JPH02129060A - Production of oxide superconductor - Google Patents
Production of oxide superconductorInfo
- Publication number
- JPH02129060A JPH02129060A JP63283441A JP28344188A JPH02129060A JP H02129060 A JPH02129060 A JP H02129060A JP 63283441 A JP63283441 A JP 63283441A JP 28344188 A JP28344188 A JP 28344188A JP H02129060 A JPH02129060 A JP H02129060A
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconductor
- critical temperature
- heat treatment
- powder
- based oxide
- 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
- 239000002887 superconductor Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 abstract description 25
- 229910052745 lead Inorganic materials 0.000 abstract description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 8
- 239000011812 mixed powder Substances 0.000 abstract description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 4
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 4
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910014454 Ca-Cu Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 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】
［発明の目的〕
（産業上の利用分野）
この発明は、８ｌ−Ｓｒ−Ｃａ−Ｃｕ−０系の酸化物超
電導体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 manufacturing an 8l-Sr-Ca-Cu-0 based oxide superconductor.
（従来の技術）
１９８６年に４０に以上の高い臨界温度を有するＬａ−
Ｂａ−Ｃｕ−０系の層状ペロブスカイト型の酸化物系超
電導体が発表されて以来、酸化物系の超電導材料が注目
を集めた。また、１９８７年にはＹ−Ｂａ−Ｃｕ−０系
で代表される酸素欠陥を有する欠陥ペロブスカイト型の
酸化物超電導体の臨界温度が液体窒素温度（−７７Ｋ）
より高い、約９０にであることが確認された。この発見
により冷媒として高価な液体ヘリウムに代えて、より安
価な液体窒素を用いた超電導体の応用が可能となり、各
所で盛んに研究が行われている。(Prior art) In 1986, La-
Since the Ba-Cu-0 layered perovskite type oxide superconductor was announced, oxide superconducting materials have attracted attention. Furthermore, in 1987, the critical temperature of a defective perovskite-type oxide superconductor with oxygen defects represented by the Y-Ba-Cu-0 system was determined to be the liquid nitrogen temperature (-77K).
It was found to be higher, around 90. This discovery has made it possible to apply superconductors using cheaper liquid nitrogen instead of expensive liquid helium as a refrigerant, and research is being actively conducted in various places.
また、１９８８年には臨界温度が１０５に近辺と高いＢ
ｉ−Ｓｒ−Ｃａ−Ｃｕ−０系の酸化物超電導体が発見さ
れるに至った。このＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系の酸
化物超電導体は、Ｙ−Ｂａ−Ｃｕ−０系の酸化物超電導
体に比べて臨界温度が高く、たとえば液体窒素によって
冷却を行う際に実用上充分な熱的マージンがとれるばか
りでな（、高価な希土類元素が不要であること、水分に
対する化学的安定性が高いこと、酸素が抜けにくいこと
などの利点があり、より優れた超電導体として注目を集
めている。In addition, in 1988, the critical temperature of B was as high as around 105.
An i-Sr-Ca-Cu-0 based oxide superconductor has been discovered. This Bi-Sr-Ca-Cu-0 based oxide superconductor has a higher critical temperature than the Y-Ba-Cu-0 based oxide superconductor, which makes it difficult to use in practical applications when cooling with liquid nitrogen, for example. It not only has a sufficient thermal margin (no need for expensive rare earth elements), has high chemical stability against moisture, and is difficult to escape oxygen, and is attracting attention as a superior superconductor. are collecting.
