JPH04114920A - Superconductive metal oxide t1-pb, ln-sr-cu-o composition - Google Patents
Superconductive metal oxide t1-pb, ln-sr-cu-o compositionInfo
- Publication number
- JPH04114920A JPH04114920A JP2226442A JP22644290A JPH04114920A JP H04114920 A JPH04114920 A JP H04114920A JP 2226442 A JP2226442 A JP 2226442A JP 22644290 A JP22644290 A JP 22644290A JP H04114920 A JPH04114920 A JP H04114920A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- superconducting
- sample
- mixture
- metal oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 229910044991 metal oxide Inorganic materials 0.000 title abstract description 7
- 150000004706 metal oxides Chemical class 0.000 title abstract description 7
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 229910002480 Cu-O Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229910052791 calcium Inorganic materials 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 229910052712 strontium Inorganic materials 0.000 abstract 1
- 229910052716 thallium Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- -1 S r COa Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 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)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
【発明の詳細な説明】
発明の背景
Ｈ，Ｍａｅｄａら、 Ｊｐｎ、 ］、 ＾ｐｐｌ
、Ｐｈｙｉ、 ２７． Ｌ２０９（１９８８）、
は、ＢＩＳｒＣａＣｕ２０．に近い組成及び約１５０
にの超伝導転移温度（ｉｕｐ＋＋ｃｏｎｄｕｃ＋ｉｎｇ
ｔｒａｎＳｉｔｉｏｎ Ｉｅｍｐｅｒａｌｕｒｅ）を有
する、Ｂ１−８ｒＣｕ−０系の超伝導酸化物を開示して
いる。[Detailed Description of the Invention] Background of the Invention H, Maeda et al., Jpn, ], ^ppl
, Phyi, 27. L209 (1988),
is BISrCaCu20. composition close to and about 150
superconducting transition temperature (iup++conduc+ing
Discloses a B1-8rCu-0 based superconducting oxide having a tranSition Iemperalure).
Ｍ、Ｔａｋａｎｏら、Ｉｐｎ、 １． Ａｐｐｐｌ
、 ｌ’「、ｙ＋、 ２７． Ｌ１０４１（１９
８ｇ）は、Ｂ１−３ｒ−Ｃａ−Ｃｕ−０系においてＢ１
を部分的にＰｂて置き換えると高Ｔｃ相の体積分率の増
加をもたらすことを開示している。M. Takano et al., Ipn. 1. Apppl
, l'", y+, 27. L1041 (19
8g) is B1 in the B1-3r-Ca-Cu-0 system.
It is disclosed that partial replacement of Pb by Pb results in an increase in the volume fraction of the high Tc phase.
Ｂｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕ＝０．７ ：Ｑ、３
：１１ １８の出発組成物が２４４時間に亘って１ｌ
ｌｉ！にて加熱された。その高Ｔｃ相は、約１１５にで
の超伝導の生起を示す。Bi:Pb:Sr:Ca:Cu=0.7 :Q, 3
:11 18 starting compositions were added to 1 liter over 244 hours.
li! heated at. The high Tc phase exhibits the onset of superconductivity at about 115.
ｚ、 ２． Ｓｈａｎｇ ら、Ｎａｔｕｒｅ ３３２．
１３８ （１９８８）、 は、公称組成ＴＩ Ｃａ
ＢａＣｕ３０９＋ｘを有する試料の、Ｔ ｌ−Ｃａ−Ｂ
ａ−Ｃｕ−０系における超伝導性を開示している。z, 2. Shang et al., Nature 332.
138 (1988), with nominal composition TI Ca
T l-Ca-B of the sample with BaCu309+x
Discloses superconductivity in the a-Cu-0 system.
Ｒ，Ｍ、ｌ１ａｘｅｎ ら、Ｐｈｙｓ、 Ｒｅｖ、
Ｌｅｆｔ、 ６０．１６５７ （１９８８）は、Ｔ ｌ
−Ｂａ−Ｃａ−Ｃｕ−０系の２つの超伝導相即ち、Ｔ１
２Ｂａ２Ｃａ２Ｃｕ３０１ｏ及びＴＩ Ｂａ Ｃａ
Ｃｕ２Ｏ３を開示している。R, M, l1axen et al., Phys, Rev.
