JP2533108B2 - Superconducting material - Google Patents
Superconducting materialInfo
- Publication number
- JP2533108B2 JP2533108B2 JP62069954A JP6995487A JP2533108B2 JP 2533108 B2 JP2533108 B2 JP 2533108B2 JP 62069954 A JP62069954 A JP 62069954A JP 6995487 A JP6995487 A JP 6995487A JP 2533108 B2 JP2533108 B2 JP 2533108B2
- Authority
- JP
- Japan
- Prior art keywords
- critical
- oxygen
- temperature
- composition
- magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- 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
Description
【発明の詳細な説明】 《産業上の利用分野》 本発明は、超伝導性材料に関し、特に、比較的高温に
臨界温度を有する超伝導性材料に関する。TECHNICAL FIELD The present invention relates to a superconducting material, and more particularly to a superconducting material having a critical temperature at a relatively high temperature.
《従来の技術》 これまでに知られている超伝導体は、極低温の液体ヘ
リウム（沸点4.2K）による冷却が不可欠であり、このた
め冷却コストが膨大になり、ひいては、作り出す超伝導
状態の規模も小さくなるという欠点があった。又、ヘリ
ウムの資源的偏在が超伝導体の広範な普及を阻害してい
た。《Prior art》 It is indispensable to cool superconductors known up to now by cryogenic liquid helium (boiling point 4.2K), which results in enormous cooling cost, and eventually in superconducting state. It had the drawback of being smaller in scale. In addition, the uneven distribution of helium in resources has hindered the widespread use of superconductors.
しかしながら、極く最近、超伝導の臨界温度Tc（転移
開始温度）が液体窒素温度（沸点77K）を越える超伝導
体が報告されている。例えば、米国ヒューストン大学C.
W.Chuらのグループは、臨界温度が94Kのバリウム−イッ
トリウム−銅−酸素系の酸化物を見い出したことを報告
している（Phys.Rev.Letter,vol.58,P.908-909,198
7）。However, very recently, a superconductor having a superconducting critical temperature Tc (transition initiation temperature) exceeding liquid nitrogen temperature (boiling point 77K) has been reported. For example, University of Houston C.
W. Chu et al. Reported that they found oxides of the barium-yttrium-copper-oxygen system with a critical temperature of 94 K (Phys. Rev. Letter, vol. 58, P. 908-909, 198).
7).
又、東京大学の北沢らのグループはバリウム−イッテ
ルビウム−銅−酸素系の酸化物において、臨界温度が95
Kのものを報告しており、同じく東京大学の高木らのグ
ループはバリウム−エルビウム−銅−酸素系の酸化物に
おいて、95Kの臨界温度を報告している（いずれも、Ja
p.Journal of Appl.Phys.,vol.26,4月号、1987）。Also, the group of Kitazawa et al. Of the University of Tokyo has a critical temperature of 95% in barium-ytterbium-copper-oxygen system oxides.
Takagi et al.'S group at the University of Tokyo also reported a critical temperature of 95 K in barium-erbium-copper-oxygen-based oxides (both Ja
p.Journal of Appl.Phys., vol.26, April issue, 1987).
更に、上記３種の酸化物の第２成分をスカンジウム、
ルテチウム、ツリウム、ホルミウム、ディスプロシウ
ム、ガドリニウム等で置換した酸化物においても、90K
程度の臨界温度が報告されている。Further, the second component of the above three kinds of oxides is scandium,
90K even in oxides substituted with lutetium, thulium, holmium, dysprosium, gadolinium, etc.
Some critical temperatures have been reported.
これら各種の超伝導体はすべて一般式： BaxMyCu3O9-zで表される。All of these various superconductors are represented by the general formula: BaxMyCu 3 O 9-z .
但し、ＭはＹ、Yb、Er、Sc、Lu、Tm、Ho、Dy及びGdよ
り選ばれた一種の元素であり、ｘは１〜３、好ましくは
約２、ｙは0.5〜1.5、好ましくは約１で表わされる酸素
欠損ペロブスカイト型結晶構造を有している。又、これ
らの各種の超伝導体のうち、ＭのYb、Ym、Er、Ho、Dy及
びGdはすべて強い磁場のもとで磁性を有するイオンとし
て酸化物中に存在している。However, M is one kind of element selected from Y, Yb, Er, Sc, Lu, Tm, Ho, Dy and Gd, x is 1 to 3, preferably about 2, y is 0.5 to 1.5, preferably It has an oxygen-deficient perovskite type crystal structure represented by about 1. Of these various superconductors, Yb, Ym, Er, Ho, Dy and Gd of M are all present in the oxide as ions having magnetism under a strong magnetic field.