ところで、このＢｉ−９ｒ−Ｃａ−Ｃｕ−０系酸化物超
電導体には、零抵抗を示す臨界温度（以下、Ｔｃｅｎｄ
と記す。）が約８０にの化学式
％式％（１）
で表される低臨界温度相と、Ｔｃｅｎｄが約１１０にの
化学式
％式％（）
で表される高臨界温度相の２種類の超電導相が存在して
いることが確認されている。また、このＢｉ−Ｓｒ−Ｃ
ａ−Ｃｕ−０系酸化物超電導体は、Ｙ−Ｂａ−Ｃｕ−０
系酸化物超電導体などと同様に結晶性の酸化物であるた
め、たとえばＢｌ２０３ 、ＳｒＣＯ３、ＣａＣＯ３、
ＣｕＯなどの粉末を原料粉として用いた、通常の焼成法
によって゛作製することが試みられているが、このよう
な方法によって得られたＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系
酸化物超電導焼結体は上記低臨界温度相と高臨界温度相
とが混在したものとして得られるため、Ｔｃｅｎｄは８
０に程度の低いものしか得られていないのが現状である
。By the way, this Bi-9r-Ca-Cu-0 based oxide superconductor has a critical temperature (hereinafter referred to as Tcend) at which it exhibits zero resistance.
It is written as There are two types of superconducting phases: a low critical temperature phase represented by the chemical formula % formula % (1) where Tcend is approximately 80, and a high critical temperature phase represented by the chemical formula % formula % () where Tcend is approximately 110. It has been confirmed that it exists. Moreover, this Bi-Sr-C
The a-Cu-0 based oxide superconductor is Y-Ba-Cu-0
Since it is a crystalline oxide like other oxide superconductors, for example, Bl203, SrCO3, CaCO3,
Attempts have been made to fabricate the Bi-Sr-Ca-Cu-0 based oxide superconducting method using a powder such as CuO as a raw material powder. Since the solid is obtained as a mixture of the above-mentioned low critical temperature phase and high critical temperature phase, Tcend is 8
At present, only a low level of 0 has been obtained.
このような問題に対して、Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−０
系酸化物超電導体にＰｂやＳｂを添加し、Ｂｉの一部を
ＰｂやＳｂで置換することによって、高臨界温度相の体
積比を大幅に増加することができるという報告がある。For such problems, Bi-Sr-Ca-Cu-0
There is a report that the volume ratio of the high critical temperature phase can be significantly increased by adding Pb or Sb to the oxide superconductor and replacing part of Bi with Pb or Sb.
しかしながら、上述した通常の焼成法によって８ｌ−Ｓ
ｒ−Ｃａ−Ｃｕ−０系酸化物超電導体を作製する際に、
ＰｂやＳｂをたとえば酸化物などの化合物として添加し
たとしても、ＰｂやＳｂの化合物は蒸気圧が高いために
熱処理時に揮散しやすく、組成の制御が非常に難しいと
いう問題がある。よって、酸化物超電導体の原料粉末に
ＰｂやＳｂの化合物を単に添加しただけでは、高臨界温
度相を再現性よくかつ効率よく得ることができない。However, 8l-S by the normal firing method mentioned above.
When producing an r-Ca-Cu-0 based oxide superconductor,
Even if Pb or Sb is added as a compound such as an oxide, the Pb or Sb compound has a high vapor pressure and easily volatilizes during heat treatment, making it extremely difficult to control the composition. Therefore, simply adding a Pb or Sb compound to the raw material powder of an oxide superconductor does not allow a high critical temperature phase to be obtained with good reproducibility and efficiency.
（発明が解決しようとする課題）
上述したように、Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物
超電導体は、低臨界温度相と高臨界温度相とが混在した
ものとして得られるため、高臨界温度相の特性を生かす
ことができないという問題があった。(Problems to be Solved by the Invention) As mentioned above, the Bi-Sr-Ca-Cu-0 based oxide superconductor is obtained as a mixture of a low critical temperature phase and a high critical temperature phase. There was a problem that the characteristics of the critical temperature phase could not be utilized.
また、Ｂｌの一部をＰｂやＳｂで置換することによって
高臨界温度相の生成比率を高めるという報告もなされて
いるが、この方法は焼成時における組成制御が極めて難
しく、再現性に乏しいという問題があった。It has also been reported that replacing a portion of Bl with Pb or Sb increases the generation ratio of the high critical temperature phase, but this method has the problem of extremely difficult composition control during firing and poor reproducibility. was there.
