JPH0437605A - Oxide superconducting material and its production - Google Patents
Oxide superconducting material and its productionInfo
- Publication number
- JPH0437605A JPH0437605A JP2139260A JP13926090A JPH0437605A JP H0437605 A JPH0437605 A JP H0437605A JP 2139260 A JP2139260 A JP 2139260A JP 13926090 A JP13926090 A JP 13926090A JP H0437605 A JPH0437605 A JP H0437605A
- Authority
- JP
- Japan
- Prior art keywords
- starting materials
- oxalates
- nitrates
- carbonates
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001301 oxygen Substances 0.000 claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 239000007858 starting material Substances 0.000 claims abstract description 15
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 13
- 150000002823 nitrates Chemical class 0.000 claims abstract description 13
- 150000003891 oxalate salts Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010304 firing Methods 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- 229910002480 Cu-O Inorganic materials 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract 1
- 230000007812 deficiency Effects 0.000 abstract 1
- 238000009877 rendering Methods 0.000 abstract 1
- 239000002887 superconductor Substances 0.000 description 17
- 239000010949 copper Substances 0.000 description 12
- 238000005245 sintering Methods 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 and oxides of La Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid 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
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
（発明の属する技術分野）
本発明は新しい超伝導材料とその製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Technical field to which the invention pertains) The present invention relates to a new superconducting material and a method for producing the same.
（従来の技術および開門点）
従来、Ｌａ２ＣａＣｕ２０６や
Ｌａ２ＳｒＣｕｚ○６などの２−１−２−６組成化合物
は、他の銅酸化物超伝導体と同様、ＣｕＯ２面を有する
にもかかわらず、超伝導性を示さなかった（例えば、１
Ｂ、Ｔｏｒｒａｎｃｅ他： Ｐｈｙ、 Ｒｅｖ、 Ｌｅ
ｔｔ、、 ６０（１９８８）５４２、土倉：固体物理、
２３（１９８８）８０２＞。 その理由は明らかではな
いが、例えば、Ｌａ２ＣａＣｕ２０６では正孔濃度が低
すぎるか、あるいはＣｕ０２面に多くの酸素欠損があり
、ＣｕＯ２面の一様性が乱されているためであり、また
Ｌａ２ＳｒＣｕ２ｏ６では正孔濃度を増すために過剰の
酸素を注入するとその酸素はＣｕＯ２面とＣｕＯ２面の
間に入り、所々でＣ’ ｕ Ｏ２面同志が連なった構造
になるために、Ｃｕ０２面の一様性が乱されるためなど
の理由が考えられる（例えば、Ｊ、Ｋｏｎｄｏ他：工Ｐ
取祠辷」拳−５７（１９８８）４３３４）。(Prior art and opening point) Conventionally, 2-1-2-6 composition compounds such as La2CaCu206 and La2SrCuz○6 have no superconductivity despite having a CuO2 surface like other copper oxide superconductors. did not indicate gender (e.g. 1
B. Torrance et al.: Phy, Rev, Le
tt., 60 (1988) 542, Dokura: Solid State Physics,
23 (1988) 802>. The reason for this is not clear, but for example, in La2CaCu206, the hole concentration is too low, or there are many oxygen vacancies on the Cu02 surface, which disturbs the uniformity of the CuO2 surface, and in La2SrCu2o6, the hole concentration is too low. When excessive oxygen is injected to increase the pore concentration, the oxygen enters between the CuO2 planes and forms a structure in which C' u O2 planes are connected in some places, which disturbs the uniformity of the Cu02 plane. There may be reasons such as because the
``Toryaku'' Ken-57 (1988) 4334).
（発明の目的）
本発明は上述の問題点に鑑みなされたものであり、Ｌａ
２ＣａＣｕ２０６やＬａ２ＳｒＣｕ２０６において問題
となる正孔濃度の不足とＣｕＯ２面の乱れをなくして超
伝導性を発現させ、新しい超伝導材料を提供することを
目的とする。(Object of the invention) The present invention has been made in view of the above-mentioned problems.
The purpose of this invention is to eliminate the problem of insufficient hole concentration and disorder of the CuO2 surface in 2CaCu206 and La2SrCu206, to develop superconductivity, and to provide a new superconducting material.
