JPH02311354A - Production of bi-based superconducting oxide calcined compact having high critical current density - Google Patents
Production of bi-based superconducting oxide calcined compact having high critical current densityInfo
- Publication number
- JPH02311354A JPH02311354A JP1131784A JP13178489A JPH02311354A JP H02311354 A JPH02311354 A JP H02311354A JP 1131784 A JP1131784 A JP 1131784A JP 13178489 A JP13178489 A JP 13178489A JP H02311354 A JPH02311354 A JP H02311354A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- pbo
- sintered body
- layer containing
- oxide sintered
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000000843 powder Substances 0.000 claims abstract description 50
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 4
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract description 3
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract description 3
- 230000001413 cellular effect Effects 0.000 abstract 2
- 101100296543 Caenorhabditis elegans pbo-4 gene Proteins 0.000 abstract 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 abstract 1
- 239000011369 resultant mixture Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- 238000001354 calcination Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000004857 zone melting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000909 Lead-bismuth eutectic Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 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
- 239000002244 precipitate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、高臨界温度および高臨界電流密度を有する
Ｂｉ系超伝導酸化物焼結体の製造法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a Bi-based superconducting oxide sintered body having a high critical temperature and a high critical current density.
高温超伝導を示す酸化物の１つとしてＢｉ系超超伝導酸
化物報告され、このＢｉ系超伝導酸化物焼結体は、Ｂ１
２Ｏ３粉末、Ｓ ｒ ＣＯａ粉末、Ｃｕ０＝２＋２：２
：３、
となるように配合し、混合し、仮焼し、焼結することに
より製造されている。Bi-based superconducting oxide has been reported as one of the oxides exhibiting high-temperature superconductivity, and this Bi-based superconducting oxide sintered body is B1
2O3 powder, S r COa powder, Cu0=2+2:2
:3, It is manufactured by blending, mixing, calcining, and sintering.
上記Ｂｉ系超伝導酸化物焼結体は、成分組成がＢ １２
Ｓ ｒ ２ Ｃａ ＩＣＬｌ ２０ ｘからなり臨界
温度が約８０ Ｋの超伝導相（以下、低Ｔｃ相という）
および成分組成がＢ １２ Ｓ ｒ ２ Ｃａ ２ Ｃ
ｔ＋ ａ Ｏｘからなり臨界温度か約１１０にの超伝導
相（以下、高Ｔｃ用という）の２相から主としてなり、
これら２相が混在している（その他、成分組成がＢ ｌ
２ Ｓ ｒ ２ Ｃｕ Ｏｘからなり臨界温度が約１
０にの相も存在すると言われているが、極く微量である
ために無視してよい）。The Bi-based superconducting oxide sintered body has a component composition of B 12
A superconducting phase consisting of S r 2 Ca ICLl 20 x with a critical temperature of approximately 80 K (hereinafter referred to as the low Tc phase)
and the component composition is B 12 S r 2 Ca 2 C
It mainly consists of two phases: a superconducting phase (hereinafter referred to as "high Tc") consisting of t+ a Ox at a critical temperature of about 110,
These two phases are mixed (in addition, the component composition is B l
2 S r 2 Cu Ox and has a critical temperature of approximately 1
It is said that there is also a phase at 0, but the amount is so small that it can be ignored).
上記低Ｔｃ相は安定して生ずるために単なる熱処理ては
減少さぜることは難しい。そこで最近では上記Ｂｉ系酸
化物のＢｉの一部をｐｂで置換することにより高Ｔｃ用
が安定して得られるという報告がなされている。Since the above-mentioned low Tc phase is stably generated, it is difficult to reduce it by mere heat treatment. Recently, it has been reported that a high Tc product can be stably obtained by substituting a part of Bi in the Bi-based oxide with pb.
