EP0464068A1 - Dense superconductive bodies with preferred orientation - Google Patents

Dense superconductive bodies with preferred orientation

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Publication number
EP0464068A1
EP0464068A1 EP90904806A EP90904806A EP0464068A1 EP 0464068 A1 EP0464068 A1 EP 0464068A1 EP 90904806 A EP90904806 A EP 90904806A EP 90904806 A EP90904806 A EP 90904806A EP 0464068 A1 EP0464068 A1 EP 0464068A1
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EP
European Patent Office
Prior art keywords
superconductor
copper
oxygen
crystals
hours
Prior art date
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EP90904806A
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German (de)
French (fr)
Inventor
Martin Dr. Schwarz
Iris Küllmer
Joachim Dr. Bock
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Hoechst AG
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Hoechst AG
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    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/653—Processes involving a melting step
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4504—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing rare earth oxides
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4504—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing rare earth oxides
    • C04B35/4508—Type 1-2-3
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4521—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing bismuth oxide
    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4521—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing bismuth oxide
    • C04B35/4525—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing bismuth oxide also containing lead oxide
    • 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

Definitions

  • the present invention relates to dense, oxide-ceramic superconducting bodies containing copper and an advantageous, regular arrangement of the crystallites, and to a process for their production.
  • the task was therefore to create massive superconductors in which the crystalline regions in the
  • the invention relates to massive, oxide ceramic
  • Examples of copper-containing, oxide-ceramic superconductors according to the invention are compounds of the general formula MBa 2 Cu 3 O X , where M is yttrium or an element of numbers 61 to 71 and x is a number between 6.5 and 7.2, oxide-ceramic superconductors of the system
  • superconductors of the formulas (Bi, Pb) 2 (Sr, Ca) 2 CuO a can be used (see M. Takano et al, Jap. J. Appl. Phys. 27, 6 (1988), L 1041), Bi 2 (Sr, Ca) 2 CuO b ,
  • Additives to dense bodies sinters, so their structure is completely random with regard to the size and shape of the grains.
  • the grains consist of small, irregularly shaped crystalline areas with portions of amorphous areas.
  • the proportion of the additives copper fluoride and potassium fluoride is in particular 0.042-0.44 mol per 100 g of copper of the superconductor. With these additives, the crystals of the superconductors generally have a ratio of
  • the superconductor of the formula MBa 2 Cu 3 O X according to the invention is generally 6.0 to 6.33 g / cm 3 .
  • the superconductors according to the invention can be manufactured in that a powdery copper in
  • the mixture is cooled to a temperature of at least 400 ° C. at which there is no longer any liquid phase, for example to temperatures of 880 to 900 ° C., and the mixture is prepared at this temperature in the presence of an oxygen containing atmosphere for at least one hour, but preferably at least 5 hours. It is particularly preferred if the duration of the heating in both stages is in the range from 10 to 20 hours, preferably at 15 hours. In some cases, the additive can be used during the manufacture of the starting product
  • YBa 2 Cu 3 O X powder is mixed with 5% by weight of finely powdered CUF 2 and pressed to shaped articles under a pressure of approx. 300 MPa (3 kbar).
  • the shaped bodies are sintered as follows:
  • a micrograph of the sample produced shows one
  • the black powder is then pressed into tablets under a pressure of 300 MPa (3 kbar)

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

Supraconducteur compact en céramique oxydée, contenant du cuivre sous forme de réseau cristallin, qui se compose de cristaux enchevêtrés sensiblement parallèles et renferme également pour 100 g de cuivre du supraconducteur 0,04 à 0,5 mole de CuF2 ou KF. Est également décrit un procédé de frittage pour sa fabrication . Le supraconducteur cuprifère peut par exemple être constitué de bismuth, strontium, calcium, plomb ainsi que de cuivre et d'oxygène.Compact superconductor made of oxidized ceramic, containing copper in the form of a crystal lattice, which consists of entangled crystals substantially parallel and also contains per 100 g of copper of the superconductor 0.04 to 0.5 mole of CuF2 or KF. Also described is a sintering process for its manufacture. The copper-bearing superconductor can for example consist of bismuth, strontium, calcium, lead as well as copper and oxygen.

