JPH01153518A - Oxide superconductor and production thereof - Google Patents
Oxide superconductor and production thereofInfo
- Publication number
- JPH01153518A JPH01153518A JP62308632A JP30863287A JPH01153518A JP H01153518 A JPH01153518 A JP H01153518A JP 62308632 A JP62308632 A JP 62308632A JP 30863287 A JP30863287 A JP 30863287A JP H01153518 A JPH01153518 A JP H01153518A
- Authority
- JP
- Japan
- Prior art keywords
- oxide superconductor
- nitrogen
- producing
- oxide
- superconductor according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910052788 barium Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 230000002950 deficient Effects 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 claims abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 abstract description 3
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 2
- 229910052691 Erbium Inorganic materials 0.000 abstract description 2
- 229910052693 Europium Inorganic materials 0.000 abstract description 2
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 2
- 229910052689 Holmium Inorganic materials 0.000 abstract description 2
- 229910052765 Lutetium Inorganic materials 0.000 abstract description 2
- 229910052772 Samarium Inorganic materials 0.000 abstract description 2
- 229910052775 Thulium Inorganic materials 0.000 abstract description 2
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- 206010021143 Hypoxia Diseases 0.000 abstract 1
- 229910052779 Neodymium Inorganic materials 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229910052706 scandium Inorganic materials 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000010949 copper Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- UUXFWHMUNNXFHD-UHFFFAOYSA-N barium azide Chemical compound [Ba+2].[N-]=[N+]=[N-].[N-]=[N+]=[N-] UUXFWHMUNNXFHD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052720 vanadium 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】
［発明の目的］
（産業上の利用分野）
本発明は酸化物超電導体に係り、特に臨界温度の高い酸
化物超電導体及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to an oxide superconductor, and particularly to an oxide superconductor having a high critical temperature and a method for producing the same.
（従来の技術）
近年、Ｂａ−Ｌａ−Ｃｕ−０系の層状ペロブスカイト型
酸化物が高い臨界温度を有する可能性のあることが発表
されて以来、各所で酸化物超電導体の研究が行な”われ
ている（Ｚ、Ｐｈｙｓ、Ｂ Ｃｏｎｄｅｎｓｅｄ Ｍａ
ｔｔｅｒ ８４゜ｐ、１８９−１９３（１９８Ｂ））。(Prior art) In recent years, it has been announced that layered perovskite oxides based on Ba-La-Cu-0 may have a high critical temperature, and since then, research on oxide superconductors has been conducted in various places. Condensed Ma
tter 84°p, 189-193 (198B)).
その中でもＹ−Ｂａ−Ｃｕ−０系に代表される酸素欠陥
を有する欠陥ペロブスカイト型（ＡＢ ＣＯ型）の酸
化物超電導体は、Ｔｃ２８７−δ
が９０に以上と液体窒素以上の高い温度を示すため非常
に有望な材料である（Ｐｈｙｓ、Ｒｅｖ、Ｌｅｔｔ、ｖ
ｏｌ、５８Ｎｏ、９．ｐ９０８−９１０（１９８７））
。Among these, defective perovskite type (AB CO type) oxide superconductors with oxygen vacancies, such as the Y-Ba-Cu-0 system, exhibit a Tc287-δ of 90 or higher, which is higher than liquid nitrogen. It is a very promising material (Phys, Rev, Lett, v
ol, 58 No. 9. p908-910 (1987))
.
（発明が解決しようとする問題点）
この様にペロブスカイト型の酸化物超電導体は前述の如
く非常に有望な材料であるが、より高い臨界温度（Ｔｅ
）への要求は大なるものである。(Problems to be solved by the invention) As mentioned above, perovskite-type oxide superconductors are very promising materials, but they have a higher critical temperature (Te
) is in great demand.
本発明はこの様な問題点を解決するためになされたもの
であり、臨界温度が高い酸化物超電導体を得ることを目
的としてなされたものである。The present invention has been made to solve these problems, and has been made for the purpose of obtaining an oxide superconductor with a high critical temperature.
［発明の構成］
（問題点を解決するための手段及び作用）本発明は、Ｌ
ｎ元素（ＬｎはＹ 、 Ｌａ 、 ９ａ 、 Ｎｄ 、
Ｓｍ 、 Ｅｕ 、 Ｇｄ 。[Structure of the invention] (Means and effects for solving the problems) The present invention is based on L
n element (Ln is Y, La, 9a, Nd,
Sm, Eu, Gd.
Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ等の希土類元素の
少なくとも一種）、ＡＥ元素（Ｂａ、Ｃａ及びＳｒの少
なくとも一種）及びＣｕを主成分とする酸化物超電導体
において、構成成分として窒素を含有する酸化物超電導
体である。すなわち本発明は従来より研究されているＬ
ｎ−ＡＥ−Ｃｕ−０系の酸化物超電導体の構成元素であ
る酸素の一部を窒素で置換したことを特徴とするもので
ある。In an oxide superconductor whose main components are at least one of rare earth elements such as Dy, Ho, Er, Tm, Yb, and Lu), an AE element (at least one of Ba, Ca, and Sr), and Cu, nitrogen is used as a constituent component. It is an oxide superconductor containing. That is, the present invention is based on L
It is characterized in that a part of oxygen, which is a constituent element of the n-AE-Cu-0-based oxide superconductor, is replaced with nitrogen.
本発明の酸化物超電導体は、例えば以下に示す製造方法
により得ることができる。The oxide superconductor of the present invention can be obtained, for example, by the manufacturing method shown below.
Ｙ、Ｃｕ、Ｂａ等の酸化物超電導体の構成元素を十分混
合する。混合の際にはＹ Ｏ、Ｂａｄ、Ｃｕ０等の酸
化物を原料として用いることができる。Constituent elements of the oxide superconductor, such as Y, Cu, and Ba, are thoroughly mixed. At the time of mixing, oxides such as Y 2 O, Bad, Cu0, etc. can be used as raw materials.
また、これらの酸化物のほかに、焼成後酸化物に転化す
る炭酸塩、水酸化物等の化合物を用いてもよい。さらに
は共沈法等で得たしゅう酸塩等を用いても良い。ペロブ
スカイト型酸化物超電導体を構成する元素は、基本的に
化学量論比の組成となるように混合するが、多少ずれて
いても構わない。In addition to these oxides, compounds such as carbonates and hydroxides that are converted into oxides after firing may be used. Furthermore, oxalate obtained by a coprecipitation method or the like may also be used. The elements constituting the perovskite-type oxide superconductor are basically mixed so as to have a stoichiometric composition, but there may be a slight deviation.
例えばＹ−Ｂａ−Ｃｕ−０系ではＹｌｍｏｌに対しＢａ
２ ｍｏｌ、Ｃｕ３ ｍｏｌが標準組成であるが、実用
上は、Ｙ １ｍｏｌに対し、Ｂａ２±０．８ ｍｏｌ
、 Ｃｕ３±０．２ ｍｏｌ程度のずれは問題ない。ま
た製造上の問題、例えば焼結性等を考慮して、原料とし
ては上記範囲を更゛に越える比率での混合（例えばＣｕ
を３±０．４ ｍｏｌ等）も構わない。これは主相とし
てこの様ないわゆるｌ：２：３の組成の物が生じていれ
ば良いためであり、超電導特性が得られる限り、異相の
存在をさまたげるものではないからである。For example, in the Y-Ba-Cu-0 system, Ba
The standard composition is 2 mol, Cu3 mol, but in practice, Ba2 ± 0.8 mol is used for 1 mol of Y.
, A deviation of about Cu3±0.2 mol is not a problem. In addition, in consideration of manufacturing problems such as sinterability, the raw materials are mixed at a ratio that exceeds the above range (for example, Cu
(3±0.4 mol, etc.) is also acceptable. This is because it is sufficient that the main phase has such a so-called l:2:3 composition, and as long as superconducting properties are obtained, the existence of a different phase is not hindered.
前述の原料を混合した後、仮焼・粉砕し所望の形状に成
形した後、９３０−１０００℃程度で焼成する。After mixing the above raw materials, they are calcined and pulverized to form a desired shape, and then fired at about 930-1000°C.
仮焼は必ずしも必要ではない。焼成・仮焼は十分な酸素
が供給できるような酸素含有雰囲気、例えば大気フロー
中等で行なうことが好ましい。Calcining is not necessarily necessary. Firing and calcination are preferably carried out in an oxygen-containing atmosphere where sufficient oxygen can be supplied, such as in an atmospheric flow.
