JPH01122511A - Oxide ceramic superconducting fiber - Google Patents
Oxide ceramic superconducting fiberInfo
- Publication number
- JPH01122511A JPH01122511A JP62280670A JP28067087A JPH01122511A JP H01122511 A JPH01122511 A JP H01122511A JP 62280670 A JP62280670 A JP 62280670A JP 28067087 A JP28067087 A JP 28067087A JP H01122511 A JPH01122511 A JP H01122511A
- Authority
- JP
- Japan
- Prior art keywords
- superconducting
- oxide
- fibers
- diameter
- oxide ceramic
- 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
- 239000000835 fiber Substances 0.000 title claims abstract description 45
- 239000011224 oxide ceramic Substances 0.000 title claims abstract description 23
- 229910052574 oxide ceramic Inorganic materials 0.000 title claims abstract description 23
- 239000002887 superconductor Substances 0.000 abstract description 30
- 239000000843 powder Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000009987 spinning Methods 0.000 abstract description 5
- 229910052691 Erbium Inorganic materials 0.000 abstract description 4
- 229910052765 Lutetium Inorganic materials 0.000 abstract description 4
- 229910052775 Thulium Inorganic materials 0.000 abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 abstract description 4
- 229910052788 barium Inorganic materials 0.000 abstract description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 abstract description 4
- 229910052692 Dysprosium Inorganic materials 0.000 abstract description 3
- 229910052693 Europium Inorganic materials 0.000 abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 abstract description 3
- 229910052689 Holmium Inorganic materials 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract 2
- 229910052772 Samarium Inorganic materials 0.000 abstract 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- -1 hydroxydiylcellulose Polymers 0.000 description 3
- 238000005339 levitation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920005596 polymer binder Polymers 0.000 description 2
- 239000002491 polymer binding agent Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229910000750 Niobium-germanium Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910000657 niobium-tin Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-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)
- Inorganic Fibers (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
A、産業上の利用分野
本発明は超電導マグネットや超電導送電線に使用可能な
酸化物セラミックス超電導繊維に関するものである。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to oxide ceramic superconducting fibers that can be used in superconducting magnets and superconducting transmission lines.
旦−亘」虹へ1」L
従来超電導体の最高の臨界温度はNb3Geの23.3
Kが最高であった。実用材料としてはNb3Snの17
Kが最高であった。従来の材料を使用する場合液体ヘリ
ウムによる冷却を必要とした。The highest critical temperature of conventional superconductors is 23.3 for Nb3Ge.
K was the best. As a practical material, Nb3Sn 17
K was the best. Using conventional materials required cooling with liquid helium.
最近酸化物超電導体が極めて高い臨界温度を有すること
が見出され、この分野における研究が活発に実施される
ようになった。臨界温度が高い材料としては、40に級
超電導体(La+ −、Sr y) 2CLI04[C
hem、l、ett、429(1987)] 、90に
級超電導体としてBa、YCu307−、 [Phys
、Rev、1.ett、58(1987)405]がす
でに見出されている。90に級高温超電導材料の出現に
より液体窒素(77K)を用いることが可能となった。Recently, it has been discovered that oxide superconductors have extremely high critical temperatures, and research in this field has become active. Materials with high critical temperatures include class 40 superconductors (La+-, Sry) 2CLI04[C
hem, L. ett, 429 (1987)], 90-class superconductors such as Ba, YCu307-, [Phys
, Rev, 1. ett, 58 (1987) 405] has already been found. With the advent of 1990-grade high temperature superconducting materials, it became possible to use liquid nitrogen (77K).
またY以外でもLu、 Yb、 Tm、 Er等でも9
0に級と見られる超電導現象がすでに観察されている。In addition to Y, Lu, Yb, Tm, Er, etc. also have 9
Superconductivity phenomena that appear to be on the order of zero have already been observed.
高温超電導の応用はジョセフソン素子に代表されるよう
なエレクトロニクス分野への応用と超電導発電機、磁気
浮上列車、超電導送電線に代表されるような電気機器分
野への応用に大別される。Applications of high-temperature superconductivity can be broadly divided into electronics applications, such as Josephson devices, and electrical equipment applications, such as superconducting generators, magnetic levitation trains, and superconducting power transmission lines.
