JP2803823B2 - Method for producing T1-based oxide superconductor - Google Patents
Method for producing T1-based oxide superconductorInfo
- Publication number
- JP2803823B2 JP2803823B2 JP63278322A JP27832288A JP2803823B2 JP 2803823 B2 JP2803823 B2 JP 2803823B2 JP 63278322 A JP63278322 A JP 63278322A JP 27832288 A JP27832288 A JP 27832288A JP 2803823 B2 JP2803823 B2 JP 2803823B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- oxide superconductor
- based oxide
- powder
- producing
- 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 - Fee Related
Links
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
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Description
【発明の詳細な説明】 「産業上の利用分野」 この発明は臨界温度が高いことで知られているT1系酸
化物超電導体の製造方法に関する。The present invention relates to a method for producing a T1-based oxide superconductor known to have a high critical temperature.
「従来の技術」 近年、常電導状態から超電導状態に遷移する臨界温度
（Tc）が液体窒素温度を超える値を示す酸化物系の超電
導体が種々発見されている。この種の酸化物超電導体
は、Ｙ−Ba−Cu−Ｏ系あるいはBi−Sr−Ca−Cu−Ｏ系な
どで代表される酸化物であって、Ｙ−Ba−Cu−Ｏ系の酸
化物では90Kを超える臨界温度を示し、Bi−Sr−Ca−Cu
−Ｏ系の酸化物では100Kを超える臨界温度を示すことが
確認されている。[Background Art] In recent years, various oxide-based superconductors have been discovered in which a critical temperature (Tc) at which a transition from a normal conducting state to a superconducting state exceeds a liquid nitrogen temperature. This type of oxide superconductor is an oxide represented by a Y-Ba-Cu-O system or a Bi-Sr-Ca-Cu-O system, and is a Y-Ba-Cu-O system oxide. Shows a critical temperature exceeding 90K, Bi-Sr-Ca-Cu
It has been confirmed that a -O-based oxide exhibits a critical temperature exceeding 100K.
「発明が解決しようとする課題」 ところで、最近に至り、アメリカ合衆国、アーカンソ
ー大学のA.M.Hermannらが120K近傍から電気抵抗が低下
し、100K近傍で零抵抗を示すT1−Ba−Ca−Cu−Ｏ系の酸
化物超電導体を発見したことが明らかとなり、その結果
を基に世界中の各研究機関で新種の酸化物超電導体の開
発が進められている。[Problems to be Solved by the Invention] By the way, recently, the United States, AMHermann et al. Of the University of Arkansas, T1-Ba-Ca-Cu-O system whose electric resistance decreases from around 120K and shows zero resistance around 100K. It became clear that they had discovered oxide superconductors, and based on the results, research institutes around the world are developing new types of oxide superconductors.
この系の酸化物超電導体は、Hermannらが、NATURE VO
L.332 10 MARCH 1988などにおいて公表した内容から明
らかなように、 T12Ca1.5Ba1Cu3O8.5＋Ｘ （Tc＝103K）、 T12Ca2Ba1Cu3Ox （Tc＝106K）、 T12Ca2Ba2Cu3Ox （Tc＝102K）、 なる組成と臨界温度を示すものである。The oxide superconductor of this system is described by Hermann et al.
L.332 10 MARCH is clear from published by contents in such 1988, T1 2 Ca 1.5 Ba 1 Cu 3 O 8.5 + X (Tc = 103K), T1 2 Ca 2 Ba 1 Cu 3 Ox (Tc = 106K), T1 2 Ca 2 Ba 2 Cu 3 Ox (Tc = 102K), which shows the following composition and critical temperature.
以上のように種々の酸化物超電導体が発見されつつあ
る状況であるが、超電導体はより高い温度で抵抗が零に
なることが好ましいので、前記従来の酸化物超電導体の
臨界温度を向上させる製造方法あるいは手段が種々試み
られている状況である。Although various oxide superconductors are being discovered as described above, it is preferable that the resistance of the superconductor becomes zero at a higher temperature, so that the critical temperature of the conventional oxide superconductor is improved. Various production methods or means are being attempted.
本発明は前記背景に鑑みてなされたもので、臨界温度
が107K〜120Kを示すとともに、高い臨界電流密度を示す
T1系酸化物超電導体を製造することができる方法の提供
を目的とする。The present invention has been made in view of the above background, and has a critical temperature of 107K to 120K and shows a high critical current density.
