JPH02263726A - Production of superconducting ceramic fiber - Google Patents
Production of superconducting ceramic fiberInfo
- Publication number
- JPH02263726A JPH02263726A JP1259828A JP25982889A JPH02263726A JP H02263726 A JPH02263726 A JP H02263726A JP 1259828 A JP1259828 A JP 1259828A JP 25982889 A JP25982889 A JP 25982889A JP H02263726 A JPH02263726 A JP H02263726A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic fiber
- superconducting ceramic
- fiber
- superconducting
- heat treatment
- 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 61
- 239000000919 ceramic Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 22
- 239000011812 mixed powder Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 239000002887 superconductor Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000006060 molten glass Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 229910000018 strontium carbonate Inorganic materials 0.000 abstract 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000006911 nucleation Effects 0.000 description 5
- 238000010899 nucleation Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 229920006240 drawn fiber Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
- H10N60/0801—Manufacture or treatment of filaments or composite wires
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/20—Permanent superconducting devices
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
- Y10S505/733—Rapid solidification, e.g. quenching, gas-atomizing, melt-spinning, roller-quenching
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
- Y10S505/739—Molding, coating, shaping, or casting of superconducting material
- Y10S505/74—To form wire or fiber
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
- Y10S505/742—Annealing
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Crystallography & Structural Chemistry (AREA)
- Structural Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Glass Compositions (AREA)
- Manufacture, Treatment Of Glass Fibers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、超電導セラミックスファイバの製造方法に関
するもである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a superconducting ceramic fiber.
従来、超電導セラミックスファイバなどの超電導線材は
、例えば「銀シースバイブ伸線法」により製造されてい
る。この方法では、まず原料としてＢ １ ０ ｓ
Ｓ ｒ ＣＯＳＣａ ＣＯｓ Ｃｕ ０等が秤量、混合
された後、予備焼結されて微粉末に粉砕される。次いで
、この原料混合粉末を銀（Ａｇ ）バイブに充填した後
、冷間加工を経て伸線され、細径化される。しかる後、
その線材を熱処理することにより、超電導現象を呈する
線材とされている。Conventionally, superconducting wires such as superconducting ceramic fibers have been manufactured by, for example, the "silver sheath vibe wire drawing method." In this method, first, B 10 s is used as a raw material.
After S r COSCa COs Cu 0, etc. are weighed and mixed, they are pre-sintered and ground into fine powder. Next, this raw material mixed powder is filled into a silver (Ag) vibrator, and then cold-worked and wire-drawn to reduce the diameter. After that,
By heat-treating the wire, the wire exhibits superconductivity.
しかしながら、従来の製造方法では下記のような問題が
あった。第１は、バイブを冷間加工によって伸線してい
るため、長尺な線材を連続して得られないことである。However, conventional manufacturing methods have the following problems. First, since the vibrator is drawn by cold working, it is not possible to continuously obtain a long wire rod.
第２は、原料混合粉末をバイブに充填して伸線している
ため、バイブの内部で原料混合粉末が途切れることがあ
り、従って十分な細径化ができないことである。第３は
、銀シースで覆った状態で熱処理しているため、超電導
セラミックスの作製において重要な酸素の供給が不十分
になることである。Second, since the raw material mixed powder is filled in a vibrator for wire drawing, the raw material mixed powder may be interrupted inside the vibrator, and therefore, sufficient diameter reduction cannot be achieved. Third, since heat treatment is performed while covered with a silver sheath, the supply of oxygen, which is important in the production of superconducting ceramics, becomes insufficient.
［課題を解決するための手段〕
本発明者は上記課題の解決のため、鋭意研究を重ねた結
果、長尺であって可撓性が高く、しかも高い臨界電流密
度を有する超電導セラミックスファイバの製造方法を見
出した。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventor has conducted intensive research and has succeeded in manufacturing a superconducting ceramic fiber that is long, highly flexible, and has a high critical current density. I found a way.
この製造方法においては、まず第１工程として、超電導
酸化物を構成し得る原料混合粉末が用意され、その融点
温度以上での加熱溶融の後に、急速冷却によって超伝導
組成のガラス母材が形成される。ここで、加熱溶融温度
は原料混合粉末の融点プラス４００℃を越えないように
することが望ましい。これは、原料混合粉末中の蒸気圧
の高い成分が揮散しないようにするためである。また、
急冷処理は例えば原料融液を鉄板上に流してプレスすれ
ばよい。また、原料に炭酸塩を使用したとき：ごは、カ
ーボンを除去するため８００℃程度で仮焼してもよい。In this manufacturing method, in the first step, a raw material mixed powder that can constitute a superconducting oxide is prepared, and after being heated and melted above its melting point temperature, a glass base material having a superconducting composition is formed by rapid cooling. Ru. Here, it is desirable that the heating melting temperature does not exceed the melting point of the raw material mixed powder plus 400°C. This is to prevent components with high vapor pressure in the raw material mixed powder from volatilizing. Also,
The rapid cooling process may be performed, for example, by pouring the raw material melt onto an iron plate and pressing it. Further, when carbonate is used as a raw material: rice may be calcined at about 800° C. to remove carbon.
次に、第２工程として、超伝導組成のガラス母材を第１
図のような紡糸装置にセットし、所望の外径のファイバ
に線引きする。第１図に示すように、ガラス母材１は石
英製のダミー棒２に固着され、このガラス母材１は石英
管３に挿入される。Next, as a second step, a glass base material with a superconducting composition is
Set it in the spinning device as shown in the figure and draw it into a fiber of the desired outer diameter. As shown in FIG. 1, a glass base material 1 is fixed to a dummy rod 2 made of quartz, and this glass base material 1 is inserted into a quartz tube 3.
そして、石英管３の外側にはヒーター４が設けられてい
る。ダミー棒２が母材送り装置５によって下降されると
、そのダミー棒２の先端のガラス母材］はヒーター４で
加熱され、軟化して線引きが始められる。線引きされた
ファイバ６はキャプスタン７を経由して、巻取部８に巻
き取られる。なおこのときの線引き温度は、ガラス母材
１の粘性が１０６〜１０’ ［ｐｏｉｓｅ ］の範囲
に相当する温度であることが望ましい。A heater 4 is provided outside the quartz tube 3. When the dummy rod 2 is lowered by the base material feeding device 5, the glass base material at the tip of the dummy rod 2 is heated by the heater 4, softened, and wire drawing begins. The drawn fiber 6 passes through a capstan 7 and is wound into a winding section 8 . Note that the drawing temperature at this time is preferably a temperature corresponding to a viscosity of the glass base material 1 in the range of 10 6 to 10' [poise].
次に、第３工程として、線引きされたファイバの熱処理
による再結晶化を行なう。熱処理条件については、アモ
ルファス状態から数多くの結晶を大きく成長させるため
に、結晶核生成温度（結晶核生成の速度が最大となる温
度）で１時間以上保持した後、結晶成長温度（結晶成長
の速度が最大となる温度）で２０時間以上保持する。結
晶核生成温度はガラスの粘性が１０ 〜１０１２［ｐｏ
ｌｓｅ ］の範囲に相当する温度であり、結晶成長温度
は原料の組成によって異なる。また、結晶核の生成を促
進するために、核形成剤としてＡｇを添加することも有
効である。ここで、Ａｇは超電導特性に悪影響を及ぼさ
ない（“Ａｐｐｌｉｅｄ ｐｈｙｓｉｃｓ Ｌｅｔｔｅ
ｒ５２（１９）、９ Ｍａｙ 、１９８Ｂ ’）。Next, as a third step, the drawn fiber is recrystallized by heat treatment. Regarding the heat treatment conditions, in order to grow large numbers of crystals from an amorphous state, the temperature is maintained at the crystal nucleation temperature (the temperature at which the rate of crystal nucleation is maximum) for more than one hour, and then the crystal growth temperature (the temperature at which the rate of crystal growth is the highest) is maintained. (maximum temperature) for 20 hours or more. The crystal nucleation temperature is determined when the viscosity of the glass is 10 to 1012 [po
lse ], and the crystal growth temperature varies depending on the composition of the raw material. Furthermore, in order to promote the generation of crystal nuclei, it is also effective to add Ag as a nucleating agent. Here, Ag does not have a negative effect on superconducting properties (“Applied physics Lette
r52(19), 9 May, 198B').
次に、望ましくは次の第４工程が付加される。Next, the following fourth step is preferably added.
すなわち、第３工程で得られた超電導セラミックスファ
イバをＡｇ等の金属で被覆し、圧延機やプレス機等で加
圧して熱処理を行なう。ここで上記の加圧はファイバの
側面方向から、すなちわ電流の方向と直交する方向から
行なうのが望ましく、その程度はファイバのへき間柱が
高まり得る程度、たとえば１ｔｏｎ／ｃｄ程度以上の圧
力で行なうのが望ましく、熱処理は前述の結晶成長温度
で２０時間程度以上行なうのが望ましい。上記の加圧お
よび熱処理は１回だけでもよいが、複数回繰り返すのが
より望ましい。さらに、加圧と熱処理の組み合せとして
は、加圧の終了後に熱処理するものの他、加圧中から熱
処理を開始するものや、加圧と熱処理を並行的に行なう
ものもある。なお、前述の金属による被覆は、ファイバ
全体が被覆可能な方法であれば、いかなるものでもよい
。例えば金属パイプにファイバを挿入したり、２枚のテ
ープ状金属でファイバを被覆したり、金属の融液中にフ
ァイバを浸漬（ディッピング）することが考えられる。That is, the superconducting ceramic fiber obtained in the third step is coated with a metal such as Ag, and heat-treated by applying pressure using a rolling mill, a press machine, or the like. Here, it is preferable that the above-mentioned pressure is applied from the side direction of the fiber, that is, from the direction perpendicular to the direction of the current, and the pressure is set to a level that can increase the fiber spacing, for example, a pressure of about 1 ton/cd or more. The heat treatment is preferably carried out at the above-mentioned crystal growth temperature for about 20 hours or more. The above pressurization and heat treatment may be performed only once, but it is more desirable to repeat them multiple times. Furthermore, as a combination of pressurization and heat treatment, there are cases in which heat treatment is performed after completion of pressurization, cases in which heat treatment is started during pressurization, and cases in which pressurization and heat treatment are performed in parallel. Note that the above-mentioned metal coating may be performed by any method as long as the entire fiber can be coated. For example, the fiber may be inserted into a metal pipe, the fiber may be covered with two metal tapes, or the fiber may be dipped into a metal melt.
本発明によれば、ガラス母材およびファイバには被覆が
なく、酸素の出入りが自由となっているので、超電導セ
ラミックス中の酸素が欠乏したりすることがない。また
、理論密度に近いアモルファス状態から超電導結晶を析
出、成長させているために、超電導セラミックス粉末を
加圧形成する従来の方法に較べて、密度の高い緻密な超
電導セラミックスからなるファイバが得られ、臨界電流
密度の向上に対して有効に働く。また、ガラス母材から
長尺のファイバを連続して紡糸することが可能であり、
ファイバ径の制御も任意に行ないうる。According to the present invention, the glass base material and the fiber are not coated and oxygen can freely enter and exit, so that the superconducting ceramic will not be depleted of oxygen. In addition, since superconducting crystals are precipitated and grown from an amorphous state close to the theoretical density, fibers made of dense superconducting ceramics can be obtained compared to the conventional method of forming superconducting ceramic powder under pressure. Works effectively to improve critical current density. In addition, it is possible to continuously spin long fibers from a glass base material,
The fiber diameter can also be controlled arbitrarily.
更に、加圧および熱処理の組み合せからなる工程を付加
すれば、超電導結晶のへき間柱を高めることにより、臨
界電流密度の飛躍的向上が可能になる。Furthermore, by adding a process consisting of a combination of pressurization and heat treatment, the critical current density can be dramatically improved by increasing the interstitial pillars of the superconducting crystal.
以下、本発明の好適な実施例を説明する。 Hereinafter, preferred embodiments of the present invention will be described.
（実施例１）
まず、Ｂ１ ０ 、 Ｐｂ Ｏ，Ｓｒ Ｃｏ 、
ＣａＣＯ３およびＣｕＯを
Ｂ１ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１，
６：０． ４：２：２：”３
となるように秤量し、混合した。この混合された粉末を
白金るつぼに入れて、１１５０℃で４０分間溶融した後
、冷却された鉄板上に融液を流し、もう１枚の鉄板でプ
レスして２１１ＩＩＩの厚さの板ガラスを得た。このガ
ラスを横７１１１１１縦５（至）に加工し、これを石英
製のダミー棒の先端に取付けた後、４３５℃に加熱され
た電気炉に挿入して線引し、幅１．５關、厚さ１００μ
ｍ１長さ１０ｍのテープ状ファイバを得た。(Example 1) First, B1 0 , Pb O, Sr Co ,
CaCO3 and CuO as B1:Pb:Sr:Ca:Cu-1,
6:0. They were weighed and mixed so that the ratio was 4:2:2:3.The mixed powder was placed in a platinum crucible and melted at 1150°C for 40 minutes, then the melt was poured onto a cooled iron plate. Pressed with another iron plate to obtain a plate glass with a thickness of 211III.This glass was processed into a width of 711111 and a length of 5 (to).After attaching it to the tip of a dummy rod made of quartz, it was heated to 435℃. Insert it into a heated electric furnace and draw it to a width of 1.5 mm and a thickness of 100 μm.
A tape-shaped fiber with m1 length of 10 m was obtained.
このファイバは可撓性に優れており、直径が１０ｍ＋ｓ
のマンドレルにも十分に巻きつけることができた。次に
、このテープ状ファイバを熱処理炉に入れて、４３０℃
で４時間の処理（結晶核の生成処理）をした後、８２０
℃に昇温しで、さらに６０時間の熱処理（結晶成長処理
）をした。このようにして得られた超電導セラミックス
ファイバの特性（臨界温度Ｔ 、臨界電流密度Ｊ ）を
、ＣＣ
公知の４端子法で測定したところ、Ｔ （Ｒ−０）一
８６″に、Ｊ ＝１０ＯＡ／ｃｄ（７７’に、零磁場
下）の超電導特性を得た。This fiber has excellent flexibility and has a diameter of 10m+s.
I was able to wrap it around a mandrel. Next, this tape-shaped fiber was placed in a heat treatment furnace at 430°C.
After 4 hours of treatment (crystal nucleus generation treatment), 820
The temperature was raised to .degree. C., and heat treatment (crystal growth treatment) was performed for an additional 60 hours. The characteristics (critical temperature T, critical current density J) of the superconducting ceramic fiber obtained in this way were measured using the CC well-known four-terminal method, and it was found that T (R-0) - 86'', J = 10OA/ cd (at 77', under zero magnetic field) superconducting properties were obtained.
（実施例２）
実施例１の工程において、熱処理条件のみを変化させた
。すなわち、テープ状ファイバを熱処理炉に入れて、４
２３℃で４時間の処理をした後、８６０℃に昇温しで１
００時間の熱処理をした。(Example 2) In the process of Example 1, only the heat treatment conditions were changed. That is, the tape-shaped fiber is placed in a heat treatment furnace and subjected to 4
After 4 hours of treatment at 23°C, the temperature was raised to 860°C and 1
Heat treatment was performed for 00 hours.
その結果、Ｔ ＣＲ繍０）−１０１’に、Ｊ −Ｃ １００Ａ／ｃｊ（７７″に１零磁場下）の特性を得た。As a result, T CR 0)-101', J-C A characteristic of 100 A/cj (under 1 zero magnetic field at 77'') was obtained.
（実施例３）
まず、Ｂ１ ０ 、 Ｐｂ ０％Ｓｒ Ｃｏ 、Ｃ
ａＣＯ３およびＣｕＯを
Ｂｉ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１，
６：０． ４：２：２：３
となるように秤量し、混合した。その混合された原料の
重量の２０％に相当するＡ ｇ ２０を秤量し、上記の
原料混合粉末に加えた。この原料粉末を白金るつぼに入
れ、１１５０℃で４０分間溶融した後、冷却された鉄板
上に融液を流し、もう１枚の鉄板でプレスして２ ｍｍ
の厚さの板ガラスを得た。そして、このガラスを実施例
１と同一方法で線引し、同一温度条件で熱処理を行なっ
て超電導セラミックスファイバを得た。(Example 3) First, B1 0 , Pb 0%Sr Co , C
aCO3 and CuO as Bi:Pb:Sr:Ca:Cu-1,
6:0. They were weighed and mixed in a ratio of 4:2:2:3. A g 20 corresponding to 20% of the weight of the mixed raw materials was weighed and added to the raw material mixed powder. This raw material powder was placed in a platinum crucible and melted at 1150°C for 40 minutes, then the melt was poured onto a cooled iron plate and pressed with another iron plate to form a 2 mm piece.
A plate glass with a thickness of . Then, this glass was drawn in the same manner as in Example 1, and heat treated under the same temperature conditions to obtain a superconducting ceramic fiber.
上記の方法によるファイバの作製を２回行ない、それぞ
れ得られた２つのファイバ（サンプルＡ。The above method was used to fabricate fibers twice, resulting in two fibers (Sample A).
Ｂ）の特性を４端子法で測定したところ、サンプルＡで
はＴ （Ｒ−０）−８７”Ｋ、Ｊ 箇２５０Ｃ
Ａ／ｃｄｃ７７’に、零磁場下）、サンプルＢではＴ
（Ｒ−０）＝１０２’ＫＳＪ −２５０Ａ／ｃｄＣ
（７７’ＩＣ１零磁場下）の特性を得た。実施例１のも
のに比べて臨界電流密度Ｊ が向上した理由は、Ａｇの
添加によって結晶核の生成が促進され、より緻密な組織
となったためであると考えられる。When the characteristics of B) were measured using the four-terminal method, sample A had T(R-0)-87"K, J (at 250C A/cdc77', under zero magnetic field), and sample B had T.
A characteristic of (R-0)=102'KSJ -250A/cdC (77'IC1 under zero magnetic field) was obtained. The reason why the critical current density J was improved compared to that of Example 1 is considered to be that the addition of Ag promoted the generation of crystal nuclei, resulting in a more dense structure.
（実施例４）
まず、実施例１と同様の方法でテープ状ファイバを作製
した。次に、結晶核生成のための第１段階の熱処理を行
なうことなく、直接に室温から８２０℃まで昇温し、６
０時間の熱処理（結晶成長処理）を施した。このように
して得られた超電導セラミックスファイバの特性を、公
知の４端子法テｉＴ？］定したとコロ、Ｔ （Ｒ−０
）−４０’Ｋ、Ｊ −１ＯＡ／ｃｄ （４，２π、零
磁場下）であつた。実施例１，２に比べれば劣るものの
、はぼ十分な超電導特性が得られている。(Example 4) First, a tape-shaped fiber was produced in the same manner as in Example 1. Next, the temperature was directly raised from room temperature to 820°C without performing the first stage heat treatment for crystal nucleation.
Heat treatment (crystal growth treatment) was performed for 0 hours. The characteristics of the superconducting ceramic fiber obtained in this way were evaluated using the known four-terminal method. ] set and colo, T (R-0
) -40'K, J -1OA/cd (4,2π, under zero magnetic field). Although inferior to Examples 1 and 2, almost sufficient superconducting properties were obtained.
（実施例５）
まず、実施例１と同様の方法でテープ状ファイバを作製
した。次に、結晶核生成のため第１段階の熱処理を行な
うことなく、直接に室温から８６０℃まで昇温し、１０
０時間の熱処理（結晶成長処理）を施した。このように
して得られた超電導セラミックスファイバの特性を、公
知の４端子法で測定したところ、Ｔ −（Ｒ−０）−
８０玉、Ｊ ＝１ＯＡ／ｃシ（７７’に、零磁場下）
であった。(Example 5) First, a tape-shaped fiber was produced in the same manner as in Example 1. Next, the temperature was directly raised from room temperature to 860°C without performing the first stage heat treatment for crystal nucleation.
Heat treatment (crystal growth treatment) was performed for 0 hours. The characteristics of the superconducting ceramic fiber obtained in this way were measured using a known four-probe method, and it was found that T -(R-0)-
80 balls, J = 1OA/c (at 77', under zero magnetic field)
Met.
（実施例６）
実施例１と同一の方法で作製したテープ状ファイバ２１
を、第２図のように幅３關、厚さ３００μｍの２枚のＡ
ｇテープ２２．２３で挟み、プレス機によって２０ｔｏ
ｎ／ｃ−の圧力を加えた。次いで、このファイバを８５
０℃で５０時間の熱処理をした後、上記のプレス機によ
る加圧と熱処理を、同一条件で再度繰り返した。このよ
うにして得られたファイバの特性を４端子法で調べたと
ころ、７７’に、零磁場下でＪ −３５００Ａ／ｃｄ
の高い臨界電流密度が観測された。(Example 6) Tape-shaped fiber 21 produced by the same method as Example 1
As shown in Figure 2, two sheets of A with a width of 3 mm and a thickness of 300 μm are
Sandwiched with g tape 22.23 and pressed 20 to
A pressure of n/c- was applied. This fiber is then
After heat treatment at 0° C. for 50 hours, the above pressurization and heat treatment were repeated again under the same conditions. When the characteristics of the fiber obtained in this way were investigated using the four-terminal method, it was found that 77'
A high critical current density was observed.
（実施例７）
まず、仕込み組成を
Ｂｉ ：Ｐｂ ：Ｓｒ ：Ｃａ ：Ｃｕ−１，６：０
．４：２：２：３
となるように秤量し、混合した。そして、８００℃で１
０時間の仮焼きをした後、粉砕して再度混合した。この
混合粉末を白金るつぼに入れ、１１５０℃で２０分間溶
融した後、実施例１と同一方法でガラス化、線引した。(Example 7) First, the charging composition was Bi:Pb:Sr:Ca:Cu-1,6:0
．． They were weighed and mixed in a ratio of 4:2:2:3. And 1 at 800℃
After calcination for 0 hours, the mixture was ground and mixed again. This mixed powder was placed in a platinum crucible and melted at 1150° C. for 20 minutes, and then vitrified and wire-drawn in the same manner as in Example 1.
次に、このファイバを熱処理炉に入れ、４２３℃の温度
条件で４時間の熱処理を行ない、８６０℃に昇温しで更
に２４０時間の熱処理を行なって超電導セラミックスフ
ァイバを得た。Next, this fiber was placed in a heat treatment furnace and heat treated at 423° C. for 4 hours, then heated to 860° C. and further heat treated for 240 hours to obtain a superconducting ceramic fiber.
上記の方法により得られたファイバの特性を４端子法で
測定したところ、Ｔ （Ｒ−０）−６８π、Ｊ ＝
５１Ａ／ｃｄ （４，２″に１零磁場下）、の特性を得
た。When the characteristics of the fiber obtained by the above method were measured using the four-terminal method, T (R-0)-68π, J =
A characteristic of 51 A/cd (under 1 zero magnetic field at 4.2'') was obtained.
以上、詳細に説明したように、原料を溶融、急冷するこ
とによって超電導組成のガラス母材を作製し、このガラ
ス母材を電気炉で線引することによってファイバが得ら
れるので、このファイバは長尺かつ可撓性に優れたもの
とすることができる。As explained in detail above, a glass base material with a superconducting composition is produced by melting and rapidly cooling raw materials, and a fiber is obtained by drawing this glass base material in an electric furnace. It can be made to be long and have excellent flexibility.
また、ファイバの外径についても任意に制御することが
できる。さらに、アモルファス状態から結晶化させるこ
とで緻密な結晶組織が得られるので、臨界電流密度Ｊ
の向上に対しても有効である。Furthermore, the outer diameter of the fiber can also be controlled arbitrarily. Furthermore, since a dense crystal structure can be obtained by crystallizing from an amorphous state, the critical current density J
It is also effective for improving
一方、金属被覆した後に加圧、熱処理をすることで、Ｊ
を飛躍的に向上できるので、送電用ケ−プルやマグネ
ットへの応用が期待できる。On the other hand, by applying pressure and heat treatment after metal coating, J
Since this technology can dramatically improve the performance, it can be expected to be applied to power transmission cables and magnets.
【図面の簡単な説明】
第１図はファイバを線引きするための紡糸装置を示す図
、第２図はファイバに金属を被覆する状態を示す図であ
る。
１・・・ガラス母材、２・・・ダミー棒、４・・・ヒー
ター２１・・・テープ状ファイバ、２２．２３・・・Ａ
ｇテープ。
第１目BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a spinning device for drawing a fiber, and FIG. 2 is a diagram showing a state in which the fiber is coated with metal. DESCRIPTION OF SYMBOLS 1...Glass base material, 2...Dummy rod, 4...Heater 21...Tape-shaped fiber, 22.23...A
g tape. 1st eye
Claims (10)
ス母材とする第１工程と、前記ガラス母材を加熱してフ
ァイバに線引きする第２工程と、前記ファイバを熱処理
によって超電導セラミックスファイバとする第３工程と
を備えることを特徴とする超電導セラミックスファイバ
の製造方法。1. A first step of heating and melting the raw material mixed powder and then cooling it to form a glass base material, a second step of heating the glass base material and drawing it into a fiber, and a third step of heating the fiber to form a superconducting ceramic fiber through heat treatment. A method for manufacturing a superconducting ceramic fiber, comprising the steps of:
バを加圧する第４工程を更に備える請求項１記載の超電
導セラミックスフィバの製造方法。2. The method for manufacturing a superconducting ceramic fiber according to claim 1, further comprising a fourth step of pressurizing the superconducting ceramic fiber obtained in the third step.
バを加圧して熱処理する第４工程を更に備える請求項１
記載の超電導セラミックスフィバの製造方法。3. Claim 1 further comprising a fourth step of pressurizing and heat-treating the superconducting ceramic fiber obtained in the third step.
The method for manufacturing the superconducting ceramic fiber described above.
バを金属で被覆し、加圧して熱処理する第４工程を更に
備える請求項１記載の超電導セラミックスフィバの製造
方法。4. 2. The method for producing a superconducting ceramic fiber according to claim 1, further comprising a fourth step of coating the superconducting ceramic fiber obtained in the third step with a metal, pressurizing it, and heat-treating it.
の融点以上であって当該融点プラス４００℃以下である
請求項１，２，３または４記載の超電導セラミックスフ
ァイバの製造方法。5. 5. The method for producing a superconducting ceramic fiber according to claim 1, wherein the heating and melting temperature in the first step is higher than the melting point of the raw material mixed powder and lower than or equal to the melting point plus 400°C.
から多数の結晶核を均一に生成させる第１の熱処理工程
と、前記結晶核に超電導結晶を成長させる第２の熱処理
工程とを有する請求項１，２，３，４または５記載の超
電導セラミックスファイバの製造方法。6. 2. The second step comprises a first heat treatment step for uniformly generating a large number of crystal nuclei from the amorphous state of the fiber, and a second heat treatment step for growing superconducting crystals on the crystal nuclei. , 3, 4 or 5, the method for producing a superconducting ceramic fiber.
のための結晶核の析出を促進する核形成剤が添加されて
いる請求項１，２，３，４，５または６記載の超電導セ
ラミックスファイバの製造方法。7. The superconductor according to claim 1, 2, 3, 4, 5, or 6, wherein the raw material mixed powder contains a nucleating agent that promotes precipitation of crystal nuclei for recrystallization in the third step. Method of manufacturing ceramic fiber.
ラミックスファイバの製造方法。8. 8. The method for manufacturing a superconducting ceramic fiber according to claim 7, wherein the nucleating agent is Ag.
かの工程を複数回繰り返す工程である請求項３または４
記載の超電導セラミックスファイバの製造方法。9. 4. The fourth step is a step of repeating pressurization and/or heat treatment multiple times.
A method for manufacturing the superconducting ceramic fiber described.
がＡｇである請求項４または９記載の超電導セラミック
スファイバの製造方法。10. The method for manufacturing a superconducting ceramic fiber according to claim 4 or 9, wherein the metal coating the superconducting ceramic fiber is Ag.
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1259828A JPH02263726A (en) | 1988-11-18 | 1989-10-04 | Production of superconducting ceramic fiber |
| US07/435,039 US4975416A (en) | 1988-11-18 | 1989-11-13 | Method of producing superconducting ceramic wire |
| AU44635/89A AU4463589A (en) | 1988-11-18 | 1989-11-14 | Method of producing superconducting ceramic wire |
| DE68922965T DE68922965T2 (en) | 1988-11-18 | 1989-11-17 | Method of making superconducting ceramic wires. |
| SU894742467A RU1831470C (en) | 1988-11-18 | 1989-11-17 | Process of manufacture of a superconductor ceramic wire |
| ES89121306T ES2075843T3 (en) | 1988-11-18 | 1989-11-17 | PRODUCTION METHOD OF A CERAMIC SUPERCONDUCTOR WIRE. |
| EP89121306A EP0369464B1 (en) | 1988-11-18 | 1989-11-17 | Method of producing superconducting ceramic wire |
| KR1019890016741A KR920003025B1 (en) | 1988-11-18 | 1989-11-18 | Method of producing superconducting ceramic wire |
| CN89108697A CN1027776C (en) | 1988-11-18 | 1989-11-18 | Method of producing superconducting ceramic wire |
| BR898905840A BR8905840A (en) | 1988-11-18 | 1989-11-20 | SUPERCONDUCTIVE CERAMIC WIRE PRODUCTION METHOD |
| US07/612,457 US5229357A (en) | 1988-11-18 | 1990-11-14 | Method of producing superconducting ceramic wire and product |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29221088 | 1988-11-18 | ||
| JP63-292210 | 1988-11-18 | ||
| JP1259828A JPH02263726A (en) | 1988-11-18 | 1989-10-04 | Production of superconducting ceramic fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02263726A true JPH02263726A (en) | 1990-10-26 |
Family
ID=17778945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1259828A Pending JPH02263726A (en) | 1988-11-18 | 1989-10-04 | Production of superconducting ceramic fiber |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH02263726A (en) |
| KR (1) | KR920003025B1 (en) |
| AU (1) | AU656665B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4134747A (en) * | 1977-03-16 | 1979-01-16 | Corning Glass Works | Method of forming transparent and opaque portions in a reducing atmosphere glass |
| US4861751A (en) * | 1987-07-23 | 1989-08-29 | Standard Oil Company | Production of high temperature superconducting materials |
-
1989
- 1989-10-04 JP JP1259828A patent/JPH02263726A/en active Pending
- 1989-11-18 KR KR1019890016741A patent/KR920003025B1/en not_active IP Right Cessation
-
1993
- 1993-04-22 AU AU37099/93A patent/AU656665B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| KR920003025B1 (en) | 1992-04-13 |
| AU656665B2 (en) | 1995-02-09 |
| AU3709993A (en) | 1993-07-29 |
| KR900007752A (en) | 1990-06-01 |
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