（問題点を解決するための手段）
上記問題点を解決するため、本発明による酸化物超伝導
体では、
Ｌａ２−ｘｃａｘ＋ｙｓｒｚｃｕ２０６−δで表記され
る化学式において、０．１≦Ｘ≦１．３、−０．３≦Ｙ
≦１．０．０≦Ｚ≦１．０かつ０≦Ｙ＋ｚ≦１．５から
なる範囲の組成であることを特徴としている。(Means for Solving the Problems) In order to solve the above problems, in the oxide superconductor according to the present invention, in the chemical formula expressed as La2-xcax+ysrzcu206-δ, 0.1≦X≦1.3, −0.3≦Y
It is characterized by having a composition in the range of ≦1.0.0≦Z≦1.0 and 0≦Y+z≦1.5.
本発明は上記酸化物超伝導体を製造する方法も提供する
ものであり、Ｌａ、Ｃａ、Ｓｒのそれぞれの炭酸塩、硝
酸塩、シュウ酸塩、酸化物、Ｃｕの炭酸塩、硝酸塩、シ
ュウ酸塩、酸化物ないしは金属Ｃｕを出発原料とし、該
出発原料を混合した後、４気圧以上の酸素分圧雰囲気中
で、９００℃〜１１００℃の温度範囲で焼成することを
特徴とする。The present invention also provides a method for manufacturing the above-mentioned oxide superconductor, which includes carbonates, nitrates, oxalates, and oxides of La, Ca, and Sr, and carbonates, nitrates, and oxalates of Cu. The method is characterized in that an oxide or metal Cu is used as a starting material, and after the starting materials are mixed, they are fired in an oxygen partial pressure atmosphere of 4 atm or more at a temperature in the range of 900°C to 1100°C.
また、第二の本発明による酸化物超伝導体の製造方法に
よれば、Ｌａ、Ｃａ、Ｓｒのそれぞれの炭酸塩、硝酸塩
、シュウ酸塩、酸化物、Ｃｕの炭酸塩、硝酸塩、シュウ
酸塩、酸化物ないしは金属Ｃｕを出発原料とし、該出発
原料を混合した後、一旦４気圧未満の酸素分圧中、９０
０℃〜１１００℃の温度範囲で焼成し、その後詰焼結体
を酸素分圧４気圧以上の雰囲気中で９００℃〜１１００
℃の温度範囲で焼鈍することを特徴とする。Further, according to the method for producing an oxide superconductor according to the second invention, carbonates, nitrates, oxalates and oxides of La, Ca and Sr, carbonates, nitrates and oxalates of Cu , an oxide or metal Cu is used as a starting material, and after mixing the starting materials, the mixture is once heated to 90°C in an oxygen partial pressure of less than 4 atm.
The packed sintered body is fired at a temperature range of 0°C to 1100°C, and then heated to a temperature of 900°C to 1100°C in an atmosphere with an oxygen partial pressure of 4 atm or more.
It is characterized by annealing in the temperature range of ℃.
本発明による酸化物超伝導体によれば、３価のＬａサイ
トの一部を２価のＣａあるいはＣａとＳｒで置換して、
Ｌａ２−ｘＣａｘ＋ｙＳｒｚＣｕ２０６−＋ｙ（０，１
≦Ｘ≦１．３、−０．３≦Ｙ≦１、Ｏ１０≦Ｚ≦１．０
かつ０≦Ｙ＋Ｚ≦１．５）で表記される組成とする。According to the oxide superconductor according to the present invention, a part of the trivalent La site is replaced with divalent Ca or Ca and Sr, so that La2-xCax+ySrzCu206-+y(0,1
≦X≦1.3, -0.3≦Y≦1, O10≦Z≦1.0
and 0≦Y+Z≦1.5).
上述の組成範囲でないとき、超伝導を示さないからであ
る。This is because superconductivity is not exhibited when the composition is not in the above-mentioned range.
