CN1031621A - 制造超导体陶瓷的方法及其产品 - Google Patents
制造超导体陶瓷的方法及其产品 Download PDFInfo
- Publication number
- CN1031621A CN1031621A CN88106291.XA CN88106291A CN1031621A CN 1031621 A CN1031621 A CN 1031621A CN 88106291 A CN88106291 A CN 88106291A CN 1031621 A CN1031621 A CN 1031621A
- Authority
- CN
- China
- Prior art keywords
- superconducting ceramics
- superconductor
- chemical substance
- family
- pottery
- 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.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims description 10
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 230000009467 reduction Effects 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000002887 superconductor Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 230000000737 periodic effect Effects 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 239000010949 copper Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052790 beryllium Inorganic materials 0.000 description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000272194 Ciconiiformes Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910003808 Sr-Cu Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/83—Macromolecular compounds
-
- 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
-
- 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
- H10N60/0661—Processes performed after copper oxide formation, e.g. patterning
- H10N60/0716—Passivating
-
- 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
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
- H10N60/855—Ceramic superconductors
- H10N60/857—Ceramic superconductors comprising copper oxide
-
- 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
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/901—Printed circuit
-
- 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
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/922—Static electricity metal bleed-off metallic stock
- Y10S428/9265—Special properties
- Y10S428/93—Electric superconducting
-
- 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
- Y10S505/70—High TC, above 30 k, superconducting device, article, or structured stock
- Y10S505/701—Coated or thin film device, i.e. active or passive
-
- 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
- Y10S505/70—High TC, above 30 k, superconducting device, article, or structured stock
- Y10S505/701—Coated or thin film device, i.e. active or passive
- Y10S505/702—Josephson junction present
-
- 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
- Y10S505/70—High TC, above 30 k, superconducting device, article, or structured stock
- Y10S505/701—Coated or thin film device, i.e. active or passive
- Y10S505/703—Microelectronic device with superconducting conduction line
-
- 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