このＢｊの一部をｐｂで置換したＢｉ系超伝導酸化物焼
結体は、ＰｂＯ粉末をモル比で、Ｃｕ０＝ １．Ｂ：０
．４ ： ２ ： ２ ： ３、の割合になるように配
合し、混合し、大気中、温度ニア５υ〜８７０℃、８〜
２００時ＩＨＪ保持の条件で仮焼し、ついで焼結するこ
とにより製造される。上記ＰｂＯは、仮焼および焼結工
程において高Ｔｃ用の発生を促進する触媒的な作用をし
、高Ｔｃ用が安定して得られ、主として高Ｔｃ用のみか
らなるＢｉ系超伝導酸化物焼結体が比較的簡単に得られ
るのである。この方法で得られたＢｊ系酸化物焼結体は
Ｂｉ２５ｒ２Ｃａ２Ｃｕ３０Ｘからなる高Ｔｃ相中にＰ
ｂＣａＯ系酸化物相、例えばＰｂ２Ｃａ０４などの不純
物第２相が分散した組織となっている。This Bi-based superconducting oxide sintered body in which a part of Bj is replaced with Pb has a molar ratio of PbO powder of Cu0=1. B:0
．． Blend and mix in a ratio of 4:2:2:3, in the atmosphere at a temperature of 5υ~870℃, 8~
It is manufactured by calcining under the conditions of holding IHJ at 200 hours and then sintering. The above-mentioned PbO acts as a catalyst to promote the generation of high Tc in the calcination and sintering process, so that high Tc can be stably obtained, and the Bi-based superconducting oxide sintered mainly consists only of high Tc. Solids can be obtained relatively easily. The Bj-based oxide sintered body obtained by this method contains P in the high Tc phase consisting of Bi25r2Ca2Cu30X.
It has a structure in which a bCaO-based oxide phase, for example, an impurity second phase such as Pb2Ca04 is dispersed.
上述のように、ＰｂＯは仮焼および焼結工程においては
高Ｔｃ用生成のための触媒的役割をはたし、有効な成分
であるが、仮焼および焼結して高Ｔｃ用を主体としたＢ
ｉ系超伝導酸化物焼結体が得られてしまうと、その後の
Ｐｂｏは不必要となり、焼結体中にＰｂＣａＯ系酸化物
相などの形で析出分散している不純物第２相は、逆に焼
結体の臨界電流密度Ｊｃを低下させる原因となっていた
。As mentioned above, PbO plays a catalytic role in the calcination and sintering process for the production of high Tc products, and is an effective component. B did
Once the i-based superconducting oxide sintered body is obtained, Pbo is no longer necessary, and the impurity second phase precipitated and dispersed in the sintered body in the form of a PbCaO-based oxide phase, etc. This caused a decrease in the critical current density Jc of the sintered body.
そこで、本発明者等は、上記ＰｂＣａＯ系酸化物相など
の不純物第２Ｆ［］が残留しない高Ｔｃ用を有するＢｉ
系超伝導酸化物焼結体を製造すべく研究を行った結果、
５ｒＣ０３：ＣａＣＯ３：Ｃｕ０＝２：２：２：３とな
るように配合し混合しプレス成形し、ついで通常の条件
で仮焼して得られた多孔質仮焼体の内部を帯域溶融法を
用いて溶融Ｐｂｏを通過させることによりＰｂｏ液相と
上記多孔質仮焼体固相の境界相て高Ｔｃ用のみを析出さ
せることができ＝ ６ ＝
るという知見を得たのである。Therefore, the present inventors developed a Bi
As a result of research to produce a superconducting oxide sintered body, we found that the composition was mixed and press-formed in a ratio of 5rC03:CaCO3:Cu0=2:2:2:3, and then calcined under normal conditions. By passing molten Pbo through the interior of the porous calcined body obtained by using the zone melting method, only the high Tc component is precipitated in the boundary phase between the Pbo liquid phase and the porous calcined body solid phase. We obtained the knowledge that = 6 = can be done.
この発明は、かかる知見にもとづいてなされたものであ
って、
通常の条件で仮焼して得られた多孔質仮焼体の上面に、
ＰｂＯを含む層を載置し、帯域溶融法により上記ＰｂＯ
を含む層を溶融させながら上記多孔質仮焼体の内部を移
動させる高臨界電流密度を有するＢｉ系超伝導酸化物焼
結体の製造法に特徴を有するものである。This invention was made based on this knowledge, and on the upper surface of a porous calcined body obtained by calcining under normal conditions,
A layer containing PbO is placed, and the above PbO is melted by a zone melting method.
The present invention is characterized by a method for producing a Bi-based superconducting oxide sintered body having a high critical current density in which the layer containing the oxide is moved inside the porous calcined body while melting the layer.
つぎに、この発明の高臨界電流密度を有するＢｉ系超伝
導酸化物焼結体の製造法を図面を用いて説明する。Next, a method for producing a Bi-based superconducting oxide sintered body having a high critical current density according to the present invention will be explained with reference to the drawings.
