JPH02141425A - Bismuth-based oxide superconducting material and production thereof - Google Patents
Bismuth-based oxide superconducting material and production thereofInfo
- Publication number
- JPH02141425A JPH02141425A JP63273776A JP27377688A JPH02141425A JP H02141425 A JPH02141425 A JP H02141425A JP 63273776 A JP63273776 A JP 63273776A JP 27377688 A JP27377688 A JP 27377688A JP H02141425 A JPH02141425 A JP H02141425A
- Authority
- JP
- Japan
- Prior art keywords
- bismuth
- superconducting material
- compounds
- based oxide
- phase
- 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
- 239000000463 material Substances 0.000 title claims abstract description 35
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 16
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 20
- 238000010586 diagram Methods 0.000 claims abstract description 16
- 239000002887 superconductor Substances 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 239000005749 Copper compound Substances 0.000 claims 4
- 150000001880 copper compounds Chemical class 0.000 claims 4
- 150000001622 bismuth compounds Chemical class 0.000 claims 3
- 229940043430 calcium compound Drugs 0.000 claims 3
- 150000001674 calcium compounds Chemical class 0.000 claims 3
- 150000002611 lead compounds Chemical class 0.000 claims 3
- 150000003438 strontium compounds Chemical class 0.000 claims 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- 239000011575 calcium Substances 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- 150000002823 nitrates Chemical class 0.000 claims 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 229910002480 Cu-O Inorganic materials 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005404 magnetometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 oxide Chemical compound 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance 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)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
（背景）
ビスマス系酸化物超伝導体は１９８８年２月に前出らに
より見いだされた。この物質は１１０に付近から急激な
電気抵抗の減少が観測されると同時に、この温度付近で
のマイスナー効果も認められる。ｌｌ０Ｋという温度は
これまで最高の臨界温度を持つとされていたＹＢａ、Ｃ
ｕ、Ｏ，の９ＯＫを太き（上回り、将来の応用が期待さ
れている。DETAILED DESCRIPTION OF THE INVENTION (Background) A bismuth-based oxide superconductor was discovered by the aforementioned et al. in February 1988. In this material, a rapid decrease in electrical resistance is observed near 110, and at the same time, the Meissner effect is also observed near this temperature. The temperature of 10K was thought to be the highest critical temperature for YBa, C.
It is thicker than the 9OK of u, O, and is expected to be applied in the future.
１１０にの臨界温度を持つ相を単結晶として取り出すこ
とが可能であることは知られているが、このようにして
単結晶を取り出しても超伝導材料として利用することは
できない。従って、この時点では１１０にの臨界温度を
持つ実質的に単独相からなる材料は得られておらず、製
造された材料には必ず８０に相あるいは半導体相および
Ｃａ。Although it is known that it is possible to extract a phase with a critical temperature of 110 °C as a single crystal, even if the single crystal is extracted in this way, it cannot be used as a superconducting material. Therefore, at this point in time, no material has been obtained that consists essentially of a single phase with a critical temperature of 110 degrees Celsius, and the materials produced always contain 80 degrees Celsius phase or semiconducting phase and Ca.
ｐｂｏ、等の不純物が共存していた。また、化合物は特
定できないが、Ｘ線回折図には１１０に相思外の小さな
回折線が観測される。このようないくつかの相の混合は
超伝導特性を著しく損なうためｌｌ０Ｋ相のみからなる
材料の出現が望まれていた。鉛の添加によって１１０に
相の割合を太き（できることが報告されているが、１１
０に相単独の材料を得ることは困難を極めた。Impurities such as pbo were present. Further, although the compound cannot be identified, an unexpectedly small diffraction line is observed at 110 in the X-ray diffraction diagram. Since such a mixture of several phases significantly impairs superconducting properties, it has been desired to develop a material consisting only of the 110K phase. It has been reported that the phase ratio can be increased to 110 by adding lead, but
It was extremely difficult to obtain a material with only phase 0.
この発見以降、構造に関する数多くの研究がなされ、そ
の結果、上記の１１０に相はＢｉ−０層の間に３枚の、
８０に相は２枚の、半導体相は１枚のＣｕ−０層をそれ
ぞれ有していることが明らかとなった。Since this discovery, numerous studies have been conducted on the structure, and as a result, the above 110 phase has three layers between the Bi-0 layers.
It became clear that the phase had two Cu-0 layers and the semiconductor phase had one Cu-0 layer.
（本発明の目的と発明にいたった経緯）本発明の目的は
実質的に１１０に相のみからなる超伝導材料およびその
製造方法を提供することにある。この目的を達成するた
め種々検討した結果、いくつかの限られた条件下、限ら
れた仕込み組成において実質的に８０に相および半導体
相を含まないＢｉ系超超伝導材料得ることに成功した。(Object of the present invention and background of the invention) An object of the present invention is to provide a superconducting material consisting essentially of only the 110 phase and a method for producing the same. As a result of various studies to achieve this objective, we succeeded in obtaining a Bi-based superconducting material substantially free of 80 phase and semiconductor phase under some limited conditions and with a limited charging composition.
さらに本願発明者らは上記１１０に相のみよりなる超伝
導体の作製法の検討過程において、Ｘ線回折図にはｌｌ
０Ｋ相の回折線のみしか現れていないにもかかわらず磁
化率の測定を行った場合、１１０に付近および９０から
Ｉ ＯＯＫ付近の両方て大きな変化が現れるという現象
を確認した。このようにしてＣｕ−０３層の構造をもつ
ものの中に１１０−に相思外に９０から１００Ｋ付近に
超伝導転移温度をもつ物質が存在することを知るにいた
り本発明を完成した。Furthermore, in the process of studying the method for producing a superconductor consisting only of phases in 110 above, the inventors of the present application discovered that the X-ray diffraction diagram
When the magnetic susceptibility was measured even though only the 0K phase diffraction line appeared, a phenomenon was confirmed in which large changes appeared both near 110 and from 90 to near IOOK. In this way, the present invention was completed by discovering that among materials having a Cu-03 layer structure, there existed a substance having a superconducting transition temperature in the vicinity of 90 to 100K.