- Y10S505/70—High TC, above 30 k, superconducting device, article, or structured stock
- Y10S505/704—Wire, fiber, or cable
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
- Y10T428/239—Complete cover or casing
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/3158—Halide monomer type [polyvinyl chloride, etc.]
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (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)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
Abstract
具有高Tc的超导体陶瓷材料的制备方法，包括
在烧结之前将陶瓷各组分与一种醇或氟利昂混合。
醇或氟利昂的作用是在烧结时还原陶瓷，因而可将过
量的氧由超导结构中除去。然后将超导体陶瓷用有
机树脂薄膜涂覆，用于避免空气的作用。
Description
本发明涉及超导体技术领域。
长久以来已知如汞和铅等金属;如NbNd，Nb3Ge和NbGa等金属互化物;以及如Nb3（Al0.8Ge0.2）等三元金属材料可显示超导性。然而上述熟知的惯用的超导体材料的转化温度不能超过25°K。
近年来，超导体陶瓷引起了广泛注意。国际商业机器公司（IBM）在苏黎世实验室的研究人员首先报导了一种新材料，即Ba-La-Cu-O类型的高温超导体氧化物。接着也提出了La-Sr-Cu（Ⅱ）-O类型的超导体氧化物。已发现的其他类型的超导体材料是（YBa2）Cu3O6-8。鉴于在事实上，这类型超导体陶瓷的晶体结构中可形成类分子-原子单元，而其晶胞一层结构中，基本上电子在一个方向上移动。然而在上述熟知的材料中电子是在三个方向上移动，因此这类型的超导体陶瓷就具有较高的转化温度。
本领域的研究人致力于提高Tco的工作，在该温度下电阻消失，使其高过前人所达的水平，最好能使其高过氮的沸点（77°K）甚至更高温度。如我们在欧洲专利申请87309081.5号中所述，对具化学计量式（A1-xBx）yCuzOw的超导体陶瓷已进行了研究，该式中，A表示一个或多个周期表Ⅲa族元素，如稀土元素，B表示一个或多个周期表Ⅱa族元素，如碱土金属元素包括铍和镁。在接着进行的研究中，我们报导过该超导体表面与空气接触时，可令其难于获得稳定的高Tco。
因此本发明目的在于提供一种超导体陶瓷，而它可具有比先有技术所能达到的更高的转化温度，以及提供制造具有稳定的转化温度的超导体陶瓷。
在以前研制具有可应用价值的超导体材料中，人们注意力集中在如何通过改变其组成或组分元素的摩尔比以期提高Tc。按照本发明主要提供一种制备超导体陶瓷的改进方法，根据该方法，在形成超导体结构之后，立即将超导体涂覆一种有机树脂保护薄膜，这样可以避免从周围大气中吸收水分，尤其是当超导体冷却至液氮温度以转化成超导相时，避免从空气中吸收水分。水分的吸收可导致超导体陶瓷性能降低。
在一优选实施例中，将组成超导体陶瓷的原料化学物质研细，压制及烧制成形。为了使组成均匀，重复该操作一次或多次之后，研细的粉末与不含水的液体混合，接着将其压制成其中含液体的压制物。将压制物慢慢加热，因而可避免急骤的还原作用。并在500-1400℃下烧结。将压制体自炉中取出后，立即用有机树脂薄膜涂覆压制体。该有机树脂的实例是环氧树脂，含氟树脂和聚酰亚胺树脂。按实验所知，它的温度可提高到90-120K。
按照本发明的超导体材料具有如附图所示的变型的钙钛矿型的三重结构。每一层结构中主要由一个铜原子2和在铜原子2周围的氧原子5。氧空位7在超导性中起重要作用。为了由超导体陶瓷中除去过量的氧，需在烧结之前将不含水的还原液体加入陶瓷材料中。该还原液体的实例是甲醇、乙醇和氟利昂如氟利昂113。还原液体与陶瓷材料中所含的氧作用而生成水汽和二氧化碳。
由于通过在充分包含于陶瓷中的还原液体的作用而消除氧，可使沿C轴向的原子间距缩短，因而可得到很高的转化温度。
对本发明特点，本专业人员可通过下列实施例而得到清楚的了解。
附图1为按本发明的超导体陶瓷的变型钙钛矿型结构的图示。
下列各实施例将进一步说明超导体陶瓷的的制法，该超导体陶瓷符合化学计量式（A1-xBx）yCuzOw，其中A是一个或多个周期表Ⅲa族元素，如稀土元素，B是一个或多个周期表Ⅱa族元素，如碱土金属元素包括铍和镁，并且x＝0-1;y＝2.0-4.0;最好是2.5-3.5;z＝1.0-4.0，最好是1.5-3.5，w＝4.0-10.0，最好是6.0-8.0。实例为YBa2Cu3O7-x，YCa2Cu3O7-x。
实施例1
预定量的BaCO3，CaCO3，CuO和Y2O3（High Purity Chemical Industries Co.Ltd出品，纯度99.95%或以上）用于制备按上式的超导体陶瓷材料，该式中，x＝0.67，y＝3，z＝3和w＝6-8，即符合式（YBa2）Cu3O6-8或（YBaCa）Cu3O6-8。其中w值可通过调整烧结条件来控制。
在球磨机中混匀后，高纯度的化学料在500公斤/cm2下在封器（capsule）中压制，并形成圆柱状片料（直径10毫米，高3毫米）。将片料在500-1100℃（如950℃）下，在氧化气氛中（如空气中）加热（烧结）和氧化8小时，该步骤以下称之为预烧结。接着将片料在球磨机中研细，使其平均粒径为20-0.003微米（如0.5微米或以下）。将步骤重复3-5次。在其中需小心处理以避免在产物中产生Y2BaCuO5或氧化铜相。
然后，将平均粒径为20-0.0003微米的粉末在球磨机中与甲醇混合均匀，在1吨/厘米2压力下在封器中压制成片状料。
然后将片料烧结，该步骤以下称之为主烧结。主烧结是在氧化氛中（如空气中），在500-1400℃下进行10-50小时，例如在930℃下烧结15小时。烧结进行时，以每小时10-1000℃速率（如每小时100℃），由室温升至预定温度。当升温时，陶瓷材料通过醇的作用而部分还原。然后在每小时100℃速率下，将温度降至400℃。
接着，钙钛矿型结构形成致密构型。然后经过于有机硅树脂溶液中浸涂，及在150℃下于无水空气中进行热固化2小时或30分钟，从而在片料上覆涂树脂层。当覆涂环氧树脂时，热固化是在于空气中，在150℃下进行30分钟，或在240℃下进行5分钟。