本発明の特徴は窒素の添加・含有であるが、例えば窒素
ガス中焼結等の手段では、焼結体に窒素を導入してＴｃ
を向上するという効果をあげることは困難である。本発
明では酸化物超電導体中に窒素を導入する方法として、
少なくとも原料の一部を窒素含有化合物の形態で添加す
る。例えばＬｎ元素の窒化物、硝酸銅（無水硝酸銅が好
ましい）、アジ化バリウム等のアジ化合物等が窒素含有
化合物としてあげることができる。この中でアジ化バリ
ウムなどのアジ化合物は特に有効である。A feature of the present invention is the addition/containment of nitrogen. For example, by means such as sintering in nitrogen gas, nitrogen is introduced into the sintered body and Tc
It is difficult to achieve the effect of improving In the present invention, as a method for introducing nitrogen into an oxide superconductor,
At least a portion of the raw material is added in the form of a nitrogen-containing compound. Examples of nitrogen-containing compounds include nitrides of the Ln element, copper nitrate (anhydrous copper nitrate is preferred), and azide compounds such as barium azide. Among these, azide compounds such as barium azide are particularly effective.
これらの窒素含を化合物は、従来用いていた酸化物の一
部を置換する形で秤量して混合する。例えばＹ：Ｂａ：
Ｃｕ＝ｌ：２：３の標準組成比で混合する場合を想定す
る。通常、Ｙ Ｏ、Ｂａｄ、ＣｕＯをそれぞれ、０．
５ｍｏｌ、２ｍｏ Ｉ、３ｍｏｌ用意するわけであるが
、Ｙｌ（原子比）に対し２の窒素というときには、Ｂａ
Ｏの１／３ｍｏｌをＢａ（Ｎ３）２で置換し、結局、Ｂ
ａＯを５／３ｍｏｌ、Ｂ ａ （Ｎ ３） ２を１／３
ｍｏ１とし、Ｙ２Ｏ３を０．５ｍｏ１％Ｃｕ Ｏを３０
１０１用意することになる。These nitrogen-containing compounds are weighed and mixed in such a manner that they replace a portion of the oxides conventionally used. For example, Y:Ba:
Assume that Cu is mixed at a standard composition ratio of 2:3. Usually, YO, Bad, and CuO are each 0.
5 mol, 2 mo I, and 3 mol are prepared, but when 2 moles of nitrogen are used for Yl (atomic ratio), Ba
1/3 mol of O was replaced with Ba(N3)2, and eventually B
5/3 mol of aO, 1/3 of B a (N 3) 2
mo1, Y2O3 is 0.5mo1%CuO is 30
101 will be prepared.
この様な原料を焼結することにより、Ｔｃが向上した酸
化物超電導体を得ることができる。By sintering such raw materials, an oxide superconductor with improved Tc can be obtained.
なお、このような窒素含有化合物の混合量は、ＬｎＡＥ
２Ｃｕ３ＮｘＯ７−６−ｘ（δは酸素欠陥を表わす）で
表わしたとき、Ｘ≦４の窒素を含有するように、酸化物
又は焼成により酸化物となる化合物と窒素含有化合物を
混合することが望ましい。In addition, the mixing amount of such a nitrogen-containing compound is LnAE
It is desirable to mix an oxide or a compound that becomes an oxide upon firing with a nitrogen-containing compound so that when expressed as 2Cu3NxO7-6-x (δ represents an oxygen defect), X≦4 nitrogen is contained.
僅かの混合で窒素添加の効果は生じるが、Ｘ≧１でＴｃ
向上の効果が顕著となる。また多量の混合はＴｃ向上の
効果が得られず、実用上は１≦ｘ≦３程度が好ましい。The effect of nitrogen addition occurs with a small amount of mixing, but when X≧1, Tc
The improvement effect becomes noticeable. In addition, if a large amount is mixed, the effect of improving Tc cannot be obtained, and practically, it is preferable that about 1≦x≦3.
焼結は前述のような方法で行なえば良い。しかしながら
、２００−４００℃の間は例えば４０℃／Ｈ以下程度以
下部速度でゆっくり昇温することが望ましい。Sintering may be performed by the method described above. However, between 200 and 400°C, it is desirable to slowly raise the temperature at a rate of, for example, 40°C/H or less.
この様な昇温はＴｃの向上に有効である。Such a temperature increase is effective in improving Tc.