Left, 60.1657 (1988)
- Two superconducting phases of the Ba-Ca-Cu-0 system, namely T1
2Ba2Ca2Cu301o and TI Ba Ca
Discloses Cu2O3.
Ｍ、 Ａ、 Ｓｕｂｔａｍａｎｉａｎ、米国特許「超伝
導金属酸化物Ｔ ｌ−Ｐｂ−Ｃａ−３ｒ−Ｃｕ−０組成
物、その製造方法及びその使用」、特許番号第４．８９
４．３６１号明細書は、公称式Ｔ Ｉ Ｐ ｂ 、
Ｃａ ｂＳ ｒ 。M.A. Subtamanian, U.S. Patent No. 4.89, “Superconducting Metal Oxide Tl-Pb-Ca-3r-Cu-0 Composition, Method of Preparation and Use thereof”
No. 4.361 specifies the nominal formula T I P b ,
CabSr.
Ｃ１，ＩｄＯアを有する超伝導組成物を開示し、式中、
ａは約１／１０−３／２であり、ｂは約 １〜４であり
、Ｃは約１〜３であり、ｄは約１〜５であり、ｅは約３
／１０〜１であり、及び、ｙが約１７２〜３である場合
にｘ＝ （ａ＋ｂ＋ｃ＋ｄ十ｅ＋ｙ）であり、更に、前
記組成物は少なくとも７０にの超伝導転移温度を有する
。Discloses a superconducting composition having C1,IdO, where:
a is about 1/10-3/2, b is about 1-4, C is about 1-3, d is about 1-5, and e is about 3
/10~1 and x=(a+b+c+d+y) where y is about 172~3, and the composition has a superconducting transition temperature of at least 70°C.
Ｍ、 Ａ、 Ｓｕｂｔａｍａｎｉａｎ ら、 Ｎａ
ｔｕｒｅ ２４２．２４９ （１９８８）は、Ｔｌ−Ｐ
ｂ−３ｒ−Ｃａ−Ｃｕ−０系の２つの超伝導相、即ち、
（ＴＩ Ｐｂ ）Ｓｒ２ＣａＯ，５０，５
Ｃｕ Ｏ及び（Ｔ Ｉ Ｐ ｂ ） Ｓ ｒ
２２７ ０．５０．５
Ｃａ２Ｃｕ３０９を開示し、これらの相は各々約８０Ｋ
及び約１１５にの超伝導臨界温度（ｓｕｐｅｒｃｏｎｄ
ｕｃｌｉｎｇ ｘｅ＋ｏ−＋ｅｓｉＳｔａｎｃｅ ｔｅ
ｍｐｅｒａｔｕｒｅ）を有する。M, A, Subtamanian et al., Na
ture 242.249 (1988) is Tl-P
Two superconducting phases of the b-3r-Ca-Cu-0 system, namely:
(TIPb)Sr2CaO,50,5CuO and (TIPb)Sr
227 0.50.5 Ca2Cu309, each of these phases approximately 80K
and the superconducting critical temperature of about 115
ucling xe+o-+esi Stance te
mperature).
発明の要約
本発明は、Ａがイツトリウムもしくはランタニド希土類
元素又はこれらの混合物であり、ＢがＰｂもしくはＢｉ
又はこれらの混合物であり、Ｘが約０〜０８であり、ｙ
が約θ〜０５であり、及び、Ｚが約６５〜７．５である
、公称式％式％
Ｏを有する、新規の超伝導組成物を提供する。SUMMARY OF THE INVENTION The present invention provides that A is yttrium or a lanthanide rare earth element or a mixture thereof, and B is Pb or Bi.
or a mixture thereof, where X is about 0-08, and y
is about θ˜05 and Z is about 65 to 7.5.
