JPH02192419A - Oxide superconductor composition - Google Patents
Oxide superconductor compositionInfo
- Publication number
- JPH02192419A JPH02192419A JP1012583A JP1258389A JPH02192419A JP H02192419 A JPH02192419 A JP H02192419A JP 1012583 A JP1012583 A JP 1012583A JP 1258389 A JP1258389 A JP 1258389A JP H02192419 A JPH02192419 A JP H02192419A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- oxide
- oxide superconductor
- composition
- superconductor composition
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 239000002887 superconductor Substances 0.000 title claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 3
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 abstract 2
- 238000010304 firing Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000005292 diamagnetic effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- -1 66PbO Chemical class 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 101100296543 Caenorhabditis elegans pbo-4 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 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
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 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、Ｂ ｉ−８ｒ−Ｃａ−Ｃｕ−０系酸化物超電
導体組成物に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a B i-8r-Ca-Cu-0 based oxide superconductor composition.
（従来の技術）
現在、超電導体としては、ＮｂＴｉ、Ｎｂ、Ｓｎで代表
される金属系超電導体が実用化されているが、これらの
臨界温度（Ｔｃ・・・超電導状態になる温度）は２０Ｋ
（絶対温度、以下同様）程度である。(Prior art) Metal-based superconductors represented by NbTi, Nb, and Sn are currently in practical use as superconductors, but their critical temperature (Tc...the temperature at which they become superconducting) is 20K.
(absolute temperature, the same applies hereafter).
亦、近年、 Ｐｈｙｓｉｃａｌ Ｒｅｖｅｖ Ｌｅｔｔ
ｅｒｓ ５８（１９７ｇ） ｐｐ９０ｇ−９１０に於い
て、７７にで超電導現象を示すアルカリ土類元素及び酸
化鋼から成る複合酸化物超電導体が報告され、高価な液
体ヘリウムから安価な液体窒素温度での使用が可能とな
った。更に、Ｊａｐ、Ｊ、Ａｐｐｌ、Ｌａｔｔｅｒｓ
２７（１９８８） Ｌ２０９で、Ｔｃが１１０Ｋ及び８
０にであるＢ ｉ−３ｒ−Ｃａ−Ｃｕ−０系の酸化物超
電導体が報告され注目を集めるところとなった。In addition, in recent years, Physical Revev Lett
ers 58 (197g) pp90g-910, a composite oxide superconductor consisting of alkaline earth elements and oxidized steel that exhibits superconductivity was reported in 77, and it was used at temperatures ranging from expensive liquid helium to inexpensive liquid nitrogen. became possible. Additionally, Jap, J., Appl., Latters.
27 (1988) L209, Tc is 110K and 8
A B i-3r-Ca-Cu-0 based oxide superconductor, which has a B i-3r-Ca-Cu-0 structure, was reported and attracted attention.
（発明が解決しようとする課題）
然し乍ら、上記Ｂ ｉ−８ｒ−Ｃａ−Ｃｕ−Ｏｆｆ酸化
物超電導体を焼結体（バルク体）として製造する場合、
Ｔｃ＝１１０にの相と８０にの相とが混在して来る為、
１１０に相の単相化が非常に困難であると云う問題点が
あった。因みに、現在知られているこれらの相は、
１１０に相がＢ ｌ ２Ｓ ｒ ｚＣａ ２Ｃｕ ３０
１０＋δ、８０に相がＢ ｌ ２ Ｓ ｒ’ ２ Ｃａ
Ｉ Ｃｕ ｚ Ｏｓ＋ｓとされている。又Ｂ ｌ ２
Ｓ ｒ ｚＣａ ｚＣｕ ３０１０．５は、一般に行な
われている酸化性雰囲気での焼成法では、得られる焼結
体の反磁性磁化率が非常に小さく、焼結体中のＴｃ＝１
１０に相の含有率が小さなものしか得られていないのが
実状であった。(Problems to be Solved by the Invention) However, when producing the above Bi-8r-Ca-Cu-Off oxide superconductor as a sintered body (bulk body),
Since the phase at Tc=110 and the phase at Tc=80 are mixed,
110 had a problem in that it was extremely difficult to convert the phase into a single phase. Incidentally, these currently known phases are: 110 and B l 2S r zCa 2Cu 30
10+δ, the phase at 80 is B l 2 S r' 2 Ca
It is said that I Cu z Os+s. Also B l 2
When S r zCa zCu 3010.5 is fired in a commonly used oxidizing atmosphere, the diamagnetic susceptibility of the resulting sintered body is extremely small, and Tc in the sintered body is 1.
In reality, only those with a small phase content of 10% were obtained.