この発明は、このような従来技術の課題に対処するため
になされたもので、高臨界温度相の生成比率を高めたＢ
ｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導体、さらには
高臨界温度相単相の８ｌ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化
物超電導体を再現性よく得ることを可能にした酸化物超
電導体の製造方法を提供することを目的としている。This invention was made in order to deal with the problems of the prior art, and it is a B
An oxide that makes it possible to obtain an i-Sr-Ca-Cu-0 based oxide superconductor and furthermore a high critical temperature single phase 8l-Sr-Ca-Cu-0 based oxide superconductor with good reproducibility. The purpose is to provide a method for manufacturing superconductors.
［発明の構成］
（課題を解決するための手段）
この発明の酸化物超電導体の製造方法は、旧−Ｓｒ−Ｃ
ａ−Ｃｕ−０系酸化物超電導体または加熱により前記Ｂ
ｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導体となる混合
原料を、Ｐｂおよび／またはＳｂが存在する雰囲気下で
熱処理することを特徴としている。[Structure of the Invention] (Means for Solving the Problems) The method for producing an oxide superconductor of the present invention comprises
a-Cu-0 based oxide superconductor or by heating the B
The method is characterized in that the raw material mixture that becomes the i-Sr-Ca-Cu-0-based oxide superconductor is heat-treated in an atmosphere containing Pb and/or Sb.
この発明において使用される被熱処理体となる出発物は
、たとえば以下のようにして作製される。The starting material that becomes the object to be heat treated used in this invention is produced, for example, as follows.
まず、Ｂｉ、Ｓｒｓ Ｃａｓ ＣｕのＢｉ−Ｓｒ−Ｃａ
−Ｃｕ−０系酸化物超電導体の構成元素を充分に混合す
る。これら構成元素の化合物としては、８１２０ ！
、ＳｒＣＯ３、ＣａＣＯ３、ＣｕＯなどの酸化物や炭酸
塩を用いることができる他、炭酸塩以外の加熱により酸
化物に転化する硝酸塩、水酸化物などの化合物や、さら
にシュウ酸塩のような有機酸塩や有機金属などを用いて
もよい。これらＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超
電導体の構成元素は、基本的に高臨界温度相として解明
された、
化学式：Ｂｉ２５ｒ２Ｃａ２Ｃｕ３０ｘ −（ＩＩ
）の原子比を満足するように混合するが、多少製造条件
などとの関係でずれていても差支えない。たとえば、Ｂ
ｌ ２ｓｏｌ ｌこ対してＳｒ ２± ０．４ｓｏｌ
、Ｃａ２±０．４＋ｇｏｌ 、Ｃｕ ３士 ０．６ｓｏ
ｌ程度のずれは問題ない。First, Bi-Sr-Ca of Bi, Srs Cas Cu
- The constituent elements of the Cu-0 based oxide superconductor are thoroughly mixed. Compounds of these constituent elements include 8120!
In addition to oxides and carbonates such as , SrCO3, CaCO3, and CuO, compounds such as nitrates and hydroxides that are converted to oxides by heating other than carbonates, and organic acids such as oxalates can be used. Salts, organic metals, etc. may also be used. The constituent elements of these Bi-Sr-Ca-Cu-0-based oxide superconductors are basically elucidated as a high critical temperature phase, and have the chemical formula: Bi25r2Ca2Cu30x -(II
), but there may be a slight deviation depending on the manufacturing conditions. For example, B
l 2sol l whereas Sr 2± 0.4sol
, Ca2±0.4+gol, Cu 3 0.6so
A deviation of about l is not a problem.
このようにして得られた各構成元素を所定の比率で含有
する混合粉末を出発物として用いてもよいし、この混合
粉末をプレス成形法や公知の成形手段によって所要形状
の成形体とし、この成形体を出発物として用いてもよい
。The thus obtained mixed powder containing each constituent element in a predetermined ratio may be used as a starting material, or this mixed powder may be formed into a molded body of the desired shape by press molding or known molding means. A molded body may be used as a starting material.