これらの組成物の超伝導臨界温度は、その組成に応じて
、４２Ｋから ＩＮＫの範囲内である。The superconducting critical temperature of these compositions ranges from 42 K to INK, depending on their composition.
これらの超伝導組成物は、２つの段階の熱、処理によっ
て製造される。第１段階では、Ａがイツトリウムもしく
はランタニド希土類元素又はこれらの混合物を表す時に
、適切な量のＣａＣＯ３と、Ｓ ｒ ＣＯａ と、Ｃｕ
Ｏと、Ａ−０とから成る混合物をＩｆｆ〜２０時間に亘
って８５０〜９５０℃で加熱することによって、公称前
駆体（ＣａＡ）−Ｙ Ｙ
Ｓ ｒ ２ Ｃｕ ２０２を製造する。第２段階では、
次式中でＢがｐｂもしくはＢ１又はこれらの混合物を表
す時に、式（ＴＩ Ｂ）（Ｃａ Ａ）１−ｒ
Ｘ ｂｙ ’Ｉ
Ｓ ｒ Ｃｕ ２０ Ｋに従って、適切な量のＴｌ２
Ｏ３とＢ−０とが前記第１段階から得られる公称前駆体
の中に加えられ、その後で、このＴ】含有混合物又はペ
レット化試料が、約８８０〜９１１Ｏ℃に加熱され、及
び、密封された雰囲気の中に、即ち、金のような非反応
性金属が作られ及び反応物の逃散を防ぐ密封された袋の
中で、約１〜１２時間に亘って保たれる。These superconducting compositions are produced by a two-step thermal process. In the first step, appropriate amounts of CaCO3, S r COa , Cu
The nominal precursor (CaA)-YYSr2Cu 202 is prepared by heating a mixture consisting of O and A-0 at 850-950<0>C for Iff~20 hours. In the second stage,
When B represents pb or B1 or a mixture thereof in the following formula, the formula (TI B) (Ca A) 1-r
Appropriate amount of Tl2 according to X by 'I S r Cu 20 K
O3 and B-0 are added into the nominal precursor obtained from the first stage, after which the T]-containing mixture or pelletized sample is heated to about 880-911 O<0>C and sealed. A non-reactive metal such as gold is made and kept in a sealed bag to prevent escape of reactants for about 1 to 12 hours.
発明の説明
本発明は、Ａがイツトリウムもしくはランタニド希土類
元素又はこれらの混合物であり、ＢがＰｂもしくはＢｉ
又はこれらの混合物であり、Ｘが約０−０．８であり、
ｙが約θ〜０．５であり、及び、２が約６．５〜７５で
ある、公称式％式％
Ｏを有する高温超伝導金属酸化物に係わる。DESCRIPTION OF THE INVENTION The present invention provides that A is yttrium or a lanthanide rare earth element or a mixture thereof, and B is Pb or Bi.
or a mixture thereof, where X is about 0-0.8;
The present invention relates to high temperature superconducting metal oxides having the nominal formula % O, where y is about θ ~ 0.5 and 2 is about 6.5 to 75.
Ｃａ：Ａ：Ｓｒ：Ｃｕ＝１−ｙ：ｙ：２：２の原子モル
比を有する、適量の高純度試薬である、ＣａＣ０と、Ｓ
ｒ ＣＯ３と、ＣｕＯと、Ａ−０との粉末が、例えば
乳鉢の中で摩砕することによって混合される。上記のＡ
−０金属酸化物は、Ｙ ＯＳＴ−ａ Ｏ１Ｃａ Ｏ
１Ｐ ｒ ６０ ｔ １．Ｎｄ ○ 、Ｓｍ Ｏ、Ｅ
ｕ２Ｏ３，Ｇｄ２０３、Ｔｂ４Ｏ７、Ｄｙ２Ｏ３、Ｈｏ
０−、 Ｅ ｒ ２０３−、 Ｔ ｍ ２０３−Ｙｂ
ＯもしくはＬｕ２Ｏ３又はこれらの混合物を表す。十
分に混合された混合物が約１０〜２０時間に亘って炉内
で８５０〜９５０°Ｃに加熱され、その後で、炉への供
給電力のスイッチを切ることによって炉内の温度が室温
にまで冷却される。Suitable amounts of high purity reagents CaC0 and S with an atomic molar ratio of Ca:A:Sr:Cu=1-y:y:2:2.