Description

Beschreibung description
Dichte, supraleitende Körper mit Textur Dense, superconducting body with texture
Die vorliegende Erfindung betrifft dichte, oxidkeramische supraleitende Körper mit einem Gehalt an Kupfer und einer vorteilhaften, regelmäßigen Anordnung der Kristallite sowie ein Verfahren zu ihrer Herstellung. The present invention relates to dense, oxide-ceramic superconducting bodies containing copper and an advantageous, regular arrangement of the crystallites, and to a process for their production.
Die jüngst aufgefundenen Hochtemperatur-supraleitenden Verbindungen auf der Basis von Y-Ba-Cu-O, Bi-Sr-Ca-Cu-O oder Tl-Ba-Ca-Cu-O versprechen hinsichtlich ihrer hohen kritischen Temperaturen Tc eine Vielzahl attraktiver The recently found high-temperature superconducting compounds based on Y-Ba-Cu-O, Bi-Sr-Ca-Cu-O or Tl-Ba-Ca-Cu-O promise a multitude of attractive features with regard to their high critical temperatures T c
Anwendungsmöglichkeiten. Nachteilig ist dabei, daß die für Anwendungen eines Massivkörpers (d. h. nicht in Form dünner Schichten) die für viele Anwendungszwecke entscheidende Stromtragefähigkeit nur niedrige Werte aufweist. Als Gründe hierfür werden neben Verunreinigungen an den Korngrenzen ("weak links") vor allem die Tatsache angesehen, daß diese Supraleiter eine schichtartige Kristallstruktur aufweisen, die zu einer Anisotropie wichtiger physikalischer Possible uses. The disadvantage here is that the current carrying capacity, which is decisive for many applications, has only low values for applications of a solid body (i.e. not in the form of thin layers). In addition to impurities at the grain boundaries ("weak links"), the main reasons for this are the fact that these superconductors have a layer-like crystal structure which leads to an anisotropy of important physical
Eigenschaften führt. Beispielsweise hat man an  Properties leads. For example, you have on
Einkristallen von YBa2Cu3O7-X nachgewiesen, daß Single crystals of YBa 2 Cu 3 O 7-X demonstrated that
supraleitende Ströme nur in einer Ebene fließen, die senkrecht zur Gitterachse c verläuft. Ein ungestörter Stromfluß kann deshalb nur dann beobachtet werden, wenn die einzelnen Kristalle parallel zueinander ausgerichtet und eng benachbart sind. Günstig für eine parallele Ausrichtung ist es, wenn die einzelnen (nicht miteinander verbundenen) Kristallite eine Vorzugsrichtung aufweisen, beispielsweise langgestreckt sind.  superconducting currents flow only in a plane that is perpendicular to the lattice axis c. An undisturbed current flow can therefore only be observed if the individual crystals are aligned parallel to one another and closely adjacent. It is favorable for a parallel alignment if the individual (not interconnected) crystallites have a preferred direction, for example they are elongated.
Es bestand daher die Aufgabe, massive Supraleiter zu schaffen, bei denen die kristallinen Bereiche im The task was therefore to create massive superconductors in which the crystalline regions in the
wesentlichen parallel zueinander angeordnet sind. Die Erfindung löst diese Aufgabe. Sie beruht auf der are arranged substantially parallel to each other. The invention solves this problem. It is based on the
Erkenntnis, daß beim Sintern von Pulvern oxidkeramischer, Kupfer im Kristallgitter enthaltender Supraleiter-Pulver die Additive CUF2 und KF die Ausbildung texturierter Proben begünstigen. Recognition that when sintering powders of oxide ceramic superconductor powder containing copper in the crystal lattice, the additives CUF 2 and KF favor the formation of textured samples.
Gegenstand der Erfindung sind massive, oxidkeramische The invention relates to massive, oxide ceramic