（発明の目的）
本発明は、上記に鑑みなされたもので、上記のＢｉ
Ｓｒ Ｃａ Ｃｕ Ｏ系酸化物超電導体２２２３１
Ｇ＋δ
のＴ、ｃ＝１１０に相を増大させるべく鋭意研究した結
果、Ｂｉ及びＳｒの一部をｐｂで置換し、更にＭｇ、Ｂ
、Ｂａ、Ｋ及びＺｎを適当量含有させることがＴｃ＝１
１０に相の増大に極めて有効で且つ短時間での焼成が可
能となることを知見し、ここに本発明を提供せんとする
ものである。(Object of the invention) The present invention has been made in view of the above, and the present invention has been made in view of the above.
Sr Ca Cu O-based oxide superconductor 22231
As a result of intensive research to increase the phase to T of G+δ, c=110, some of Bi and Sr were replaced with pb, and further Mg, B
, Ba, K and Zn in appropriate amounts is Tc=1.
The inventors have found that this method is extremely effective in increasing the phase size and can be fired in a short period of time, and the present invention is therefore intended to be provided here.
（課題を解決する為の手段）
上記目的を達成する本発明の酸化物超電導体組成物は、
組成式が
Ｂｉ Ｐｂ Ｓｒ Ｃａ Ｃｕ ０２
−ｘ ｘ ２−ｘ／２ ２ ３ １０＋δ
（但し、０．２≦Ｘ≦０．６）
で表される酸化物であって、該酸化物がＭｇ、Ｂ、Ｂａ
、Ｋ及びＺｎから選ばれた少なくとも１種をを０．１５
〜１．０モル％含有することを特徴とするものである。(Means for Solving the Problems) The oxide superconductor composition of the present invention that achieves the above objects is
The composition formula is Bi Pb Sr Ca Cu 02
-x x 2-x/2 2 3 10+δ
(However, 0.2≦X≦0.6), and the oxide is Mg, B, Ba
, at least one selected from K and Zn at 0.15
It is characterized by containing ~1.0 mol%.
ここで、０．２≦Ｘ≦０．６としたのは、Ｘが０．２未
満の場合、焼結速度が遅くなり高Ｔｃ相、即ちＴ ｃ
＝ １１０ Ｋ相の生成が少なくなり、またＸが０．６
を超える場合、Ｃａ、ＰｂＯ４等の不純物が生成しＴｃ
やＪｃ（臨界電流密度）が大きく低下する傾向となるか
らである。Here, the reason for setting 0.2≦X≦0.6 is that when X is less than 0.2, the sintering rate becomes slow and a high Tc phase occurs
= 110 The generation of K phase is reduced and X is 0.6
If it exceeds Tc, impurities such as Ca and PbO4 will be generated.
This is because the current density and Jc (critical current density) tend to decrease significantly.
又、Ｍｇ、Ｂ、Ｂａ、Ｋ及びＺｎの含有率を０゜１５〜
１．０モル％としたのは、０．１５モル％未満の場合は
系の焼成温度が高くなり、それに伴い安定なＣａ２Ｐｂ
Ｏ４の増加をまねくことになり、１．０モル％を超える
と粒界に常伝導相が増加しＴｃを低下させるからである
。In addition, the content of Mg, B, Ba, K and Zn is 0°15~
The reason for setting it to 1.0 mol% is that if it is less than 0.15 mol%, the firing temperature of the system will be high, and accordingly, stable Ca2Pb
This is because if it exceeds 1.0 mol %, the normal conductive phase will increase at the grain boundaries and Tc will decrease.
（作用）
上記構成の酸化物超電導体は、各構成元素の酸化物或い
は炭酸化物を所望量秤量して混合し、これを焼成する所
謂酸化物焼結法によって主に生成されるが、この時、Ｂ
ｉ及びＳｒサイトの一部がｐｂにより置換され、これに
より反応が促進されてＴ ｃ ＝ １１０ Ｋ相が多く
生成される。又、Ｍｇ。(Function) The oxide superconductor having the above structure is mainly produced by the so-called oxide sintering method in which desired amounts of oxides or carbonates of each constituent element are weighed and mixed and then fired. , B
Some of the i and Sr sites are replaced by pb, which promotes the reaction and produces a large amount of T c = 110 K phase. Also, Mg.
Ｂ、Ｂａ、に或いはＺｎの存在が反磁性磁化率に大きく
影響し、粒成長を促進する。その結果、Ｔｃ＝１１０に
相の生成率が一層向上し、焼成時間が大幅に短縮される
。このような特性は１反応性スパッタ法或いは蒸着法に
於いても充分予想されるところである。The presence of B, Ba, or Zn greatly affects the diamagnetic susceptibility and promotes grain growth. As a result, the phase formation rate is further improved to Tc=110, and the firing time is significantly shortened. Such characteristics can be fully expected in one-reactive sputtering or vapor deposition.