本発明による第一の酸化物超伝導体の製造方法によれば
、Ｌａの炭酸塩、硝酸塩、シュウ酸塩、酸化物の一種以
上、Ｃａの炭酸塩、硝酸塩、シュウ酸塩、酸化物の一種
以上、Ｓｒの炭酸塩、硝酸塩、シュウ酸塩、酸化物の一
種以上、Ｃｕの炭酸塩、硝酸塩、シュウ酸塩、酸化物、
金属Ｃｕの一種以上を出発原料とし、酸素分圧４気圧以
上の雰囲気で、加熱焼成する。このように、酸素分圧４
気圧以上の高圧酸素中で焼成あるいは焼鈍処理をするこ
とにより、正孔濃度を増加させ、超伝導体にすることが
できる。すなわち、本発明の酸化物超伝導体では上述の
高圧酸素中での焼成や焼鈍により、酸素欠損によるＣｕ
０２面の乱れや酸素原子同志の結合の不連続性をなくし
、−様なＣｕＯ２を形成したことを特徴とする。According to the first method for producing an oxide superconductor according to the present invention, one or more of carbonates, nitrates, oxalates, and oxides of La, carbonates, nitrates, oxalates, and one or more oxides of Ca. Above, one or more types of Sr carbonates, nitrates, oxalates, oxides, Cu carbonates, nitrates, oxalates, oxides,
One or more types of metal Cu are used as starting materials, and heated and fired in an atmosphere with an oxygen partial pressure of 4 atm or more. In this way, the oxygen partial pressure 4
By performing firing or annealing treatment in high-pressure oxygen above atmospheric pressure, the hole concentration can be increased and the material can be made into a superconductor. That is, in the oxide superconductor of the present invention, Cu due to oxygen vacancies is removed by firing or annealing in the above-mentioned high-pressure oxygen.
It is characterized by eliminating disorder in the 02 plane and discontinuity in the bonds between oxygen atoms, forming --like CuO2.
このときの焼成温度は９００°Ｃ〜１１００°Ｃの温度
範囲であるが、９００°Ｃ未満であると、焼結体になら
ない恐れがあるとともに、十分酸素を押し込むことがで
きない恐れがある。一方１１００℃を越えると焼結成分
の一部が溶融し、良好な焼結体が得られない恐れがある
。The firing temperature at this time is in the range of 900°C to 1100°C, but if it is less than 900°C, there is a risk that the sintered body will not be obtained and oxygen will not be able to be pushed in sufficiently. On the other hand, if the temperature exceeds 1100° C., a part of the sintered components may melt, and a good sintered body may not be obtained.
本発明による第二の製造方法によれば、上記第一の製造
方法を実施する前に、４気圧未満の酸素分圧雰囲気にお
いて、焼結体を形成する。これは大量生産を行なう場合
に、取り扱いを簡便にするためである。この第一の焼結
工程において、焼結温度が９００℃未満であると、焼結
体にならない恐れがあり、１１００°Ｃを越えると、焼
結成分の一部が溶融し、良好な焼結体が得られない恐れ
がある。According to the second manufacturing method of the present invention, a sintered body is formed in an oxygen partial pressure atmosphere of less than 4 atmospheres before carrying out the first manufacturing method. This is to simplify handling when mass production is performed. In this first sintering step, if the sintering temperature is less than 900°C, there is a risk that the sintered body will not be formed, and if it exceeds 1100°C, a part of the sintered components will melt, resulting in good sintering. There is a risk that you may not be able to get the body.
この第一の焼結工程で、焼結させた焼結体を、さらに４
気圧以上の酸素分圧雰囲気中で、９００℃〜１１００℃
の温度範囲で加熱する。９００℃未満であると、十分酸
素を押し込めない恐れがあり、１１００℃を越えると、
焼結成分の一部が溶融し、良好な焼結体が得られない恐
れがあるからである。In this first sintering step, the sintered body is further
900°C to 1100°C in an oxygen partial pressure atmosphere above atmospheric pressure
Heat within the temperature range. If the temperature is less than 900℃, there is a risk that oxygen cannot be pushed in sufficiently, and if it exceeds 1100℃,
This is because a part of the sintered component may melt and a good sintered body may not be obtained.
また、酸素分圧が４気圧未満であると、第一の製造方法
と同様に、酸化物超伝導体にすることが困難である。Further, if the oxygen partial pressure is less than 4 atmospheres, it is difficult to make an oxide superconductor as in the first manufacturing method.
