JPH0574232A - Degradation preventing method for oxide superconductor - Google Patents
Degradation preventing method for oxide superconductorInfo
- Publication number
- JPH0574232A JPH0574232A JP3261366A JP26136691A JPH0574232A JP H0574232 A JPH0574232 A JP H0574232A JP 3261366 A JP3261366 A JP 3261366A JP 26136691 A JP26136691 A JP 26136691A JP H0574232 A JPH0574232 A JP H0574232A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- oxide superconductor
- glass
- polycrystalline
- oxide superconducting
- 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 20
- 238000000034 method Methods 0.000 title claims description 11
- 230000015556 catabolic process Effects 0.000 title abstract 3
- 238000006731 degradation reaction Methods 0.000 title abstract 3
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 230000006866 deterioration Effects 0.000 claims description 6
- 239000000155 melt Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000006121 base glass Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000009545 invasion Effects 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910002480 Cu-O Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- 229910015901 Bi-Sr-Ca-Cu-O Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000003891 oxalate salts Chemical class 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 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)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸化物超伝導体の劣化
防止方法に関し、特にH2Oによる酸化物超伝導体の劣化
を防止する方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of preventing deterioration of an oxide superconductor, and more particularly to a method of preventing deterioration of an oxide superconductor due to H 2 O.
【０００２】[0002]
【従来の技術】酸化物超伝導体は、臨界温度が高く優れ
た特性を有し、液体窒素温度で使用が可能であるため、
その応用が期待されている。応用の中で酸化物超伝導体
を用いた磁石、磁気シールド、無摩擦軸受け等は酸化物
超伝導体の多結晶体を用いたものである2. Description of the Related Art Oxide superconductors have high critical temperature and excellent characteristics, and can be used at liquid nitrogen temperature.
Its application is expected. Among the applications, magnets using oxide superconductors, magnetic shields, frictionless bearings, etc. use polycrystalline oxide superconductors.
【０００３】[0003]
【発明が解決しようとする課題】酸化物超伝導体は、H2
O に対して弱く、多結晶体の結晶粒界に入り込んだ H2O
と反応しやすく、 H2O、特に水蒸気のある雰囲気で保持
すると超伝導特性が劣化し、臨界温度や臨界電流密度が
低下することが知られている。したがって、この材料を
長期間に亘り、使用することが困難であった。[Problems to be Solved by the Invention] Oxide superconductors contain H 2
H 2 O that is weak against O and enters the grain boundaries of polycrystalline
It is known that they react easily with H 2 O, especially when kept in an atmosphere with water vapor, the superconducting properties deteriorate, and the critical temperature and critical current density decrease. Therefore, it was difficult to use this material for a long period of time.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、酸化物超
伝導多結晶体の劣化防止方法について種々研究した結
果、酸化物超伝導多結晶体の表面をガラス質で被覆する
ことにより結晶粒界へのH2Oの侵入を防止できることを
見出し、これにより酸化物超伝導体の長期使用が可能と
なった。Means for Solving the Problems As a result of various studies on a method for preventing deterioration of an oxide superconducting polycrystal, the present inventors have found that a crystal is formed by coating the surface of the oxide superconducting polycrystal with glass. We have found that H 2 O can be prevented from penetrating into the grain boundaries, which has enabled the long-term use of oxide superconductors.
【０００５】すなわち、本発明の要旨は、酸化物超伝導
体表面に 600℃以下でガラス化する材料を被覆しガラス
化させることを特徴とする酸化物超伝導体の劣化防止方
法にある。That is, the gist of the present invention resides in a method for preventing deterioration of an oxide superconductor, which comprises coating the surface of the oxide superconductor with a material that vitrifies at 600 ° C. or lower and vitrifying it.
【０００６】本発明の対象とする酸化物超伝導体は、 T
l-Ba-Ca-Cu-O系、Bi(Pb)-Sr-Ca-Cu-O 系、 Bi-Sr-Ca-Cu
-O系、Y-Ba-Cu-O 系等の高臨界温度の化合物をさす。The oxide superconductor targeted by the present invention is T
l-Ba-Ca-Cu-O system, Bi (Pb) -Sr-Ca-Cu-O system, Bi-Sr-Ca-Cu
-O system, Y-Ba-Cu-O system and other compounds with high critical temperature.