The powders of r CO3, CuO and A-0 are mixed, for example by grinding in a mortar. A above
-0 metal oxide is Y OST-a O1Ca O
1P r 60 t 1. Nd ○, Sm O, E
u2O3, Gd203, Tb4O7, Dy2O3, Ho
0-, E r 203-, T m 203-Yb
Represents O or Lu2O3 or a mixture thereof. The well-mixed mixture is heated in the furnace to 850-950°C for approximately 10-20 hours, after which the temperature in the furnace is cooled to room temperature by switching off the power supply to the furnace. be done.
得られた生成物が再び摩砕され、その後で、Ｔｌ：Ｐｂ
Ｂｉ：Ｃａ：Ａ：Ｓｒ：Ｃｕ＝Ｉ−ｘ：ｙ、 ：
ｌｙ ：ｙ ：２：２の原子モル比に従って、適量
のＴＩ Ｏ、ＰｂＯ及び／又はＢ１２Ｏ３が前記生成
物と混合される。次に、このＴＩ含有混合物は直接的に
加熱されてもよく、又は、この混合物は、初めにペレッ
トもしくは他の形状に成形された後で、加熱されてもよ
い。前記ＴＩ含有混合物を加熱する際の雰囲気が注意深
（調整される場合にたけ、本発明の超伝導生成物が生成
される。The product obtained is milled again, after which Tl:Pb
Bi:Ca:A:Sr:Cu=I-x:y, :
According to the atomic molar ratio of ly :y :2:2, appropriate amounts of TIO, PbO and/or B12O3 are mixed with the product. The TI-containing mixture may then be heated directly, or the mixture may be first formed into pellets or other shapes and then heated. The superconducting products of the present invention are produced if the atmosphere in which the TI-containing mixture is heated is carefully controlled.
この条件を実現する方法の１つは、金のような非反応性
金属で作られた袋又は管の中に前記混合物を封じ込める
ことである。その後で、この密封された試料が１〜１２
時間に亘って約８８０〜９８０℃に加熱される。焼結の
後は、その試料を炉から直接取り出すことが可能である
か、又は電源を切って炉が冷えるにまかせて、炉内で冷
却することが可能である。密封された前記容器を開封す
ると、黒色の超伝導試料が得られる。One way to achieve this condition is to confine the mixture in a bag or tube made of a non-reactive metal such as gold. Afterwards, this sealed sample is
It is heated to about 880-980°C over a period of time. After sintering, the sample can be removed directly from the furnace, or it can be cooled in the furnace by turning off the power and allowing the furnace to cool. When the sealed container is opened, a black superconducting sample is obtained.
実施例１
ＣａＣＯ（１，６０１ｇ）と、Ｙ２Ｏ３（０，４５２ｇ
）と、Ｓ ｒ ＣＯ３（５，９０５ｇ ）と、Ｃｕ Ｏ
（３，１８２ｇ ）との各高純度試薬（２９９，９％）
を、Ｃａ：Ｙ：Ｓ ｒ ： Ｃｕ＝ ０．８： ０．
２： ２ ＋ ２の原子モル比に従って、めのう乳鉢内
で十分に混合した。その混合物を炉内に入れ、１０時間
に亘って９２０℃に加熱し、その後で再粉砕した。次に
、Ｔ１２０３（０，５２６ｇ ）及びＰ ｂ Ｏ（０，
５１５ｇ）を、ＴＩ・Ｐ １）Ｃａ ：Ｙ：Ｓｒ
：Ｃｕ＝０．５ ：０．５ ：０．８ ＋０．２
：２：２の原子モル比に従って、か焼されたＣａＹ
−３ｒ−Ｃｕ−０混合物（２，Ｇ ｇ ）と混合した。Example 1 CaCO (1,601g) and Y2O3 (0,452g
), S r CO3 (5,905 g ), and Cu O
(3,182g) and each high purity reagent (299.9%)
, Ca:Y:Sr:Cu=0.8:0.