（実施例１）
Ｌａ２０３、ＣａＣｏ３、ＳｒＣＯ２およびＣｕＯを出
発原料として、
Ｌａ１．５ｃａ１．２９ｓｒｏ、 ２ｘｃｕ２０ｂ−ａ
の組成となるよう秤量、混合した。この粉体を約Ｉｔ／
ｃｍ”の圧力でベレット状に成形し、酸素圧１気圧、３
気圧、４気圧、６気圧、８気圧の下で各々１０５０℃、
２０時間焼成した。得られた焼結体の抵抗率の温度依存
性を第１図に示す。(Example 1) Using La203, CaCo3, SrCO2 and CuO as starting materials, La1.5ca1.29sro, 2xcu20b-a
They were weighed and mixed to have the following composition. This powder is approximately It/
Formed into a pellet shape at a pressure of
1050℃ under atmospheric pressure, 4 atmospheres, 6 atmospheres, and 8 atmospheres, respectively.
It was baked for 20 hours. FIG. 1 shows the temperature dependence of the resistivity of the obtained sintered body.
第１図より、４気圧以上の酸素分圧の雰囲気中で焼成し
た試料は超伝導体となり、８気圧の酸素分圧焼成により
、７Ｃ”＝３９に、 ＴＣｚｅｒｏ＝２５にの臨界温度
を示すことがわかる。また、８気圧の酸素中焼成の試料
では、第２図に示すように、帯磁率が負となっており、
超伝導を示すことがわかる。また、この特性は、完全反
磁性と比較するとマイスナ一体積分率は約８％であり、
バルクの超伝導体であることが確認できた。さらに、粉
末Ｘ線回折による結晶構造解析の結果、第３図に示すよ
うに焼結体はほぼ単相の２−１−２−６構造を示すこと
が判明した。From Figure 1, the sample fired in an atmosphere with an oxygen partial pressure of 4 atm or more becomes a superconductor, and by firing at an oxygen partial pressure of 8 atm, it exhibits a critical temperature of 7C'' = 39 and TCzero = 25. In addition, as shown in Figure 2, in the sample fired in oxygen at 8 atm, the magnetic susceptibility is negative.
It can be seen that it exhibits superconductivity. In addition, this property has a Meissner volume fraction of approximately 8% compared to complete diamagnetism.
It was confirmed that it is a bulk superconductor. Further, as a result of crystal structure analysis by powder X-ray diffraction, it was found that the sintered body had a substantially single-phase 2-1-2-6 structure as shown in FIG.
（実施例２）
Ｌａ２０３、Ｃａ （ＮＯ３）２、Ｓｒ （ＮＯ３）２
、Ｃｕ （ＮＯ３）２を出発原料として
Ｌａｘ、 ６ｓｃａｔ、ｚ＋５Ｓｒｏ、 １ｃ＋ｃｕ２
０６−δの組成となるよう秤量、混合し、ベレット状に
プレス成形した後、大気中酸素分圧０．２気圧で、１０
５０°Ｃｌ２Ｏ時間加熱して焼結体を得た。この場合第
１図から理解できるように、酸素分圧４気圧未満では超
伝導体とならない。そこで次に、該焼結体をＡｒ８０％
、０２２０％の雰囲気下で５０気圧の圧力を印加しなが
ら１０００℃で１０時間焼鈍処理をした。(Example 2) La203, Ca (NO3)2, Sr (NO3)2
, Lax, 6scat, z+5Sro, 1c+cu2 using Cu (NO3)2 as the starting material
After weighing and mixing to give a composition of 06-δ and press-forming into a pellet shape, the mixture was heated to 10
A sintered body was obtained by heating for 50°C12O hours. In this case, as can be understood from FIG. 1, if the oxygen partial pressure is less than 4 atmospheres, it will not become a superconductor. Therefore, next, the sintered body was made of Ar80%
Annealing treatment was performed at 1000° C. for 10 hours while applying a pressure of 50 atm in an atmosphere of 0.0220%.
上記熱処理によりＴ ｃ ｅ”＝２４ Ｋの超伝導体が
得られた。A superconductor with T c e''=24 K was obtained by the above heat treatment.
（実施例３）
Ｌａ２Ｑ３、Ｃａｂ、ＣｕＯを出発原料としてＬａ１．
５Ｃａｔ、５Ｃｕ２０６−ａの組成となるよう秤量、混
合し、ベレット状にプレス成形した後、Ａｒ９８％、０
２２％、全圧１気圧の雰囲気中で、１０００°Ｃｌ２Ｏ
時間焼成し、焼結体を得た。該焼結体は超伝導性を示さ
なかったが、酸素分圧８気圧の下で、１０５０℃、２０
時間焼鈍処理をすることにより、Ｔｃ””’：８．４に
の超伝導体が得られた。(Example 3) Using La2Q3, Cab, and CuO as starting materials, La1.