第１図は、多孔質仮焼体の上面にＰｂＯを含む層を載置
した状態を示す断面立面概略図、第２図は、帯域溶融法
によりＰｂＯを含む層を溶融しながら下方に移動しつつ
ある状態を示す断面立面概略図である。Fig. 1 is a schematic cross-sectional elevational view showing a state in which a layer containing PbO is placed on the upper surface of a porous calcined body, and Fig. 2 shows a layer containing PbO moving downward while being melted by the zone melting method. FIG.
まず、Ｂｉ２Ｏ３，ＳｒＣＯ３，ＣａＣＯ３およびＣｕ
Ｏの混合粉末を通常の条件で仮焼して得られた多孔質仮
焼体１を台２の上に立置し、その上端面３の上にＰｂＯ
を含む層４を載置し、ヒーター５により上記ＰｂＯを含
む層４を加熱すると溶融し、上記ＰｂＯを含む層は多孔
質仮焼体１の内部に浸透し、上記ヒーター５を加熱しな
がら極めて低速度で移動せしめると、ＰｂＯ液相４′は
多孔質仮焼体１内部を移動して高Ｔｅ相のみを析出させ
る。このようにして多孔質仮焼体１の内部を上記ＰｂＯ
液相４′が通過した後には、上記多孔質仮焼体１は焼結
されて第２図に示される高Ｔｃ相のみからなるＢｉ系超
伝導酸化物焼結体の１′生成される。First, Bi2O3, SrCO3, CaCO3 and Cu
A porous calcined body 1 obtained by calcining a mixed powder of O under normal conditions is placed on a stand 2, and a PbO
When the layer 4 containing PbO is heated by the heater 5, the layer 4 containing PbO is melted, and the layer containing PbO penetrates into the inside of the porous calcined body 1. When moved at a low speed, the PbO liquid phase 4' moves inside the porous calcined body 1 and precipitates only the high Te phase. In this way, the inside of the porous calcined body 1 is covered with the PbO
After the liquid phase 4' has passed, the porous calcined body 1 is sintered to produce a Bi-based superconducting oxide sintered body 1' consisting only of the high Tc phase as shown in FIG.
上記多孔質仮焼体１の形状は、円柱または角柱などの柱
状体であることが好ましく、さらに上記ＰｂＯを含む層
４は、ＰｂＯ粉末、ＰｂＯ圧粉体、ＰｂＯ焼結体、Ｐｂ
ＣａＯ系酸化物粉末、ＰｂＣａＯ系酸化物圧粉体、Ｐ
ｂ Ｃ’ａ Ｏ系酸化物焼結体、ＰｂＢＯ系酸化物粉末
、ＰｂＢＯ系酸化物圧粉体、ＰｂＢＯ系酸化物焼結体、
ＰｂＳ ｒ。The shape of the porous calcined body 1 is preferably a columnar body such as a cylinder or a rectangular column, and the layer 4 containing PbO is composed of PbO powder, PbO green compact, PbO sintered body, PbO
CaO-based oxide powder, PbCaO-based oxide compact, P
b C'a O-based oxide sintered body, PbBO-based oxide powder, PbBO-based oxide green compact, PbBO-based oxide sintered body,
PbSr.
系酸化物粉末、ＰｂＳ ｒｏ系酸化物圧粉体、ＰｂＳ
ｒＯ系酸化物焼結体、ＰｂＢ ｉ Ｏ系酸化物＝ ７
−
粉末、ＰｂＢｉＯ系酸化物圧粉体、ＰｂＢｉＯ系酸化物
焼結体、Ｐ ｂ Ｃｕ’ｏ系酸化物粉末、ＰｂＣｕＯ系
酸化物圧粉体、ＰｂＣｕＯ系酸化物焼結体などから構成
することができる。oxide powder, PbS ro-based oxide compact, PbS
rO-based oxide sintered body, PbB i O-based oxide = 7
- It can be composed of powder, PbBiO-based oxide green compact, PbBiO-based oxide sintered body, PbCu'o-based oxide powder, PbCuO-based oxide green compact, PbCuO-based oxide sintered body, etc. can.
つぎに、この発明を実施例にもとづいて具体的に説明す
る。Next, the present invention will be specifically explained based on examples.