（本発明の構成）
本発明はビスマス系酸化物超伝導材料およびその製造方
法に関するものである。(Structure of the present invention) The present invention relates to a bismuth-based oxide superconducting material and a method for producing the same.
前述のごと＜Ｂｉ系超超伝導体は１１０に相、８０に相
および半導体相の３つの相が知られており、ＣｕＫ、線
によるＸ線回折図において２０約４．７°にｌｌ０Ｋ相
の回折線が、約５．７°に８０に相の回折線が、約７．
２°に半導体相の回折線が現れる。また、不純物として
含まれるＣａ、ｐｂ○４は１７．８°に現れ、そのほか
に１６５°などに不純物と思われる小さな回折線が認め
られることがある。本発明の超伝導材料の特徴は約５，
７°および約７．２°の回折線の強度が約４．７°の回
折線の強度の５％以下であり、ＣｕＯ３層構造の割合が
極めて高い。ここでいう回折線の強度とはベースライン
から回折線の頂点までの距離をいう。As mentioned above, Bi-based superconductors are known to have three phases: a 110 phase, an 80 phase, and a semiconductor phase. The diffraction line is at about 5.7 degrees, the phase at 80 degrees, and the diffraction line at about 7 degrees.
A diffraction line of the semiconductor phase appears at 2°. Further, Ca and pb○4 contained as impurities appear at 17.8°, and in addition, small diffraction lines that are thought to be impurities may be observed at 165° and so on. The superconducting material of the present invention has approximately 5 characteristics:
The intensity of the diffraction lines at 7° and about 7.2° is 5% or less of the intensity of the diffraction line at about 4.7°, and the proportion of the CuO three-layer structure is extremely high. The intensity of a diffraction line here refers to the distance from the baseline to the apex of the diffraction line.
本発明の超伝導材料のもうひとつの特徴は９０〜１００
にで超伝導体に転移する相を含んでいるという点である
。この場合、約５．７°および約７．２°に回折線が認
められてもよい。また多少の他の不純物を含んでもよい
。いずれにしても９０〜１００Ｋ付近の臨界温度を有す
る超伝導体（以下９５に相と呼ぶ）を含んでいる必要が
ある。この９５に相は２θ約４．７°に回折線を示し、
Ｘ線回折図から見るかぎり１１０に相と同一である。Another feature of the superconducting material of the present invention is 90-100
The point is that it contains a phase that transforms into a superconductor. In this case, diffraction lines may be observed at about 5.7° and about 7.2°. It may also contain some other impurities. In any case, it is necessary to contain a superconductor (hereinafter referred to as phase 95) having a critical temperature in the vicinity of 90 to 100K. This 95 phase shows a diffraction line at about 4.7° 2θ,
As seen from the X-ray diffraction diagram, the phase is the same as 110.
１１０に相は高い臨界温度を持つが、臨界電流は比較的
低く、このため臨界温度を測定する場合微弱な電流で行
わないと低温側にすそをひき、見掛は上臨界温度が低（
観測されるほどである。Although the phase 110 has a high critical temperature, the critical current is relatively low. Therefore, when measuring the critical temperature, unless it is done with a weak current, it will draw its tail to the low temperature side, and the upper critical temperature will appear to be low (
So much so that it has been observed.
方、９５に相は臨界温度こそ１１０に相より低いものの
、後述の実施例に示されるように強いビン止め力を有し
、従って高い臨界電流Ｊｃを示す。On the other hand, although the critical temperature of the phase 95 is lower than that of the phase 110, it has a strong bottle-holding force as shown in the examples described later, and therefore exhibits a high critical current Jc.
このため特に線材として非常に有望である。Therefore, it is very promising especially as a wire rod.
ビスマス系酸化物超伝導材料はＢｉ、５ｒＳＣａＳＣｕ
、Ｏからなり、Ｂｉの一部をｐｂで置換すると１１０に
相の割合が増えるといわれている。Bismuth-based oxide superconducting materials include Bi, 5rSCaSCu
, O, and it is said that when a part of Bi is replaced with pb, the phase ratio increases to 110.
これら元素の組成により異なった特性を示す事が知られ
ており、鉛を含まない系の場合Ｂｉ：Ｓｒ：Ｃａ：Ｃｕ
＝１：１：１：２の時に最も１１０に相の割合が多くな
ると言われており、一方Ｂｉ：Ｓｒ：Ｃａ：Ｃｕ＝２：
２：１：２の場合、８０に相がほとんどとなる。ｐｂは
Ｂｊのうちモル比で０．１から０．４の範囲で置換され
る。本発明の超伝導材料はｐｂを含む系であり、約５．
７０および約７．２°の回折強度を約４．７°のそれの
５％以下にするにはＢ ｉ、Ｐｂｙ（Ｓ ｒｕＣａｖＣ
ｕ ｗ） ２０ ａなる仕込み組成が好適に用いられる
。It is known that these elements exhibit different properties depending on their composition, and in the case of lead-free systems, Bi:Sr:Ca:Cu
It is said that the phase ratio is highest at 110 when = 1:1:1:2, while Bi:Sr:Ca:Cu = 2:
In the case of 2:1:2, most of the phases are at 80. pb is substituted with Bj in a molar ratio of 0.1 to 0.4. The superconducting material of the present invention is a system containing pb, and about 5%.
In order to make the diffraction intensity at about 70° and about 7.2° less than 5% of that at about 4.7°, B i, Pby (S ruCavC
A charging composition of u w) 20 a is preferably used.