エレクトロニクス分野への応用も非常に重要な課題であ
り、特に高温超電導体の応用はエレクトロニクス分野へ
の応用から始まるであろう。しかし産業界、社会に与え
るインパクトの大きさを考えた場合、電気機器への高温
超電導の応用こそが重要である。Application to the electronics field is also a very important issue, and the application of high-temperature superconductors in particular will begin with application to the electronics field. However, when considering the magnitude of the impact it will have on industry and society, the application of high-temperature superconductivity to electrical equipment is important.
高温超電導の電気機器への応用の要素技術となるのは超
電導マグネット技術である。超電導マグネットを利用し
たものとしてはM HD発電、磁気浮上列車、高エネル
ヤー粒子加速装置、超電導発電機、超電導変圧器、NM
R−CTなどが挙げられる。高温超電導体をマグネット
の分野に使用できれば超電導マグネット応用機器の経済
性が格段に向上する。また経済性が格段に向上すること
により新しい応用分野、あるいは超電導送電線への応用
が開IJることが期待される。Superconducting magnet technology is an elemental technology for the application of high-temperature superconductivity to electrical equipment. Things that use superconducting magnets include MHD power generation, magnetic levitation trains, high-energy particle accelerators, superconducting generators, superconducting transformers, and NM.
Examples include R-CT. If high-temperature superconductors can be used in the field of magnets, the economic efficiency of superconducting magnet application equipment will be greatly improved. Furthermore, it is expected that new application fields or applications to superconducting power transmission lines will open up due to the dramatic improvement in economic efficiency.
しかして、該超電導体がマグネットに使用されるために
は必要条件としてマグネットに巻υるような線材である
ことが要求される。従来の液体ヘリウム温度で使用され
ている超電導材料(金属または金属間化合物)について
は種々の線材化およびケーブル化技術が確立されている
が、最近の高温超電導体は酸化物セラミックスであり、
従来の超電導材料の線材化技術は適用できない。However, in order for the superconductor to be used in a magnet, it is required that the superconductor be a wire that can be wound around a magnet. Although various wire and cable technologies have been established for superconducting materials (metals or intermetallic compounds) used at conventional liquid helium temperatures, recent high-temperature superconductors are oxide ceramics,
Conventional technology for making wires from superconducting materials cannot be applied.
ところで線材内での超電導状態の本質的安定化を達成す
るために、フィラメントは細い方が有利である。臨界温
度の低い従来の超電導材料では直流用マグネットとして
の使用の為には通常、約20μm程度以下で使用されて
おり、また交流用マグネットとしての使用の為には、ヒ
ステリシス損失を小さくする為に、通常0.6μm程度
で使用されているが、本発明の酸化物セラミックス高温
超電導体は臨界温度が高い分、太い径のフィラメントで
の使用が可能となる。しかしこれも1000μm程度が
上限であり、より好ましくは100μm以下のフィラメ
ントとすることが望まれている。Incidentally, in order to achieve essential stabilization of the superconducting state within the wire, it is advantageous for the filament to be thin. Conventional superconducting materials with low critical temperatures are usually used at a thickness of about 20 μm or less for use as DC magnets, and for use as AC magnets in order to reduce hysteresis loss. Although the oxide ceramic high temperature superconductor of the present invention has a high critical temperature, it can be used with a filament having a large diameter. However, the upper limit of this is also about 1000 μm, and it is desired that the filament is more preferably 100 μm or less.
従来、かかる酸化物セラミックス高温超電導体=3−
を線材化する方法としては、銀合金インゴットに穴をあ
け、セラミックス粉を詰めて線材としたのち熱処理する
方法がすでに提案されている。しかし高温超電導体を銀
等の金属中空管に詰めて線材化する場合には(1)直径
100μm〜200μm以下の極細線材とすることが極
めて困難である、(2)高温超電導体が断線することな
く、かつ全線域にわたって電導性が均一である状態にす
ることは困難である、以上2点の極めて大きな問題があ
り、直径が実質的に1000μm以下である酸化物セラ
ミックス超電導繊維は従来、成功裡に得られていなかっ
た。Conventionally, as a method for forming such an oxide ceramic high-temperature superconductor into a wire, a method has already been proposed in which a hole is made in a silver alloy ingot, the wire is filled with ceramic powder, and the wire is heat-treated. However, when high-temperature superconductors are packed into hollow tubes made of metal such as silver and made into wires, (1) it is extremely difficult to make ultra-fine wires with a diameter of 100 μm to 200 μm or less, and (2) the high-temperature superconductors may break. It is difficult to achieve a state in which the conductivity is uniform over the entire wire region without causing any damage.There are two extremely serious problems mentioned above, and oxide ceramic superconducting fibers with a diameter of substantially 1000 μm or less have not been successful in the past. I wasn't getting it right.