After weighing and mixing to have a composition of 5Cat, 5Cu206-a and press-molding into a pellet shape, Ar98%, 0
22%, 1000°Cl2O in an atmosphere with a total pressure of 1 atm.
A sintered body was obtained by firing for a period of time. Although the sintered body did not exhibit superconductivity, it was sintered at 1050°C and 20°C under an oxygen partial pressure of 8 atm.
By performing time annealing treatment, a superconductor with Tc""': 8.4 was obtained.
（実施例４）
１、、ａ２（Ｃ２０４）３、ＣａＣＯ３、ＳｒＣＯ２、
Ｃｕを出発原料とし、
Ｌａｘ、 ６７ｃａ１．５ｓｒｏ、 １７ｃｕ２０６−
δの組成となるように秤量、混合し、プレス成形した後
、８気圧の酸素圧力の下で、酸素を５１／分の割合で流
しながら１０５０℃、２０時間焼成した。得られた焼結
体はＴｃ′Ｌｅ”＝２６．１にの超伝導体であった。こ
の場合、Ｌａ、ＣａおよびＳｒの原子の総和はＣｕ２モ
ルに対し３モルより大きいため、得られた焼結体は２−
１−２−６構造化合物にわずかのＣａＯを不純物として
含むものであった。(Example 4) 1, a2(C204)3, CaCO3, SrCO2,
Using Cu as a starting material, Lax, 67ca1.5sro, 17cu206-
After weighing and mixing so as to have a composition of δ and press-molding, they were fired at 1050° C. for 20 hours under an oxygen pressure of 8 atmospheres while flowing oxygen at a rate of 51/min. The obtained sintered body was a superconductor with Tc′Le”=26.1. In this case, since the sum of La, Ca, and Sr atoms was larger than 3 moles per 2 moles of Cu, the obtained sintered body The sintered body is 2-
The 1-2-6 structure compound contained a small amount of CaO as an impurity.
（実施例５）
その他、組成および焼成時の酸素分圧、焼成温度の異な
る各種試料について、ゼロ抵抗を示す温度Ｔｃをまとめ
て第１表に示す。(Example 5) In addition, Table 1 shows the temperature Tc at which zero resistance is exhibited for various samples having different compositions, oxygen partial pressures during firing, and firing temperatures.
なお、実施例でも示されているように、本発明の超伝導
材料の組成は（Ｌａ＋Ｃａ＋Ｓｒ）対Ｃｕの原子数の比
が厳密な意味で３：２でなくても２：１あるいは１：１
までは２−１−２−６構造組成物が主な相を形成し、超
伝導性を示すことは明らかである。As shown in the examples, the composition of the superconducting material of the present invention is such that the ratio of the number of atoms of (La+Ca+Sr) to Cu may not be 3:2 in a strict sense, but may be 2:1 or 1:1.
It is clear that the 2-1-2-6 structural composition forms the main phase and exhibits superconductivity.
Ｌａ２−ｘ
Ｃａｌ＋ｙ
ｒｚ
第１表
Ｃｕ：Ｏｒ＋−δにおける焼成条件とＴｃの関係（以下
余白）
第１表（続き）
（発明の効果）
以上説明したように、
Ｌａ２−ＸＣａ１＋ＹＳｒＺＣｕ２Ｏ６−δ（０，１≦
Ｘ≦１．３、−０．３≦Ｙ≦１．０．０≦Ｚ≦１．０か
つＯ≦Ｙ＋Ｚ≦１．５）はＴｃの最高が２６にの新しい
超伝導体であり、超伝導材料として利用できる。La2-x Cal+yrz Table 1 Relationship between firing conditions and Tc in Cu:Or+-δ (blank below) Table 1 (continued) (Effects of the invention) As explained above, La2-XCa1+YSrZCu2O6-δ(0,1 ≦
X≦1.3, -0.3≦Y≦1.0.0≦Z≦1.0 and O≦Y+Z≦1.5) is a new superconductor with a maximum Tc of 26, and is a superconductor. Can be used as a material.