ここでＸは０．１５０から０．２１５、ｙは０゜０３０
から０．０９０．２は０．７２０から０゜８００（但し
ｘ＋ｙ＋ｚ＝１） 、ｕを０．２００から０．２９０、
■を０．２５０から０．３５５、Ｗを０．４３０から０
．５３０ （但しｕ＋ｖ＋ｗ−１）の範囲である。特に
、微量の不純物をも含まない超伝導材料を得るためには
ＢｉｘＰｂｙ（Ｓｒ ｕＣａ ｖＣ１３ｗ） ｚｏ ａ
なる仕込み組成において、Ｘは０．１８５から０２１０
、ｙは０．０３０から０．０５０、Ｚは０．７５０から
０．７７０（イ旦しｘ十ｙ＋ｚ−１）、ｕは０゜２５５
から０゜２９０、Ｖは０．２７５から０．３］０．ｗは
０゜４３０から０．４５５（但しｕ＋ｖ＋ｗ＝ｌ）の範
囲が好適に用いられる。Here, X is 0.150 to 0.215, y is 0°030
From 0.090.2 is 0.720 to 0°800 (x+y+z=1), u is 0.200 to 0.290,
■ from 0.250 to 0.355, W from 0.430 to 0
．． 530 (however, the range is u+v+w-1). In particular, in order to obtain a superconducting material that does not contain even a trace amount of impurities, BixPby (Sr uCa vC13w) zo a
In the charging composition, X is 0.185 to 0210
, y is 0.030 to 0.050, Z is 0.750 to 0.770 (Idanshixy+z-1), u is 0°255
to 0°290, V is 0.275 to 0.3]0. The range of w from 0°430 to 0.455 (where u+v+w=l) is preferably used.
原料は水酸化物、酸化物、炭酸塩、硝酸塩、しゅう酸塩
、酢酸塩など焼成により分解あるいは反応して酸化物に
変化するものなら何でも用いることができる。Any raw material that can be decomposed or reacted and converted into an oxide upon firing, such as hydroxide, oxide, carbonate, nitrate, oxalate, and acetate, can be used.
製造にあたり、これら原料は均一に混合される。During production, these raw materials are mixed uniformly.
混合はどのような方法で行ってもよい。例えば各原料を
メノウ乳鉢で粉砕しながら混合してもよいし、ボールミ
ルを用いてもよい。各金属化合物のうち少なくともＣｕ
の化合物として硝酸塩を用いることが望ましい。この場
合、水などの溶媒に溶解または分散させる。この溶液を
撹拌しながら加熱乾燥させることが望ましく、スプレー
ドライ法で乾燥しながら混合することもできる。各金属
化合物としてそれぞれの硝酸塩を用いてもよいことは勿
論である。また、炭酸塩や酸化物を硝酸に溶解させても
よい。これとは別に、スパッタリング法等により形成さ
れた薄膜も均一に混合するのに良い方法である。Mixing may be performed by any method. For example, each raw material may be mixed while being ground in an agate mortar, or a ball mill may be used. Of each metal compound, at least Cu
It is desirable to use nitrate as the compound. In this case, it is dissolved or dispersed in a solvent such as water. It is desirable to heat and dry this solution while stirring, and it is also possible to mix while drying using a spray drying method. Of course, each nitrate may be used as each metal compound. Further, carbonates and oxides may be dissolved in nitric acid. Apart from this, a thin film formed by sputtering or the like is also a good method for uniformly mixing.
このようにして得られた混合物あるいは生成物は仮焼せ
ずにそのまま本焼成を行らてもよいが、通常仮焼を行う
。つまり、酸化物以外の化合物の混合物は通常８００°
Ｃ前後の温度で仮焼される。Although the mixture or product thus obtained may be subjected to main firing as it is without being calcined, calcining is usually performed. In other words, mixtures of compounds other than oxides are usually 800°
It is calcined at a temperature around C.
しかし、仮焼は必須ではない。酸化物の混合物あるいは
スパッタリング法等により、形成された酸化物薄膜ある
いは金属薄膜については仮焼をする必要はない。仮焼雰
囲気は空気、酸素、あるいは不活性ガスと酸素の混合物
のいずれでもよい。However, calcination is not essential. There is no need to calcinate an oxide thin film or a metal thin film formed by a mixture of oxides, a sputtering method, or the like. The calcination atmosphere may be air, oxygen, or a mixture of inert gas and oxygen.
次に焼成を行う。焼成前の原料が粉末状態であればあら
かじめ成型を行う。その大きさ、形状はどのようなもの
でもかまわない。例えば、ペレットでもよいし線状のも
のでもよい。焼成は通常空気中で行われるが、酸素分圧
をＯから０．１５気圧、好ましくは０．０３から０．１
気圧に保つことが望ましい。このために酸素を窒素、ア
ルゴン、等の不活性ガスで希釈してもよいし、空気を上
記不活性ガスで希釈してもよい。温度は酸素分圧や組成
によって異なるがいずれの場合も融点直下から融点の下
５０℃の範囲が望ましい。ビスマス系酸化物超伝導体の
場合、融点を越える温度で反応させることができない。Next, firing is performed. If the raw material before firing is in a powder state, it is molded in advance. It can be of any size or shape. For example, it may be a pellet or a linear one. Firing is usually carried out in air, but the oxygen partial pressure is adjusted from O to 0.15 atm, preferably from 0.03 to 0.1.
It is desirable to maintain the pressure at atmospheric pressure. For this purpose, oxygen may be diluted with an inert gas such as nitrogen or argon, or air may be diluted with the above-mentioned inert gas. The temperature varies depending on the oxygen partial pressure and composition, but in any case it is preferably in the range from just below the melting point to 50° C. below the melting point. In the case of bismuth-based oxide superconductors, they cannot be reacted at temperatures exceeding their melting point.
−度融解した試料は超伝導性を示さなくなるからである
。本発明における超伝導材料の融点は酸素分圧０．２気
圧のとき約８４５℃となる。酸素分圧を下げることによ
り、広い温度範囲で、比較的短時間で生成物を得ること
ができる。This is because a sample that has been melted to a certain degree no longer exhibits superconductivity. The melting point of the superconducting material in the present invention is approximately 845° C. when the oxygen partial pressure is 0.2 atm. By lowering the oxygen partial pressure, products can be obtained over a wide temperature range and in a relatively short time.
焼成時間は概ね１２時間以上を必要とする。冷却過程は
焼成時と同じ酸素分圧で行ってもよいがより高い酸素分
圧で行ってもよい。むしろ高い酸素分圧のほうが、生成
した超伝導材料に流すことのできる電流が太き（なる。The firing time generally requires 12 hours or more. The cooling process may be performed at the same oxygen partial pressure as during firing, or may be performed at a higher oxygen partial pressure. In fact, the higher the oxygen partial pressure, the thicker the current that can be passed through the generated superconducting material.