実施例 １
原料粉末として、いずれも平均粒径：１０μｓのＢｉ
Ｏ粉末、Ｓ ｒ ＣＯａ粉末、Ｃａ ＣＯａ粉末およ
びＣｕＯ粉末を用意し、こ゛れら粉末をモル比で、
ＣｕＯ−２： ２ ： ２ ： ３の割合になるように
配合し、混合したのち、直径： ２ｈ＋ｍ、高さ：１０
０關の寸法を有する円柱形状にプレス成形し、この成形
体を大気中、温度＝８００℃、１０時間保持の条件で仮
焼し、円柱状多孔質仮焼体を作製した。Example 1 As the raw material powder, Bi with an average particle size of 10 μs was used as the raw material powder.
Prepare O powder, S r COa powder, Ca COa powder, and CuO powder, and mix these powders in a molar ratio of CuO-2: 2: 2: 3. After mixing, : 2h+m, height: 10
The molded body was press-molded into a cylindrical shape having a dimension of 0.5 mm, and this molded body was calcined in the atmosphere at a temperature of 800° C. for 10 hours to produce a cylindrical porous calcined body.
一方、原料粉末として平均粒径：２ｔ１ｍのＰｂＯ粉末
を用意し、上記ＰｂＯ粉末をプレス成形して−９＝
＝ ８ −
直径： ２０＋ｎｍ、厚さ：ｌＯ＋ｎｍの寸法を有する
ＰｂＯ圧粉体を作製した。On the other hand, PbO powder with an average particle size of 2t1m was prepared as a raw material powder, and the PbO powder was press-molded to produce a PbO compact having dimensions of -9 = = 8 - diameter: 20+nm and thickness: lO+nm. .
上記円柱状多孔質仮焼体を立置し、さらに円柱状多孔質
仮焼体の上端面に上記ＰｂＯ圧粉体を載置してその周囲
をヒーターにて温度：９００℃に加熱し、上記ＰｂＯ圧
粉体が溶融して円柱状多孔質仮焼体内部に浸透、したの
ち、上記ヒーターを円柱状多孔質仮焼体の長手方向下方
に速度：５ｍｍ／時でゆっくりと移動せしめ、Ｂｉ系超
伝導酸化物焼結体を作製した。The above-mentioned cylindrical porous calcined body was placed upright, and the above-mentioned PbO compact was placed on the upper end surface of the cylindrical porous calcined body, and the surrounding area was heated to a temperature of 900°C with a heater, and the above-mentioned After the PbO green compact melts and penetrates into the inside of the cylindrical porous calcined body, the heater is slowly moved downward in the longitudinal direction of the cylindrical porous calcined body at a speed of 5 mm/hour. A superconducting oxide sintered body was fabricated.
このようにして得られたＢｉ系超伝導酸化物焼結体のｐ
ｂ含有量を測定するとともに、臨界温度ＴｃおよびＴｅ
値より１５に低い温度での臨界電流密度Ｊｃを測定して
、それらの結果を第１表に示した。p of the Bi-based superconducting oxide sintered body thus obtained
While measuring the b content, the critical temperature Tc and Te
The critical current density Jc at a temperature 15 times lower than that value was measured and the results are shown in Table 1.
実施例 ２
実施例１で作製した円柱状多孔質仮焼体の上端面に、Ｐ
ｂＯ粉末＝８７モル％およびＣａＯ粉末：１３モル％の
配合組成を有する混合粉末をプレス成形して得られた直
径： ２０ｍｍ、厚さ：１０ｍｍの寸法を有するＰｂＣ
ａＯ系酸化物圧粉体を載置し、実施例１と同様にヒータ
ーにより温度： ８５０ ’Ｃに加熱して上記ＰｂＣａ
Ｏ系酸化物圧粉体を溶融せしめ、上記円柱状多孔質仮焼
体内部に浸透させたのち、上記ヒーターを速度：２ｍｍ
／時で下方に移動せしめ、Ｂｉ系超伝導酸化物焼結体を
作製し、そのｐｂ含有量を測定するとともに、臨界温度
Ｔｃおよび臨界電流密度Ｊｃを測定して、それらの結果
を第１表に示した。Example 2 P was applied to the upper end surface of the cylindrical porous calcined body produced in Example 1.
PbC having dimensions of diameter: 20 mm and thickness: 10 mm obtained by press-molding a mixed powder having a composition of bO powder = 87 mol% and CaO powder: 13 mol%
The aO-based oxide green compact was placed and heated to 850'C using a heater in the same manner as in Example 1, and the PbCa powder was heated to 850'C.