所望の形状に焼成した後、酸素中で加熱処理することに
より、超電導特性を向上することができる。この加熱処
理は通常、８００−９８０℃程度である。After firing into a desired shape, the superconducting properties can be improved by heat-treating in oxygen. This heat treatment is usually about 800-980°C.
これは焼結後の徐冷工程で実施しても良い。またプラズ
マ酸化法を用いれば、例えば２００℃以下程度の低温で
の処理でも、十分な酸素の供給を行なうことができる。This may be carried out in the slow cooling step after sintering. Furthermore, if a plasma oxidation method is used, sufficient oxygen can be supplied even during processing at a low temperature of about 200° C. or lower, for example.
この様にして得られた酸化物超電導体は酸素欠陥δを有
するＬｎＢａ Ｃｕ３０．、（δは通常１以下）の酸
素欠陥型ペロブスカイト構造となり、Ｎ元素は０元素を
置換したかたちで存在していると考えられる。The oxide superconductor thus obtained is LnBa Cu30. , (δ is usually 1 or less), and an oxygen-deficient perovskite structure is formed, and it is thought that the N element exists in the form of substituting 0 element.
また上述の粉末焼結に限らず、蒸着法、スパッタリング
法、ＣＶＤ法などの方法による膜状の酸化物超電導体を
形成することもできる。更に酸化物超電導体ペーストを
用いたスクリーン印刷法、ゾル・ゲル法等を用いての製
造もできる。更に金属管等のシース材を用いての線材化
、溶湯急冷法を用いての線材化等も可能である。In addition to the powder sintering described above, a film-like oxide superconductor can also be formed by a method such as a vapor deposition method, a sputtering method, or a CVD method. Furthermore, it can also be manufactured using a screen printing method using an oxide superconductor paste, a sol-gel method, or the like. Furthermore, it is also possible to make a wire using a sheath material such as a metal tube, or to make a wire using a molten metal quenching method.
なお本発明酸化物超電導体ではＢａをＳｒ、Ｃａの少な
くとも一種で置換することができ、この様な置換によっ
ても臨界電流密度を向上することができる。この効果は
０．０１ｍｏ１％以上で顕著となるが、実用上は８０ｓ
＋ｏ１％以下、さらには２０ＩＩｌｏ１％以下程度が好
ましい。またＣｕ元素の一部を更にＴＩ 、Ｖ、Ｃｒ、
Ｆｅ＋Ｇｏ。In the oxide superconductor of the present invention, Ba can be replaced with at least one of Sr and Ca, and such substitution can also improve the critical current density. This effect becomes noticeable at 0.01 mo1% or more, but in practical use
+o1% or less, more preferably about 20IIlo1% or less. In addition, a part of the Cu element is further added to TI, V, Cr,
Fe+Go.
旧４ｎ等で置換しても良い。この置換も超電導特性を損
なわない程度で、実用上は２Ｄｍｏ１％以下程度までで
ある。またＬｎ元素を二種以上含有するのも、臨界電流
密度の向上には有効である。更にＦの添加など、主体と
なる超電導体の基本的性質をかえない範囲での諸元素の
添加は超電導特性を低下せしめないかぎり構わない。It may be replaced with the old 4n or the like. This substitution is also to the extent that it does not impair the superconducting properties, and in practice it is limited to about 2Dmo1% or less. Furthermore, containing two or more types of Ln elements is also effective in improving the critical current density. Furthermore, addition of various elements, such as the addition of F, within a range that does not change the basic properties of the main superconductor may be added as long as it does not deteriorate the superconducting properties.
（実施例） 以下に本発明の詳細な説明する。(Example) The present invention will be explained in detail below.
実施例−１
Ｙ Ｏ、Ｂ ａ Ｏ，Ｂ ａ （Ｎａ ） ２及びＣ
ｕＯを、それぞれ、１１．２９ｇ、３１．５８ｇ、７．
ａ８ｇ、２３．８６ｇ （モル比で０．５：５／３：１
／３：３）用意し、十分混合した。この混合原料を成形
した後、２００−４００℃を６時間かけて昇温し、次い
で１ 、５１１をかけて９７０℃に昇温し、９−１０時
間焼結した。Example-1 Y O, B a O, B a (Na) 2 and C
uO, 11.29 g, 31.58 g, 7.
a8g, 23.86g (molar ratio 0.5:5/3:1
/3:3) was prepared and thoroughly mixed. After molding this mixed raw material, the temperature was raised to 200-400°C over 6 hours, then heated to 970°C over 1,511°C, and sintered for 9-10 hours.