（実施例） 次に実施例について述べる。(Example) Next, an example will be described.
（１）Ｂｉ２０３、ＳｒＣＯ３、ＣｕＯ及びｐｂ。(1) Bi203, SrCO3, CuO and pb.
等の構成金属の酸化物或いは炭酸化物粉末をＢ” １．
６６ＰｂＯ，３４Ｓｒ１．８３°ａ２°ｕ３０ｔｏ＋
６” ”となるようなモル比で秤量配合し、これを７５
０〜８１０℃で仮焼し、更に粉砕・仮焼を繰り返し平均
粒径５μｍで上記組成式（串）の仮焼粉末を得た。これ
を組成物■とする。1. Oxide or carbonate powder of constituent metals such as
66PbO, 34Sr1.83°a2°u30to+
Weigh and mix in a molar ratio such that the ratio is 75
Calcination was carried out at 0 to 810°C, and further pulverization and calcining were repeated to obtain a calcined powder having an average particle size of 5 μm and having the above composition formula (skewer). This is referred to as composition (2).
（２）上記組成物■に、ＭｇＯ，Ｂ、Ｏ，、ＢａＣ０１
、Ｋ、Ｏ及びＺｎＯを夫々所定量添加して混合し、所望
形状に成型した後大気中８１０〜８６０℃で焼成した。(2) In the above composition (■), MgO, B, O,, BaC01
, K, O, and ZnO were added and mixed in predetermined amounts, molded into a desired shape, and then fired in the air at 810 to 860°C.
（３）上記（２）で得た焼結体について、アルキメデス
法により比重を、電気抵抗を測定してＴｃ（ｍｉｄ）を
定め、交流磁化率測定法により超電導体比率（Ｔｃ＝１
１０に相の比率）を測定した。(3) Regarding the sintered body obtained in (2) above, the specific gravity was measured by the Archimedes method, the electrical resistance was determined to determine Tc (mid), and the superconductor ratio (Tc = 1
The ratio of phases to 10) was measured.
その結果を第１表に示す。The results are shown in Table 1.
（以下余白）
但し、第１表中■′■及び■は、夫々上記と同じ条件で
合成した
Ｂ ｌ ２Ｓ ｒ ２Ｃａ ２Ｃｕ ３０１０＋ａ
”’■２Ｂ ｌ ｈ９Ｐ ｂ ｏ、ｔ Ｓ ｒ’
１．９ｓｃ ａ ２Ｃｕ ３０ｙ”’■Ｂ ｌ １．
３Ｐ ｂ ｏ、７Ｓ ｒ １．ｓｓｃ ａ ２Ｃｕ ３
０ｙ”’■である。また各添加元素の添数字は組成物■
及び■′に対するモル％を表す。(The following are blank spaces) However, ■'■ and ■ in Table 1 are B l 2S r 2Ca 2Cu 3010+a synthesized under the same conditions as above, respectively.
”'■2B l h9P b o,t S r'
1.9sc a 2Cu 30y'''■B l 1.
3P b o, 7S r 1. ssc a 2Cu 3
0y'''■.The subscript number of each additive element is the composition■
It represents mol% with respect to and ■'.
第１表に於いて、試料ＮＱＩのｐｂ無添加ではＴｃ＝１
１０に相は１０ｖｏ１％であるのに対し、Ｂｉ及びＳｒ
の一部をｐｂで置換する辱とによりＴｃ＝１１０に相が
２８ｖｏ１％まで高くなり、焼成時間を１６０時間まで
延長してもＴｃ＝１１０に相の生成量は３５ｖｏ１％程
度である。これに対し、本発明に基づきに、Ｍｇ、Ｚｎ
、Ｂａ、Ｂを所定量添加したものは８０時間の焼成時間
でもＴｃ＝１１０に相がいずれも３０ｖｏ１％以上とな
り試料＆２よりも優れていることが理解される。また、
Ｔｃ（ｍｉｄ）においても９５に以上が達成された。更
に、比重は、焼結が進行するに従い超電導結晶の粒成長
と共に小さくなる傾向にある。よって第１表によればに
１Ｍｇ、Ｚｎ、Ｂａ、Ｂの添加によって、短時間に焼成
でき焼結が充分に進行していることが理解される。In Table 1, Tc=1 for sample NQI without pb addition.