An object of the present invention is to provide a method capable of manufacturing a T1-based oxide superconductor.
「課題を解決するための手段」 請求項１に記載した発明は前記課題を解決するために
T1化合物とBa化合物とCu化合物を混合し、加熱してT12B
a2Cu3OxあるいはT12Ba2Cu2Oxなる組成の複合化合物を作
成し、次いで該複合化合物とCaOを混合した後で酸素雰
囲気中において熱処理することによりT1−Ba−Ca−Cu−
Ｏ系の酸化物超電導体を生成させるものである。“Means for Solving the Problem” The invention described in claim 1 is for solving the problem.
Mix the T1 compound, the Ba compound and the Cu compound, and heat to mix T1 2 B
a 2 Cu 3 Ox or T1 2 Ba 2 Cu 2 Ox A composite compound having a composition of: is prepared, and then the composite compound is mixed with CaO and then heat-treated in an oxygen atmosphere to obtain T1-Ba-Ca-Cu-.
This is for generating an O-based oxide superconductor.
請求項２に記載した発明は前記課題を解決するため
に、T12OまたはT12O3とBaCO3CuOを混合し、加熱してT12
Ba2Cu3OxあるいはT12Ba2Cu2Oxなる組成の複合化合物を
作成し、該複合化合物とCaOを混合した後で酸素雰囲気
中において熱処理して、T1−Ba−Ca−Cu−Ｏ系の酸化物
超電導体を生成させるものである。For the invention described in claim 2 for solving the above problems, a mixture of T1 2 O or T1 2 O 3 and BaCO 3 CuO, heated to T1 2
A composite compound having a composition of Ba 2 Cu 3 Ox or T1 2 Ba 2 Cu 2 Ox is prepared, and the composite compound and CaO are mixed and then heat-treated in an oxygen atmosphere to form a T1-Ba-Ca-Cu-O system. To produce an oxide superconductor of
「作用」 T12Ba2Cu3OxあるいはT12Ba2Cu2Oxなる組成の複合化合
物と、CaOを熱拡散反応させることにより、臨界温度の
高いT1系の酸化物超電導体が生成する。また、T1化合物
とBa化合物とCu化合物の熱拡散反応により複合化合物が
生成する。[Function] By performing thermal diffusion reaction of CaO with a composite compound having a composition of T1 2 Ba 2 Cu 3 Ox or T1 2 Ba 2 Cu 2 Ox, a T1-based oxide superconductor having a high critical temperature is generated. Further, a composite compound is formed by a thermal diffusion reaction of the T1 compound, the Ba compound, and the Cu compound.
以下に本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail.
本発明を実施してT1−Ba−Ca−Cu−Ｏ系の酸化物超電
導体を製造するには、まず、出発物を調整する。この出
発物としては、T1化合物とBa化合物とCu化合物を用い
る。前記化合物としては、各元素の酸化物、塩化物、炭
酸塩、硫化物、フッ化物などのいずれでも良い。この例
で具体的に用いるのは、T12O粉末であるいはT12O3粉末
と、BaCO3粉末とCuO粉末を用いる。なお、用いる化合物
は粒状、粉末状を問わないが、できる限り粒径の小さな
ものが好ましい。In order to manufacture the T1-Ba-Ca-Cu-O-based oxide superconductor by carrying out the present invention, first, a starting material is prepared. As this starting material, a T1 compound, a Ba compound and a Cu compound are used. The compound may be any of oxides, chlorides, carbonates, sulfides, and fluorides of each element. Is used specifically in this example, using a T1 2 O powder or in T1 2 O 3 powder, the BaCO 3 powder and CuO powder. The compound used may be in the form of particles or powder, but preferably has as small a particle size as possible.
ここで前記T12O粉末とBaCO3粉末とCuO粉末を用意した
ならば、T1:Ba:Cu＝2:2:2あるいは2:2:3の割合になるよ
うに秤量して均一に混合し、混合粉末を作製する。次
に、混合粉末を酸素ガス中あるいは大気中において810
℃で５時間加熱して仮焼することにより不要成分を除去
し、Tl2Ba2Cu3xあるいはT12Ba2Cu2Oxなる組成、あるい
は、これらの組成の化合物を主成分とする複合化合物を
作製する。なお、前記仮焼の温度は780〜830℃の範囲が
好ましく、仮焼時間は数時間〜数10時間程度が好まし
い。Here, if the T1 2 O powder, BaCO 3 powder and CuO powder were prepared, T1: Ba: Cu = 2: 2: 2 or 2: 2: 3, and weighed and mixed uniformly. , To prepare a mixed powder. Next, the mixed powder is placed in oxygen gas or air for 810 minutes.