应用制得的陶瓷材料，对其温度和电阻率之间的关系进行研究。当温度由300K下降时，电阻开始在约110K下降，并在98K消失。当温度值在室温和转化温度之间反复升降时，重复测定该转化温度98K。作为参考，另制备相同的超导体陶瓷材料并进行测试，结果表示，重复温度升降时，转化温度降至63K。
覆涂于超导体材料的有机树脂最好选自软性树脂。这是由于在固化时由树脂所产生的收缩和膨胀造成超导体材料局部应力的产生是不希望出现的。
实施例2
重复实施例1的操作，但50%的Y用Yb代替，并用Sr代替Ca，用氟利昂代替甲醇，Y和Yb以氧化物或氟化物形式加入。结果表示，Tc开始温度测定值为130°K而Tco值为101°K，它可保持一周或更长时间。
上述实施例仅为了说明本发明，而未包括用于制备本发明超导体陶瓷材料的各元素组合情况，和各种不同方法的应用情况，其他组合情况下也可有效地产生改良的超导体材料。
按本发明所用的超导体陶瓷也可按化学计量式（A1-xBx）yCuzOwXv来制备，该式中，A是一个或多个周期表Ⅲa元素，如稀土元素，B是一个或多个周期表Ⅱa元素，如碱土金属元素包括铍和镁，X是一个或多个下列元素如Ge，Sn，Pb，F或Cl，x＝0-1，y＝2.0-4.0，最好等于2.5-3.5;z＝1.0-4.0，最好等于1.5-3.5;w＝4.0-10.0，最好等于6.0-8.0，v＝0-3，例如该式可为YBa2Cu3O6-8。此外按本发明所用的超导体陶瓷还可以按化学计量式（A1-xBx）yCuzOw来制备，该式中，A为一个或多个周期表Vb族元素，如Bi，Sb和As，B为一个或多个周期表Ⅱa族元素，如碱土金属元素，并且x＝0.3-1，y＝2.0-4.0，最好等于2.5-3.5;z＝1.0-4.0，最好等于1.5-3.5，w＝4.0-10.0，最好等于6.0-8.0，例如该式可为BiCaSrCu3O6-8。
上面已对若干优选实施例进行描述，但应提出的是，本发明并不局限于所述实施例，而在不超出本发明按权利要求书所述的范围内，可进行适当修正。例如可用金刚石类碳作为保护超导体陶瓷薄膜。碳材料的制备方法可参见中国专利申请88101061.8号（1888年2月24日）。此外，在主烧结中应用磁场对于调校晶体轴是有效的。在本说明书中，Ⅲa族元素是指一组包括以下资料所述的过渡元素，即“物理与化学词典”（由日本Iwanami出版）。在这方面，Ⅲa族元素包括如下述资料所述的典型的元素，即“The Penguin Dictionary of Science”（由Penguin Books 出版）。
Claims (14)
1、一种制造超导体陶瓷的方法，其中包括：
制备组成超导体陶瓷的化学物质，
将所述化学物质按预定组成研细和混合成粉末，
将所述粉末压制成形，
将所述压制物烧结，使其具有超导性，
将所述超导体压制物外表面涂覆有机树脂薄膜。
2、按权利要求1所述方法，其中所述有机树脂为环氧树脂。
3、按权利要求1所述方法，其中所述有机树脂为含氟树脂。
4、按权利要求1所述方法，其中所述有机树脂为聚酰亚胺树脂。
5、按权利要求1所述方法，其中所述有机树脂为有机硅树脂。
6、按权利要求1的陶瓷，其中所述化学物质是按化学计量式（A1-xBx）yCuzOw来制备，其中A是一个或多个选自周期表Ⅲa族的元素或周期表Vb族的元素例如Bi，Sb和As，B为一个或多个选自周期表Ⅱa族的元素，x＝0.3-1，y＝2.0-4.0，z＝1.0-4.0，并且w＝4.0-10.0。
7、一种制造超导体陶瓷的方法，其中包括：
制备组成超导体陶瓷的化学物质，
将所述化学物质按预定组成研细和混合成粉末，
将所述化学物质与还原液体混合，并且将所述化学物质和所述还原液的混合物烧结，使其具有超导性。
8、按权利要求7之陶瓷，其中所述还原液体是一种醇。
9、按权利要求7之陶瓷，其中所述还原液体是甲醇。
10、按权利要求7之陶瓷，其中所述还原液体是乙醇。
11、按权利要求7之陶瓷，其中所述还原液体是氟利昂。
12、一种陶瓷超导体，其中包括：
一种压制的陶瓷超导体材料，它可符合化学计量式（A1-xBx）yCuzOw，其中A是一个或多个选自周期表Ⅲa族的元素或Vb族元素例如Bi，Sb和As，B是一个或多个周期表Ⅱa族元素，并且x＝0.3-1，y＝2.0-4.0;z＝1.0-4.0和w＝4.0-10.0，和
一种覆盖于所述超导体陶瓷材料暴露表面的树脂层。
13、一种制造超导体器件的方法，其中包括：制备由预定量的超导体陶瓷组分所组成的混合物，烧结该混合物，就位形成陶瓷超导体以及用保护薄层覆盖暴露表面。
14、一种超导体器件，其中包括在一基质上的超导体模版，以及覆盖所述模版的保护薄膜。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111165A CN1061866A (zh) | 1987-08-27 | 1991-11-21 | 超导体陶瓷的制造方法 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP214743/87 | 1987-08-27 | ||
| JP62214743A JPH0649626B2 (ja) | 1987-08-27 | 1987-08-27 | 酸化物超電導材料 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111165A Division CN1061866A (zh) | 1987-08-27 | 1991-11-21 | 超导体陶瓷的制造方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031621A true CN1031621A (zh) | 1989-03-08 |
| CN1023624C CN1023624C (zh) | 1994-01-26 |
Family
ID=16660855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88106291.XA Expired - Fee Related CN1023624C (zh) | 1987-08-27 | 1988-08-25 | 表面带有覆盖层的超导体陶瓷 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5075284A (zh) |
| EP (1) | EP0305168B1 (zh) |