Supraleiter, die Kupfer im Kristallgitter enthalten und die ca. 0,04 bis 0,5 Mol Kupfer-(II)-fluorid oder Kaliumfluorid pro 100 g Kupfer des Supraleiters enthalten. Die Superconductors that contain copper in the crystal lattice and that contain approx. 0.04 to 0.5 mol of copper (II) fluoride or potassium fluoride per 100 g of copper of the superconductor. The
Additive scheinen für die günstigen Eigenschaften des Additives seem to have favorable properties
Supraleiters nicht entscheidend zu sein, da diese bei Superconductor not to be critical as this at
Herauslösen des Additivs nicht verschlechtert werden; ihre Gegenwart ist jedoch erforderlich, um zu erreichen, daß die einzelnen kristallinen Bereiche im wesentlichen parallel zueinander angeordnet verwachsen. Removal of the additive cannot be deteriorated; however, their presence is necessary in order to ensure that the individual crystalline regions grow together arranged essentially parallel to one another.
Beispiele für kupferhaltige, oxidkeramische Supraleiter gemäß der Erfindung sind Verbindungen der allgemeinen Formel MBa2Cu3OX, wobei M für Yttrium oder ein Element der Nummern 61 bis 71 steht und x eine Zahl zwischen 6,5 und 7,2 ist, oxidkeramische Supraleiter des Systems Examples of copper-containing, oxide-ceramic superconductors according to the invention are compounds of the general formula MBa 2 Cu 3 O X , where M is yttrium or an element of numbers 61 to 71 and x is a number between 6.5 and 7.2, oxide-ceramic superconductors of the system
Bi-Sr-Ca-Cu-O oder des Systems Bi-Pb-Sr-Ca-Cu-O.  Bi-Sr-Ca-Cu-O or the system Bi-Pb-Sr-Ca-Cu-O.
Einsetzbar sind beispielsweise Supraleiter der Formeln (Bi,Pb)2(Sr,Ca)2CuOa (vgl. M. Takano et al, Jap. J. Appl. Phys. 27, 6 (1988), L 1041), Bi2(Sr,Ca)2CuOb, For example, superconductors of the formulas (Bi, Pb) 2 (Sr, Ca) 2 CuO a can be used (see M. Takano et al, Jap. J. Appl. Phys. 27, 6 (1988), L 1041), Bi 2 (Sr, Ca) 2 CuO b ,
Bi2(Sr,Ca)3Cu2Oc und Bi2(Sr,Ca)4Cu3Od. Bi 2 (Sr, Ca) 3 Cu 2 O c and Bi 2 (Sr, Ca) 4 Cu 3 O d .
Bevorzugt sind Verbindungen des Systems MBa2Cu3OX, Compounds of the MBa 2 Cu 3 O X system are preferred,
insbesondere für den Fall, daß M = Y ist. Wenn man dagegen ein feines Pulver aus YBa2Cu3OX in Abwesenheit von especially if M = Y. If, on the other hand, a fine powder of YBa 2 Cu 3 O X is absent from
Additiven zu dichten Körpern sintert, so ist deren Gefüge hinsichtlich der Größe und Form der Körner völlig regellos aufgebaut. Insbesondere bestehen die Körner aus kleinen, unregelmäßig geformten kristallinen Bereichen mit Anteilen amorpher Bereiche. Der Anteil der Additive Kupferfluorid und Kaliumfluorid liegt insbesondere bei 0,042 - 0,44 Mol pro 100 g Kupfer des Supraleiters. Bei diesen Zusätzen weisen die Kristalle der Supraleiter im allgemeinen ein Verhältnis von Additives to dense bodies sinters, so their structure is completely random with regard to the size and shape of the grains. In particular, the grains consist of small, irregularly shaped crystalline areas with portions of amorphous areas. The proportion of the additives copper fluoride and potassium fluoride is in particular 0.042-0.44 mol per 100 g of copper of the superconductor. With these additives, the crystals of the superconductors generally have a ratio of
Länge/Durchmesser von 3:1 - 30:1 auf. Die Dichte Length / diameter from 3: 1 - 30: 1. The concentration
erfindungsgemäßer Supraleiter der Formel MBa2Cu3OX liegt im allgemeinen bei 6,0 bis 6,33 g/cm3. The superconductor of the formula MBa 2 Cu 3 O X according to the invention is generally 6.0 to 6.33 g / cm 3 .
Die erfindungsgemäßen Supraleiter lassen sich dadurch hersteilen, daß man einen pulverfδrmigen, Kupfer im The superconductors according to the invention can be manufactured in that a powdery copper in