Mixed well in an agate mortar according to the atomic molar ratio of 2:2+2. The mixture was placed in a furnace and heated to 920° C. for 10 hours before being reground. Next, T1203 (0,526 g) and P b O (0,
515g), TI・P 1)Ca:Y:Sr
:Cu=0.5 :0.5 :0.8 +0.2
:calcined CaY according to the atomic molar ratio of 2:2
-3r-Cu-0 mixture (2,G g ).
そのＴ１含有混合物を、直径１０ ｍｍ及び厚さ約１．
５状
ｍｍの円板材の試料にペレット化した。その後で、この
ペレット試料を、機械を使って、厚さ０．０５ｍｍの４
Ｎ金箔で作られた金製の袋の中に封じ込めた。The T1-containing mixture was cut into a 10 mm diameter and approximately 1.5 mm thick.
The sample was pelletized into a 5-mm disk material sample. Afterwards, this pellet sample was machined into 0.05 mm thick 4
It was sealed in a gold bag made of N gold leaf.
その袋の中の前記試料の焼結を、流動する酸素雰囲気の
中で、３時間に亘って９５０℃で実施し、その後、炉へ
の供給電力のスイッチを切ることによって、前記試料を
室温まで冷却した。袋を炉から取り出して開封し、黒色
のペレットを得た。Sintering of the sample in the bag is carried out at 950° C. for 3 hours in a flowing oxygen atmosphere, after which the sample is brought to room temperature by switching off the power supply to the furnace. Cooled. The bag was removed from the oven and opened to yield black pellets.
第１図は、標準的な四端子法を使用して測定した、前記
焼結試料の電気抵抗の温度依存性を示す。FIG. 1 shows the temperature dependence of the electrical resistance of the sintered sample, measured using the standard four-terminal method.
１０８にの超伝導臨界温度Ｔｃ が達成された。A superconducting critical temperature Tc of 108 was achieved.
（ｚｅｒｏ）
超伝導量子干渉計（Ｓｕｐｅ＋ｅｏｎｄｕｃｔｉｎｇ
ｑｕａｎｔａｍｉｎｔｅｒｆｅｒｅｎｃｅ ｄｅｖｉｃ
ｅ （ＳＱＵＩＤ） ）によって測定された前記試料の
磁化を、第２図に示す。反磁性転移生起温度は１． ［
１８Ｋであり、これは前述の電気抵抗測定結果と一致し
ている。第３図は、前記塊状試料のＸ線回折パターンを
示す。この測定結果から、その試料の結晶相が正方晶相
に属することが示される。第３図のＸ線回（斤パターン
から、その結晶相が、格子定数ａ ＝ ０．３８０ｎｍ
及びＣ＝に、Ｉ９４ｎｍを有する２４７ｍｌｌｌｌ１１
対称の正方晶相に属することが示される。Ｐ４／ｍｍｍ
対称の回折ピークは、前記Ｘ線回折図の中に示され及び
指数表示されている。第４図は、本発明の（ＴＩ、Ｐｂ
、）（Ｃａ 、Ｙ ） Ｓ ｒ ２ Ｃｕ ２０７の構
造を示す。(zero) Superconducting quantum interferometer (Supe+eonducting)
quantum interference device
The magnetization of the sample measured by e (SQUID) is shown in FIG. The diamagnetic transition temperature is 1. [
18K, which is consistent with the electrical resistance measurement results described above. FIG. 3 shows the X-ray diffraction pattern of the bulk sample. This measurement result shows that the crystal phase of the sample belongs to the tetragonal phase. The X-ray circuit in Figure 3 (from the loaf pattern, the crystal phase has a lattice constant a = 0.380 nm
and C=247mllll11 with I94nm
It is shown to belong to a symmetric tetragonal phase. P4/mm
Symmetrical diffraction peaks are shown in the X-ray diffractogram and indexed. FIG. 4 shows the (TI, Pb) of the present invention.