C[Iが 決しよ゛と る。題、
本発明はかかる状況下、酸化物セラミックス高温超電導
体の極細繊維を提供せんとするものである。C[I will decide. Under such circumstances, the present invention aims to provide ultrafine fibers of oxide ceramic high temperature superconductors.
D9問題1、を、決する為の手段
本発明者らは上記目的に鑑みて鋭意検討し、繊維紡糸技
術とセラミックス成形技術を融合使用することにより、
酸化物セラミックス超電導体の細線化を試みた結果、均
一、高強度で直径が実質的に1000μm以下の酸化物
セラミックス超電導I Iffが得られ、本発明を完成
するに到った。以下、本発明の詳細な説明する。Means for determining D9 Problem 1 The present inventors have made extensive studies in view of the above objectives, and by combining fiber spinning technology and ceramic molding technology,
As a result of attempts to thin the oxide ceramic superconductor, an oxide ceramic superconductor Iff with uniformity, high strength, and a diameter of substantially 1000 μm or less was obtained, and the present invention was completed. The present invention will be explained in detail below.
本発明の酸化物セラミックス超電導体繊維は、直径が実
質的に1000μm以下であることが必須である。本発
明の数値の範囲外では実用性に乏しい。It is essential that the oxide ceramic superconductor fiber of the present invention has a diameter of substantially 1000 μm or less. If the value is outside the range of the present invention, it is not practical.
好ましい直径は5004m以下である。より好ましくは
200μm以下、もっとも好ましくは100μm以下で
ある。更には、磁場が無い状態における臨界温度(Tc
)が35に以上、好ましくは77に以上、磁場が無い状
態における臨界電流(Jc)がIA/am2以」二、好
ましくはIOA/cm2以上のものがより好適なもので
ある。また気孔率が10容量%以下、好適には5容量%
以下であるものがより好ましい。A preferred diameter is 5004 m or less. The thickness is more preferably 200 μm or less, most preferably 100 μm or less. Furthermore, the critical temperature in the absence of a magnetic field (Tc
) is 35 or more, preferably 77 or more, and the critical current (Jc) in the absence of a magnetic field is IA/am2 or more, preferably IOA/cm2 or more. In addition, the porosity is 10% by volume or less, preferably 5% by volume.
The following are more preferable.
本発明の酸化物セラミックス超電導繊維の最大の特徴は
、上記の様に極めて細い繊維であるという点に存するが
、本発明の繊維はおどろくべき事に、かかる極めて細い
繊維であるにしかかわらず、なんらの強度支持体を要さ
ないものであり、この様になんらの支持体を有さない単
独繊維状物質として、充分取り扱いに耐えるものであり
、実用性に極めて優れるのである。もちろん、支持体を
併用することを妨げるものではない。The greatest feature of the oxide ceramic superconducting fibers of the present invention is that they are extremely thin fibers as described above, but surprisingly, despite being extremely thin fibers, the fibers of the present invention have no It does not require a strong support, and as a single fibrous material without any support, it can be handled satisfactorily and is extremely practical. Of course, this does not preclude the use of a support in combination.