Gitter enthaltenden Supraleiter mit 0,04 bis 0,5 Mol, vorzugsweise 0,042 bis 0,44 Mol, insbesondere 0,045 bis 0,3 Mol Kupferfluorid oder Kaliumfluorid pro 100 g Kupfer des Supraleiters mischt, die Mischung unter einen Druck von mindestens 1 MPa zu einem Formkörper verformt und diesen mindestens eine Stunde bei Temperaturen von 980 bis 1200°C erhitzt. Ein alternativer Herstellungsprozeß geht von einem zur Bildung eines Supraleiters führenden Gemisch der Mixes superconductor containing lattice with 0.04 to 0.5 mol, preferably 0.042 to 0.44 mol, in particular 0.045 to 0.3 mol, of copper fluoride or potassium fluoride per 100 g of copper of the superconductor, the mixture under a pressure of at least 1 MPa Shaped molded body and heated at least one hour at temperatures from 980 to 1200 ° C. An alternative manufacturing process is based on a mixture which leads to the formation of a superconductor
Ausgangskomponenten, wie z. B. der betreffenden Starting components, such as. B. the concerned
Metalloxide, -carbonate oder -nitrate aus, dem CUF2 oder KF zugesetzt wird und das in analoger Weise zur Reaktion gebracht wird. Dabei tritt fast immer mindestens teilweise eine schmelzflüssige Phase auf. Wahrscheinlich ist diese schmelzflüssige Phase verantwortlich für die Ausbildung zusammenhängender kristalliner Bereiche. Dieses Erhitzen dauert mindestens zwei Stunden, vorzugsweise mindestens 5 Stunden. In allen Fällen ist es vorteilhaft, wenn man das Erhitzen in einer Atmosphäre vornimmt, die freien Metal oxides, carbonates or nitrates from which CUF 2 or KF is added and which is reacted in an analogous manner. A molten phase almost always occurs at least partially. This molten phase is probably responsible for the formation of coherent crystalline areas. This heating takes at least two hours, preferably at least 5 hours. In all cases, it is advantageous to do the heating in an atmosphere that is free
Sauerstoff enthält. Es ist ferner vorteilhaft, wenn man nach diesem Schritt auf eine Temperatur von mindestens 400°C abkühlt, bei der keine flüssige Phase mehr vorhanden ist, beispielsweise auf Temperaturen von 880 bis 900°C, und man den Ansatz bei dieser Temperatur in Gegenwart einer Sauerstoff enthaltenden Atmosphäre mindestens eine Stunde, vorzugsweise aber mindestens 5 Stunden hält . Besonders bevorzugt ist es, wenn die Dauer des Erhitzens in beiden Stufen im Bereich von 10 bis 20 Stunden, vorzugsweise bei 15 Stunden liegt. In einigen Fällen kann man das Additiv bereits bei der Herstellung des Ausgangsprodukts Contains oxygen. It is also advantageous if, after this step, the mixture is cooled to a temperature of at least 400 ° C. at which there is no longer any liquid phase, for example to temperatures of 880 to 900 ° C., and the mixture is prepared at this temperature in the presence of an oxygen containing atmosphere for at least one hour, but preferably at least 5 hours. It is particularly preferred if the duration of the heating in both stages is in the range from 10 to 20 hours, preferably at 15 hours. In some cases, the additive can be used during the manufacture of the starting product
(oxidkeramischer Supraleiter mit Kupfer im Kristallgitter) einsetzen. (use oxide ceramic superconductor with copper in the crystal lattice).
Die Stromtragfähigkeit der Produkte, die nach diesem The current carrying capacity of the products after this
Verfahren erhalten werden, ist deutlich höher als bei Process obtained is significantly higher than that of
Produkten, die ohne Additive gepreßt und gesintert wurden. Products that have been pressed and sintered without additives.
Die Erfindung wird durch die Beispiele näher erläutert. The invention is illustrated by the examples.
Beispiel 1 example 1
YBa2Cu3OX-Pulver wird mit 5 Gew.-% fein gepulvertem CUF2 gemischt und unter einem Druck von ca. 300 MPa (3 kbar) zu Formkörpern gepreßt. Die Formkörper werden wie folgt gesintert: YBa 2 Cu 3 O X powder is mixed with 5% by weight of finely powdered CUF 2 and pressed to shaped articles under a pressure of approx. 300 MPa (3 kbar). The shaped bodies are sintered as follows:
Aufheizen in 10 h auf 1000°C Heating up to 1000 ° C in 10 h
20 h Tempern bei 1000°C Annealing for 20 h at 1000 ° C
Abkühlen in 2 h auf 900°C Cooling to 900 ° C in 2 h
10 h Tempern bei 900°C  Annealing for 10 h at 900 ° C
Abkühlen in 10 h auf 20°C Cooling to 20 ° C in 10 h
Schliffbilder der hergestellten Probe zeigen ein A micrograph of the sample produced shows one
geordnetes, texturiertes Gefüge mit einkristallinen Domänen in der Größenordnung von ca. 100-1000 um, die lamellar angeordnet sind. Man erkennt in Fig. 1 bis 4 große, geordnet aufgebautet kristalline Bereiche und  ordered, textured structure with single-crystalline domains in the order of 100-1000 µm, which are lamellar. 1 to 4 show large, ordered crystalline regions and
Zwillingsdomänen, die auch über Korngrenzen, hinweg parallel verlaufen.  Twin domains that also run parallel across grain boundaries.
Beispiel 2 Example 2
Wenn man Beispiel 1 mit einem Pulver gleicher  If you compare example 1 with a powder
Zusammensetzung aber mit anderem Sauerstoffgehalt oder anderer Korngrößen-Verteilung wiederholt, so werden dichte supraleitende Körper mit Textur und vergleichbaren  However, if the composition is repeated with a different oxygen content or with a different grain size distribution, then dense superconducting bodies with texture and comparable will be obtained
Eigenschaften erhalten. Beispiel 3 (Herstellung eines Ausgangsprodukts) Get properties. Example 3 (Preparation of a starting product)
2 mol Bi2O3, 4 mol SrCO3, 4 mol CaO und 8 mol CuO werden in einem Achatmörser zerkleinert, gründlich gemischt und in einen Tiegel aus A12O3 überführt. Die Probe wird an Luft schnell auf 800 - 820°C erhitzt, dort 20 Stunden gehalten und schnell auf Raumtemperatur abgekühlt. Das geglühte Pulver wird zerkleinert und noch weitere zwei Male wie beschrieben thermisch und mechanisch behandelt. 2 mol Bi 2 O 3 , 4 mol SrCO 3 , 4 mol CaO and 8 mol CuO are crushed in an agate mortar, mixed thoroughly and transferred to a crucible made of A1 2 O 3 . The sample is quickly heated in air to 800 - 820 ° C, held there for 20 hours and quickly cooled to room temperature. The annealed powder is crushed and thermally and mechanically treated a further two times as described.
Anschließend wird das schwarze Pulver unter einem Druck von 300 MPa (3 kbar) zu Tabletten gepreßt, diese auf The black powder is then pressed into tablets under a pressure of 300 MPa (3 kbar)
MgO-Platten gelegt und, wie im folgenden beschrieben, an Luft behandelt: Lay MgO plates and treat them in air as described below:
Aufheizen in 3 Stunden auf 870°C Heating up to 870 ° C in 3 hours
80 Stunden Tempern bei 870°C dreimal folgenden Temperaturzyklus durchlaufen: Carry out the following temperature cycle three times for 80 hours at 870 ° C:
Abkühlen in 3 Stunden auf 600°C Cooling down to 600 ° C in 3 hours
3 Stunden Tempern bei 600°C  3 hours annealing at 600 ° C
Aufheizen in 3 Stunden auf 870°C  Heating up to 870 ° C in 3 hours
3 Stunden Tempern bei 870°C anschließend:  3 hours annealing at 870 ° C then:
Abkühlen in 3 Stunden auf 600°C  Cooling down to 600 ° C in 3 hours
3 Stunden Tempern bei 600°C  3 hours annealing at 600 ° C
Abkühlen in 3 Stunden auf RT  Cool to RT in 3 hours
Leitfähigkeit: Tc (R=O)= 98 K Conductivity: T c (R = O) = 98 K.
SQUID-Messung: 35 % supraleitender Anteil bei 4 K mit 100  SQUID measurement: 35% superconducting component at 4 K with 100
Gauß gemessen  Gauss measured
Man erhält ein Gemisch aus Bi2(Sr,Ca)2CuOb, A mixture of Bi2 (Sr, Ca) 2 CuO b is obtained ,
Bi2(Sr,Ca)3Cu2Oc und Bi2(Sr,Ca)4Cu3Od. Bi 2 (Sr, Ca) 3 Cu 2 O c and B i2 (Sr, Ca) 4 Cu 3 O d .