【０００７】酸化物超伝導多結晶体の製造方法として
は、構成元素を含む原料の混合物を焼成することにより
得られる。粉末原料としては、酸化物、炭酸塩、硝酸
塩、シュウ酸塩等が用いられる。A method for producing an oxide superconducting polycrystal is obtained by firing a mixture of raw materials containing constituent elements. As the powder raw material, oxides, carbonates, nitrates, oxalates and the like are used.
【０００８】酸化物超伝導多結晶体を製造するには、ま
ず、原料粉末を所定の組成に配合し、アルコール、アセ
トン等の液体とともに、ボールミルで混合する。混合粉
末を700〜800 ℃程度の温度で仮焼し、炭酸塩、硝酸
塩、シュウ酸塩等を分解する。得られた仮焼粉末を所望
の形状に成形し、それぞれの化合物が生成する温度で、
焼成する。その温度は、以下の通りである。In order to produce an oxide superconducting polycrystal, first, raw material powders are mixed into a predetermined composition and mixed with a liquid such as alcohol or acetone in a ball mill. The mixed powder is calcined at a temperature of about 700 to 800 ° C to decompose carbonates, nitrates, oxalates and the like. The obtained calcined powder is molded into a desired shape, at a temperature at which each compound is produced,
Bake. The temperature is as follows.
【０００９】Bi-Pb-Sr-Ca-Cu-O系… 820〜850 ℃ Bi-Sr-Ca-Cu-O 系 … 850〜880 ℃ Y-Ba-Cu-O 系 … 900〜1000℃ Tl-Ba-Ca-Cu-O 系 … 900〜1000℃Bi-Pb-Sr-Ca-Cu-O system 820 to 850 ° C Bi-Sr-Ca-Cu-O system 850 to 880 ° C Y-Ba-Cu-O system 900 to 1000 ° C Tl- Ba-Ca-Cu-O system… 900-1000 ℃
【００１０】酸化物超伝導体に被覆する 600℃以下で溶
融するガラスとしては、例えばPb-Si-Cd-Bi-O 系、Pb-B
-Al-Si-O系、B-V-Zn-O 系等のガラス組成物を挙げること
ができる。これらは絶縁性を有し、酸化物超伝導多結晶
膜の保護膜として用いることができる。Examples of the glass that melts at 600 ° C. or below to coat the oxide superconductor include Pb-Si-Cd-Bi-O system and Pb-B.
Examples thereof include -Al-Si-O type and BV-Zn-O type glass compositions. These have insulating properties and can be used as a protective film for an oxide superconducting polycrystalline film.
【００１１】その一例として、Pb-Si-Cd-Bi-O 系ガラス
の組成としては、以下に示す組成であればよく、必要で
あれば Cr2O3等の添加物を少量加えてもよい。As an example thereof, the composition of the Pb-Si-Cd-Bi-O type glass may be any of the compositions shown below, and if necessary, a small amount of additives such as Cr 2 O 3 may be added. .
【００１２】PbO 50〜60重量％ SiO2 15〜30重量％ CdO 5〜15重量％ Bi2O3 5〜15重量％PbO 50-60 wt% SiO 2 15-30 wt% CdO 5-15 wt% Bi 2 O 3 5-15 wt%
【００１３】上記組成のガラスは、空気中、 500〜600
℃に加熱することにより、容易に溶融してガラス化す
る。ガラス化する温度が上記の温度より高いと、酸化物
超伝導多結晶体と反応し、超伝導特性に影響を及ぼす。
特に、 PbO、Bi2O3 量が少ないと、ガラス化する温度が
高くなるため好ましくない。The glass having the above composition is 500 to 600 in air.