本発明の酸化物セラミックス超電導繊維は、その製造方
法については何等の制限もないが、製造方法の例として
は、酸化物超電導体の粉末あるいは加熱処理することに
よって酸化物超電導体になり得る物質の粉末を、ポリマ
ーバインダー中に分散後、繊維紡糸技術により繊維化し
、焼成を行なうことによりポリマーバインダーを除去し
得られる。この場合製造方法として粉末の分散媒の種類
により、水溶液分散法、有機溶剤分散法、ポリマー融液
分散法等が:また紡糸方法の種類により、湿式紡糸法、
乾湿式紡糸法、乾式紡糸法、溶融紡糸法等が、種々の組
合せで採用し得る。The oxide ceramic superconducting fiber of the present invention has no limitations on the manufacturing method, but examples of the manufacturing method include powder of an oxide superconductor or materials that can become an oxide superconductor by heat treatment. The powder can be obtained by dispersing the powder in a polymer binder, turning it into fibers by a fiber spinning technique, and removing the polymer binder by firing. In this case, manufacturing methods include aqueous solution dispersion, organic solvent dispersion, polymer melt dispersion, etc., depending on the type of powder dispersion medium; and wet spinning,
Wet-dry spinning methods, dry spinning methods, melt spinning methods, etc. can be employed in various combinations.
上記の酸化物超電導体としては、熱処理によってセラミ
ックス系焼結体を形成するものであって、ある温度以下
で超電導現象を示すものならば特に限定されないが、な
かでも銅酸化物を含むものが好ましい。The above-mentioned oxide superconductor is not particularly limited as long as it forms a ceramic sintered body through heat treatment and exhibits a superconducting phenomenon below a certain temperature, but those containing copper oxide are particularly preferred. .
具体的には(La、 Ba)、cuOtや一般式LnB
a、Cu5O,,(但し、LnはY、 Lu、 Yb、
Tm、 Er、 Ho、 Dy。Specifically, (La, Ba), cuOt and general formula LnB
a, Cu5O, (however, Ln is Y, Lu, Yb,
Tm, Er, Ho, Dy.
Gd、 Eu、 Smのすくなくとも1種、χは0<4
≦0.5を表わす。)で表わされるものが挙げられる。At least one of Gd, Eu, and Sm, χ is 0<4
≦0.5. ).
上記Ln、 Ba、 Cu、 Oはそれぞれその一部が
F等によって置換されていても良い。Part of each of the above Ln, Ba, Cu, and O may be substituted with F or the like.
また上記の加熱処理することによって酸化物超電導体に
なり得る物質としては、上記酸化物超電導体を形成する
それぞれの金属の酸化物、硝酸塩または炭酸塩等からな
るものが挙げられる。Further, examples of the substance that can be turned into an oxide superconductor by the heat treatment include those made of oxides, nitrates, carbonates, etc. of the respective metals forming the oxide superconductor.
具体的には
(a) Lnの酸化物、硝酸塩または炭酸塩、(但しL
nはY、 Lu、 Yb、 Tm、 Er、
Ho、 Dy、 Gd、 Eu。Specifically, (a) an oxide, nitrate or carbonate of Ln (however, Ln
n is Y, Lu, Yb, Tm, Er,
Ho, Dy, Gd, Eu.
Smのすくなくとも1種)
(b) Baの酸化物、硝酸塩または炭酸塩、及び
(c) Cuの酸化物、硝酸塩または炭酸塩からなるも
のが挙げられる。上記(b)としてはBaの酢酸塩また
はフッ化物であっても良い。また上記(c)としてはC
uのグルコン酸塩またはフッ化物であってし良い。At least one type of Sm) (b) Ba oxide, nitrate or carbonate; and (c) Cu oxide, nitrate or carbonate. The above (b) may be Ba acetate or fluoride. Also, for (c) above, C
gluconate or fluoride.
より具体的には、上記(a)として、y、o3゜Y(N
O,l)3等が、また」1記(b)としテBaCO3゜
Ba(NO3)2.8aF2等が、上記(c)としてC
ub。More specifically, as (a) above, y, o3゜Y(N
O, l) 3, etc., as in Section 1 (b), BaCO3゜Ba(NO3)2.8aF2, etc. as in (c) above, C
ub.
CLI(No3)、、 CuF2・2H20等が挙げら
れる。Examples include CLI (No. 3), CuF2.2H20, and the like.
これらの各成分を、酸化物超電導体の組成比となるよう
に混合して用いれば良いが、該混合物をあらかじめ温度
800〜1000℃の条件下で、1時間〜5時間、仮焼
きしたものを用いるとより効果が大きい。These components may be used by mixing them so as to have the composition ratio of the oxide superconductor, but the mixture may be calcined in advance at a temperature of 800 to 1000°C for 1 to 5 hours. It is more effective when used.