Unnecessary components are removed by calcination by heating at 5 ° C. for 5 hours to obtain a composition of Tl 2 Ba 2 Cu 3 x or T1 2 Ba 2 Cu 2 Ox, or a composite compound containing a compound of these compositions as a main component. Is prepared. The calcination temperature is preferably in the range of 780 to 830 ° C., and the calcination time is preferably several hours to several tens of hours.
前記のように作成された複合化合物を十分に粉砕して
粒径を揃え、これにCaO粉末をT1:Ba:Ca:Cu＝2:2:1:2あ
るいは2:2:2:3または2:2:3:3の割合になるように均一に
混合し、0.1〜10t/cm2程度の圧力を加える圧粉成形処理
を施して所望の形状の圧粉成形体を得る。ここで行う圧
粉成形処理には、機械プレス、静水圧プレスなどを用い
ることが好ましいがこれらの方法に限定されるものでは
なく、混合粉末を圧密できる方法であれば、いかなる方
法を用いても差し支えない。The composite compound prepared as described above is sufficiently pulverized to uniform particle diameters, and CaO powder is mixed with T1: Ba: Ca: Cu = 2: 2: 1: 2 or 2: 2: 2: 3 or 2 : 2: 3: 3 to obtain a green compact having a desired shape by performing a green compacting treatment by applying a pressure of about 0.1 to 10 t / cm 2 . It is preferable to use a mechanical press, a hydrostatic pressure press, or the like for the compacting process performed here, but it is not limited to these methods, and any method may be used as long as the mixed powder can be compacted. No problem.
前記圧粉成形体を得たならば、これを酸素ガス雰囲気
中において、870℃で１時間程度加熱する熱処理を施し
て焼結する。なおこの熱処理は、850〜890℃で１〜30時
間の範囲で行うことが好ましい。以上の熱処理によっ
て、T12Ba2Cu2Oxなる組成、あるいは、T12Ba2Cu3Oxなる
組成の複合化合物とCaOとが反応してT1−Ba−Ca−Cu−
Ｏ系の酸化物超電導体が生成する。Once the green compact is obtained, it is sintered in an oxygen gas atmosphere by heating at 870 ° C. for about 1 hour. The heat treatment is preferably performed at 850 to 890 ° C. for 1 to 30 hours. By the above heat treatment, T1 2 Ba 2 Cu 2 Ox, or a composite compound having a composition of T1 2 Ba 2 Cu 3 Ox reacts with CaO and T1-Ba-Ca-Cu-
O-based oxide superconductor is generated.
以上の方法により臨界温度で107K〜120Kを示し、臨界
電流密度の高い優れたT1系酸化物超電導体を製造するこ
とができる。By the above method, an excellent T1-based oxide superconductor having a critical temperature of 107K to 120K and a high critical current density can be manufactured.
ところで、本発明方法を用いて薄膜状あるいは厚膜状
のT1系超電導体を製造することができる。By the way, a thin or thick T1-based superconductor can be manufactured by using the method of the present invention.
この場合、MgOあるいはSrTiO3などからなる基板上に
化学気相蒸着法、スパッタリング法またはレーザPVD法
などの薄膜形成法、あるいはドクターブレード法などの
厚膜形成法を実施してT12Ba2Cu2OxあるいはT12Ba2Cu3Ox
なる組成の複合化合物層を形成し、更にこの層の上にCa
O層を形成する手順を必要回数行って積層膜を形成し、
この積層膜を前記と同等の条件で熱処理すれば、元素の
相互拡散を進行させてT1系の酸化物超電導層を生成させ
ることができる。In this case, a thin film forming method such as a chemical vapor deposition method, a sputtering method or a laser PVD method, or a thick film forming method such as a doctor blade method is performed on a substrate made of MgO or SrTiO 3 or the like to perform T1 2 Ba 2 Cu 2 Ox or T1 2 Ba 2 Cu 3 Ox
To form a composite compound layer having a composition of
Perform the procedure of forming the O layer as many times as necessary to form a laminated film,
If this laminated film is heat-treated under the same conditions as described above, the interdiffusion of elements can be advanced to generate a T1-based oxide superconducting layer.