After melting the O-based oxide green compact and permeating it into the cylindrical porous calcined body, the heater was heated at a speed of 2 mm.
/ hour to produce a Bi-based superconducting oxide sintered body, its pb content was measured, and its critical temperature Tc and critical current density Jc were also measured, and the results are shown in Table 1. It was shown to.
実施例 ３
Ｐｂ０・２ Ｂ ２０３粉末をプレス成形して得られた
直径：２０＋ｎ＋ｎ、厚さ：１０ｍｍの寸法を有するＰ
ｂＢＯ系酸化物圧粉体を、実施例１で作製した円柱状多
孔質仮焼体の上端面に載置し、実施例１と同様にヒータ
ーにより温度、８００℃に加熱して上記ＰｂＢＯ系酸化
物圧粉体を溶融せしめ、円柱状多孔質仮焼体内部に浸透
させたのち、上記ヒーターを速度：５ｍｍ／時で下方に
移動せしめ、Ｂ１系超伝導酸化物焼結体を作製した。得
られたＢｊ系超超伝導酸化物焼結含まれるｐｂ含有足を
測定するとともに臨界温度Ｔｃおよび臨界電流密度Ｊｃ
を測定し、それらの結果を第１表に示した。Example 3 P having dimensions of diameter: 20+n+n and thickness: 10 mm obtained by press-molding Pb0.2B 203 powder
The bBO-based oxide green compact was placed on the upper end surface of the cylindrical porous calcined body produced in Example 1, and heated to 800°C with a heater in the same manner as in Example 1 to form the PbBO-based oxide powder. After the compacted powder was melted and permeated into the cylindrical porous calcined body, the heater was moved downward at a speed of 5 mm/hour to produce a B1 superconducting oxide sintered body. The resulting Bj-based superconducting oxide was sintered and the PB content was measured, as well as the critical temperature Tc and critical current density Jc.
were measured and the results are shown in Table 1.
実施例 ４
ＰｂＯ粉末：２０モル％およびＢｉ２Ｏ３粉末：８０モ
ル％の配合組成を有する混合粉末を、プレス成形して圧
粉体とし、この圧粉体を温度二６８０℃で焼結して、直
径： ２０ｍｍ、厚さ：１０ｍｍのＰｂＢｉＯ系酸化物
焼結体を作製し、このＰｂＢｉＯ系酸化物焼結体を実施
例］て作製した円柱状多孔質仮焼体の上端面に載置した
のちヒーターにより温度二８００℃に加熱してＰｂＢｉ
Ｏ系酸化物焼結体を溶融せしめ、この溶融体が上記円筒
状多孔質仮焼体内部に浸透してから上記ヒーターを速度
：２＋＋＋＋ｎ／時で降下させ、Ｂｉ系超伝導酸化物焼
結体を作製した。上記Ｂｉ系超伝導酸化物焼結体に含ま
れるＰｂを測定するとともに、臨界温度Ｔｃおよび臨界
電流密度Ｊｃを測定し、それらの結果を第１表に示した
。Example 4 A mixed powder having a composition of PbO powder: 20 mol% and Bi2O3 powder: 80 mol% was press-molded into a green compact, and this green compact was sintered at a temperature of 2,680°C to obtain a diameter : A PbBiO-based oxide sintered body having a thickness of 20 mm and a thickness of 10 mm was produced, and this PbBiO-based oxide sintered body was placed on the upper end surface of the cylindrical porous calcined body produced in Example], and then heated. PbBi was heated to a temperature of 2,800°C.
The O-based oxide sintered body is melted, and after this melt penetrates into the inside of the cylindrical porous calcined body, the heater is lowered at a rate of 2+++n/hour to form the Bi-based superconducting oxide sintered body. was created. The Pb contained in the Bi-based superconducting oxide sintered body was measured, as well as the critical temperature Tc and critical current density Jc, and the results are shown in Table 1.
