JPH0818911B2 - Method for producing single crystal of T1-Ca-Ba-Cu-O high temperature superconducting material - Google Patents
Method for producing single crystal of T1-Ca-Ba-Cu-O high temperature superconducting materialInfo
- Publication number
- JPH0818911B2 JPH0818911B2 JP63217773A JP21777388A JPH0818911B2 JP H0818911 B2 JPH0818911 B2 JP H0818911B2 JP 63217773 A JP63217773 A JP 63217773A JP 21777388 A JP21777388 A JP 21777388A JP H0818911 B2 JPH0818911 B2 JP H0818911B2
- Authority
- JP
- Japan
- Prior art keywords
- high temperature
- single crystal
- atomic ratio
- superconducting material
- temperature superconducting
- 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 - Lifetime
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- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はTl−Ca−Ba−Cu−Ｏ系高温超電導材料の単結
晶製造方法に関するものである。TECHNICAL FIELD The present invention relates to a method for producing a single crystal of a Tl—Ca—Ba—Cu—O high temperature superconducting material.
［従来技術］ Tl−Ca−Ba−Cu−Ｏ系では他の酸化物超電導材料と同
様CuOやCuO＋（Ca,Ba）Ｏをフラックスとして使用した
単結晶の成長が試みられたが、安定して製造することが
難しい状態にあった。[Prior Art] In the Tl-Ca-Ba-Cu-O system, the growth of a single crystal using CuO or CuO + (Ca, Ba) O as a flux was attempted similarly to other oxide superconducting materials. It was in a difficult state to manufacture.
［発明が解決しようとする課題］ 従来の原料原子比ではいわゆる高温相と呼ばれるTcの
高いmmサイズの結晶が得られなかった。これは高温相の
晶出する原料原子比や生成する構造が不明であったため
構造条件がずれていたことによるからであった。[Problems to be Solved by the Invention] With the conventional atomic ratio of raw materials, it was not possible to obtain a so-called high temperature phase crystal having a high Tc and a size of mm. This is because the atomic ratio of the raw material to crystallize out of the high temperature phase and the structure to be formed were unknown, so that the structural conditions were deviated.
［問題点を解決するための手段とその効果］ そこで発明者らはかかる課題を解決せんとして精力的
に努力した結果、特許請求の範囲に記載の製造方法を見
い出したものであって、 結晶成長に使用する原料中の（Ca＋Cu）の原子比が60
〜80mol.％,TlとBaの原子比が1:1でかつ（Ta＋Ba）の原
子比が20mol.％〜40mol.％となるよう配合原子比を調整
すること 原料融合後の910〜860℃の温度範囲内で１〜12時間温
度を保持することを要件にしたものである。即ち、T1系
超電導体の高温相の結晶中の原子比はTl:Ca:Ba:Cu＝2:
2:2:3であるが、フラックス法による単結晶育成には原
料として2223原子比にさらにフラックス材を添加する必
要がある。発明者らはフラックス材として、（CaO＋Cu
O）を使用し、その添加量の最適化を図った。その結果
は第１図に示す通りで、原料としてTl:Ca:Ba＝2:6:2:6
の時に最も高いTcを有する結晶が得られることが判明し
た。これはこの原料原子比が丁度高温相結晶が晶出する
原料原子比の範囲にあるためである。また、（Ca＋Cu）
が60〜80mol.％内のその他の原料原子比でも原料溶融後
910〜860℃の温度内で１〜12時間保持することにより高
温相の生成が進行することが判明した。これは高温相が
上記温度内で包晶反応により生成するためである。保持
時間は原料原子比や温度によって異なるが900℃では１
時間程度、860℃付近では12時間程度の反応時間が必要
である。[Means for Solving Problems and Effects Thereof] The inventors of the present invention have made vigorous efforts to solve such problems, and as a result, have found the manufacturing method described in the scope of claims, which is crystal growth. The atomic ratio of (Ca + Cu) in the raw material used for is 60