Claims

Patentansprüche: Claims:
1. Massiver, oxidkeramischer Supraleiter mit einem Gehalt von Kupfer im Kristallgitter, dadurch gekennzeichnet, daß er aus im wesentlichen parallel angeordneten, miteinander verwachsenen Kristallen besteht und er noch pro 100 g Kupfer des Supraleiters 0,04 bis 0,5, insbesondere 0,042 bis 0,44 Mol CuF2 oder KF enthält. 1. Solid, oxide-ceramic superconductor with a content of copper in the crystal lattice, characterized in that it consists of essentially parallel, intergrown crystals and he still 0.04 to 0.5, in particular 0.042 to 0, per 100 g of copper of the superconductor , 44 moles of CuF 2 or KF.
2. Supraleiter gemäß Anspruch 1, dadurch gekennzeichnet, daß der Kupfer enthaltende Supraleiter aus Wismut, Strontium, Calcium, Kupfer und Sauerstoff aufgebaut ist. 2. Superconductor according to claim 1, characterized in that the copper-containing superconductor is composed of bismuth, strontium, calcium, copper and oxygen.
3. Supraleiter gemäß Anspruch 1, dadurch gekennzeichnet, daß der kupferhaltige Supraleiter aus Wismut, Calcium, Strontium, Blei, Kupfer und Sauerstoff aufgebaut ist. 3. Superconductor according to claim 1, characterized in that the copper-containing superconductor is composed of bismuth, calcium, strontium, lead, copper and oxygen.
4. Massiver Supraleiter gemäß Anspruch 1, dadurch 4. Solid superconductor according to claim 1, characterized
gekennzeichnet, daß der Kupfer enthaltende Supraleiter eine Zusammensetzung der allgemeinen Formel MBa2Cu3OX aufweist, wobei M für Yttrium oder ein Element der Nummern 61 bis 71 steht und x eine Zahl zwischen 6,5 und 7,2 ist. characterized in that the copper-containing superconductor has a composition of the general formula MBa 2 Cu 3 O X , where M is yttrium or an element of numbers 61 to 71 and x is a number between 6.5 and 7.2.
5. Supraleiter gemäß Anspruch 1, dadurch gekennzeichnet, daß in den Kristallen das Verhältnis von 5. Superconductor according to claim 1, characterized in that in the crystals the ratio of
Länge/Durchmesser im Mittel bei 3:1 - 30:1 liegt.  Length / diameter is 3: 1 - 30: 1 on average.
6. Supraleiter gemäß Anspruch 4, dadurch gekennzeichnet, daß M für Y steht und er eine Dichte von 6,0 bis 6,33 g/cim3 aufweist. 6. Superconductor according to claim 4, characterized in that M stands for Y and it has a density of 6.0 to 6.33 g / cim 3 .
7. Verfahren zur Herstellung eines massiven 7. Process for making a massive
oxidkeramischen Supraleiters, der im Kristallgitter Kupfer enthält und im wesentlichen aus oxide-ceramic superconductor in the crystal lattice Contains and essentially consists of copper