実施例 ５
ＰｂＯ粉末：９０モル％およびＳｒＯ粉末：１０モー
１１ ＝
ル％の配合組成を有する混合粉末をプレス成形して圧粉
体とし、この圧粉体を温度ニア００℃で焼結して、直径
＝２０祁、厚さ＋ＩＯ＋＋＋＋ｎのＰｂＳ’ｒＯ系酸化
物焼結体を作製し、このＰｂ５ｒ’Ｏ系酸化物焼結体を
実施例１で作製した円柱状多孔質仮焼体の上端面に載置
したのち、実施例４と全く同一条件でＢ１系超伝導酸化
物焼結体を作製し、上記Ｂｉ系超伝導酸化物焼結体に含
まれるＰ ｂ Ｍ臨界温度Ｔｃおよび臨界電流密度Ｊｅ
を測定し、それらの結果を第１表に示した。Example 5 PbO powder: 90 mol% and SrO powder: 10 mol%
11 = A mixed powder having a composition of 1% is press-molded to form a compact, and this compact is sintered at a temperature of near 00°C to form a PbS'rO-based oxidized powder having a diameter of 20mm and a thickness of +IO++++n. After preparing a sintered body and placing this Pb5r'O-based oxide sintered body on the upper end surface of the cylindrical porous calcined body prepared in Example 1, B1 was prepared under exactly the same conditions as in Example 4. The P b M critical temperature Tc and critical current density Je contained in the Bi-based superconducting oxide sintered body are prepared.
were measured and the results are shown in Table 1.
実施例 ６
ＰｂＯ粉末、６６モル％およびＣｕＯ粉末：３４モル％
の配合組成を有する混合粉末をプレス成形して圧粉体と
し、この圧粉体を温度＝６００℃で焼結して、直径：
２０ｍｍ５厚さ：１０ｍｍのＰｂＣｕＯ系酸化物焼結体
を作製した。得られたＰｂＣｕＯ系酸化物焼結体を上記
円柱状多孔質仮焼体の上端面に載置し、温度ニア５０℃
で加熱溶融して上記円筒体多孔質仮焼体に浸透させたの
ち、」二記ヒーターを３＋ｏｍ／時の速度で降下させ、
Ｂｉ系超伝導酸化物焼粘体を作製した。得られたＢｉ系
超伝導酸化物焼結体に含まれるＰｂ量を測定し、さらに
臨界温度Ｔｃおよび臨界電流密度Ｊｃを測定してそれら
の結果を第１表に示した。Example 6 PbO powder, 66 mol% and CuO powder: 34 mol%
A mixed powder having a blending composition of is press-molded to form a green compact, and this green compact is sintered at a temperature of 600°C to obtain a diameter of:
A PbCuO-based oxide sintered body of 20 mm and thickness: 10 mm was produced. The obtained PbCuO-based oxide sintered body was placed on the upper end surface of the cylindrical porous calcined body, and the temperature near 50°C.
After melting by heating and infiltrating the cylindrical porous calcined body, the heater is lowered at a speed of 3+ om/hour,
A Bi-based superconducting oxide sintered body was produced. The amount of Pb contained in the obtained Bi-based superconducting oxide sintered body was measured, and the critical temperature Tc and critical current density Jc were also measured, and the results are shown in Table 1.
従来例
Ｂｉ２Ｏ３粉末、ＰｂＯ粉末、Ｓ ｒ ＣＯａ粉末、Ｃ
ｕ０＝ Ｌ、Ｓ：０．４ ： ２ ： ２ ＋ ３、の
割合になるように配合し、混合し、大気中、温度＝８７
０℃、３時間保持の条件で仮焼し、ついで、通常の条件
で焼結してＢｉ系超伝導酸化物焼結体を作製した。この
ようにして得られたＢｉ系超伝導酸化物焼結体のｐｂ含
有量を測定するとともに臨界温度Ｔｃおよび臨界電流密
度Ｊｃを測定し、その結果を第１表に示した。Conventional examples Bi2O3 powder, PbO powder, S r COa powder, C
u0 = L, S: Blend and mix in the ratio of 0.4: 2: 2 + 3, in the atmosphere, temperature = 87
It was calcined at 0° C. for 3 hours, and then sintered under normal conditions to produce a Bi-based superconducting oxide sintered body. The pb content of the Bi-based superconducting oxide sintered body thus obtained was measured, as well as the critical temperature Tc and critical current density Jc, and the results are shown in Table 1.
第１表の結果から、この発明の製造法で作製したＢｉ系
超伝導酸化物焼結体は、従来例と比べて臨界温度Ｔｃが
ほぼ同程度に高く、ｐｂ含有量は少なく、臨界電流密度
Ｊｃは格段にすぐれていることがわかる。From the results in Table 1, it can be seen that the Bi-based superconducting oxide sintered body produced by the production method of the present invention has a critical temperature Tc that is almost as high as that of the conventional example, a lower PB content, and a critical current density. It turns out that JC is much better.