˜80mol.%, Tl to Ba atomic ratio is 1: 1 and (Ta + Ba) atomic ratio is 20mol.% To 40mol.%. The requirement is to keep the temperature within the temperature range for 1 to 12 hours. That is, the atomic ratio in the crystal of the high temperature phase of the T1 superconductor is Tl: Ca: Ba: Cu ＝ 2:
Although it is 2: 2: 3, in order to grow a single crystal by the flux method, it is necessary to further add a flux material as a raw material in an atomic ratio of 2223. As a flux material, the inventors have used (CaO + Cu
O) was used to optimize the addition amount. The result is as shown in Fig. 1. As a raw material, Tl: Ca: Ba ＝ 2: 6: 2: 6
It was found that the crystal with the highest Tc was obtained at. This is because the atomic ratio of the raw materials is just in the range of the atomic ratio of the raw materials at which the high temperature phase crystal is crystallized. Also, (Ca + Cu)
After melting the raw materials even with other raw material atomic ratios within 60-80 mol.%
It was found that the formation of the high temperature phase proceeds by holding the temperature within the range of 910 to 860 ° C for 1 to 12 hours. This is because the high temperature phase is generated by the peritectic reaction within the above temperature. The holding time depends on the raw material atomic ratio and the temperature, but it is 1 at 900 ° C.
The reaction time is about 12 hours at about 860 ℃.
［実施例］ 各原料原子比におけるTc（Ｋ）は次の通りであった。
すなわち、 原料原子比 Tc（Ｋ） Tl: Ca: Ba: Cu ２ ２ ２ ３ 108−110 ２ ３ ２ 3.75 114−115 ２ ４ ２ 4.5 115 ２ ５ ２ 5.25 118 ２ ６ ２ 6 118−120 ２ ７ ２ 6.75 115 ２ ８ ２ 7.5 94 上記原料原子比でTl2O3,CaO,BaO2,CuOを混合、約１〜
2ton/cm2でペレット成形したものを原料とした。原料は
内径10〜12mmφのAuパイプ中に封入し、さらにこのAuパ
イプをPtるつぼ内に挿入し、炉内に入れ、結晶を成長さ
せた。成長条件は第２図に示すとおりである。炉内は流
量200〜500ml/分のO2ガスフローとし、原料チャージ量
は２〜5gとした。冷却後試料を粉砕フラックスより結晶
を取り出したところ、結晶は0.5〜2.5mm四方のサイズの
ものが得られた。これらの結晶をDC帯磁率測定によりTc
を測定したところ108〜120Kの種々のTcを持つ結晶が得
られた。このうち118〜120KのTcを示す結晶は0.5〜1.5m
m四方程度であった。[Example] Tc (K) at each raw material atomic ratio was as follows.
That is, the raw material atomic ratio Tc (K) Tl: Ca: Ba: Cu 2 2 2 3 108-110 2 3 2 3.75 114-115 2 4 2 4.5 115 2 5 2 5.25 118 2 6 2 6 118-120 2 7 2 6.75 115 2 8 2 7.5 94 Tl 2 O 3 , CaO, BaO 2 and CuO are mixed in the above atomic ratio of raw materials, about 1 to
The raw material was pelletized at 2 ton / cm 2 . The raw material was enclosed in an Au pipe having an inner diameter of 10 to 12 mmφ, and the Au pipe was further inserted into a Pt crucible and put into a furnace to grow crystals. The growth conditions are as shown in FIG. The flow rate of O 2 gas in the furnace was 200 to 500 ml / min, and the raw material charge amount was 2 to 5 g. After cooling, the crystals were taken out from the crushed flux, and crystals having a size of 0.5 to 2.5 mm square were obtained. Tc of these crystals was measured by DC susceptibility.
Was measured, and crystals with various Tc of 108-120K were obtained. Of these, crystals with a Tc of 118-120K are 0.5-1.5m.