このような方法を行うことにより臨界温度と臨界電流
密度の高い膜状のT1系酸化物超電導体を形成することが
できる。By performing such a method, a film-like T1-based oxide superconductor having a high critical temperature and a high critical current density can be formed.
「実施例」 T1:Ba:Cu＝2:2:3あるいは2:2:2となるようにT12O粉末
とBaCO3粉末とCuO粉末を混合して各混合粉末を作製し、
各混合粉末を大気中において810℃で５時間仮焼してT12
Ba2Cu3OxあるいはT12Ba2Cu2Oxなる組成の複合化合物を
作製した。(Example) T1: Ba: Cu = 2: 2: 3 or 2: 2: 2 to prepare a mixed powder by mixing T1 2 O powder and BaCO 3 powder and CuO powder so as to be,
Each mixed powder was calcined for 5 hours at 810 ° C. in air T1 2
A composite compound having a composition of Ba 2 Cu 3 Ox or T1 2 Ba 2 Cu 2 Ox was prepared.
続いて前記各複合化合物を個々に粉砕して粒径を揃
え、各々にCaO粉末をT1:Ba:Ca:Cu＝2:2:1:2あるいは2:
2:2:3または2:2:3:3の割合になるように混合して各混合
粉末を得た。Subsequently, each of the composite compounds was individually pulverized and the particle diameters were adjusted, and each of the CaO powders was T1: Ba: Ca: Cu = 2: 2: 1: 2 or 2:
Each mixed powder was obtained by mixing at a ratio of 2: 2: 3 or 2: 2: 3: 3.
次に前記各混合粉末を機械プレスで1t/cm2の圧力をか
けて圧粉成形し、厚さ1.5mm、直径13mmのペレット状成
形体を複数得た。Next, each of the mixed powders was pressed with a mechanical press under a pressure of 1 t / cm 2 to obtain a plurality of pellet-shaped compacts having a thickness of 1.5 mm and a diameter of 13 mm.
更に前記各ペレット状成形体を酸素ガス雰囲気中にお
いて870℃で１時間加熱する熱処理を施してT1−Ba−Ca
−Cu−Ｏ系の酸化物超電導体を複数製造した。Further, each of the pellet-shaped compacts was subjected to a heat treatment of heating at 870 ° C. for 1 hour in an oxygen gas atmosphere, so that T1-Ba-Ca
-A plurality of Cu-O-based oxide superconductors were manufactured.
以上のように得られた各酸化物超電導体の臨界温度
（Tc）と77Kにおける臨界電流密度（Jc）を測定した。
その結果を各酸化物超電導体の出発物組成とともに第１
表に示す。なお、第１表には、T12Ba2Cu3Oxの組成の複
合化合物の超電導特性も併せて記載した。更に、第１表
に記載した各酸化物超電導体の比抵抗−温度特性を第１
図に示す。The critical temperature (Tc) and the critical current density (Jc) at 77 K of each oxide superconductor obtained as described above were measured.
The results are shown together with the starting composition of each oxide superconductor in the first place.
It is shown in the table. Note that Table 1, were are also described superconducting properties of the composite compound of the composition of T1 2 Ba 2 Cu 3 Ox. Further, the specific resistance-temperature characteristics of each oxide superconductor described in Table 1
Shown in the figure.
第１表と第１図から明らかなように本発明方法を実施
して得られたT1系酸化物超電導体は臨界温度（Tc）で10
7K〜120Kの優秀な値を示した。また、各酸化物超電導体
は臨界電流密度の値も優れており、750〜1400A/cm2を示
した。 As is clear from Table 1 and FIG. 1, the T1 oxide superconductor obtained by carrying out the method of the present invention has a critical temperature (Tc) of 10%.
Excellent values from 7K to 120K were shown. In addition, each oxide superconductor also has an excellent critical current density value, which is 750 to 1400 A / cm 2 .
「発明の効果」 以上説明したように本発明は、T1化合物とBa化合物と
Cu化合物を混合し、加熱して得たT12Ba2Cu3OxあるいはT
12Ba2Cu2Oxなる組成の複合化合物とCaOを混合して反応
を行わせ、前記複合酸化物を基にT1系の酸化物超電導体
を生成させるので、107K〜120Kの極めて高い臨界温度を
示すとともに、臨界電流密度の高いT1系酸化物超電導体
を製造できる効果がある。"Effect of the Invention" As described above, the present invention relates to a T1 compound and a Ba compound.