ところで、これまでの超伝導体の長年の研究におい
て、超伝導体に磁性不純物を固溶させることにより、臨
界磁場や臨界電流が向上することが知られている（例え
ば、F.Fischerら、Appl.Phys.,vol.16,p.1,1978等を参
照）。By the way, in many years of research on superconductors, it has been known that solid solution of magnetic impurities in the superconductor improves the critical magnetic field and the critical current (for example, F. Fischer et al., Appl. .Phys., Vol.16, p.1,1978 etc.).
一般に第２種超伝導体において、磁性不純物の添加に
より臨界磁場や臨界電流が向上する理由は、第２種超伝
導体の中を貫通している量子化された磁束（ボルテック
ス）が、固溶された磁性不純物によりエネルギー的に安
定化されピン止めされるために、外部磁場等が加わって
も、磁束の移動、即ち超伝導状態の局所的破壊が起こり
にくくなるからであると説明される。Generally, the reason why the critical magnetic field and the critical current are improved by the addition of magnetic impurities in the type 2 superconductor is that the quantized magnetic flux (vortex) penetrating through the type 2 superconductor becomes a solid solution. It is explained that, because the magnetic impurities are stabilized by energy and pinned, the movement of the magnetic flux, that is, the local destruction of the superconducting state is unlikely to occur even when an external magnetic field or the like is applied.
《発明が解決しようとする問題点》 しかしながら、これまで知られていたシュブレル化合
物等のすべての超伝導体においては、磁性不純物の添加
により臨界温度が大きく低下してしまうという問題があ
った。それに対して最近、酸素欠損ペロブスカイト型結
晶構造を有する超伝導体は、磁性を有するイオンが多量
に超伝導体に含まれるにもかかわらず超伝導の臨界温度
が低下せず、極めて良好である事が見い出された。<< Problems to be Solved by the Invention >> However, in all known superconductors such as the Schbrel compound, there has been a problem that the critical temperature is greatly lowered by the addition of magnetic impurities. On the other hand, recently, superconductors having an oxygen-deficient perovskite-type crystal structure are extremely good because the superconducting critical temperature does not decrease despite the fact that a large amount of magnetic ions are contained in the superconductor. Was found.
そこで、本発明者等は前記一般式中の金属Ｍについて
種々検討した結果、Ｍとして非磁性の希土類金属及びＮ
として磁性を有する希土類金属を組み合わせることがで
き、これによって素材の選択の幅を大きく広げることが
できるのみならず、臨界磁場及び臨界電流を改善するこ
とができることを見い出し本発明に到達した。Therefore, the inventors of the present invention have made various studies on the metal M in the above general formula, and as a result, as the M, a non-magnetic rare earth metal and N
As a result, the inventors have found that it is possible to combine a rare earth metal having magnetism, which not only greatly expands the selection range of the raw material, but also improves the critical magnetic field and the critical current, and has reached the present invention.
従って本発明の第１の目的は、比較的高温の臨界温度
と、高い臨界磁場及び高い臨界電流値を有する超伝導材
料を提供することにある。Therefore, a first object of the present invention is to provide a superconducting material having a relatively high critical temperature, a high critical magnetic field and a high critical current value.
本発明の第２の目的は、比較的高温の臨界温度を有す
る超伝導体の素材を容易に選択するための方法を提供す
ることにある。A second object of the present invention is to provide a method for easily selecting a superconductor material having a relatively high critical temperature.