なお、上記円柱状多孔質仮焼体の上端面に載置するＰｂ
Ｏを含む層として実施例ではＰｂＯ圧粉体、ＰｂＣａＯ
系酸化物圧粉体、ＰｂＢＯ系酸化物圧粉体、ＰｂＢｉＯ
系酸化物焼結体、ＰｂＳ ｒｏ系酸化物焼結体およびＰ
ｂＣｕＯ系酸化物焼結体を用いたが、上記圧粉体および
焼結体に限定されることなく、ＰｂＯを含む混合粉末と
して円柱状多孔質仮焼体上端面に載置しても全く同じ効
果か得られることがわかった。Note that the Pb placed on the upper end surface of the cylindrical porous calcined body
In the examples, the layer containing O is PbO compact, PbCaO
PbBO-based oxide compact, PbBO-based oxide compact, PbBiO
oxide sintered body, PbS ro-based oxide sintered body, and PbS ro-based oxide sintered body,
bCuO-based oxide sintered body was used, but it is not limited to the above-mentioned compacted powder and sintered body, and even if it is placed as a mixed powder containing PbO on the upper end surface of a cylindrical porous calcined body, the same result will be obtained. I found that it was effective.
高臨界温度Ｔｃを有し、さらに従来よりも優れた臨界電
流密度Ｊｃを有するＢｉ系超伝導酸化物焼結体を提供す
ることができ、高温超伝導技術の発展に大いに貢献しう
るちのである。It is possible to provide a Bi-based superconducting oxide sintered body that has a high critical temperature Tc and a critical current density Jc superior to conventional ones, and will greatly contribute to the development of high-temperature superconducting technology. .
第１図は、多孔質仮焼体の上面に°ＰｂＯを含む層を載
置した状態を示す断面立面概略図、第２図は、帯域溶融
法によりＰｂＯを含む層を溶融しながら下方に移動させ
つつある状態を示す断面立面概略図である。
１：多孔質仮焼体、
１’：Ｂｉ系超伝導酸化物焼結体、
＝ １５ −
２：台、 ３：上端面、４ ： Ｐｂ
Ｏを含む層、 ４’ ： ｐ ｂ ｏ液相、５：ヒー
ター。
出願入量 三菱金属株式会社Fig. 1 is a schematic cross-sectional elevational view showing a state in which a layer containing °PbO is placed on the upper surface of a porous calcined body, and Fig. 2 is a schematic cross-sectional elevation view showing a state in which a layer containing °PbO is placed on the upper surface of a porous calcined body. FIG. 2 is a schematic cross-sectional elevational view showing a state in which it is being moved; 1: porous calcined body, 1': Bi-based superconducting oxide sintered body, = 15-2: stand, 3: upper end surface, 4: Pb
layer containing O, 4': pbo liquid phase, 5: heater. Application intake Mitsubishi Metals Corporation
Claims (8)
Ｏ＿３粉末およびＣｕＯ粉末をモル比で、 １／２Ｂｉ＿２Ｏ＿３：ＳｒＣＯ＿３：ＣａＣＯ＿３：
ＣｕＯ＝２：２：２：３、 となるように配合し、混合し、プレス成形し、ついで通
常の条件で仮焼して得られた多孔質仮焼体の上端面に、
ＰｂＯを含む層を載置し、上記ＰｂＯを含む層を溶融さ
せながら上記多孔質仮焼体の上端から下端に向って上記
ＰｂＯを含む層の溶融域を移動させることを特徴とする
高臨界電流密度を有するＢｉ系超伝導酸化物焼結体の製
造法。(1) Bi_2O_3 powder, SrCO_3 powder, CaC
The molar ratio of O_3 powder and CuO powder is 1/2Bi_2O_3:SrCO_3:CaCO_3:
CuO=2:2:2:3, mixed, press-molded, and then calcined under normal conditions.
A high critical current characterized in that a layer containing PbO is placed, and the melting region of the layer containing PbO is moved from the upper end to the lower end of the porous calcined body while melting the layer containing PbO. A method for producing a Bi-based superconducting oxide sintered body having density.