また、上記したＢｉ−３ｒ−Ｃａ−Ｃｕ−０系酸化物超
電導体の各構成元素を所定の比率で含有する混合粉末を
８００℃程度の温度で仮焼して反応させ、この仮焼物を
ボールミル、サンドグラインダ、その他公知の方法で粉
砕した酸化物超電導体粉末を出発物として用いてもよい
。さらには、この酸化物超電導体粉末をプレス成形法や
公知の成形手段によって成形した成形体や、この成形体
を予め焼成して得た焼結体を出発物として用いてもよい
。In addition, a mixed powder containing each constituent element of the Bi-3r-Ca-Cu-0 based oxide superconductor described above in a predetermined ratio is calcined at a temperature of about 800°C to react, and this calcined product is ball milled. An oxide superconductor powder pulverized by a sand grinder or other known method may be used as a starting material. Furthermore, a molded body obtained by molding this oxide superconductor powder by a press molding method or a known molding method, or a sintered body obtained by pre-sintering this molded body may be used as the starting material.
なお、予め反応させた酸化物超電導体を出発物として用
いる際には、単に焼成した焼結体に限らず、相対密度の
高い溶融凝固体や単結晶体を用いることも可能であるし
、またその形状も単にバルク形状に限らず、線材化した
ものや薄膜など各種形態のものを使用することが可能で
ある。In addition, when using a pre-reacted oxide superconductor as a starting material, it is not only possible to use a simply fired sintered body, but also a molten solidified body or a single crystal body with a high relative density. Its shape is not limited to just a bulk shape, but various shapes such as a wire rod or a thin film can be used.
そして、これら出発物をＰｂやＳｂが存在する雰囲気中
で熱処理し、目的とする酸化物超電導体を得る。These starting materials are then heat treated in an atmosphere containing Pb and Sb to obtain the desired oxide superconductor.
この雰囲気は、ＰｂやＳｂを含んでいればよく、化合物
でもよい。Ｐｂを含む化合物やＳｂを含む化合物として
は、ＰｂおよびＳｂの酸化物、フッ化物、塩化物などが
例示され、これらＰｂやＳｂを含む化合物が存在する酸
素含有雰囲気中において熱処理を行う。This atmosphere only needs to contain Pb and Sb, and may be a compound. Examples of the compound containing Pb and the compound containing Sb include oxides, fluorides, and chlorides of Pb and Sb, and the heat treatment is performed in an oxygen-containing atmosphere where these compounds containing Pb and Sb are present.
この雰囲気中の酸素分圧としては、０．０１ａｔｍ〜１
０ａｔｅというように各種の条件を設定することが可能
である。The oxygen partial pressure in this atmosphere is 0.01 atm to 1
It is possible to set various conditions such as 0ate.
このようなＰｂやＳｂの化合物が存在する酸素含有雰囲
気は、熱処理炉中にＰｂやＳｂの化合物を直接配置し、
熱処理時に同時に加熱することによって熱処理炉内にＰ
ｂやＳｂの化合物を存在させたり、あるいは別途Ｐｂや
Ｓｂの化合物を加熱してＰｂやＳｂの化合物が存在する
酸素含有雰囲気を作製し、この雰囲気を熱処理炉中に導
入するなどによって得られる。The oxygen-containing atmosphere in which such Pb and Sb compounds exist can be created by placing the Pb and Sb compounds directly in the heat treatment furnace.
P in the heat treatment furnace by heating at the same time during heat treatment.
This can be obtained by creating an oxygen-containing atmosphere in which a Pb or Sb compound is present, or by separately heating a Pb or Sb compound, and introducing this atmosphere into a heat treatment furnace.