The phase in 10 is 10vo1%, while Bi and Sr
By substituting a part of PB with PB, the amount of phase produced at Tc=110 increases to 28vol%, and even if the firing time is extended to 160 hours, the amount of phase produced at Tc=110 is about 35vo1%. On the other hand, based on the present invention, Mg, Zn
It is understood that the sample to which predetermined amounts of , Ba, and B were added had a Tc of 110 and a phase of 30 vol 1% or more even after a firing time of 80 hours, which was superior to sample &2. Also,
Tc (mid) of 95 or higher was also achieved. Further, as sintering progresses, the specific gravity tends to decrease as the grains of the superconducting crystal grow. Therefore, according to Table 1, it is understood that by adding 1 Mg, Zn, Ba, and B, sintering can be performed in a short time and the sintering progresses sufficiently.
尚、上記実施例では所謂単純混合系による場合ついて述
べたが、これに限定されず、例えば出発物質を上記と同
様とし、
（ｉ ）Ｓ ｒ２Ｃｕ ＯＸ化合物（合成温度９００−
９５０℃）（ｉｉ）Ｃａ ２Ｃｕ Ｏ，化合物（合成温
度８８０−９３０℃）（＋ｎ ） Ｂ ｉＩ Ｃｕ １
０ □化合物及びＢ ｌ ｏ、ａＰ ｂ ｏ、３０ ｇ
化合物（合成温度５００〜６００℃）
（ＩＶ）Ｂ ｉｌ、８Ｐ ｂ Ｏ，３Ｃｕ ｔｏ 、化
合物（合成温度５５０〜６００℃）を
予め調製しておき、（ｉ）＋（ｉｉ）＋（ｉｎ）或いは
（ｉ）＋（…）＋（ｔｖ）の組合せで上記組成になるよ
う混合し、これを所望の形状に成型した後、８１０〜８
８０℃で焼成して得ることも可能である。この場合、５
ｒＣＯ，及びＣａＣ０，とＣｕ Ｏとを先に合成するの
で未反応の炭酸塩が残らず、また直接中間物から出発す
るので安定なＴ ｃ ＝ ８０ Ｋ相が生成しにくい反
面Ｔｃ＝１１０に相が得易く、更に、焼成時間が短縮出
来る、等のメリットがある。In the above example, a so-called simple mixed system was described, but the case is not limited to this. For example, the starting material is the same as above, and (i) S r2Cu OX compound (synthesis temperature 900-
950°C) (ii) Ca2CuO, compound (synthesis temperature 880-930°C) (+n) B iI Cu 1
0 □ Compound and B lo, aP b o, 30 g
Compound (synthesis temperature 500-600°C) (IV) B il, 8P b O, 3Cu to , compound (synthesis temperature 550-600°C) is prepared in advance, and (i) + (ii) + (in) or (i) + (...) + (tv) is mixed to give the above composition, and after molding it into a desired shape, 810-8
It can also be obtained by firing at 80°C. In this case, 5
Since rCO, CaC0, and CuO are synthesized first, no unreacted carbonate remains, and since the process starts directly from intermediates, it is difficult to form a stable T c = 80 K phase. It has the advantage of being easy to obtain and shortening the firing time.
（発明の効果） 叙上の如く１本発明の酸化物超電導体組成物は。(Effect of the invention) As described above, the oxide superconductor composition of the present invention is as follows.
高Ｔｃ相（ＩＩＯＫ相）を多く含み、しかも従来に比べ
短い焼成時間で得られるものであり、超電導物質の用途
開発を推進する上でその実益は極めて大である。It contains a large amount of high Tc phase (IIOK phase) and can be obtained in a shorter sintering time than conventional ones, so it is extremely beneficial in promoting the development of applications for superconducting materials.
一以上一one or more one
Claims (1)
ａ＿２Ｃｕ＿３Ｏ＿１＿０＿＋＿δ（但し、０．２≦ｘ
≦０．６） で表される酸化物であって、該酸化物がＭｇ、Ｂ、Ｂａ
、Ｋ及びＺｎから選ばれた少なくとも１種をを０．１５
〜１．０モル％含有することを特徴とする酸化物超電導
体組成物。1. The composition formula is Bi_2_-_xPb_xSr_2_-_x_/_2C
a_2Cu_3O_1_0_+_δ (however, 0.2≦x
≦0.6), the oxide is Mg, B, Ba
, at least one selected from K and Zn at 0.15
An oxide superconductor composition characterized by containing ~1.0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1012583A JPH02192419A (en) | 1989-01-20 | 1989-01-20 | Oxide superconductor composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1012583A JPH02192419A (en) | 1989-01-20 | 1989-01-20 | Oxide superconductor composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02192419A true JPH02192419A (en) | 1990-07-30 |
Family
ID=11809377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1012583A Pending JPH02192419A (en) | 1989-01-20 | 1989-01-20 | Oxide superconductor composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02192419A (en) |
-
1989
- 1989-01-20 JP JP1012583A patent/JPH02192419A/en active Pending
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