T1 2 Ba 2 Cu 3 Ox or T obtained by mixing and heating a Cu compound
1 2 Ba 2 Cu 2 Ox A composite compound having a composition of CaO and a mixture of CaO are reacted to produce a T1-based oxide superconductor based on the composite oxide. And an effect that a T1-based oxide superconductor having a high critical current density can be produced.
また、T1化合物とBa化合物とCu化合物として具体的
に、T12OまたはT12O3とBaCO3とCuOを用いることがで
き、これらの化合物を用いることで107K〜120Kの極めて
高い臨界温度を示すとともに、臨界電流密度の高いT1系
酸化物超電導体を製造できる効果がある。Moreover, specifically as T1 compound and Ba compound and Cu compound, it can be used CuO and T1 2 O or T1 2 O 3 and BaCO 3, the very high critical temperature of 107K~120K by using these compounds As described above, there is an effect that a T1-based oxide superconductor having a high critical current density can be manufactured.
第１図は実施例で得られたT1系酸化物超電導体の抵抗−
温度特性を示す図である。FIG. 1 shows the resistance of the T1-based oxide superconductor obtained in Example.
It is a figure which shows a temperature characteristic.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C01G 1/00 - 57/00 C04B 35/00 H01L 39/00 - 39/24 H01B 12/00──────────────────────────────────────────────────続 き Continuation of the front page (58) Field surveyed (Int. Cl. 6 , DB name) C01G 1/00-57/00 C04B 35/00 H01L 39/00-39/24 H01B 12/00
Claims (2)
加熱してT12Ba2Cu3OxあるいはT12Ba2Cu2Oxなる組成の複
合化合物を作成し、該複合化合物とCaOを混合した後で
酸素雰囲気中において熱処理してT1−Ba−Ca−Cu−Ｏ系
の酸化物超電導体を生成させることを特徴とするT1系酸
化物超電導体の製造方法。1. A mixture of a T1 compound, a Ba compound and a Cu compound,
Heating to prepare a composite compound having a composition of T1 2 Ba 2 Cu 3 Ox or T1 2 Ba 2 Cu 2 Ox, mixing the composite compound and CaO, and then performing a heat treatment in an oxygen atmosphere to obtain T1-Ba-Ca- A method for producing a T1-based oxide superconductor, which comprises producing a Cu-O-based oxide superconductor.
加熱してT12Ba2CU3OxあるいはT12Ba2Cu2Oxなる組成の複
合化合物を作成し、該複合化合物とCaOを混合した後で
酸素雰囲気中において熱処理してT1−Ba−Ca−Cu−Ｏ系
の酸化物超電導体を生成させることを特徴とするT1系酸
化物超電導体の製造方法。2. A mixture of T1 2 O or T1 2 O 3 with BaCO 3 and CuO,
Heating to prepare a composite compound having a composition of T1 2 Ba 2 CU 3 Ox or T1 2 Ba 2 Cu 2 Ox, mixing the composite compound and CaO, and then performing a heat treatment in an oxygen atmosphere to obtain T1-Ba-Ca- A method for producing a T1-based oxide superconductor, which comprises producing a Cu-O-based oxide superconductor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278322A JP2803823B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing T1-based oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63278322A JP2803823B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing T1-based oxide superconductor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02124715A JPH02124715A (en) | 1990-05-14 |
| JP2803823B2 true JP2803823B2 (en) | 1998-09-24 |
Family
ID=17595714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63278322A Expired - Fee Related JP2803823B2 (en) | 1988-11-02 | 1988-11-02 | Method for producing T1-based oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2803823B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07115920B2 (en) * | 1989-05-29 | 1995-12-13 | 財団法人国際超電導産業技術研究センター | Oxide superconducting material and method for producing the same |
| US5306698A (en) * | 1991-10-10 | 1994-04-26 | International Business Machines Corporation | Methods for producing Tl2 Ca2 Ba2 Cu3 oxide superconductors |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4962083A (en) * | 1988-02-12 | 1990-10-09 | University Of Arkansas | High temperature T1-Ba-Ca-Cu-O and T1-Sr-Cu-O superconductor |
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1988
- 1988-11-02 JP JP63278322A patent/JP2803823B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02124715A (en) | 1990-05-14 |
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