langgestreckten, parallel angeordneten, miteinander verwachsenen Kristallen besteht, dadurch  elongated, parallel, interwoven crystals
gekennzeichnet, daß man einen pulverförmigen  characterized that you have a powdered
Supraleiter, der Kupfer im Gitter enthält, mit 0,04 bis 0,5, vorzugsweise 0,042 bis 0,44 Mol CUF2 oder Superconductor containing copper in the lattice with 0.04 to 0.5, preferably 0.042 to 0.44 mol CUF 2 or
Kaliumfluorid pro 100 g Kupfer des Supraleiters  Potassium fluoride per 100 g copper of the superconductor
vermischt, die Mischung unter einem Druck von  mixed, the mixture under a pressure of
mindestens 1 MPa zu einem Formkörper verformt und diesen mindestens 5 Stunden bei 980 bis 1200°C, insbesondere 1000 bis 1050°C erhitzt.  deformed at least 1 MPa into a shaped body and heated this at least 5 hours at 980 to 1200 ° C, in particular 1000 to 1050 ° C.
8. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß man das Erhitzen in einer Atmosphäre vornimmt, die freien Sauerstoff enthält. 8. The method according to claim 7, characterized in that one carries out the heating in an atmosphere which contains free oxygen.
EP90904806A 1989-03-25 1990-03-22 Dense superconductive bodies with preferred orientation Pending EP0464068A1 (en)

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DE3909882 1989-03-25

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DE4108445A1 (en) * 1991-03-15 1992-09-17 Abb Patent Gmbh METHOD FOR PRODUCING WIRE
CN113643853B (en) * 2021-08-13 2023-03-03 中国科学院电工研究所 Application of KF as raw material in preparation of 122-series iron-based superconductor and preparation method of 122-series iron-based superconductor

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JPS63242922A (en) * 1987-03-30 1988-10-07 Sumitomo Electric Ind Ltd Superconducting material
DK158581C (en) * 1987-07-10 1990-11-12 Haldor Topsoe As PROCEDURE FOR MANUFACTURING SUPER CONDUCTIVE PRODUCTS
DK158579C (en) * 1987-07-10 1990-11-12 Haldor Topsoe As PROCEDURE FOR THE PREPARATION OF A SUPERVISORY METAL CERAMIC CRYSTALLIC COMPOUND
EP0351037A1 (en) * 1988-06-15 1990-01-17 Corning Glass Works Fluoride enhanced superconductors

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GR3019088T3 (en) 1996-05-31
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ES2082796T3 (en) 1996-04-01
EP0389960B1 (en) 1996-01-17
JPH04505602A (en) 1992-10-01
JP3021639B2 (en) 2000-03-15
EP0389960A1 (en) 1990-10-03
DE59010060D1 (en) 1996-02-29
DE3909882A1 (en) 1990-09-27

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