, )(Ca,Y)S r 2 Cu 207 structure is shown.
ｎ
実施例２
そのＹ ○ 成分を、Ｌ ａ Ｏ、Ｃｅ Ｏ２Ｐ ｒ
Ｏ、Ｎ ｄ Ｏ、Ｓ ｍ２０３Ｅｕ Ｏ、Ｇｄ
２Ｏ３，Ｔｂ４Ｏ７゜Ｄｙ Ｏ、Ｈｏ Ｏ、Ｅｒ２Ｏ３
゜
Ｔｍ２０３．Ｙｂ２Ｏ３及びＬｕ２ｏ３の中の１つによ
って置き換えたことを除いて、実施例１の処理工程を繰
り返した。得られた超伝導試料のＸＲＤパターンは全て
、第３図に示される結晶構造と類似の結晶構造を有する
ことを示した。電気抵抗測定から決定された前記試料の
超伝導臨界温度は次の通りである。n Example 2 The Y ○ component is L a O, Ce O2P r
O, N d O, S m203Eu O, Gd
2O3, Tb4O7゜Dy O, Ho O, Er2O3
゜Tm203. The process steps of Example 1 were repeated, except that Yb2O3 and Lu2o3 were substituted. The XRD patterns of the superconducting samples obtained all showed that they had a crystal structure similar to that shown in FIG. The superconducting critical temperature of the sample determined from electrical resistance measurements is as follows.
元素 Ｌｕ Ｃ＋ Ｐ＋ Ｎｄ Ｓｍ
Ｅｕ Ｇｄ Ｔｂ Ｄ７ ｎｏ Ｅ＋ Ｔ
ｍ Ｙｂ ＬｕＫｌ
実施例３
Ｃａ ／ Ｙ比を次式のように変化させたことを除いて
、実施例１の処理工程を繰り返した。Element Lu C+ P+ Nd Sm
Eu Gd Tb D7 no E+ T
m Yb LuKl Example 3 The process steps of Example 1 were repeated, except that the Ca/Y ratio was varied as follows:
ＴＣ（ｚｅｒＯ）
Ｔｌｏ、５Ｐｂｏ、５ＣａＳｒ２Ｃｕ２０！７８ＫＴｌ
ｏ５Ｐｂｏ５Ｃａｏ９Ｙｏ、１Ｓｒ２Ｃｕ２ｏ２
１ｏ３ＫＴ１ｏ、５Ｐｂｏ５Ｃａｏ、８５Ｙｏ１５Ｓｒ
２Ｃｕ２０，１ｏ７ＫＴ１ｏ、５Ｐｂｏ、５Ｃａｏ、８
Ｙｏ２Ｓｒ２Ｃｕ２０□１ｏ８ＫＴＩｏ、５Ｐｂｏ、５
Ｃａｏ、７Ｙｏ、３Ｓｒ２Ｃｕ２ｏ！９８ＫＴ Ｉｏ、
５Ｐｂｏ、５Ｃａｏ、ＧＹ、４Ｓ ｒ２Ｃｕ２０．
７８ＫＴ１ｏ、５Ｐｂｏ、５Ｃａｏ、５Ｙｏ、５
Ｓｒ２Ｃｕ２ｏ２４４ＫＴＩｏ、５Ｐｂｏ、５Ｃａｏ、
３Ｙｏｙ Ｓ ｒ２ＣＩＪ２０２ 半導体電気
抵抗測定から決定された各試料の超伝導臨界温度が、そ
の組成の後に示されている。TC(zerO) Tlo, 5Pbo, 5CaSr2Cu20!78KTl
o5Pbo5Cao9Yo, 1Sr2Cu2o2
1o3KT1o, 5Pbo5Cao, 85Yo15Sr
2Cu20, 1o7KT1o, 5Pbo, 5Cao, 8
Yo2Sr2Cu20□1o8KTIo, 5Pbo, 5
Cao, 7Yo, 3Sr2Cu2o! 98KT Io,
5Pbo, 5Cao, GY, 4S r2Cu20.