By heating to ℃, it easily melts and vitrifies. If the temperature of vitrification is higher than the above temperature, it reacts with the oxide superconducting polycrystal and affects the superconducting properties.
In particular, if the amounts of PbO and Bi 2 O 3 are small, the vitrification temperature becomes high, which is not preferable.
【００１４】ガラスの被覆方法としては、上記成分の粉
末をペースト状にし、酸化物超伝導多結晶体表面に塗布
する。塗布方法としては、ガラス粉末のペーストを刷毛
により酸化物超伝導多結晶体に塗る方法、ペースト中に
酸化物超伝導多結晶体を浸漬する方法等がある。As a method for coating glass, powder of the above-mentioned components is made into a paste and applied to the surface of the oxide superconducting polycrystal. Examples of the application method include a method of applying a glass powder paste to the oxide superconducting polycrystal with a brush and a method of immersing the oxide superconducting polycrystal in the paste.
【００１５】酸化物超伝導多結晶体上のペーストの塗布
厚は、溶融して得られるガラス皮膜の厚さが0.01〜1mm
程度であればよい。ガラス皮膜の厚さが0.01mm以下で
は、酸化物超伝導多結晶体表面に均一に皮膜形成され
ず、下地の酸化物超伝導体が表面に露出する場所が存在
し、その部分から、 H2Oとの反応が進行して酸化物超伝
導多結晶体の劣化が進行する。ガラス皮膜を1mm より厚
くすること実用上不要であり、工業的でない。The coating thickness of the paste on the oxide superconducting polycrystal is such that the thickness of the glass film obtained by melting is 0.01 to 1 mm.
It only has to be about. The thickness of the glass coating at 0.01mm or less, not uniformly coating formed on the oxide superconductor polycrystalline surface, the oxide superconductor base exists a place exposed to the surface, from that part, H 2 The reaction with O proceeds and the oxide superconducting polycrystalline body deteriorates. It is not industrially necessary to make the glass film thicker than 1 mm, which is not industrial.
【００１６】表面に塗ったペーストの焼成は、 500〜60
0 ℃で 1時間以上行うことにより、下地の酸化物超伝導
多結晶体と反応せず容易にガラス化する、The firing of the paste applied to the surface is 500 to 60
By performing the treatment at 0 ° C. for 1 hour or more, it easily vitrifies without reacting with the underlying oxide superconducting polycrystal.
【００１７】[0017]
実施例１及び比較例１ Bi2O3 、PbO 、SrCO3 、CaCO3 及び CuOの粉末を、組成
比がBi0.96Pb0.24Sr1. 00Ca1.00Cu1.60Oxになるように配
合し、ボールミル中でエタノールとともに24時間混合
し、乾燥した後、 800℃空気中で12時間仮焼した。この
仮焼粉末を用い、5×2 ×1mm の棒状に成形し、 850℃
で48時間空気中で焼成し、超伝導体とした。 Example 1 and Comparative Example 1 Bi2O3 , PbO, SrCO3 , CaCO3 And CuO powder, composition
The ratio is Bi0.96Pb0.24Sr1. 00Ca1.00Cu1.60OxTo be
And mix with ethanol in a ball mill for 24 hours
After drying, it was calcined in air at 800 ° C for 12 hours. this
Using calcined powder, form into a rod of 5 × 2 × 1mm, 850 ℃
Then, it was fired in air for 48 hours to obtain a superconductor.
【００１８】この酸化物超伝導多結晶体を、 Pb-Si-Cd-
Bi-Oを主成分とするガラス粉末のペースト中に浸漬し、
120℃で 1時間乾燥した後、 530℃で 1時間焼成した。This oxide superconducting polycrystal was used as Pb-Si-Cd-
Immerse in a paste of glass powder whose main component is Bi-O,
After drying at 120 ° C for 1 hour, it was baked at 530 ° C for 1 hour.
【００１９】得られたガラス被覆酸化物超伝導多結晶体
及び比較のため、ガラスを被覆していないものとを90℃
の水の中に、それぞれ10分、30分、60分浸漬したときの
超伝導特性の変化を測定した。結果を表１に示す。The obtained glass-coated oxide superconducting polycrystalline body and, for comparison, those not coated with glass were heated to 90 ° C.