また、高圧酸素処理により磁化率測定における１１０に
相と９５に相の分離を明確にする効果もある。もちろん
焼成時と同じ酸素分圧のままで冷却し、その後焼成温度
以下の温度に再加熱し、高圧力酸素処理を行ってもよい
。Furthermore, the high-pressure oxygen treatment has the effect of clarifying the separation of the 110 phase and the 95 phase in magnetic susceptibility measurements. Of course, high-pressure oxygen treatment may be performed by cooling with the same oxygen partial pressure as during firing, and then reheating to a temperature below the firing temperature.
以下に実施例により更に詳細に説明する。This will be explained in more detail with reference to Examples below.
実施例Ｉ
Ｂｉ、０３、ＰｂＯ，，５ｒＣｏ３、ＣａＣｏ、１、Ｃ
ＵＯをＢｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕの比がＯ９ｓ：ｏ
、１５：０．８６：０．８６：１．３３になるように秤
り取った。この組成はＢ ｒ ｘ ｐ ｂ ｙ （ｓｒ
１．Ｃａ ｖＣｕ ｗ） ｚｏ ａという組成式にお
いてＸ−０，２、ｙ＝０．０３８、Ｚ＝０．７６３、Ｕ
−０２８１、■＝０．２８］、ｗ−・０．４３８に相当
する。これらを加熱しながら過剰の硝酸に完全に溶解さ
せた。この溶液を白金の蒸発皿にいれ、絶えず撹拌しな
がら加熱蒸発させ、溶媒である水を除いた。このとき、
過剰の硝酸も同時に除かれる。生成した硝酸塩の混合物
をアルミナ製のルツボにいれ、更に加熱を続けた。硝酸
塩が分解しＮＯ７が発生する。最終的に８００°ＣでＮ
ｏ、が生成しなくなるまで加熱した。これをメノウ乳鉢
で粉砕し直径１３ｍｍ、厚さ約１ｍｍのペレットに成型
した。焼成には内径１００ｍｍ、長さ６００ｍｍの管状
炉を用いた。ペレットをアルミナ製のボートに置き、こ
れを炉の中心部分に設置した。アルゴンと酸素の比を１
２＝１に調整し、毎分２５０ｃｃの流通下、８３５°Ｃ
で１２時間反応させた。Example I Bi,03,PbO,,5rCo3,CaCo,1,C
The ratio of UO to Bi:Pb:Sr:Ca:Cu is O9s:o
, 15:0.86:0.86:1.33. This composition is B r x p b y (sr
1. In the composition formula Ca vCu w) zo a, X-0,2, y=0.038, Z=0.763, U
−0281, ■=0.28], w−·0.438. These were completely dissolved in excess nitric acid while heating. This solution was placed in a platinum evaporating dish and heated and evaporated with constant stirring to remove water as a solvent. At this time,
Excess nitric acid is also removed at the same time. The resulting nitrate mixture was placed in an alumina crucible, and heating was continued. Nitrate decomposes and NO7 is generated. Finally, at 800°C, N
The mixture was heated until o was no longer produced. This was crushed in an agate mortar and molded into pellets with a diameter of 13 mm and a thickness of about 1 mm. A tubular furnace with an inner diameter of 100 mm and a length of 600 mm was used for firing. The pellets were placed in an alumina boat, which was placed in the center of the furnace. The ratio of argon and oxygen is 1
Adjusted to 2=1, flowed at 250cc/min, 835°C
The mixture was allowed to react for 12 hours.
反応後、室温まで冷却した後、これを再度粉砕し、上記
と同じ大きさのペレットに成型し、同条件で更に７２時
間反応させた。その後、約２℃／ｍｉｎで徐冷した。温
度が７５０ ’Ｃに達した時点から酸素分圧を１気圧と
し、そのまま室温まで冷却することにより実施例１の試
料を得た。After the reaction, it was cooled to room temperature, and then ground again, molded into pellets of the same size as above, and reacted for an additional 72 hours under the same conditions. Thereafter, it was slowly cooled at a rate of about 2° C./min. When the temperature reached 750'C, the oxygen partial pressure was set to 1 atm, and the sample of Example 1 was obtained by cooling to room temperature.
このもののＸ線回折測定を行い、抵抗の温度依存性およ
び磁化率の温度依存性を調べた。結果をそれぞれ図１、
図２および図３に示す。図１に示されるように２０約４
．７°の回折線が現れ、約５．７°および約７．２°の
回折線は全く認められない。また、図２に示されるよう
に抵抗測定からは１１０に相のみの存在が示唆される。This material was subjected to X-ray diffraction measurement to examine the temperature dependence of resistance and the temperature dependence of magnetic susceptibility. The results are shown in Figure 1 and
Shown in FIGS. 2 and 3. 20 approx. 4 as shown in Figure 1
．． A 7° diffraction line appears, and no diffraction lines at about 5.7° and about 7.2° are observed. Furthermore, as shown in FIG. 2, resistance measurements suggest the presence of only a phase at 110.
一方、図３のマイスナー効果を表す曲線には明らかに１
１０に相と９５に相のシグナルが認められる。両者の体
積分率の比はほぼ１：１であり、これらの和は全体積の
約９２％を占める。従って本実施例の試料はほとんど同
一の構造すなわちＣｕ−０３層構造を持つ２種類の超伝
導体の１：１の混合物であると結論できる。On the other hand, the curve representing the Meissner effect in Figure 3 clearly shows 1
Phase signals are observed at 10 and 95. The ratio of their volume fractions is approximately 1:1, and the sum of these accounts for approximately 92% of the total volume. Therefore, it can be concluded that the sample of this example is a 1:1 mixture of two types of superconductors having almost the same structure, that is, the Cu-03 layer structure.