第１図は仕込み組成
Ｌａｘ、 ５ｃａ１．２９ｓｒｏ、 ２１ｃｕ２０６−
δからなる焼結体で、１０５０℃、２０時間、酸素雰囲
気中で、各種の酸素分圧中で焼成した場合の抵抗率の温
度依存性を示す図、第２図は仕込み組成
Ｌａ１．５ｃａ１２９ｓｒｏ、 ２ｘｃｕ２０６−δか
らなる焼結体で、１０５０℃、２０時間、８気圧の酸素
雰囲気中で焼成した場合の直流帯磁率の温度依存性（磁
場中冷却）を示す図、第３図は仕込み組成
Ｌａ１．５ｃａ１．２９ｓｒｏ ２】ｃｕ２０６−ｖか
らなる焼結体で、１０５０℃、２０時間、８気圧の酸素
雰囲気中で焼成した場合の粉末Ｘ線回折パターンを示す
図である。Figure 1 shows the preparation composition Lax, 5ca1.29sro, 21cu206-
Figure 2 shows the temperature dependence of resistivity when a sintered body made of δ is fired at 1050°C for 20 hours in an oxygen atmosphere at various oxygen partial pressures. A diagram showing the temperature dependence of DC magnetic susceptibility (cooling in a magnetic field) when a sintered body made of 2xcu206-δ is fired at 1050°C for 20 hours in an oxygen atmosphere of 8 atm. Figure 3 shows the charging composition La1. .5ca1.29sro 2] A diagram showing a powder X-ray diffraction pattern of a sintered body made of CU206-V, which was fired at 1050° C. for 20 hours in an oxygen atmosphere of 8 atm.
Claims (3)
＿２Ｏ＿６＿−＿δで表記される化学式において、０．
１≦Ｘ≦１．３、−０．３≦Ｙ≦１．０、０≦Ｚ≦１．
０かつ０≦Ｙ＋Ｚ≦１．５からなる範囲の組成であるこ
とを特徴とする酸化物超伝導材料。(1) La_2_-_XCa_1_+_YSr_ZCu
In the chemical formula expressed as _2O_6_-_δ, 0.
1≦X≦1.3, -0.3≦Y≦1.0, 0≦Z≦1.
An oxide superconducting material characterized by having a composition in the range of 0 and 0≦Y+Z≦1.5.
シュウ酸塩、酸化物、Ｃｕの炭酸塩、硝酸塩、シュウ酸
塩、酸化物ないしは金属Ｃｕを出発原料とし、該出発原
料を混合した後、４気圧以上の酸素分圧雰囲気中で、９
００℃〜１１００℃の温度範囲で焼成することを特徴と
する酸化物超伝導材料の製造方法。(2) Carbonates and nitrates of La, Ca, and Sr,
Oxalates, oxides, Cu carbonates, nitrates, oxalates, oxides or metal Cu are used as starting materials, and after mixing the starting materials, in an oxygen partial pressure atmosphere of 4 atmospheres or more,
A method for producing an oxide superconducting material, the method comprising firing at a temperature range of 00°C to 1100°C.
シュウ酸塩、酸化物、Ｃｕの炭酸塩、硝酸塩、シュウ酸
塩、酸化物ないしは金属Ｃｕを出発原料とし、該出発原
料を混合した後、一旦４気圧未満の酸素分圧中、９００
℃〜１１００℃の温度範囲で焼成し、その後、該焼結体
を酸素分圧４気圧以上の雰囲気中で９００℃〜１１００
℃の温度範囲で焼鈍することを特徴とする酸化物超伝導
材料の製造方法。(3) Carbonates and nitrates of La, Ca, and Sr,
Oxalates, oxides, Cu carbonates, nitrates, oxalates, oxides or metal Cu are used as starting materials, and after mixing the starting materials, the mixture is heated at 900° C. in an oxygen partial pressure of less than 4 atm.
The sintered body is fired at a temperature range of 900°C to 1100°C in an atmosphere with an oxygen partial pressure of 4 atm or more.
A method for producing an oxide superconducting material, the method comprising annealing at a temperature range of °C.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS649813A (en) * | 1987-01-27 | 1989-01-13 | Agency Ind Science Techn | Superconductor and production thereof |
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1990
- 1990-05-29 JP JP2139260A patent/JP2698689B2/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS649813A (en) * | 1987-01-27 | 1989-01-13 | Agency Ind Science Techn | Superconductor and production thereof |
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| Publication number | Publication date |
|---|---|
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