It was about m square.
［本発明の効果］ これまでTl−Ca−Ba−Cu−Ｏ系超導導体の低Tc相単結
晶しか得られなかったが、本発明によりmmサイズの大型
の高温相（Tc＝118〜120K）の単結晶が安定して得られ
るようになり、産業上における実施範囲が格段に広がる
効果は極めて大きい。[Effect of the present invention] Until now, only a low Tc phase single crystal of a Tl-Ca-Ba-Cu-O-based superconductor was obtained, but according to the present invention, a large mm-sized high temperature phase (Tc = 118 to 120K) is obtained. The single crystal of 1) can be stably obtained, and the effect of greatly expanding the industrial scope is extremely large.
第１図は本発明における（Ca＋Cu）/mol.％における臨
界温度を示し、第２図は本発明の結晶成長条件における
温度プログラムを示す。FIG. 1 shows the critical temperature at (Ca + Cu) /mol.% in the present invention, and FIG. 2 shows the temperature program under the crystal growth conditions of the present invention.
Claims (2)
超電導材料の単結晶をフラックス法により製造する際
に、出発原料中の（Ca＋Cu）の原子比が60mol.％〜80mo
l.％,TlとBaの原子比が1:1でかつ（Tl＋Ba）の原子比が
20mol.％〜40mol.％であることを特徴とするTl−Ca−Ba
−Cu−Ｏ系高温超電導材料の単結晶製造方法。1. When producing a single crystal of an oxide superconducting material containing Tl, Ca, Ba and Cu as constituent elements by the flux method, the atomic ratio of (Ca + Cu) in the starting material is 60 mol.% To 80 mol.
l.%, the atomic ratio of Tl to Ba is 1: 1 and the atomic ratio of (Tl + Ba) is
20 mol.% To 40 mol.% Tl-Ca-Ba
A method for producing a single crystal of a Cu-O-based high temperature superconducting material.
12時間原料の温度を保持する請求第１項のTl−Ca−Ba−
Cu−Ｏ系高温超電導材料の単結晶製造方法。2. Within a temperature range of 910 to 860 ° C. after melting the raw materials, 1 to
The Tl-Ca-Ba- according to claim 1, which maintains the temperature of the raw material for 12 hours.
A method for producing a single crystal of a Cu-O-based high temperature superconducting material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63217773A JPH0818911B2 (en) | 1988-08-30 | 1988-08-30 | Method for producing single crystal of T1-Ca-Ba-Cu-O high temperature superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63217773A JPH0818911B2 (en) | 1988-08-30 | 1988-08-30 | Method for producing single crystal of T1-Ca-Ba-Cu-O high temperature superconducting material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0264099A JPH0264099A (en) | 1990-03-05 |
| JPH0818911B2 true JPH0818911B2 (en) | 1996-02-28 |
Family
ID=16709505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63217773A Expired - Lifetime JPH0818911B2 (en) | 1988-08-30 | 1988-08-30 | Method for producing single crystal of T1-Ca-Ba-Cu-O high temperature superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0818911B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7450824B2 (en) | 1997-05-26 | 2008-11-11 | Seiko Epson Corporation | Digital camera and printing system |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH026330A (en) * | 1988-03-07 | 1990-01-10 | Sanyo Electric Co Ltd | Production of superconducting material and superconducting single crystal |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6353043A (en) * | 1986-08-22 | 1988-03-07 | Tokyo Electric Co Ltd | Laser diode drive control circuit for laser printer |
| JPH026330A (en) * | 1988-03-07 | 1990-01-10 | Sanyo Electric Co Ltd | Production of superconducting material and superconducting single crystal |
-
1988
- 1988-08-30 JP JP63217773A patent/JPH0818911B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7450824B2 (en) | 1997-05-26 | 2008-11-11 | Seiko Epson Corporation | Digital camera and printing system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0264099A (en) | 1990-03-05 |
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