図３において注目されるのはシールディング効果を示す
曲線である。この測定によればシールディング効果によ
る磁化率の変化はマイスナー効果によるそれの３倍以上
であり、しかもそれが９０に以下で顕著である。つまり
、９５に相が大きなシールディング効果を示している。What is noteworthy in FIG. 3 is the curve showing the shielding effect. According to this measurement, the change in magnetic susceptibility due to the shielding effect is more than three times that due to the Meissner effect, and moreover, it is noticeable below 90. In other words, phase 95 shows a large shielding effect.
このことは９５に相では１１０に相に比べて磁束量子線
のピン止め力が非常に大きいことを示しており、従って
、臨界電流が大きいことを意味している。This shows that the pinning force of the magnetic flux quantum line is much larger in the 95th phase than in the 110th phase, and therefore means that the critical current is large.
実施例２
Ｂ Ｉ ２０３、 ＰｂＯ、ＳｒＣＯ３、ＣａＣＯ
２、ＣＵＯをＢｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕの比がＯｏ
ａｇｏ、２：０．８： １．０：２．Ｏになるように秤
り取った。この組成はＢ ＋ ｘ Ｐ ｂ ｙ （Ｓ
ｒ ｕＣａ ｖＣｕ ｗ） ｚｏ ＃という組成式にお
いてｘ＝０．１６７、ｙ＝０．０４２、ｚ＝０．７９２
、Ｕ＝０゜２１１、Ｖ＝０．２６３、ｗ＝０．５２６に
相当する。これをメノウ乳鉢で十分混合した。これを空
気の流通下、８１０°Ｃで１０時間仮焼した。その後、
粉砕および３時間の仮焼を２回繰り返した。Example 2 B I 203, PbO, SrCO3, CaCO
2. CUO with a Bi:Pb:Sr:Ca:Cu ratio of Oo
ago, 2:0.8: 1.0:2. I weighed it so that it was O. This composition is B + x P b y (S
r uCa vCu w) zo In the composition formula #, x = 0.167, y = 0.042, z = 0.792
, U=0°211, V=0.263, w=0.526. This was thoroughly mixed in an agate mortar. This was calcined at 810°C for 10 hours under air circulation. after that,
Grinding and 3-hour calcination were repeated twice.
得られた生成物を再度粉砕し、直径１３ｍｍ、厚さ約１
ｍｍのペレットに成型した。焼成には内径１００ｍｍ、
長さ６００ｍｍの管状炉を用いた。The obtained product was ground again to a diameter of 13 mm and a thickness of about 1
It was molded into pellets of mm. For firing, the inner diameter is 100 mm,
A tube furnace with a length of 600 mm was used.
ペレットをアルミナ製のポートに置き、これを炉の中心
部分に設置した。アルゴンと酸素の比を１２：１に調整
し、毎分２５０ＣＣの流通下、８４２°Ｃで８０時間反
応させた。その後、酸素分圧を１／１３に保ったまま約
２℃／ ｍ ｉ ｎで徐冷した。The pellets were placed in an alumina port, which was placed in the center of the furnace. The ratio of argon and oxygen was adjusted to 12:1, and the reaction was carried out at 842°C for 80 hours under a flow of 250 CC per minute. Thereafter, it was slowly cooled at about 2° C./min while keeping the oxygen partial pressure at 1/13.
生成物はやや反った形に変形しており、融点直下である
ことを示している。このもののＸ線回折測定、抵抗測定
およびマイスナー効果の測定を行つた。マイスナー効果
については室温でのインダクタンスが約１．７ｍＨのコ
イル中に試料を置き、インダクタンスの変化を調べた。The product was deformed into a slightly warped shape, indicating that it was just below the melting point. This product was subjected to X-ray diffraction measurements, resistance measurements, and Meissner effect measurements. Regarding the Meissner effect, a sample was placed in a coil with an inductance of approximately 1.7 mH at room temperature, and changes in inductance were examined.
結果をそれぞれ図４、図５および図６に示す。図４に示
されるように２０約４．７°の回折線が現れ、゛約５．
７゜および約７，２°の回折線は全く認められない（２
θ約４．７°の回折線に対する約５．７°および約７．
２°の回折線の強度はそれぞれ０％）。また、１２０に
付近から抵抗の急激な低下が見られ１０７にで抵抗Ｏと
なる。これと対応して、コイルのインダクタンスも極め
てシャープに低下している。従って本実施例の場合１１
０に相の割合が極めて高いと考えられる。The results are shown in FIGS. 4, 5 and 6, respectively. As shown in FIG. 4, a diffraction line of about 4.7 degrees appears, and a diffraction line of about 5 degrees appears.
The diffraction lines at 7° and about 7.2° are not observed at all (2
about 5.7° and about 7.0° for the diffraction line at θ about 4.7°.
The intensity of each 2° diffraction line is 0%). Further, a sudden drop in resistance is seen from around 120, and the resistance reaches O at 107. Corresponding to this, the inductance of the coil also drops extremely sharply. Therefore, in this example, 11
It is considered that the ratio of the phase to 0 is extremely high.
実施例３〜５
Ｂｉ、０３、ＰｂＯ，Ｓ ｒｃｏ、、ＣａＣ０，、ＣＵ
ＯをＢｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕの比が０゜８：０．
２：０．８： １．Ｑ： ｉ、４になるように秤り取っ
た。この組成はＢ ｉ、Ｐｂ、（Ｓ ｒｕＣａ ｖＣｕ
ｗ） ２０ ａという組成式においてｘ＝０．１９０
、ｙ＝０．０４８、ｚ＝０．７６２、ｕ＝Ｑ。Examples 3 to 5 Bi, 03, PbO, S rco,, CaC0,, CU
The ratio of O to Bi:Pb:Sr:Ca:Cu is 0°8:0.
2:0.8:1. Q: I, I weighed it so that it was 4. This composition is B i, Pb, (S ruCa vCu
w) In the composition formula 20 a, x = 0.190
, y=0.048, z=0.762, u=Q.
２５０、Ｖ＝０．３］３、ｗ＝Ｑ、４３Ｂに相当する。250, V=0.3]3, w=Q, corresponds to 43B.