| JP (1) | JPH0649626B2 (zh) |
| CN (1) | CN1023624C (zh) |
| DE (1) | DE3855627T2 (zh) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6456360A (en) * | 1987-08-27 | 1989-03-03 | Semiconductor Energy Lab | Production of oxide superconductive material |
| JPH01183483A (ja) * | 1988-01-19 | 1989-07-21 | Fujita Corp | 超電導セラミックスの表面処理方法 |
| JPH01183484A (ja) * | 1988-01-19 | 1989-07-21 | Fujita Corp | 超電導セラミックスの表面処理方法 |
| JPH01246106A (ja) * | 1988-03-29 | 1989-10-02 | Mitsubishi Mining & Cement Co Ltd | 超伝導酸化物材料 |
| EP0431170A4 (en) * | 1989-05-27 | 1992-03-11 | Foundational Juridical Person International Superconductivity Technology Center | Oxide superconductor |
| JP2851327B2 (ja) * | 1989-10-31 | 1999-01-27 | 東レ・ダウコーニング・シリコーン株式会社 | 超伝導セラミックス構造体 |
| JPH03253005A (ja) * | 1990-03-02 | 1991-11-12 | Hitachi Ltd | 超電導コイルとその製法、複合超電導導体とその製法、並びに超電導装置 |
| US5169969A (en) * | 1990-06-07 | 1992-12-08 | Akzo Nv | Process for forming mixed bimetal alkoxide-carboxylate composition and novel compositions thereof |
| DE4018870C1 (en) * | 1990-06-13 | 1991-08-14 | Josef Dr. 4000 Duesseldorf De Heyes | Superconducting tape or film prodn. - comprise electrophoretic deposition of ceramic powder on noble metal support e.g. barium oxide on platinum |
| DE4115872A1 (de) * | 1991-05-15 | 1992-11-19 | Basf Ag | Verfahren zur herstellung duenner polyimidschutzschichten auf keramischen supraleitern oder hochtemperatursupraleitern |
| DE4304573A1 (de) * | 1993-02-16 | 1994-08-18 | Forschungsgesellschaft Fuer In | Passivierungsschicht für Hochtemperatur-Supraleiter und Verfahren zu ihrer Aufbringung |
| DE10111938A1 (de) * | 2001-03-13 | 2002-09-26 | Merck Patent Gmbh | Herstellung von Hochtemperatur-Supraleiter-Pulvern in einem Pulsationsreaktor |
| JP4673668B2 (ja) * | 2005-05-17 | 2011-04-20 | 新日本製鐵株式会社 | 酸化物超電導バルク体及びその製造方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6419613A (en) * | 1987-07-14 | 1989-01-23 | Marui Sangyo Kk | Superconducting material |
| JPS6433087A (en) * | 1987-07-28 | 1989-02-02 | Sumitomo Spec Metals | Superconducting ceramics having superior water resistance |
| JPH01126284A (ja) * | 1987-11-10 | 1989-05-18 | Ube Ind Ltd | 安定化された高温超電導セラミックス |
| JPH01215776A (ja) * | 1988-02-23 | 1989-08-29 | Fujitsu Ltd | 表面処理高温超伝導体及びその製造方法 |
| DE3915402A1 (de) * | 1988-05-20 | 1989-11-23 | Asea Brown Boveri | Flexibler hochtemperatur-supraleiter din drahtform, auf der basis eines supraleitenden keramischen werkstoffs der klasse (la,ba,sr)(pfeil abwaerts)2(pfeil abwaerts)cuo(pfeil abwaerts)4(pfeil abwaerts) oder der klasse (y,se)ba(pfeil abwaerts)2(pfeil abwaerts)cu(pfeil abwaerts)3(pfeil abwaerts)06,5+y' mit se = seltene erde und 0<y<l und eines mechanischen traegers |
-
1987
- 1987-08-27 JP JP62214743A patent/JPH0649626B2/ja not_active Expired - Fee Related