本発明の酸化物セラミックス超電導繊維の性能を向上す
るうえで該繊維の気孔率を小さくすることは極めて重要
である。気孔率を低下させることによって酸化物セラミ
ックス超電導繊維の直径を極めて細くし得、また諸性能
を大幅に向上させることができる。酸化物超電導繊維の
気孔率を低下させるには粒径の細い前駆体を用いる必要
があった。In order to improve the performance of the oxide ceramic superconducting fiber of the present invention, it is extremely important to reduce the porosity of the fiber. By lowering the porosity, the diameter of the oxide ceramic superconducting fiber can be made extremely thin, and various performances can be greatly improved. In order to reduce the porosity of oxide superconducting fibers, it was necessary to use a precursor with a small particle size.
かかる意味において、」1記の酸化物超電導体の粉末、
あるいは加熱処理することによって酸化物超電導体にな
り得る物質の粉末としては、平均粒径15μm以下、好
ましくは1μm以下、更に好ましくは0.5μm以下、
とりわけ好ましくは0.2μm以下のものを用いるのが
、得られる繊維の気孔率を小さくし得、ひいては、細い
繊維を得ることができ、かつまた強伸度物性およびJc
を大きくし得る点から望ましい。In this sense, the oxide superconductor powder described in 1.
Alternatively, as a powder of a substance that can become an oxide superconductor by heat treatment, the average particle size is 15 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less,
It is especially preferable to use a fiber with a diameter of 0.2 μm or less, as this can reduce the porosity of the obtained fibers, thereby making it possible to obtain thin fibers, and also to improve the physical properties of strength, elongation, and Jc.
This is desirable because it can increase the
また上記の、バインダーとして使用するポリマーとして
は、水あるいは有機溶媒に可溶であるか、または熱可塑
性のものであり、」二連の無機粉末を凝集させることな
く分散保持する性質を有し、かつ紡糸により繊維化でき
るすべてのポリマーを挙げることができる。In addition, the above-mentioned polymer used as a binder is soluble in water or an organic solvent, or is thermoplastic, and has the property of dispersing and maintaining the two series of inorganic powders without agglomerating them. Mention may also be made of all polymers which can be made into fibers by spinning.
具体的には、ポリビニルアルコール系共重合体、ヒドロ
キシプロピルセルロース、ヒトロキシエヂルセルロース
、メチルセルロース、ポリエステル、ポリアミド、ポリ
エチレン、ポリプロピレン、ポリスチレン、ポリアクリ
ル酸エステル、ポリメタクリル酸エステル、ポリビニル
ピロリドン等を挙げることができる。また、無機粉末の
分散保持を目的に種々の分散剤を併用することも可能で
ある。Specifically, polyvinyl alcohol copolymers, hydroxypropylcellulose, hydroxydiylcellulose, methylcellulose, polyester, polyamide, polyethylene, polypropylene, polystyrene, polyacrylic ester, polymethacrylic ester, polyvinylpyrrolidone, etc. may be mentioned. Can be done. It is also possible to use various dispersants in combination for the purpose of maintaining the dispersion of the inorganic powder.
紡糸後の繊維の焼成方法としては例えば酸素の存在下、
950°C〜1000℃の温度において数分〜数時間、
好ましくは数分〜数十分間焼成した後、徐冷する方法が
挙げられる。As a method for firing the fiber after spinning, for example, in the presence of oxygen,
Several minutes to several hours at a temperature of 950°C to 1000°C,
Preferably, a method of baking for several minutes to several tens of minutes and then slowly cooling is mentioned.
E 、 −び −口」λJ1
本発明の酸化物セラミックス超電導繊維は高い強度と良
好な柔軟性を有し、超電導マグネットあるいは超電導送
電線用の超電導繊維として極めて好適に用いられる。該
繊維は単独で用いても良いが、−本一本の繊維のまわり
を銅・アルミニウム等の金属で包み込み安定化超電導線
材として用いるのが良い。The oxide ceramic superconducting fiber of the present invention has high strength and good flexibility, and is extremely suitably used as a superconducting fiber for a superconducting magnet or a superconducting power transmission line. Although the fibers may be used alone, it is preferable to wrap each fiber with a metal such as copper or aluminum and use it as a stabilized superconducting wire.