焼成温度、焼成時間および酸素分圧を表１に示される値
としたこと、および冷却時にも酸素分圧をそのままに保
ったこと以外は実施例１と同様にして焼成を行いそれぞ
れの試料を得た。Firing was performed in the same manner as in Example 1, except that the firing temperature, firing time, and oxygen partial pressure were set to the values shown in Table 1, and the oxygen partial pressure was kept unchanged during cooling, and each sample was obtained. Ta.
以下、実施例４および５についても表１に示した条件以
外は同様にして焼成を行い、それぞれ生成物を得た。こ
れらのＸ線回折図を図７に示す。Hereinafter, in Examples 4 and 5, firing was performed in the same manner except for the conditions shown in Table 1, and products were obtained respectively. These X-ray diffraction patterns are shown in FIG.
２θ約４．７°の回折線が現れ、約５．７°および約７
゜２°の回折線は全く認められないか、あってもごくわ
ずかであり、いずれのサンプルも１１０に相あるいは９
５に相の割合が極めて高いことを示している。Diffraction lines of about 4.7° 2θ appear, and diffraction lines of about 5.7° and about 7
The diffraction line at ゜2° is either not observed at all, or is very slight, and all samples have a phase of 110 or 9.
5 shows that the phase ratio is extremely high.
実施例６
Ｂｉ、０３、ＰｂＯ１ＳｒＣＯ，、Ｃａ ＣＯ！］、Ｃ
ＵＯをＢｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕの比がＯｓ：ｏ、
１５：０．８３：０．８９：１．３３になるように秤り
取った。この組成はＢ ＋ ｘ Ｐ ｂ ｙ （Ｓｒ
ｕＣａ ｖＣｕ ｗ） ｓｏ ａという組成式において
Ｘ＝０．２、ｙ＝０．０３７５、ｚ＝０．７６２５、ｕ
＝０．２７２、Ｖ−０，２９２、ｗ＝０．４３６に相当
する。これを、冷却時に酸素分圧を変化させなかったこ
と以外は実施例１と同様にして焼成を行い、実施例６の
試料を得た。Example 6 Bi, 03, PbO1SrCO,, Ca CO! ],C
UO has a Bi:Pb:Sr:Ca:Cu ratio of Os:o,
It was weighed out so that the ratio was 15:0.83:0.89:1.33. This composition is B + x P b y (Sr
In the composition formula uCa vCu w) so a, X=0.2, y=0.0375, z=0.7625, u
=0.272, V-0,292, w=0.436. This was fired in the same manner as in Example 1, except that the oxygen partial pressure was not changed during cooling, to obtain a sample of Example 6.
Ｘ線回折の結果を図８に示す。２θ約４．７゜の回折線
が大きく現れ、約５．７°および約７゜２°の回折線は
全く認められない（２θ約４．７０の回折線に対する約
５．７°および約７．２゜の回折線の強度はそれぞれ０
％）。′上記実施例２〜５においては２θ１７°から１
８″にかけて僅かながら不純物の回折線が現れているが
、本実施例においては１７．８°、１６．５°および２
９゜８°の不純物の回折線も認められない。従ってＣｕ
−０３層構造のみの超伝導材料であると考えられる。The results of X-ray diffraction are shown in FIG. The diffraction line at about 2θ of about 4.7° appears largely, and the diffraction lines at about 5.7° and about 7°2 are not observed at all (about 5.7° and about 7° for the diffraction line at about 4.70 2θ). The intensity of each diffraction line at .2° is 0.
%). 'In Examples 2 to 5 above, 2θ17° to 1
Although a slight diffraction line of impurities appears toward 8", in this example, it
Diffraction lines of impurities at 9° and 8° are also not observed. Therefore, Cu
It is considered to be a superconducting material with only -03 layer structure.
実施例７および８
Ｂ １ｘＰｂｙ（Ｓ ｒｕｃａｖＣｕ、）、Ｏ，という
組成式においてｘ＝０．２００．ｙ＝０．０３７．２−
Ｏ，７６３、ｕ＝０．２５９、ｙ＝Ｑ、３０３、ｚ＝０
．４３８としたこと以外は実施例１と同様にして焼成を
行い、実施例７の試料を得た。Examples 7 and 8 B In the composition formula of 1xPby(SrucavCu,),O, x=0.200. y=0.037.2-
O,763, u=0.259, y=Q, 303, z=0
．． A sample of Example 7 was obtained by firing in the same manner as in Example 1 except that the sample was changed to 438.
実施例８についてもｘ＝０．２００、ｙ−０゜０３７、
ｚ＝０．７６３、ＬＩ＝０．２４５、■−〇、３３０、
ｗ＝０．４２５としたこと以外は同様に焼成を行って生
成物を得た。ただし、冷却時にも１／１３の酸素分圧を
維持した。Also for Example 8, x=0.200, y-0°037,
z=0.763, LI=0.245, ■-〇, 330,
A product was obtained by calcination in the same manner except that w=0.425. However, even during cooling, the oxygen partial pressure was maintained at 1/13.
これらの電気抵抗の温度依存性を調べた。（図９）実施
例１では現れなかったが明らかに９５に相による抵抗の
低下が認められる。なお、実施例７．８の試料にはそれ
ぞれ約５．７°の回折線力（、約４．７°の回折線に対
して２％および９％の割合で認められる。それにもかか
わらず抵抗−温度曲線に８０に相が認められないのは、
試料中の１１０に相および９５に相が途切れることなく
連なっているからと考えられる。The temperature dependence of these electrical resistances was investigated. (FIG. 9) Although it did not appear in Example 1, a decrease in resistance depending on the phase is clearly observed in 95. It should be noted that in the sample of Example 7.8, the diffraction line force of about 5.7° is observed at a rate of 2% and 9% for the diffraction line of about 4.7°. -The reason why no phase is observed at 80 in the temperature curve is because
This is thought to be because the phase at 110 and the phase at 95 in the sample are continuous without interruption.