-
1988
- 1988-08-19 US US07/234,184 patent/US5075284A/en not_active Expired - Lifetime
- 1988-08-24 DE DE3855627T patent/DE3855627T2/de not_active Expired - Fee Related
- 1988-08-24 EP EP88307846A patent/EP0305168B1/en not_active Expired - Lifetime
- 1988-08-25 CN CN88106291.XA patent/CN1023624C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0305168B1 (en) | 1996-10-23 |
| JPS6456385A (en) | 1989-03-03 |
| DE3855627D1 (de) | 1996-11-28 |
| DE3855627T2 (de) | 1997-05-15 |
| JPH0649626B2 (ja) | 1994-06-29 |
| CN1023624C (zh) | 1994-01-26 |
| EP0305168A3 (en) | 1990-11-22 |
| US5075284A (en) | 1991-12-24 |
| EP0305168A2 (en) | 1989-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1023624C (zh) | 表面带有覆盖层的超导体陶瓷 | |
| EP0341266B1 (en) | Superconductivity in square-planar compound systems | |
| AU603942B2 (en) | Devices and systems based on novel superconducting material | |
| US5661114A (en) | Process of annealing BSCCO-2223 superconductors | |
| EP0356722A1 (en) | Oxide superconductor and method of producing the same | |
| US4992415A (en) | Method for fabricating ceramic superconductors | |
| US7709418B1 (en) | High transition temperature superconducting compositions | |
| US5468566A (en) | Synthesis of highly phase pure BSCCO superconductors | |
| EP0377359A1 (en) | Oxide superconducting material, process for preparing the same and applications thereof | |
| CA1340010C (en) | Superconducting composite | |
| US5744427A (en) | Thallium oxide superconductor and method of preparing the same | |
| EP0310033A2 (en) | Superconducting wire and method of producing the same | |
| EP0368765B1 (en) | Oxide superconducting material and process for preparing the same | |
| CN1061866A (zh) | 超导体陶瓷的制造方法 | |
| US5389603A (en) | Oxide superconductors, and devices and systems comprising such a superconductor | |
| DE3855230T2 (de) | Verfahren zur Herstellung eines supraleitenden Gegenstandes | |
| US5108985A (en) | Bi-Pb-Sr-Ca-Cu oxide superconductor containing alkali metal and process for preparation thereof | |
| Maqsood et al. | Role of barium addition on the properties of bismuth-based superconductors | |
| JP2916382B2 (ja) | Ｎｂ３ Ｓｎ超電導体の製造方法 | |
| US5244868A (en) | Method of making high Tc superconductor material, and article produced by the method | |
| EP0362694B1 (en) | Method of producing oxide superconducting wire | |
| US5821201A (en) | (Bi, Pb)2, Sr2 Ca2 Cu3 Ox superconductor and method of making same utilizing sinter-forging | |
| EP0436723B1 (en) | Oxide superconductor and method of producing the same | |
| EP1411154B1 (en) | Oxide high-critical temperature superconductor acicular crystal and its production method | |
| US5418214A (en) | Cuprate-titanate superconductor and method for making |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |