, comprising heating and sintering the sintered body in an oxygen-containing atmosphere, and then subjecting the sintered adhered body to a predetermined heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63155692A JPH025314A (en) | 1988-06-23 | 1988-06-23 | Manufacture of oxide superconductive wire rod |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63155692A JPH025314A (en) | 1988-06-23 | 1988-06-23 | Manufacture of oxide superconductive wire rod |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH025314A true JPH025314A (en) | 1990-01-10 |
Family
ID=15611457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63155692A Pending JPH025314A (en) | 1988-06-23 | 1988-06-23 | Manufacture of oxide superconductive wire rod |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH025314A (en) |
-
1988
- 1988-06-23 JP JP63155692A patent/JPH025314A/en active Pending
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