比較例１〜５
Ｂｉ２０３、ＰｂＯ，ＳｒＣＯ３、Ｃａ ＣＯ＊、ＣＵ
Ｏの比をそれぞれ表２の値になるように秤り取ったこと
、および冷却時に酸素分圧を変化させなめＡつたこと以
外は実施例１と同様にして生成物・をｉ専、Ｘ線回折の
測定を行った。Comparative Examples 1 to 5 Bi203, PbO, SrCO3, Ca CO*, CU
The product was exposed to X-rays in the same manner as in Example 1, except that the O ratio was measured to the values shown in Table 2, and the oxygen partial pressure was changed during cooling. Diffraction measurements were taken.
これらのＸ線回折図を図１０に示す。２θ約４゜７°の
回折線が強く現れるが、約５．７°の８０に相および不
純物の回折線が現れており、ＣｕＯ３層構造単独の超伝
導材料は得られな（Ｘ０These X-ray diffraction patterns are shown in FIG. Diffraction lines at about 4° 7° of 2θ appear strongly, but diffraction lines of phases and impurities appear at 80° at about 5.7°, making it impossible to obtain a superconducting material with a CuO three-layer structure alone (X0
図１〜３はそれぞれ実施例１で得られた試料のＸ線回折
図、電気抵抗の温度依存性、および磁イヒ率の温度依存
性を示す。
図４〜６は実施例２で得られた試料のＸ線回折図、電気
抵抗の温度依存性、およびコイルのインダクタンス変化
の温度依存性を示す。
図７は実施例３から５で得られた試料のＸ線回折図であ
る。
図８は実施例６で得られた試料のＸ線回折図である。
図９は実施例７および８で得られた試料の電気抵抗の温
度依存性を示す。
図１０は比較例１〜５で得られた試料のＸ線回折図であ
る。
以上1 to 3 show the X-ray diffraction diagram, the temperature dependence of electrical resistance, and the temperature dependence of magnetic Ich ratio of the sample obtained in Example 1, respectively. 4 to 6 show the X-ray diffraction diagram of the sample obtained in Example 2, the temperature dependence of electrical resistance, and the temperature dependence of change in inductance of the coil. FIG. 7 is an X-ray diffraction diagram of the samples obtained in Examples 3 to 5. FIG. 8 is an X-ray diffraction diagram of the sample obtained in Example 6. FIG. 9 shows the temperature dependence of the electrical resistance of the samples obtained in Examples 7 and 8. FIG. 10 is an X-ray diffraction diagram of samples obtained in Comparative Examples 1 to 5. that's all
Claims (11)
．７゜に回折線が現れ、かつ、約５．７゜および約７．
２゜の回折線の強度のいずれもが約４．７゜の回折線の
強度の５％以下であることを特徴とするビスマス、鉛、
ストロンチウム、カルシウム、銅および酸素からなるビ
スマス系酸化物超伝導材料。(1) 2θ approximately 4 in the X-ray diffraction diagram by CuK_α rays
．． A diffraction line appears at 7°, and at about 5.7° and about 7.7°.
Bismuth, lead, characterized in that the intensity of the 2° diffraction line is 5% or less of the intensity of the approximately 4.7° diffraction line,
A bismuth-based oxide superconducting material consisting of strontium, calcium, copper, and oxygen.
．７゜あるいは約７．２゜またはその両方の回折線の強
度が２θ約４．７゜の回折線の強度の５％を越え、かつ
２θ約４．７゜の回折線を示し約９０から１００Ｋの超
伝導転移温度をもつ超伝導体を少なくとも一部含んでい
ることを特徴とするビスマス、鉛、ストロンチウム、カ
ルシウム、銅および酸素からなるビスマス系酸化物超伝
導材料。(2) 2θ approximately 5 in the X-ray diffraction diagram by CuK_α rays
．． The intensity of the diffraction line at 7° or about 7.2° or both exceeds 5% of the intensity of the diffraction line at about 2θ about 4.7°, and the diffraction line is about 2θ about 4.7° and is about 90 to 100K. A bismuth-based oxide superconducting material comprising bismuth, lead, strontium, calcium, copper, and oxygen, characterized in that it contains at least a portion of a superconductor having a superconducting transition temperature of .
．７゜および約７．２゜に回折線が現れないことを特徴
とする特許請求の範囲第（１）項に記載の超伝導材料。(3) 2θ approximately 5 in the X-ray diffraction diagram by CuK_α rays
．． The superconducting material according to claim 1, characterized in that no diffraction lines appear at angles of 7° and about 7.2°.
ｕ＿ｗ）＿ｚＯ＿αなる仕込み組成を持つことを特徴と
する特許請求の範囲第（１）項または第（３）項に記載
の超伝導材料。 ここで、ｘ、ｙ、ｚ、ｕ、ｖおよびｗは以下の範囲であ
る。 ｘ＝０．１５０〜０．２１５ ｙ＝０．０３０〜０．０９０ ｚ＝０．７２０〜０．８００ ｕ＝０．２００〜０．２９０ ｖ＝０．２５０〜０．３５５ ｗ＝０．４３０〜０．５３０ 但し、ｘ＋ｙ＋ｚ＝１であり、かつｕ＋ｖ＋ｗ＝１であ
る。(4) Bi_xPb_y(Sr_uCa_vC
The superconducting material according to claim 1 or claim 3, having a charging composition of u_w)_zO_α. Here, x, y, z, u, v and w are in the following ranges. x=0.150~0.215 y=0.030~0.090 z=0.720~0.800 u=0.200~0.290 v=0.250~0.355 w=0.430 ~0.530 However, x+y+z=1 and u+v+w=1.
不純物の回折線が現れないことを特徴とする特許請求の
範囲第（１）項または第（３）項に記載の超伝導材料。(5) The superconducting material according to claim (1) or (3), wherein substantially no diffraction lines of impurities appear in an X-ray diffraction diagram using CuK_α rays.