この酸化物超電導体の超電導特性を調べたところ、臨界
温度はＴｃ＝１４９にと非常に優れたものであった。な
お第１図に、電気抵抗−温度特性曲線図を示す。また液
体窒素温度でのマイスナー効果も確認された。When the superconducting properties of this oxide superconductor were investigated, it was found that the critical temperature was extremely excellent at Tc=149. Note that FIG. 1 shows an electrical resistance-temperature characteristic curve diagram. The Meissner effect was also confirmed at liquid nitrogen temperature.
またＢａ（Ｎ３）２による置換量を変化させＬｎＡＥ２
Ｃｕｓ Ｎｘ０７−δ−。In addition, by changing the amount of substitution with Ba(N3)2, LnAE2
Cus Nx07-δ-.
（δは酸素欠陥を表わす）
で表わしたときのＸをふったところ、ｘｍ２近傍ををピ
ーク（前述の実施例の場合に相当）にしてＴｃ向上の効
果が見られた。(δ represents an oxygen defect) When X was subtracted, an effect of improving Tc was observed with a peak near xm2 (corresponding to the case of the above-mentioned example).
なおこの効果はアジ化合物を用いた場合に顕著であり、
無水硝酸銅を用いた場合アジ化合物はど顕著な効果は見
られなかった。なお、ＢａＯを用いたほうが、Ｂ ａ
ＣＯａを用いた場合より、良好の様である。This effect is remarkable when using an azide compound,
When anhydrous copper nitrate was used, no significant effect was observed with the azide compound. Note that it is better to use BaO because Ba
This seems to be better than when COa is used.
この実施例ではＬｎ元素としてＹ、ＡＥ元素としてＢａ
を用いた場合のみを示したが、他の元素でも同様の効果
が認められた。In this example, Y is used as the Ln element, and Ba is used as the AE element.
Although only the case where 2 was used was shown, similar effects were observed with other elements as well.
［発明の効果］
以上説明したように本発明によれば、臨界温度が高いＹ
−１３ａ−Ｃｕ−０系等の酸化物超電導体を得ることが
でき、工業上寄与すること大である。[Effects of the Invention] As explained above, according to the present invention, Y having a high critical temperature
It is possible to obtain oxide superconductors such as -13a-Cu-0, which will greatly contribute to industry.
第１図は、電気抵抗−温度特性曲線図。 代理人 弁理士 則 近 憲 佑 FIG. 1 is an electrical resistance-temperature characteristic curve diagram. Agent: Patent Attorney Noriyuki Chika
Claims (16)
、ＡＥ元素（Ｂａ，Ｃａ及びＳｒの少なくとも一種）及
びＣｕを主成分とする酸化物超電導体において、構成成
分として窒素を含有したことを特徴とする酸化物超電導
体。(1) Ln element (Ln is at least one rare earth element)
, an oxide superconductor containing nitrogen as a constituent component, the oxide superconductor containing an AE element (at least one of Ba, Ca, and Sr) and Cu as main components.
１：２：３の割合で含有することを特徴とする特許請求
の範囲第１項記載の酸化物超電導体。(2) The oxide superconductor according to claim 1, which contains Ln element, AE element, and Cu in an atomic ratio of substantially 1:2:3.
とする特許請求の範囲第１項乃至第２項記載の酸化物超
電導体。(3) The oxide superconductor according to claim 1 or 2, wherein the Ln element is Y and the AE element is Ba.
欠陥を表わす）で表わされる酸素欠陥型ペロブスカイト
構造を有することを特徴とする特許請求の範囲第１項乃
至第３項記載の酸化物超電導体。(4) The oxide superconductor according to claims 1 to 3, which has an oxygen-deficient perovskite structure represented by LnAE_2Cu_3O_7_-_δ (δ represents an oxygen defect).
であり、酸素の一部を置換した形で存在することを特徴
とする特許請求の範囲第１項乃至第４項記載の酸化物超
電導体。(5) The nitrogen content according to claims 1 to 4 is characterized in that the atomic ratio of nitrogen is 4 or less per 1 of the Ln element, and the nitrogen content is present in a form in which oxygen is partially substituted. Oxide superconductor.