本発明の酸化物セラミックス超電導繊維を用いる具体的
な用途としてはMHD発電、磁気浮上列車、超電導発電
機、NMR−CT、高エネルギー加速装置等を挙げるこ
とができる。Specific applications of the oxide ceramic superconducting fiber of the present invention include MHD power generation, magnetic levitation trains, superconducting generators, NMR-CT, high energy accelerators, and the like.
以下実施例により本発明をより具体的に説明する。EXAMPLES The present invention will be explained in more detail with reference to Examples below.
測定法:
超電導繊維の臨界温度(Tc)及び電流密度(Jc)は
、標準的な四端子法で超電導繊維の電気抵抗を測定する
ことで求めた。この端子は直径70μmの白金線であり
、試料の接着には銀製の導電性接着剤を用いた。試料温
度は、(クロメル−金+0.007%鉄)熱電対を用い
て測定した。Measurement method: The critical temperature (Tc) and current density (Jc) of the superconducting fiber were determined by measuring the electrical resistance of the superconducting fiber using a standard four-probe method. This terminal was a platinum wire with a diameter of 70 μm, and a silver conductive adhesive was used to adhere the sample. Sample temperature was measured using a (chromel-gold + 0.007% iron) thermocouple.
超電導繊維の引張り強さ及び伸度は、インストロン型引
張り試験機にて室温で、チャック間距離5mm、引張り
速度0.033m/秒により測定した。The tensile strength and elongation of the superconducting fibers were measured using an Instron type tensile testing machine at room temperature, with a chuck distance of 5 mm, and a tensile speed of 0.033 m/sec.
Y2O320g、 BaCO369,9gおよびCu
O43,3gをよく混合したのち、950℃で5時間仮
焼きした後、粉砕し、846メツシユのフィルターを通
ずことにより、直径15μm以下の仮焼き粉末を得た。Y2O320g, BaCO369.9g and Cu
After thoroughly mixing 3.3 g of O4, the mixture was calcined at 950° C. for 5 hours, pulverized, and passed through an 846 mesh filter to obtain calcined powder with a diameter of 15 μm or less.
参考例2
Y20320g、 BaCO369,9gおよびCuO
43,3gをよく混合したのち、950℃で5時間保持
したのち、酸素ガス流下に100℃/時間の速度で室温
まで冷却し、単一の斜方晶形のYBa、Cu307−、
の酸化物超電導体を得た。これを粉砕し、846メツシ
ユのフィルターを通すことにより、直径15μm以下の
酸化物超電導体粉末を得た。Reference example 2 Y20320g, BaCO369.9g and CuO
After thoroughly mixing 43.3 g of YBa, Cu307-
An oxide superconductor was obtained. This was pulverized and passed through an 846 mesh filter to obtain oxide superconductor powder with a diameter of 15 μm or less.
参考例3
Y(NO3)3’6H20log、 Ba(NO3)、
13.6gおよびCLI(No、)、・3H2018,
9gをそれぞれ蒸留水に溶解し、混合してから全体で3
00m12の水溶液とした。これを直径0.8mmの注
射針を取付けた注射器に入れ、0.7モル/QのLCO
3水溶液300m(!中に噴射させて共沈物の微粉を得
た。この時、系のpI■が7〜8となるようにKOI+
水溶液を適宜加えた。得られた粉末を濾過後、水で3回
洗浄し、アルコール洗浄した後、45℃で乾燥した。続
いて850℃で2時間仮焼きを行ない、粒径が0.2μ
m以下の微粉末を得た。Reference example 3 Y(NO3)3'6H20log, Ba(NO3),
13.6g and CLI (No, ), 3H2018,
Dissolve 9g of each in distilled water and mix, then add a total of 3
It was made into an aqueous solution of 00ml12. Pour this into a syringe fitted with a 0.8 mm diameter needle, and add 0.7 mol/Q of LCO.
3 aqueous solution was injected into 300 m (!) to obtain a fine coprecipitate powder. At this time, KOI +
Aqueous solution was added accordingly. The obtained powder was filtered, washed three times with water, washed with alcohol, and then dried at 45°C. Subsequently, calcination was performed at 850℃ for 2 hours, and the particle size was reduced to 0.2μ.
A fine powder of less than m was obtained.
実施例1
参考例1で調整した15μm以下の粉末]、Ogを蒸留
水15g中に分散させた。(これをA液とする)別に調
整した5%のポリビニルアルコール(以下PVAと記す
)(重合度1700、けん化度985モル%)水溶液1
5gにポリオキシエチレン(10)オクヂルフ一12=
エニルエーテル004gとドデソル硫酸ナトリウム0.
04gを加え混合した。(これをB液とする)続いてB
液中にA液を加え、よく撹拌しながらポットプレート上
で全量を30gまで濃縮し原液とした。Example 1 Powder of 15 μm or less prepared in Reference Example 1] and Og were dispersed in 15 g of distilled water. (This will be referred to as Solution A) Separately prepared 5% polyvinyl alcohol (hereinafter referred to as PVA) (polymerization degree 1700, saponification degree 985 mol%) aqueous solution 1
5 g of polyoxyethylene (10) ocdyl 12 = enyl ether 0.04 g and sodium dodesol sulfate 0.
04g was added and mixed. (Let this be liquid B) Next, B
Solution A was added to the solution, and the total amount was concentrated to 30 g on a pot plate while stirring well to obtain a stock solution.
次に20g/ρのN’aOHとu+og/σのNa、S
O4を含む水溶液を40℃に保温したものを凝固液とし
、湿式紡糸してフィラメント化し巻き取った。その後t
oog/ρのI(、S04と300g#2のNa、SO
4を含む水溶液中で中和後、水洗してボビンに巻き取っ
た。このフィラメントを50℃の乾燥機で乾燥したのち
、980℃の炉中に入れ5分保持し、100°C/Hの
速度で酸素ガス流下室温まで冷却し、直径100μmの
酸化物超電導繊維を得た。Next, 20g/ρ of N'aOH and u+og/σ of Na, S
An aqueous solution containing O4 kept at 40°C was used as a coagulating liquid, which was wet-spun into filaments and wound up. then t
oog/ρ I(, S04 and 300g#2 Na, SO
After neutralization in an aqueous solution containing No. 4, it was washed with water and wound up on a bobbin. After drying this filament in a dryer at 50°C, it was placed in a furnace at 980°C and held for 5 minutes, and then cooled to room temperature under a flow of oxygen gas at a rate of 100°C/H to obtain an oxide superconducting fiber with a diameter of 100 μm. Ta.
この繊維の臨界温度(Tc)は83にであり、77Kに
おける臨界電流(Jc) 10A/cm2であった。ま
た引張り強度が2.5MPaで切断伸度が30%であっ
た。The critical temperature (Tc) of this fiber was 83, and the critical current (Jc) at 77K was 10 A/cm2. Further, the tensile strength was 2.5 MPa and the elongation at break was 30%.
実施例2
参考例2で調整した酸化物超電導体粉末を用い、PVA
として重合度2400、けん化度98.5モル%のもの
を用いる以外は実施例1と同様にして、直径100μm
の酸化物超電導繊維を得た。Example 2 Using the oxide superconductor powder prepared in Reference Example 2, PVA
The procedure was the same as in Example 1, except that a polymer with a degree of polymerization of 2400 and a degree of saponification of 98.5 mol% was used.
oxide superconducting fibers were obtained.
この繊維のTcは81にであり、77KにおけるJc
O,4A/cm”であった。また引張り強度が1.0M
Paで、切断伸度が0.5%であった。The Tc of this fiber is 81 and the Jc at 77K.
The tensile strength was 1.0M.
Pa, and the elongation at break was 0.5%.
実施例3
参考例3の共沈法により調整した平均粒径0.2μm以
下の粉末10gを蒸留水15g中に分散させた。Example 3 10 g of powder having an average particle size of 0.2 μm or less prepared by the coprecipitation method of Reference Example 3 was dispersed in 15 g of distilled water.
(これをC液とする)別に調整した5%のPVA(重合
度3300、けん化度98.7モル%)水溶液10gに
蒸留水5g、ポリオキシエチレン(10)オクチルフェ
ニルエーテル0.06gとドデシル硫酸ナトリウム0.
