JPS63310765A - Ceramic material ensuring superconduction at high temperature - Google Patents
Ceramic material ensuring superconduction at high temperatureInfo
- Publication number
- JPS63310765A JPS63310765A JP62145245A JP14524587A JPS63310765A JP S63310765 A JPS63310765 A JP S63310765A JP 62145245 A JP62145245 A JP 62145245A JP 14524587 A JP14524587 A JP 14524587A JP S63310765 A JPS63310765 A JP S63310765A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic material
- superconduction
- high temperature
- superconducting
- material ensuring
- 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
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 3
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract 2
- 229910052772 Samarium Inorganic materials 0.000 claims abstract 2
- 229910052775 Thulium Inorganic materials 0.000 claims abstract 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract 2
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 abstract description 8
- 229910002480 Cu-O Inorganic materials 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 239000002887 superconductor Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 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
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、高温で超電導を示すセラミック系超電導化合
物に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to ceramic superconducting compounds that exhibit superconductivity at high temperatures.
従来の技術
従来、電気抵抗がＯになる超電導転移温度ＴＣの高い超
電導材料としては、Ｎｂ５Ｓｎ、Ｎｂ５Ｑｅなどの合金
系のものが知られている。しかしこれらはせいぜいＴＣ
が２３Ｋまでであり、広く実用化されるにはほど遠いも
のであった。BACKGROUND OF THE INVENTION Conventionally, alloy-based materials such as Nb5Sn and Nb5Qe are known as superconducting materials having a high superconducting transition temperature TC at which the electrical resistance becomes O. However, these are at most TC
was up to 23K, and was far from being widely put into practical use.
最近Ｊ、 Ｇ、 Ｂｅｄｎｏ ｌ ｚ等によりＢａ−Ｌ
ａ−Ｃｕ−０系酸化物混合相の焼結体が１３に以下で抵
抗率が減少すること、また直流磁化率が３０により反磁
性に転することを示し、高温超電導の可能性を示唆して
以来、各国で高温超電導体の研究が活発に行われている
。１９８７年に入って、Ｃ，Ｗ、Ｐ、Ｃｈｕ等により
Ｙ１３ａ ２ Ｃｕ ３０ｒ−ｙ系で、液体窒素温度７
７）（ヲ上回る９０に程度のＴＣを示すことが発表され
、続りてＹを他の希土類元素で置換した、組成式 Ｌｎ
Ｂａ ２ Ｃｕ ３０ｑ−ｙ （Ｌｎ Ｇ、を希土類光
％ ） テ表ワされるセラミック材料が、いずれも同程
度の高りＴＣを有する超電導体であることがわかってき
た。Recently, Ba-L by J, G, Bednolz et al.
It was shown that the resistivity of the a-Cu-0 mixed oxide sintered body decreases below 13, and that the DC magnetic susceptibility changes to diamagnetic at 30, suggesting the possibility of high-temperature superconductivity. Since then, research on high-temperature superconductors has been actively conducted in various countries. In 1987, C. W. P. Chu et al.
Y13a 2 Cu 30r-y system, liquid nitrogen temperature 7
7) (It was announced that it showed a TC of about 90, exceeding that of Ln, and subsequently, Y was replaced with another rare earth element.
It has become clear that the ceramic materials used in Ba 2 Cu 30q-y (LnG, rare earth %) are all superconductors having similar high TC.
発明が解決しようとする問題点
これらのセラミック超電導体は、通常焼結法によって製
造される。ところが従来の得られているものは焼結性が
悪く、非常に脆いという欠点があり、実用上問題があっ
た。Problems to be Solved by the Invention These ceramic superconductors are usually manufactured by a sintering method. However, the conventionally available materials have poor sinterability and are extremely brittle, which poses practical problems.
本発明はＬ ｎ−Ｂ ａ−Ｃｕ−０系超電導セラミツク
材料の特性、特にその機械的強度を改善することを目的
とする。The object of the present invention is to improve the properties of Ln-B a-Cu-0 based superconducting ceramic materials, especially their mechanical strength.