ＰｂやＳｂの化合物は、蒸気圧が高く容易に気化するが
、これらＰｂやＳｂの化合物の存在率が余り低いと、Ｂ
ｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導体中の８１と
の置換が充分に進行しないため、たとえば熱処理炉中に
ＰｂやＳｂの化合物を直接配置する際には、熱処理雰囲
気空間の容積に対して０．Ｏ１ｇ／ｃｃ以上（あるいは
２Ｘ １０”’ ｍｏｌ／ｃｃ以上）存在させることが
好ましく、別途これらＰｂやＳｂの化合物が存在する雰
囲気を熱処理炉中に導入する際にも、この値を基準にし
て導入量を設定することが好ましい。Pb and Sb compounds have high vapor pressure and easily vaporize, but if the abundance of these Pb and Sb compounds is too low, B
Since the substitution with 81 in the i-Sr-Ca-Cu-0 based oxide superconductor does not proceed sufficiently, for example, when directly placing a Pb or Sb compound in a heat treatment furnace, the volume of the heat treatment atmosphere space is 0. It is preferable to have O1g/cc or more (or 2X 10"' mol/cc or more) exist, and when separately introducing an atmosphere in which these Pb and Sb compounds exist into the heat treatment furnace, it is introduced based on this value. It is preferable to set the amount.
また、この熱処理の温度条件は、８１０℃〜８８０℃の
範囲で行うことが好ましい。熱処理温度が８１０℃未満
では反応が充分に進まず、高臨界温度相が充分に生成し
ない。また、８６０℃を超えると生成した高臨界温度相
が分解してしまう。そして、このような温度条件の下で
ｌＯ時間〜ｌＸｌ０”時間程度熱処理を行った後、徐冷
して目的とする高臨界温度相を主とするＢｉ−Ｓｒ−Ｃ
ａ−Ｃｕ−０系酸化物超電導体、さらには高臨界温度相
単相の酸化物超電導体を得る。Further, the temperature conditions for this heat treatment are preferably in the range of 810°C to 880°C. If the heat treatment temperature is less than 810° C., the reaction will not proceed sufficiently and a high critical temperature phase will not be sufficiently generated. Furthermore, if the temperature exceeds 860°C, the generated high critical temperature phase will decompose. After heat treatment is performed for approximately 10 hours to 1X10'' hours under such temperature conditions, it is slowly cooled to produce the desired Bi-Sr-C mainly having a high critical temperature phase.
An a-Cu-0 based oxide superconductor and further a high critical temperature single phase oxide superconductor are obtained.
得られるＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導体
としては、
■ 上記酸化物超電導体粉末や混合粉末を上記条件下で
焼成し、得られた焼成物を粉砕することによって得られ
る高臨界温度相の比率が高い８ｌ−Ｓｒ−Ｃａ−Ｃｕ−
０系酸化物超電導体粉末。The resulting Bi-Sr-Ca-Cu-0 based oxide superconductor is: 8l-Sr-Ca-Cu- with a high ratio of critical temperature phase
0 series oxide superconductor powder.
■ 上記酸化物超電導体粉末や混合粉末の成形体を上記
条件下で焼成することによって得られる高臨界温度相の
比率が高いＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導
体の焼結体。■ A sintered body of Bi-Sr-Ca-Cu-0 based oxide superconductor with a high ratio of high critical temperature phase obtained by firing a compact of the above-mentioned oxide superconductor powder or mixed powder under the above-mentioned conditions. .
■ 上記酸化物超電導体の焼結体や溶融凝固体などを上
記条件下で熱処理することによって得られる高臨界温度
相の比率が高いＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超
電導体。(2) A Bi-Sr-Ca-Cu-0 based oxide superconductor having a high ratio of high critical temperature phase obtained by heat treating a sintered body, a molten solidified body, etc. of the above-mentioned oxide superconductor under the above-mentioned conditions.
などである。etc.