《問題を解決するための手段》 本発明の上記の諸目的は、一般式： BaxMyNzCu3O9-u の組成物からなり、酸素欠損ペロブスカイト型結晶構造
を有することを特徴とする超伝導性材料によって達成さ
れた。ここでＭはＹ（イットリウム）、Sc（スカンジウ
ム）、La（ランタン）、及びLu（ルテチウム）の群から
選択される少なくとも１種の非磁性希土類金属、ＮはYb
（イッテルビウム）、Tm（ツリウム）、Er（エルビウ
ム）、Ho（ホルミウム）、Dy（ディスプロシウム）、Gd
（ガドリニウム）及びSm（サマリウム）の群から選択さ
れる少なくとも１種の磁性希土類金属、ｘは１〜３、ｙ
及びｚは各々0.01〜1.5、ｕは０〜３である。好ましく
は、ｘは２程度、ｙ＋ｚは１程度である。Above the objectives of the present invention "means for solving the problem" in the general formula: BaxMyNzCu 3 consists O 9-u of the composition, superconducting material characterized by having an oxygen-deficient perovskite-type crystal structure Achieved by Here, M is at least one non-magnetic rare earth metal selected from the group of Y (yttrium), Sc (scandium), La (lanthanum), and Lu (lutetium), and N is Yb.
(Ytterbium), Tm (thulium), Er (erbium), Ho (holmium), Dy (dysprosium), Gd
(Gadolinium) and Sm (samarium) at least one magnetic rare earth metal selected from the group, x is 1 to 3, y
And z are each 0.01 to 1.5, and u is 0 to 3. Preferably, x is about 2 and y + z is about 1.
本発明の酸化物においては、大部分のCuは２価の状態
で存在し、Ｍ及びＮは略３価、Baは２価であるので、Ｏ
の数は約6.5となるが、前記組成物を結晶化させる際の
焼成温度や雰囲気によっては、Cuの一部が３価の状態に
なったものが共存する場合があり、その場合、全体とし
て、Ｏの数は、6.5より若干高めに表れることになる
が、本発明においてはかかる場合を除外するものではな
く、Ba2MyN1−yCu3O6.5に近い組成が大部分を占めてい
れば足りる。又、本発明においては、目的の達成に悪影
響を与えない限り、前記組成物以外の組成物及び／又は
金属が共存する場合をも除外するものではない。In the oxide of the present invention, most of Cu exists in a divalent state, M and N are approximately trivalent, and Ba is divalent, so that O
However, depending on the firing temperature and the atmosphere when the composition is crystallized, some of the Cu may be in the trivalent state, and in that case, as a whole. , O will appear slightly higher than 6.5, but this case is not excluded in the present invention, and if the composition close to Ba 2 MyN 1 -yCu 3 O 6.5 occupies most of it. Is enough. Further, in the present invention, the case where a composition other than the above composition and / or a metal coexists is not excluded unless it adversely affects the achievement of the object.
又、磁気的な効果のために、電子素子としても、特異
な素子物性を示すと考えられる。Further, due to the magnetic effect, it is considered that the electronic device exhibits unique device physical properties.
《発明の効果》 本発明の超伝導性材料は、液体窒素温度で超伝導状態
を実現できるのみならず、臨界電流も大きく、更に、空
気中で900℃程度の高温まで加熱しても安定である。
又、組成を調整することにより、臨界電流密度Icを105
〜106A／cm2程度にすることが十分可能であるので、本
発明は産業上極めて有意義である。<Effects of the Invention> The superconducting material of the present invention not only realizes a superconducting state at liquid nitrogen temperature, but also has a large critical current, and is stable even when heated to a high temperature of about 900 ° C. in air. is there.
In addition, the critical current density Ic can be adjusted to 10 5 by adjusting the composition.
The present invention is extremely significant industrially because it can be sufficiently controlled to about 10 6 A / cm 2 .
実施例1. 本発明に係る一般式BaxMyNzCu3O9-uのＭをＹ、ＮをYb
とし、公知の方法によりx:y:x＝2:0.8:0.2のバリウム−
イットリウム−イッテルビウム−銅−酸素系組成物を調
製した。Example 1. M in the general formula BaxMyNzCu 3 O 9-u of the present invention Y, the N Yb
And x: y: x = 2: 0.8: 0.2 barium by a known method
An yttrium-ytterbium-copper-oxygen based composition was prepared.