問題点を解決するための手段
本発明者等は種々検討した結果、この種の超電導セラミ
ックスの機械的強度は、弗素（Ｆ）を含有させることに
より大ぎく向上することを見出した。Means for Solving the Problems As a result of various studies, the present inventors have found that the mechanical strength of this type of superconducting ceramic can be greatly improved by incorporating fluorine (F).
即ち本発明は、 （Ｌｎ＋−ｘ８ａｘ）３ｃｕ ３０
ｓ−ｙＦｚ＜但ししｎはＹ、 ｌ−ａ 、 Ｎｄ 、
３ｎ 。That is, the present invention provides (Ln+-x8ax)3cu 30
s-yFz<where n is Y, 1-a, Nd,
3n.
Ｅｕ 、Ｇｄ 、Ｄｙ 、Ｈｏ 、Ｅｒ 、Ｔｎおよび
Ｙｂから選ばれる選ばれる希土類元素の１種または２種
以上の組合わせ、０．２≦ｘ≦０．８．２．２≦ｙ≦３
．０．０＜Ｚ≦１．０）なる組成を有する高温超電導セ
ラミック材料である。One or a combination of two or more selected rare earth elements selected from Eu, Gd, Dy, Ho, Er, Tn and Yb, 0.2≦x≦0.8.2.2≦y≦3
．． It is a high temperature superconducting ceramic material having a composition of 0.0<Z≦1.0).
Ｊ
弗素を含有させることにより、Ｌ ｎ−Ｂａ−Ｃｕ−０
系セラミツクスの機械的強度が大幅に改善される。By containing J fluorine, L n-Ba-Cu-0
The mechanical strength of ceramics is significantly improved.
これは弗素が焼結時、鉱化剤として動き、焼結性が向上
するためと考えられる。This is thought to be because fluorine acts as a mineralizer during sintering, improving sinterability.
弗素ｆｉｉｚを１．０以下としたのは、１．０を越える
と鉱化剤としての効果がなくなり、逆に焼結密度が低下
するためである。第１図は、 ［）■ｏ２Ｙｏ、ａ Ｂ
ａ ２．ＯＣｕ ３０６．６ ＦＺで表わされるセラミ
ック材料において弗素量２と密度との関係を調べたもの
である。この図より、２が１．０を越えると、弗素を全
く含有しない場合より密度が低下していることがわかる
。The reason why fluorine fiiz is set to 1.0 or less is because if it exceeds 1.0, the effect as a mineralizing agent disappears, and conversely, the sintered density decreases. Figure 1 shows [)■o2Yo, a B
a2. The relationship between the amount of fluorine 2 and the density was investigated in the ceramic material represented by OCu 306.6 FZ. This figure shows that when 2 exceeds 1.0, the density is lower than when no fluorine is contained.
バリウム（８ａ ）のｍｘが、０．２≦ｘ≦０．８ノ範
囲外では、超電導を示すペロブスカイト相が得られなか
ったり、Ｔｃが液体窒糸温度以下になったりして、高温
超電導体が得られない。If mx of barium (8a) is outside the range of 0.2≦x≦0.8, a perovskite phase exhibiting superconductivity may not be obtained, or Tc may be below the liquid nitrogen temperature, resulting in a high-temperature superconductor. I can't get it.
またｙが２．２≦ｙ≦３．０の範囲外では、第２図に示
すように十分高いＴｃが得られない。第２図はＹｏ、９
３ａ ２．Ｉ Ｃｕ ３０９−ｙ Ｆｏ、３で表わされ
る化合物において、ｙとＴｃの関係を調べたものである
。Further, if y is outside the range of 2.2≦y≦3.0, a sufficiently high Tc cannot be obtained as shown in FIG. Figure 2 is Yo, 9
3a 2. In the compound represented by I Cu 309-y Fo, 3, the relationship between y and Tc was investigated.
本発明の超電導セラミック材料は、通常のセラミックス
と同様の方法でＶ３ｎされる。即ち例えば所定の元素の
酸化物、または加熱によって酸化物になる化合物と、弗
化物とを原料として、これらを混合し、仮焼工程を経て
１０００℃以下の温度で焼結することによって冑る。一
般に酸素欠陥を有する化合物なので、酸素雰囲気中で焼
成し、次いで酸素気流中で熱処理すると高い７’ｃが得
られることがある。The superconducting ceramic material of the present invention is subjected to V3n in the same manner as ordinary ceramics. That is, for example, an oxide of a predetermined element or a compound that becomes an oxide upon heating and a fluoride are used as raw materials, and these are mixed and sintered at a temperature of 1000° C. or lower through a calcination step. Since it is a compound that generally has oxygen vacancies, a high 7'c value may be obtained if it is fired in an oxygen atmosphere and then heat treated in an oxygen stream.
実施例
実施例１
Ｙ２０３ 、Ｂａ ＣＯ３、Ｃｕ Ｏ，ＹＦ３を出発原
料として、これらを最終組成がＹｏ９３ａ２．＋Ｃｕ
３０［１，２ＦＯ，Ｓとなるように混合し、空気中９８
０℃で焼成してセラミック材料を製造した。Examples Example 1 Using Y203, Ba CO3, Cu O, and YF3 as starting materials, the final composition was Yo93a2. +Cu
Mix to make 30[1,2FO,S, 98% in air.
A ceramic material was produced by firing at 0°C.
得られた試料は下記の比特性を示す超電導体であった。The obtained sample was a superconductor exhibiting the following specific characteristics.
超電導転移温度 ９５に
硬度 １５ＧＰａ
靭性値 ４ｔｖｌｐａｍ０５曲げ強度
６００ＭＰａ ’比較例１
実施例１と同様にして、Ｙｏ、９ Ｂａ ２． ｌ Ｃ
ｕ ３０ららの組成を有するセラミック材料を製造した
。Superconducting transition temperature: 95 Hardness: 15GPa Toughness: 4tvlpam05 Bending strength
600MPa ' Comparative Example 1 Same as Example 1, Yo, 9 Ba 2. l C
A ceramic material with a composition of u 30 ra was produced.
得られた試料は下記の比特性を示す超電導体であつた。The obtained sample was a superconductor exhibiting the following specific characteristics.
超電導転移温度 ８８．５ Ｋ
硬度 ６Ｇｐａ
靭性１ｆｉ ＩＭＰａｍＯ５曲げ強度
２００ＭＰａ
実施例２
Ｙ２Ｏ２、Ｙｂ２Ｏ３、ＢａＣＯ３、ＣｕＯ１ＢａＦ３
を出発原料として、これらを岐路組成がＹｏ゛３Ｙｂ
０９ Ｂａ ＋ ａ Ｃｌ ｓｏｂ ＋ Ｆｏ、９とな
るように混合し、酸素中９５０℃で焼成して下記の比特
性を有する超電導セラミック材料を得た。Superconducting transition temperature 88.5 K Hardness 6 Gpa Toughness 1fi IMPamO5 bending strength
200MPa Example 2 Y2O2, Yb2O3, BaCO3, CuO1BaF3
are the starting materials, and the crossroad composition is Yo゛3Yb
09 Ba + a Cl sob + Fo, 9, and fired at 950° C. in oxygen to obtain a superconducting ceramic material having the following specific characteristics.
超電導転移温度 ９０．５ Ｋ
硬度 １２Ｑｐａ
靭性値 ３．１ ＭＰａ ｍ０５曲げ強度
４５０ＭＰａ
比較例２
実施例２と同様にしてＹｏ、３ Ｙｂ Ｏ，９Ｂａ １
．８Ｃｕ３０ｂ７の組成を有するセラミック材料を製造
した。得られた試料は下記の比特性を示す超電導体であ
った。Superconducting transition temperature 90.5 K Hardness 12Qpa Toughness value 3.1 MPa m05 bending strength
450MPa Comparative Example 2 Same as Example 2 Yo, 3 Yb O, 9Ba 1
．． A ceramic material with a composition of 8Cu30b7 was produced. The obtained sample was a superconductor exhibiting the following specific characteristics.
超電導転移温度 ８５に
硬度 ４．５ＧＰａ
靭性値 ２ｔｖｌＰａｍ”５曲げ強度
２７０ＭＰａ
ブで明の効果
本発明によって、優れた超電導特性を保持し、しかも従
来よりｔよるかに礪懺的強度の大きい新規なセラミック
系超電導材料が得られたものであり、産業上極めて価値
が高い。Superconducting transition temperature: 85, hardness: 4.5GPa, toughness: 2tvlPam”5, bending strength
The present invention provides a new ceramic superconducting material that maintains excellent superconducting properties and has a much higher tensile strength than conventional materials, and is extremely valuable industrially. expensive.
第１図は、組成式 Ｄｙ Ｏ，２Ｙｏ、ａ Ｂａ ２．
００＋、、ｓＦｚのセラミック材料において、弗素ｆｆ
１ｚと密度との関係を示したものであり、第２図は組成
式Ｙｏ、ｑ １３ａ ２．Ｉ Ｃｕ ３０９−Ｙ Ｆｏ
、３で表わされるセラミック材料において、ＹとＴＣの
関係を示したものである。
特許出願人 昭栄化学工業株式会社
鼓々 ［３／ｃｍ’ＪFIG. 1 shows the composition formula: Dy O, 2Yo, a Ba 2.
In ceramic materials of 00+, sFz, fluorine ff
It shows the relationship between 1z and density, and Figure 2 shows the compositional formula Yo, q 13a 2. I Cu 309-Y Fo
, 3 shows the relationship between Y and TC in the ceramic material represented by . Patent applicant Shoei Chemical Industry Co., Ltd. Tsuzum [3/cm'J
Claims (1)
−＿ｙＦ＿ｚ（但しＬｎはＹ、Ｌａ、Ｎｄ、Ｓｍ、Ｅｕ
、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ、ＴｍおよびＹｂから選ばれ
る選ばれる希土類元素の１種または２種以上の組合わせ
、０．２≦ｘ≦０．８、２．２≦ｙ≦３．０、０＜ｚ≦
１．０）なる組成を有する高温超電導セラミック材料。1(Ln_1_−_xBa_x)_3Cu_3O_9_
-_yF_z (However, Ln is Y, La, Nd, Sm, Eu
, one or a combination of two or more rare earth elements selected from Gd, Dy, Ho, Er, Tm and Yb, 0.2≦x≦0.8, 2.2≦y≦3.0, 0<z≦
A high temperature superconducting ceramic material having a composition of 1.0).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62145245A JPS63310765A (en) | 1987-06-12 | 1987-06-12 | Ceramic material ensuring superconduction at high temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62145245A JPS63310765A (en) | 1987-06-12 | 1987-06-12 | Ceramic material ensuring superconduction at high temperature |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63310765A true JPS63310765A (en) | 1988-12-19 |
Family
ID=15380675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62145245A Pending JPS63310765A (en) | 1987-06-12 | 1987-06-12 | Ceramic material ensuring superconduction at high temperature |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63310765A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0354963A1 (en) * | 1987-09-24 | 1990-02-21 | Mitsubishi Materials Corporation | Process for producing superconductive ceramic sinter |
-
1987
- 1987-06-12 JP JP62145245A patent/JPS63310765A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0354963A1 (en) * | 1987-09-24 | 1990-02-21 | Mitsubishi Materials Corporation | Process for producing superconductive ceramic sinter |
| EP0354963A4 (en) * | 1987-09-24 | 1991-05-08 | Mitsubishi Kinzoku Kabushiki Kaisha | Process for producing superconductive ceramic sinter |
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