78KT1o, 5Pbo, 5Cao, 5Yo, 5
Sr2Cu2o244KTIo, 5Pbo, 5Cao,
3Yoy S r2CIJ202 The superconducting critical temperature of each sample, determined from semiconductor electrical resistance measurements, is shown after its composition.
実施例４ 次式のようにＣａ ／ Ｙ比を変化させ及びＰｂ。Example 4 By changing the Ca/Y ratio and Pb as shown in the following formula.
をＢｉ２Ｏ３試薬によって置き換えたことを除いて、実
施例１の処理工程を繰り返した。The process steps of Example 1 were repeated, except that the Bi2O3 reagent was replaced by the Bi2O3 reagent.
Ｔ ｌ ｏ、５Ｐ ｂｏ、ｓ Ｃａｏ、９ＭｏＩＳ ｒ
２Ｃｕ２ｏＺＴ ｌ ｏ５Ｐ ｂ ｏ、 ５Ｃａ ｏ、
ｐ、 Ｍｏ、 ２３ ｒ ２°ＬＩ２０ＺＴ Ｉ ｏ
、５Ｐ １）＋＋、５Ｃａｏ、７Ｍ０８ａ Ｓ ｒ２Ｃ
ＩＪ２ ｏ。T lo, 5P bo, s Cao, 9MoIS r
2Cu2oZT l o5P b o, 5Ca o,
p, Mo, 23 r 2°LI20ZT I o
, 5P 1) ++, 5Cao, 7M08a S r2C
IJ2 o.
ミツシュメタル酸化物は、モナザイト
ＴＣ（ｚｅｒＯ）
１０２に
９８に
８Ｋ
（Ｍｏｎａｚｉｌｅ）中に含まれる粘土の抽出の第１段
階から得られる原料である。ミツシュメタル酸化物の価
格は、個々の希土類金属酸化物の価格よりも約１０〜２
００１１ＳＤ／ｋｇ低価格である。この実施例で使用さ
れるミツシュメタル酸化物に含まれる希土類元素は次の
一覧表の通りである。Mitsushmetal oxide is a raw material obtained from the first stage of the extraction of the clay contained in Monazite TC (zerO) 102 to 98 to 8K (Monazile). The price of Mitshu metal oxide is about 10-20% lower than the price of individual rare earth metal oxides.
0011SD/kg low price. The rare earth elements contained in the Mitsushi metal oxide used in this example are as shown in the following table.
成分 ％１
Ｌａ２０３ ３１．８
Ｃｅ Ｏ２２４，５
Ｐｒ６０１． ８．９
Ｎｄ２０３ ３１．１
’Ｅｕ Ｏ、Ｇｄ Ｏ、Ｔｂ４Ｏ７゜Ｄｙ Ｏ、Ｈ
ｏ Ｏ、Ｅｒ２Ｏ３゜
Ｔｍ Ｏ、Ｙｂ Ｏ、Ｌｕ２ｏ３、及びＹ ２０３のよ
うな他の希土類金属酸化物が、０．１％未満の量で含ま
れる。Ingredients %1 La203 31.8 Ce O224,5 Pr601. 8.9 Nd203 31.1 'Eu O, Gd O, Tb4O7゜Dy O, H
Other rare earth metal oxides such as oO, Er2O3°TmO, YbO, Lu2o3, and Y203 are included in amounts less than 0.1%.
電気抵抗測定から決定された各試料の超伝導臨界温度が
、その組成の後に示されている。The superconducting critical temperature of each sample, determined from electrical resistance measurements, is shown after its composition.
第１図は超伝導組成物（ＴＩ Ｐｂ ）０．５
０．５
（Ｃａ Ｙ ）Ｓｒ Ｃｕ２Ｏ！の電気抵抗０．８
０．２ ２
と温度との関係を示し、
第２図は超伝導組成物（ＴＩ Ｐｂ ）０５
０．５
（Ｃａ Ｙ ）Ｓｒ Ｃｕ２Ｏ，の磁化と温０．８
０．２ ２
度との関係を示し、
第３図は超伝導組成物（ＴＩ Ｐｂ ）０．５
０．５
（Ｃａ Ｙ ）Ｓｒ Ｃｕ２ＯにのＸ線回折０．８
０．２ ２
パターンを示し、及び、
第４図は（ＴＩ Ｐｂ ） （Ｃａｏ、８０
．５ ０．５
Ｙ ）Ｓｒ Ｃｕ２Ｏ，の結晶構造を示す。Figure 1 shows superconducting composition (TI Pb) 0.5
0.5 (CaY)SrCu2O! electrical resistance of 0.8
0.2 2 and temperature, and Figure 2 shows the relationship between superconducting composition (TI Pb) 05
0.5 (Ca Y )Sr Cu2O, magnetization and temperature 0.8
Figure 3 shows the relationship between the superconducting composition (TI Pb) 0.2 and 0.5
0.5 X-ray diffraction of (Ca Y )Sr Cu2O 0.8
0.2 2 pattern and FIG. 4 shows (TI Pb ) (Cao, 80
．． 5 0.5 Y)SrCu2O, is shown.
Claims (1)
）Ｓｒ＿２Ｃｕ＿２Ｏ＿ｚ （式中、 Ａがイットリウムもしくはランタニド希土類元素又はこ
れらの混合物であり、 ＢがＰｂもしくはＢｉ又はこれらの混合物であり、 ｘが約０〜０．８であり、 ｙが約０〜０．５であり、及び、 ｚが約６．５〜７．５である）を有する超伝導組成（２
）前記組成物が４２Ｋ〜１０８Ｋの範囲内の超伝導臨界
温度を有する請求項１に記載の超伝導組成物。Formula (1): (T1_1_-_xB_x)(Ca_1_-_yA_y
) Sr_2Cu_2O_z (wherein A is yttrium or a lanthanide rare earth element or a mixture thereof, B is Pb or Bi or a mixture thereof, x is about 0 to 0.8, and y is about 0 to 0. 5 and z is about 6.5 to 7.5).
2.) A superconducting composition according to claim 1, wherein said composition has a superconducting critical temperature within the range of 42K to 108K.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2226442A JPH04114920A (en) | 1990-08-28 | 1990-08-28 | Superconductive metal oxide t1-pb, ln-sr-cu-o composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2226442A JPH04114920A (en) | 1990-08-28 | 1990-08-28 | Superconductive metal oxide t1-pb, ln-sr-cu-o composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04114920A true JPH04114920A (en) | 1992-04-15 |
Family
ID=16845174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2226442A Pending JPH04114920A (en) | 1990-08-28 | 1990-08-28 | Superconductive metal oxide t1-pb, ln-sr-cu-o composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04114920A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002518287A (en) * | 1998-06-18 | 2002-06-25 | インダストリアル リサーチ リミテッド | Critical doping in high-Tc superconductors to obtain maximum flux spinning and critical current |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0297422A (en) * | 1988-10-05 | 1990-04-10 | Onoda Cement Co Ltd | Production of tl-pb-sr-ca-cu-o type oxide superconductor |
| JPH02167820A (en) * | 1988-08-10 | 1990-06-28 | Sumitomo Electric Ind Ltd | Method for forming tl-base multiple oxide superconducting thin film |
-
1990
- 1990-08-28 JP JP2226442A patent/JPH04114920A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02167820A (en) * | 1988-08-10 | 1990-06-28 | Sumitomo Electric Ind Ltd | Method for forming tl-base multiple oxide superconducting thin film |
| JPH0297422A (en) * | 1988-10-05 | 1990-04-10 | Onoda Cement Co Ltd | Production of tl-pb-sr-ca-cu-o type oxide superconductor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002518287A (en) * | 1998-06-18 | 2002-06-25 | インダストリアル リサーチ リミテッド | Critical doping in high-Tc superconductors to obtain maximum flux spinning and critical current |
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