上記組成物の調製は、計算量の試薬特級BaCo3、Y
2O3、Yb2O3及びCuOの各粉末にエタノールを加えてメノ
ウ乳鉢中で、湿式混合し、ルツボに入れて900℃で12時
間予備焼成し、炉から取り出した後再び粉砕し、約1,00
0kg/cm2の圧力でプレスしてペレットとし、900℃の炉中
で５時間焼結することにより行った。The above composition was prepared by using a calculated amount of reagent grade BaCo 3 , Y
Ethanol was added to each powder of 2 O 3 , Yb 2 O 3 and CuO, wet-mixed in an agate mortar, put in a crucible, pre-baked at 900 ° C. for 12 hours, taken out of the furnace, and then pulverized again. 1,00
Pressing was performed at a pressure of 0 kg / cm 2 to obtain pellets, and sintering was performed in a furnace at 900 ° C. for 5 hours.
得られた焼結物は、Ｘ線回折により酸素欠損ペロブス
カイト型結晶構造を有することが確認された。The obtained sintered product was confirmed by X-ray diffraction to have an oxygen-deficient perovskite crystal structure.
この焼結物について、超伝導臨界温度Tc、転移温度幅
ΔTc（電気抵抗率がTc近傍の通常の値からゼロ抵抗迄変
化する時の変化率が90％及び10％になる時の温度間隔）
及び臨界電流密度Icを測定した結果を第１表に示す。For this sinter, the superconducting critical temperature Tc, transition temperature range ΔTc (temperature interval when the rate of change when the electrical resistivity changes from a normal value near Tc to zero resistance is 90% and 10%)
Table 1 shows the results of measuring the critical current density Ic.
比較例１及び2. 実施例１と同様にして、x:y:z＝2:1:0のバリウム−イ
ットリウム−銅−酸素系組成物（比較例１）及び、x:y:
z＝2:0:1のバリウム−イッテルビウム−銅−酸素系組成
物（比較例２）を調製した。 Comparative Examples 1 and 2. Similar to Example 1, x: y: z = 2: 1: 0 barium-yttrium-copper-oxygen composition (Comparative Example 1) and x: y:
A barium-ytterbium-copper-oxygen composition (Comparative Example 2) having z = 2: 0: 1 was prepared.
各試料について超伝導臨界温度Tc、転移温度幅ΔTc及
び臨界電流密度Icを測定した結果は第１表の通りであ
る。Table 1 shows the results of measuring the superconducting critical temperature Tc, the transition temperature width ΔTc and the critical current density Ic of each sample.
実施例2. 前記本発明に係る一般式BaxMyNzcu3O9-uにおいてＭを
La、ＮをErとし、x:y:z＝2:0.5:0.5のバリウム−ランタ
ン−エルビウム−銅−酸素系組成物を調製した。Example 2 In the general formula BaxMyNzcu 3 O 9-u according to the present invention, M is
La and N were set to Er, and a barium-lanthanum-erbium-copper-oxygen composition having x: y: z = 2: 0.5: 0.5 was prepared.
上記組成物の調製は、計算量の試薬特級BaCO3、La
2O3、Er2O3及びCuOの各粉末にエタノールを加えてメノ
ウ乳鉢中で、湿式混合し、ルツボに入れて950℃で12時
間予備焼成し、炉から取り出した後再び粉砕し、約1,00
0kg/cm2の圧力でプレスしてペレットとし、950℃の炉中
で６時間焼結することによって行った。The above composition was prepared by using calculated amounts of reagent grade BaCO 3 , La
Ethanol was added to each powder of 2 O 3 , Er 2 O 3 and CuO, and they were wet-mixed in an agate mortar, put in a crucible, pre-baked at 950 ° C. for 12 hours, taken out of the furnace, and then pulverized again. 1,00
It was carried out by pressing at a pressure of 0 kg / cm 2 into pellets and sintering in a furnace at 950 ° C. for 6 hours.
得られた焼結物は、Ｘ線回折により酸素欠損ペロブス
カイト型結晶構造を有することが確認された。The obtained sintered product was confirmed by X-ray diffraction to have an oxygen-deficient perovskite crystal structure.
この焼成物について、超伝導臨界温度Tc、転移温度幅
△Tc、臨界電流密度Icを測定した結果を第２表に示す。Table 2 shows the results of measuring the superconducting critical temperature Tc, transition temperature width ΔTc, and critical current density Ic of this fired product.