ｕ＿ｗ）＿ｚＯ＿αなる仕込み組成を持つことを特徴と
する特許請求の範囲第（５）項に記載の超伝導材料。 ここで、ｘ，ｙ，ｚ，ｕ，ｖおよびｗは以下の範囲であ
る。 ｘ＝０．１８５〜０．２１０ ｙ＝０．０３０〜０．０５０ ｚ＝０．７５０〜０．７７０ ｕ＝０．２５５〜０．２９０ ｖ＝０．２７５〜０．３１０ ｗ＝０．４３０〜０．４５５ 但し、ｘ＋ｙ＋ｚ＝１であり、かつｕ＋ｖ＋ｗ＝１であ
る。(6) Bi_xPb_y(Sr_uCa_vC
The superconducting material according to claim (5), having a charging composition of u_w)_zO_α. Here, x, y, z, u, v and w are in the following ranges. x=0.185~0.210 y=0.030~0.050 z=0.750~0.770 u=0.255~0.290 v=0.275~0.310 w=0.430 ~0.455 However, x+y+z=1 and u+v+w=1.
．７゜の回折線を示し９０Ｋから１００Ｋの超伝導転移
温度をもつ超伝導体を少なくとも一部含んでいることを
特徴とする特許請求の範囲第（１）項、第（３）項また
は第（５）項に記載のビスマス系酸化物超伝導材料。(7) 2θ approximately 4 in the X-ray diffraction diagram by CuK_α ray
．． Claims (1), (3), or (2), characterized in that they contain at least a portion of a superconductor that exhibits a diffraction line of 7° and has a superconducting transition temperature of 90K to 100K. The bismuth-based oxide superconducting material described in item 5).
チウム化合物、カルシウム化合物および銅化合物を均一
に混合し、仮焼したのち、あるいは仮焼せずに焼成する
ことを特徴とする特許請求の範囲第（１）〜（３）項、
第（５）項または第（７）項に記載のビスマス系酸化物
超伝導材料の製造方法。(8) Claim No. 1, characterized in that a bismuth compound, a lead compound, a strontium compound, a calcium compound, and a copper compound are uniformly mixed as raw materials and fired after calcining or without calcining. ) to (3),
The method for producing a bismuth-based oxide superconducting material according to item (5) or item (7).
物、カルシウム化合物および銅化合物のうち少なくとも
銅化合物が硝酸塩であり、これらの化合物を溶媒に溶解
または分散させた後、溶媒を除去し、更に加熱により硝
酸塩を分解することによって均一に混合することを特徴
とする特許請求の範囲第（８）項に記載のビスマス系酸
化物超伝導材料の製造方法。(9) Among bismuth compounds, lead compounds, strontium compounds, calcium compounds, and copper compounds, at least the copper compound is a nitrate, and after dissolving or dispersing these compounds in a solvent, the solvent is removed and the nitrate is further heated. The method for producing a bismuth-based oxide superconducting material according to claim (8), wherein the bismuth-based oxide superconducting material is uniformly mixed by decomposition.
合物、カルシウム化合物および銅化合物としてそれぞれ
の硝酸塩を用い、これらを溶媒に溶解させた後、溶媒を
除去し、更に加熱により硝酸塩を分解することによって
均一に混合することを特徴とする特許請求の範囲第（８
）項に記載のビスマス系酸化物超伝導材料の製造方法。(10) Use nitrates of each of the bismuth compounds, lead compounds, strontium compounds, calcium compounds, and copper compounds, dissolve them in a solvent, remove the solvent, and further decompose the nitrates by heating to mix uniformly. Claim No. 8 (8)
) A method for producing a bismuth-based oxide superconducting material according to item 1.
とを特徴とする特許請求の範囲第（８）項、第（９）項
または第（１０）項に記載のビスマス系酸化物超伝導材
料の製造方法。(11) The bismuth-based oxide according to claim (8), (9) or (10), wherein the oxygen partial pressure during firing is 0.15 atm or less. Method for manufacturing superconducting materials.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63273776A JPH02141425A (en) | 1988-06-20 | 1988-10-28 | Bismuth-based oxide superconducting material and production thereof |
| AT89110957T ATE136161T1 (en) | 1988-06-20 | 1989-06-16 | PRODUCTION OF AN OXIDE SUPERCONDUCTOR OF THE BISMUTH SYSTEM |
| EP89110957A EP0347770B1 (en) | 1988-06-20 | 1989-06-16 | Process of producing a bismuth system oxide superconductor |
| DE68926070T DE68926070T2 (en) | 1988-06-20 | 1989-06-16 | Production of an oxide superconductor of the bismuth system |
| AU36519/89A AU3651989A (en) | 1988-06-20 | 1989-06-16 | Bismuth system oxide superconductors and preparation thereof |
| KR1019890008449A KR910002024A (en) | 1988-06-20 | 1989-06-19 | Bismuth-based oxide superconductor and its manufacturing method |
| CN89106281A CN1040700A (en) | 1988-06-20 | 1989-06-20 | Bismuth system oxide superconductors and manufacture method thereof |
| US07/865,637 US5352657A (en) | 1988-06-20 | 1992-04-09 | Bismuth system oxide superconductors and preparation thereof |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-152507 | 1988-06-20 | ||
| JP15250788 | 1988-06-20 | ||
| JP63-218188 | 1988-08-30 | ||
| JP63273776A JPH02141425A (en) | 1988-06-20 | 1988-10-28 | Bismuth-based oxide superconducting material and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02141425A true JPH02141425A (en) | 1990-05-30 |
Family
ID=26481412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63273776A Pending JPH02141425A (en) | 1988-06-20 | 1988-10-28 | Bismuth-based oxide superconducting material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02141425A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04219319A (en) * | 1990-03-23 | 1992-08-10 | Rhone Poulenc Chim | Preparation of super-conducting phase based on bismuth, strontium, calcium, copper and stabilizing element |
| US11911053B2 (en) | 2020-08-14 | 2024-02-27 | Gyrus Acmi, Inc. | Stone fragment capture systems for lithotripsy systems |
-
1988
- 1988-10-28 JP JP63273776A patent/JPH02141425A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04219319A (en) * | 1990-03-23 | 1992-08-10 | Rhone Poulenc Chim | Preparation of super-conducting phase based on bismuth, strontium, calcium, copper and stabilizing element |
| US11911053B2 (en) | 2020-08-14 | 2024-02-27 | Gyrus Acmi, Inc. | Stone fragment capture systems for lithotripsy systems |
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