ることを特徴とする請求項１記載の高臨界電流密度を有
するＢｉ系超伝導酸化物焼結体の製造法。(2) The method for producing a Bi-based superconducting oxide sintered body having a high critical current density according to claim 1, wherein the shape of the porous calcined body is a cylinder or a prism.
体またはＰｂＯ焼結体からなることを特徴とする請求項
１または２記載の高臨界電流密度を有するＢｉ系超伝導
酸化物焼結体の製造法。(3) The Bi-based superconducting oxide sintered material having a high critical current density according to claim 1 or 2, wherein the layer containing PbO is made of PbO powder, PbO green compact, or PbO sintered body. How the body is manufactured.
、ＰｂＣａＯ系酸化物圧粉体、またはＰｂＣａＯ系酸化
物焼結体であることを特徴とする請求項１または２記載
の高臨界電流密度を有するＢｉ系超伝導酸化物焼結体の
製造法。(4) The high critical current density according to claim 1 or 2, wherein the layer containing PbO is a PbCaO-based oxide powder, a PbCaO-based oxide green compact, or a PbCaO-based oxide sintered body. A method for producing a Bi-based superconducting oxide sintered body having:
ＰｂＢＯ系酸化物圧粉体またはＰｂＢＯ系酸化物焼結体
であることを特徴とする請求項１または２記載の高臨界
電流密度を有するＢｉ系超伝導酸化物焼結体の製造法。(5) The layer containing PbO includes PbBO-based oxide powder,
3. The method for producing a Bi-based superconducting oxide sintered body having a high critical current density according to claim 1 or 2, which is a PbBO-based oxide compact or a PbBO-based oxide sintered body.
、ＰｂＢｉＯ系酸化物圧粉体、ＰｂＢｉＯ系酸化物焼結
体であることを特徴とする請求項１または２記載の高臨
界電流密度を有するＢｉ系超伝導酸化物焼結体の製造法
。(6) The high critical current density according to claim 1 or 2, wherein the layer containing PbO is a PbBiO-based oxide powder, a PbBiO-based oxide green compact, or a PbBiO-based oxide sintered body. A method for producing a Bi-based superconducting oxide sintered body comprising:
、ＰｂＳｒＯ系酸化物圧粉体、ＰｂＳｒＯ系酸化物焼結
体であることを特徴とする請求項１または２記載の高臨
界電流密度を有するＢｉ系超伝導酸化物焼結体の製造法
。(7) The high critical current density according to claim 1 or 2, wherein the layer containing PbO is a PbSrO-based oxide powder, a PbSrO-based oxide green compact, or a PbSrO-based oxide sintered body. A method for producing a Bi-based superconducting oxide sintered body comprising:
、ＰｂＣｕＯ系酸化物圧粉体、ＰｂＣｕＯ系酸化物焼結
体であることを特徴とする請求項１または２記載の高臨
界電流密度を有するＢｉ系超伝導酸化物焼結体の製造法
。(8) The high critical current density according to claim 1 or 2, wherein the layer containing PbO is a PbCuO-based oxide powder, a PbCuO-based oxide green compact, or a PbCuO-based oxide sintered body. A method for producing a Bi-based superconducting oxide sintered body comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1131784A JP2817199B2 (en) | 1989-05-25 | 1989-05-25 | Method for producing sintered body of B ▲ i superconducting oxide with high critical current density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1131784A JP2817199B2 (en) | 1989-05-25 | 1989-05-25 | Method for producing sintered body of B ▲ i superconducting oxide with high critical current density |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02311354A true JPH02311354A (en) | 1990-12-26 |
| JP2817199B2 JP2817199B2 (en) | 1998-10-27 |
Family
ID=15066067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1131784A Expired - Lifetime JP2817199B2 (en) | 1989-05-25 | 1989-05-25 | Method for producing sintered body of B ▲ i superconducting oxide with high critical current density |
Country Status (1)
| Country | Link |
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| JP (1) | JP2817199B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI750769B (en) * | 2019-09-03 | 2021-12-21 | 大陸商廣州力及熱管理科技有限公司 | A chain-like copper metal wick structure and manufacturing method thereof |
-
1989
- 1989-05-25 JP JP1131784A patent/JP2817199B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI750769B (en) * | 2019-09-03 | 2021-12-21 | 大陸商廣州力及熱管理科技有限公司 | A chain-like copper metal wick structure and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2817199B2 (en) | 1998-10-27 |
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