比較例３及び4. 実施例２と同様にして、x:y:z＝2:1:0のバリウム−ラ
ンタン−銅−酸素系組成物（比較例３）及び、x:y:z＝
2:0:1のバリウム−エルビウム−銅−酸素系組成物（比
較例４）を調製した。 Comparative Examples 3 and 4. Similar to Example 2, x: y: z = 2: 1: 0 barium-lanthanum-copper-oxygen based composition (Comparative Example 3) and x: y: z =
A 2: 0: 1 barium-erbium-copper-oxygen composition (Comparative Example 4) was prepared.
比較例３及び比較例４の各々の試料について超伝導臨
界温度Tc、転移温度幅ΔTc、臨界電流密度Icを測定した
結果を第２表に示す。Table 2 shows the results of measuring the superconducting critical temperature Tc, the transition temperature width ΔTc, and the critical current density Ic of each of the samples of Comparative Example 3 and Comparative Example 4.
第１表及び第２表の結果は、本発明の超伝導性材料が
従来のものに比し極めて大きな臨界電流密度を実現する
ことができたことを実証するものである。The results in Tables 1 and 2 demonstrate that the superconducting material of the present invention was able to achieve a significantly higher critical current density than the conventional ones.
Claims (1)
酸素欠損ペロブスカイト型結晶構造を有することを特徴
とする超伝導性材料（式中ＭはＹ、Sc、La及びLuの群か
ら選択される少なくとも１種の非磁性希土類金属、Ｎは
Yb、Tm、Er、Ho、Dy、Gd及びSmの群から選択される少な
くとも１種の磁性金属であり、ｘは１〜３、ｙ及びｚは
各々0.01〜５、ｕは０〜３である。）。1. A composition of the general formula BaxMyNzCu 3 O 9-u ,
A superconducting material having an oxygen-deficient perovskite type crystal structure (wherein M is at least one non-magnetic rare earth metal selected from the group of Y, Sc, La and Lu, and N is
It is at least one kind of magnetic metal selected from the group of Yb, Tm, Er, Ho, Dy, Gd and Sm, x is 1 to 3, y and z are 0.01 to 5 and u is 0 to 3 respectively. . ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62069954A JP2533108B2 (en) | 1987-03-24 | 1987-03-24 | Superconducting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62069954A JP2533108B2 (en) | 1987-03-24 | 1987-03-24 | Superconducting material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63236712A JPS63236712A (en) | 1988-10-03 |
| JP2533108B2 true JP2533108B2 (en) | 1996-09-11 |
Family
ID=13417556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62069954A Expired - Lifetime JP2533108B2 (en) | 1987-03-24 | 1987-03-24 | Superconducting material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2533108B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0283620A1 (en) | 1987-03-25 | 1988-09-28 | Semiconductor Energy Laboratory Co., Ltd. | Superconducting ceramics |
| JPS63242922A (en) * | 1987-03-30 | 1988-10-07 | Sumitomo Electric Ind Ltd | Superconducting material |
| JPS63252952A (en) * | 1987-04-08 | 1988-10-20 | Kazuo Fueki | Superconducting ceramic |
| JP2577380B2 (en) * | 1987-04-15 | 1997-01-29 | 新技術事業団 | Superconductive material |
| JPS6445766A (en) * | 1987-08-13 | 1989-02-20 | Sumitomo Electric Industries | Superconducting material and production thereof |
| JPS6445765A (en) * | 1987-08-13 | 1989-02-20 | Sumitomo Electric Industries | Superconducting material and production thereof |
| JPH01264957A (en) * | 1988-04-13 | 1989-10-23 | Semiconductor Energy Lab Co Ltd | Superconducting material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63230525A (en) * | 1987-03-18 | 1988-09-27 | Shoji Tanaka | Superconductive material |
| JPS63230524A (en) * | 1987-03-18 | 1988-09-27 | Kazuo Fueki | Superconductive material |
| JPS63236218A (en) * | 1987-03-23 | 1988-10-03 | Nippon Telegr & Teleph Corp <Ntt> | Superconductive wire |
-
1987
- 1987-03-24 JP JP62069954A patent/JP2533108B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63236712A (en) | 1988-10-03 |
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