（作 用）
この発明においては、ＰｂまたはＳｂの供給源として熱
処理雰囲気中にＰｂを含む化合物やＳｂを含む化合物を
存在させているため、これらＰｂやＳｂの化合物の雰囲
気中の存在率を制御することによって、８ｌ−Ｓｒ−Ｃ
ａ−Ｃｕ−０系酸化物超電導体のＢｌの一部を充分に組
成制御しつつＰｂやＳｂで置換することができる。これ
によって、Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導
体の混合原料を高臨界温度相として結晶化させたり、Ｂ
ｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導体の低臨界温
度相を高臨界温度相に効率よくかつ充分に組成制御しつ
つ変換することができる。したがって、得られるＢｉ−
Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導体は、高臨界温度
相の比率が高い酸化物超電導体や高臨界温度相Ｑｉ相の
酸化物超電導体となる。(Function) In this invention, since a compound containing Pb or a compound containing Sb is present in the heat treatment atmosphere as a supply source of Pb or Sb, the abundance rate of these Pb or Sb compounds in the atmosphere is controlled. By doing so, 8l-Sr-C
A part of Bl in the a-Cu-0 based oxide superconductor can be replaced with Pb or Sb while sufficiently controlling the composition. This allows the mixed raw material of the Bi-Sr-Ca-Cu-0 based oxide superconductor to be crystallized as a high critical temperature phase, and the B
The low critical temperature phase of the i-Sr-Ca-Cu-0 based oxide superconductor can be converted into the high critical temperature phase efficiently and with sufficient composition control. Therefore, the obtained Bi-
The Sr-Ca-Cu-0-based oxide superconductor becomes an oxide superconductor with a high proportion of the high critical temperature phase or an oxide superconductor with a high critical temperature phase Qi phase.
（実施例） 次に、この発明の実施例について説明する。(Example) Next, embodiments of the invention will be described.
実施例ｌ
Ｂｉ−９ｒ−Ｃａ−Ｃｕ−０系酸化物超電導体の出発原
料としてＢｉ２Ｏ３、ＳｒＣＯ３、ＣａＣＯ３、ＣｕＯ
の各粉末を、酸化物換算でｌ／２Ｂｉ２０３２２．２モ
ル％、ＳｒＯ２２，２モル％、Ｃａ０２２．２モル％３
、Ｃｕ０３３．３モル％となるように所定量秤量し、
これをボールミルで充分に混合した後、この混合粉末を
アルミナルツボに収容し、空気中において８００℃×
８時間の条件で仮焼して固相反応させた。次いで、この
仮焼物を再びボールミルで充分粉砕混合してＢｉ−Ｓｒ
−Ｃａ−Ｃｕ−〇系酸化物超電導体粉末を得た。この粉
末の陽イオン比は、ＢＩ：Ｓｒ：Ｃａ：Ｃｕ＝２：２：
２：Ｓであった。Example 1 Bi2O3, SrCO3, CaCO3, CuO as starting materials for Bi-9r-Ca-Cu-0 based oxide superconductor
Each of the powders was converted into oxides: l/2Bi20322.2 mol%, SrO222.2 mol%, Ca022.2 mol%3
, weighed a predetermined amount so that Cu0 was 33.3 mol%,
After thoroughly mixing this with a ball mill, this mixed powder was placed in an aluminum crucible and heated to 800°C in the air.
A solid phase reaction was performed by calcining for 8 hours. Next, this calcined product was sufficiently ground and mixed in a ball mill again to form Bi-Sr.
-Ca-Cu-〇-based oxide superconductor powder was obtained. The cation ratio of this powder is BI:Sr:Ca:Cu=2:2:
2:S.
次に、上記酸化物超電導体粉末を５ｇ秤量し、これを約
Ｎｏｎ／ｃ（の条件でプレス成形して成形体を作製した
。一方、ＰｂＯ粉末を２ｇ秤量し、第１図に示すように
、ＰｂＯ粉末１を耐熱性容器２中に配置し、その上方に
上記酸化物超電導体粉末の成形体３をＰｂＯ粉末１と連
続空間内に存在するように配置し、これらをアルミナ製
容器で覆って熱処理雰囲気空間５を設定した。なお、こ
の熱処理雰囲気空間５の容積は５０ｃｃとした。そして
、これらを電気炉で８５０℃Ｘ １００時間の条件で
熱処理し、室温まで徐冷して８ｌ−Ｓｒ−Ｃａ−Ｃｕ−
０系酸化物超電導焼結体を作製した。Next, 5 g of the above oxide superconductor powder was weighed, and this was press-molded under conditions of approximately Non/c to produce a molded body.Meanwhile, 2 g of PbO powder was weighed, and as shown in Fig. , PbO powder 1 is placed in a heat-resistant container 2, above which the compact 3 of the oxide superconductor powder is placed so as to exist in a continuous space with the PbO powder 1, and these are covered with an alumina container. A heat treatment atmosphere space 5 was set up.The volume of this heat treatment atmosphere space 5 was 50cc.Then, these were heat treated in an electric furnace at 850°C for 100 hours, and slowly cooled to room temperature to form 8l-Sr. -Ca-Cu-
A 0-type oxide superconducting sintered body was produced.
このようにして得られたＢｆ−９ｒ−Ｃａ−Ｃｕ−０系
酸化物超電導焼結体にＸ線回折を施したところ、高臨界
温度相の単一相であることが確認された。また、この酸
化物超電導焼結体の電気抵抗の温度依存性を４端子法に
よって測定した。その結果を第２図に示す。同図からも
明らかなように、約１０９Ｋから急激に電気抵抗が減少
し、１０５にで電気抵抗が零となった。また、電気抵抗
の急激な降下開始温度と電気抵抗が零となる値との差Δ
Ｔｃは４にであり、優れた超電導特性を有していた。When the Bf-9r-Ca-Cu-0-based oxide superconducting sintered body thus obtained was subjected to X-ray diffraction, it was confirmed that it was a single phase with a high critical temperature phase. Furthermore, the temperature dependence of the electrical resistance of this oxide superconducting sintered body was measured by a four-terminal method. The results are shown in FIG. As is clear from the figure, the electrical resistance suddenly decreased from about 109K and reached zero at 105K. Also, the difference Δ between the temperature at which the electrical resistance starts to drop rapidly and the value at which the electrical resistance becomes zero
Tc was 4, and it had excellent superconducting properties.
実施ｆ１２
実施例１と同一条件でＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸
化物超電導体粉末の成形体を作製した。一方、ｌ／２Ｓ
ｂ２ ｏ ３を２ｇ秤量し、この５ｂ２ｏ３粉末と上記
酸化物超電導体粉末の成形体を実施例１と同様に熱処理
炉中に配置し、同一条件で熱処理を行い、Ｂｉ−Ｓｒ−
Ｃａ−Ｃｕ−０系酸化物超電導焼結体を作製した。Implementation f12 A molded body of Bi-Sr-Ca-Cu-0 based oxide superconductor powder was produced under the same conditions as in Example 1. On the other hand, l/2S
Weighed 2g of b2o3, placed this 5b2o3 powder and the molded body of the oxide superconductor powder in a heat treatment furnace in the same manner as in Example 1, and heat-treated it under the same conditions to form a Bi-Sr-
A Ca-Cu-0 based oxide superconducting sintered body was produced.
このようにして得た酸化物超電導焼結体の超電導特性を
実施例１と同様に測定したところ、Ｔｃｚｅｒｏｍ １
００Ｋ、ΔＴｃ−４にと良好な値が得られた。The superconducting properties of the oxide superconducting sintered body thus obtained were measured in the same manner as in Example 1, and it was found that Tczerom 1
Good values were obtained for 00K and ΔTc-4.
実施例３
実施例１と同一条件でＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸
化物超電導体粉末の成形体を作製するとともに、ＰｂＯ
粉末を実施例１と同量秤量し、これらを実施例１と同様
に電気炉中に配置した。ただし、アルミナ製容器によっ
て形成される熱処理雰囲気空間内は、酸素分圧が１／１
３ａｔｓとなるように、アルゴンガスを充填した。この
状態で、８５０℃×８時間の条件で熱処理し、室温まで
徐冷してＢｉ−Ｓｒ−Ｃａ−Ｃｕ−０系酸化物超電導焼
結体を得た。Example 3 A molded body of Bi-Sr-Ca-Cu-0 based oxide superconductor powder was produced under the same conditions as in Example 1, and PbO
The same amount of powder as in Example 1 was weighed and placed in an electric furnace in the same manner as in Example 1. However, in the heat treatment atmosphere space formed by the alumina container, the oxygen partial pressure is 1/1
Argon gas was filled to a level of 3 ats. In this state, it was heat treated at 850° C. for 8 hours and slowly cooled to room temperature to obtain a Bi-Sr-Ca-Cu-0 based oxide superconducting sintered body.
このようにして得た酸化物超電導焼結体の超電導特性を
実施例１と同様に！１１１定したところ、Ｔｃｚｅｒｏ
−１０９ＫｓΔＴｃ −３にと良好な値が得られた。The superconducting properties of the oxide superconducting sintered body thus obtained were the same as in Example 1! 111, Tczero
A good value of -109KsΔTc -3 was obtained.
［発明の効果］
以上説明したようにこの発明によれば、Ｂｉの一部を充
分に組成制御しつつＰｂやＳｂで置換することができ、
これによって高臨界温度相のＢｌ−！３ｒ−Ｃａ−Ｃｕ
−０系酸化物超電導体を効率よく生成することが可能に
なる。[Effects of the Invention] As explained above, according to the present invention, a part of Bi can be replaced with Pb or Sb while sufficiently controlling the composition,
This results in a high critical temperature phase of Bl-! 3r-Ca-Cu
-0 series oxide superconductor can be efficiently produced.
第１図はこの発明の一実施例の熱処理状態を示す図、第
２図はこの発明の一実施例で製造したＢｉ−Ｓｒ−Ｃａ
−Ｃｕ−０系酸化物超電導体の電気抵抗の温度依存性を
示すグラフである。
１・・・・・・ＰｂＯ粉末（またはＳｂＯ粉末）、３・
・・・・・酸化物超電導体粉末の成形体、５・・・・・
・熱処理雰囲気空間。
出願人 株式会社 東芝
代理人 弁理士 須 山 佐 −
を截無九乎ＣｍΩ・蝿）
〜FIG. 1 is a diagram showing the heat treatment state of an embodiment of the present invention, and FIG. 2 is a diagram showing the state of heat treatment of an embodiment of the present invention.
It is a graph showing the temperature dependence of electrical resistance of a -Cu-0 based oxide superconductor. 1...PbO powder (or SbO powder), 3.
...Molded body of oxide superconductor powder, 5...
・Heat treatment atmosphere space. Applicant Toshiba Corporation Patent Attorney Suyama Sa
Claims (1)
たは加熱により前記Ｂｉ−Ｓｒ−Ｃａ−Ｃｕ−Ｏ系酸化
物超電導体となる混合原料を、Ｐｂおよび／またはＳｂ
が存在する雰囲気下で熱処理することを特徴とする酸化
物超電導体の製造方法。(1) Pb and/or Sb
1. A method for producing an oxide superconductor, comprising heat treatment in an atmosphere in which
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63283441A JPH02129060A (en) | 1988-11-09 | 1988-11-09 | Production of oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63283441A JPH02129060A (en) | 1988-11-09 | 1988-11-09 | Production of oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02129060A true JPH02129060A (en) | 1990-05-17 |
Family
ID=17665585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63283441A Pending JPH02129060A (en) | 1988-11-09 | 1988-11-09 | Production of oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02129060A (en) |
-
1988
- 1988-11-09 JP JP63283441A patent/JPH02129060A/en active Pending
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