、ＡＥ元素（Ｂａ，Ｃａ及びＳｒの少なくとも一種）及
びＣｕを主成分とする酸化物超電導体の製造方法におい
て、原料の少なくとも一部を窒素含有化合物としたこと
を特徴とする酸化物超電導体の製造方法。(6) Ln element (Ln is at least one kind of rare earth element)
, a method for producing an oxide superconductor containing AE elements (at least one of Ba, Ca and Sr) and Cu as main components, characterized in that at least a part of the raw material is a nitrogen-containing compound. Production method.
とを特徴とする特許請求の範囲第６項記載の酸化物超電
導体の製造方法。(7) The method for producing an oxide superconductor according to claim 6, characterized in that an azide compound is used as the nitrogen-containing compound.
を用いたことを特徴とする特許請求の範囲第７項記載の
酸化物超電導体の製造方法。(8) The method for producing an oxide superconductor according to claim 7, wherein an azide compound of an AE element is used as the nitrogen-containing compound.
用いたことを特徴とする特許請求の範囲第８項記載の酸
化物超電導体の製造方法。(9) The method for producing an oxide superconductor according to claim 8, characterized in that Ba(N_3)_2 is used as the nitrogen-containing compound.
用いたことを特徴とする特許請求の範囲第６項記載の酸
化物超電導体の製造方法。(10) The method for manufacturing an oxide superconductor according to claim 6, characterized in that an anhydrous nitrate of Cu is used as the nitrogen-containing compound.
により酸化物となる化合物及び窒素含有化合物を混合・
成形した後、焼結することを特徴とした特許請求の範囲
第６項乃至第１０項記載の酸化物超電導体の製造方法。(11) Mixing oxides of Ln elements, AE elements, and Cu, or compounds that become oxides by firing, and nitrogen-containing compounds.
The method for manufacturing an oxide superconductor according to any one of claims 6 to 10, characterized in that the oxide superconductor is sintered after being molded.
により酸化物となる化合物及び窒素含有化合物を混合・
成形した後、少なくとも２００−４００℃の間を４０℃
／以下の昇温速度で加熱した後、焼結することを特徴と
した特許請求の範囲第６項乃至第１１項記載の酸化物超
電導体の製造方法。(12) Mixing oxides of Ln element, AE element, and Cu, or compounds that become oxides by firing, and nitrogen-containing compounds.
After molding, at least 40℃ between 200-400℃
12. The method for producing an oxide superconductor according to claims 6 to 11, wherein the oxide superconductor is heated at a temperature increase rate of / or less and then sintered.
なうことを特徴とした特許請求の範囲第６項乃至第１２
項記載の酸化物超電導体の製造方法。(13) Claims 6 to 12, characterized in that the sintering is performed at a temperature range of 940-1000°C.
A method for producing an oxide superconductor as described in Section 1.
ｘ（δは酸素欠陥を表わす）で表わしたとき、ｘ≦４の
窒素を含有するように、酸化物又は焼成により酸化物と
なる化合物と窒素含有化合物を混合することを特徴とし
た特許請求の範囲第６項乃至第１３項記載の酸化物超電
導体の製造方法。(14) LnAE_2Cu_3N_xO_7_δ_-_
A patent claim characterized in that an oxide or a compound that becomes an oxide upon calcination and a nitrogen-containing compound are mixed so that x≦4 nitrogen is contained when expressed by x (δ represents an oxygen defect). A method for producing an oxide superconductor according to items 6 to 13.
範囲第１４項記載の酸化物超電導体の製造方法。(15) The method for producing an oxide superconductor according to claim 14, characterized in that 1≦x≦3.
徴とする特許請求の範囲第６項乃至第１５項記載の酸化
物超電導体の製造方法。(16) The method for producing an oxide superconductor according to claims 6 to 15, wherein the Ln element is Y and the AE element is Ba.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62308632A JPH01153518A (en) | 1987-12-08 | 1987-12-08 | Oxide superconductor and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62308632A JPH01153518A (en) | 1987-12-08 | 1987-12-08 | Oxide superconductor and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01153518A true JPH01153518A (en) | 1989-06-15 |
Family
ID=17983387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62308632A Pending JPH01153518A (en) | 1987-12-08 | 1987-12-08 | Oxide superconductor and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01153518A (en) |
-
1987
- 1987-12-08 JP JP62308632A patent/JPH01153518A/en active Pending
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