The changes in superconducting properties were measured when immersed in water for 10 minutes, 30 minutes, and 60 minutes, respectively. The results are shown in Table 1.
【００２０】[0020]
【表１】 [Table 1]
【００２１】実施例２及び比較例２ Y2O3、BaCO3 及び CuOの粉末を、組成比がBa2Cu3Oxにな
るように配合し、ボールミル中でエタノールとともに24
時間混合し、乾燥後、 800℃空気中で12時間仮焼した。
この仮焼粉末を用い、 5×2 ×1mm の棒状に成形し、 9
00℃で 5時間空気中で焼成し、超伝導体とした。Example 2 and Comparative Example 2 Y 2 O 3 , BaCO 3 and CuO powders were blended so that the composition ratio was Ba 2 Cu 3 O x, and they were mixed together with ethanol in a ball mill.
After mixing for an hour, drying, and calcination in air at 800 ° C for 12 hours.
Using this calcined powder, it was formed into a bar shape of 5 × 2 × 1 mm, and
A superconductor was obtained by firing in air at 00 ° C for 5 hours.
【００２２】この酸化物超伝導多結晶体を Pb-Si-Cd-Bi
-Oを主成分とするガラス粉末ペースト中に浸漬し、 120
℃で 1時間乾燥した後、 530℃で 1時間焼成した。This oxide superconducting polycrystal was used as Pb-Si-Cd-Bi
Immerse in -O-based glass powder paste for 120
After drying at ℃ for 1 hour, it was baked at 530 ℃ for 1 hour.
【００２３】得られたガラス被覆酸化物超伝導多結晶体
と、比較のため、ガラスを被覆していないものとを、90
℃ の水の中にそれぞれ10分、30分、60分浸漬したとき
の超伝導特性の変化を調べた。調べた結果を表２に示
す。The obtained glass-coated oxide superconducting polycrystal and a glass-uncoated oxide superconducting polycrystal were compared with each other for comparison.
Changes in superconducting properties were investigated when immersed in water at ℃ for 10, 30, and 60 minutes, respectively. The results of the examination are shown in Table 2.
【００２４】[0024]
【表２】 [Table 2]
【００２５】[0025]
【発明の効果】本発明の方法によれば、酸化物超伝導体
が劣化することなく、長期間に亘り、その特性を維持し
て使用することができる。According to the method of the present invention, the oxide superconductor can be used while maintaining its characteristics for a long period of time without deterioration.
Claims (1)
ス化する材料を被覆しガラス化させることを特徴とする
酸化物超伝導体の劣化防止方法。1. A method for preventing deterioration of an oxide superconductor, which comprises coating the surface of an oxide superconductor with a material that vitrifies at 600 ° C. or lower and vitrifying it.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261366A JPH0574232A (en) | 1991-09-13 | 1991-09-13 | Degradation preventing method for oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3261366A JPH0574232A (en) | 1991-09-13 | 1991-09-13 | Degradation preventing method for oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0574232A true JPH0574232A (en) | 1993-03-26 |
Family
ID=17360844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3261366A Pending JPH0574232A (en) | 1991-09-13 | 1991-09-13 | Degradation preventing method for oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0574232A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0769758A (en) * | 1993-09-06 | 1995-03-14 | Chubu Electric Power Co Inc | High temperature superconductor |
| US5411938A (en) * | 1993-07-30 | 1995-05-02 | University Of Chicago | Sealed glass coating of high temperature ceramic superconductors |
-
1991
- 1991-09-13 JP JP3261366A patent/JPH0574232A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411938A (en) * | 1993-07-30 | 1995-05-02 | University Of Chicago | Sealed glass coating of high temperature ceramic superconductors |
| JPH0769758A (en) * | 1993-09-06 | 1995-03-14 | Chubu Electric Power Co Inc | High temperature superconductor |
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