06gを加え混合した。(これをD液とする)続いてD
液中にC液゛を加えよく撹拌しながらホットプレート上
で全量を35gまで濃縮し原液とした。(This will be referred to as Solution C) 10 g of a separately prepared 5% PVA (polymerization degree 3300, saponification degree 98.7 mol%) aqueous solution, 5 g of distilled water, 0.06 g of polyoxyethylene (10) octylphenyl ether, and dodecyl sulfuric acid. Sodium 0.
06g was added and mixed. (Let this be liquid D) Next, D
Solution C was added to the solution and the total amount was concentrated to 35 g on a hot plate while stirring well to obtain a stock solution.
次に20g/f2のN a OHと400g#!のNa
tSO+を含む水溶液を40℃に保温したものを凝固液
とし、湿式紡糸してフィラメント化し巻き取った。その
後100g/f2のH2SO,とaoog/ρのNaz
SO4を含む水溶液中で中和後、水洗してボビンに巻き
取った。このフィラメントを50℃の乾燥機で乾燥した
のち、980℃の炉中に入れ5分保持し、100°C/
IIの速度で酸素ガス流下室温まで冷却し、直径80μ
mの酸化物超電導繊維を得た。Next, 20g/f2 Na OH and 400g#! of Na
An aqueous solution containing tSO+ kept at 40° C. was used as a coagulation solution, which was wet-spun into filaments and wound up. Then 100g/f2 H2SO, and aoog/ρ Naz
After neutralization in an aqueous solution containing SO4, it was washed with water and wound up on a bobbin. After drying this filament in a dryer at 50°C, it was placed in a 980°C oven for 5 minutes, and then heated to 100°C/
Cool to room temperature under oxygen gas flow at a rate of
An oxide superconducting fiber of m was obtained.
この繊維のTcは84にであり、77にでのJcは10
4A/cm”であった。また引張り強度が20MPaで
、切断伸度が2.6%であった。The Tc of this fiber is 84, and the Jc at 77 is 10.
The tensile strength was 20 MPa, and the elongation at break was 2.6%.
特許出願人 株式会社 り ラ しPatent applicant RiRashi Co., Ltd.
Claims (5)
徴とする酸化物セラミックス超電導繊維。(1) An oxide ceramic superconducting fiber characterized by having a diameter of substantially 1000 μm or less.
範囲第1項に記載の酸化物セラミックス 超電導繊維。(2) The oxide ceramic superconducting fiber according to claim 1, which has a diameter of substantially 500 μm or less.
囲第1項に記載の酸化物セラミックス超 電導繊維。(3) The oxide ceramic superconducting fiber according to claim 1, which has a diameter of substantially 200 μm or less.
範囲第1項に記載の酸化物セラミックス 超電導繊維。(4) The oxide ceramic superconducting fiber according to claim 1, which has a diameter of substantially 100 μm or less.
おける臨界電流が1A/cm^2以上である特許請求の
範囲第1項に記載の酸化物セラミ ックス超電導繊維。(5) The oxide ceramic superconducting fiber according to claim 1, which has a critical temperature of 35 K or higher and a critical current of 1 A/cm^2 or higher in the absence of a magnetic field.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62280670A JPH01122511A (en) | 1987-11-05 | 1987-11-05 | Oxide ceramic superconducting fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62280670A JPH01122511A (en) | 1987-11-05 | 1987-11-05 | Oxide ceramic superconducting fiber |
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Publication Number | Publication Date |
---|---|
JPH01122511A true JPH01122511A (en) | 1989-05-15 |
Family
ID=17628292
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62280670A Pending JPH01122511A (en) | 1987-11-05 | 1987-11-05 | Oxide ceramic superconducting fiber |
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Country | Link |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6248696B1 (en) | 1994-07-15 | 2001-06-19 | Basf Corporation | 7-forming, superconducting filaments through bicomponent dry spinning |
US6344167B1 (en) | 1994-02-18 | 2002-02-05 | Basf Corporation | Process for the production of superconductor containing filaments |
-
1987
- 1987-11-05 JP JP62280670A patent/JPH01122511A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6344167B1 (en) | 1994-02-18 | 2002-02-05 | Basf Corporation | Process for the production of superconductor containing filaments |
US6248696B1 (en) | 1994-07-15 | 2001-06-19 | Basf Corporation | 7-forming, superconducting filaments through bicomponent dry spinning |
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