DK172938B1 - Superconducting metal oxide phase - Google Patents
Superconducting metal oxide phase Download PDFInfo
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- DK172938B1 DK172938B1 DK199001881A DK188190A DK172938B1 DK 172938 B1 DK172938 B1 DK 172938B1 DK 199001881 A DK199001881 A DK 199001881A DK 188190 A DK188190 A DK 188190A DK 172938 B1 DK172938 B1 DK 172938B1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
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Description
i DK 172938 B1in DK 172938 B1
Den foreliggende opfindelse angår en hidtil ukendt, - bismuth-strontium-calcium-kobberoxid-fase, som er superle dende .The present invention relates to a novel, bismuth-strontium-calcium-copper-oxide phase which is superior in nature.
Referencer.References.
5 Bednorz og Muller, Z. Phys. B64, 189 (1986), beskriver en superledende fase i La-Ba-Cu-O-systemet med en superledende overgangstemperatur på ca. 35 K. Denne beskrivelse er senere blevet bekræftet af en række forskere [se f.eks.5 Bednorz and Muller, Z. Phys. B64, 189 (1986), discloses a superconducting phase of the La-Ba-Cu-O system having a superconducting transition temperature of ca. 35 K. This description has later been confirmed by a number of researchers [see e.g.
Rao and Ganguly, Current Science, 56, 47 (1987) , Chu et 10 al., Science 235, 567 (1987), Chu et al., Phys. Rev. Lett.Rao and Ganguly, Current Science, 56, 47 (1987), Chu et al., Science 235, 567 (1987), Chu et al., Phys. Rev. Lett.
58, 405 (1987), Cava et al., Phys. Rev. Lett. 58, 408 (1987),58, 405 (1987), Cava et al., Phys. Rev. Lett. 58, 408 (1987),
Bednorz et al., Europhys. Lett. 3, 379 (1987)]. Den superledende fase er blevet identificeret som materialet Lai_x(Ba,Sr,Ca)x04_y, som har tetragonal struktur af K2NiF4-15 typen, og hvor x typisk er ca. 0,15, og y angiver oxygenhuller.Bednorz et al., Europhys. Lett. 3, 379 (1987)]. The superconducting phase has been identified as the material Lai_x (Ba, Sr, Ca) x04_y, which has a tetragonal structure of the K2NiF4-15 type and where x is typically 0.15, and y denotes oxygen holes.
Wu et al., Phys. Rev. Lett. 58, 908 (1987), beskriver en superledende fase i Y-Ba-Cu-O-systemet med en superledende overgangstemperatur på ca. 90 K. Cava et al., Phys. Rev.Wu et al., Phys. Rev. Lett. 58, 908 (1987), describe a superconducting phase of the Y-Ba-Cu-O system having a superconducting transition temperature of about 90 K. Cava et al., Phys. Rev.
20 Lett. 58, 1676 (1987), har identificeret denne superledende Y-Ba-Cu-O-fase til at være orthorhombisk, forkastet, oxygenmangelfuldt perovskit YBa2Cu309.g, hvor δ er ca. 2,1, og viser pulverrontgenstrålediffraktionsmønstret og gitterparametrene .20 Light. 58, 1676 (1987), has identified this superconducting Y-Ba-Cu-O phase to be orthorhombic, discarded, oxygen deficient perovskite YBa2Cu309.g, where δ is approx. 2.1, showing the powder edge X-ray diffraction pattern and lattice parameters.
25 C. Michel et al., Z. Phys. B - Condensed Matter 68, 417 (1987), beskriver indføringen af Bi i superlederen La2-xSrxCu04_y til dannelse af oxiderneC. Michel et al., Z. Phys. B - Condensed Matter 68, 417 (1987), describes the introduction of Bi into the superconductor La2-xSrxCuO4_y to form the oxides
La2,χΒίχ>Srx_xi,Cu04.y. Studiet har været begrænset til materialer svarende til det interval, hvor der hovedsageligt 30 iagttages superledningsevne, nemlig x - x' » 0,1-0,2. Enkeltfaser er blevet opnået, når x s 3, og x' s 2. En prøve med sammensætningen La^^ ( 7Bi0 f iSr0; 2Cu04-y har superledende overgangstemperatur på ca. 42 K som bestemt ud fra målinger af specifik ledningsevne sammenlignet med ca. 38 K for 35 Lal,8Sr0,2Cu04-y· DK 172938 B1 2 C. Michel et al., Z. Phys. B - Condensed Matter 68, I 421 (1987), beskriver en ny familie af superlederoxider i • Bi-Sr-Cu-O-systemet med en sammensætning tæt påLa 2, χΒίχ> Srx_xi, Cu04.y. The study has been limited to materials corresponding to the range where mainly superconductivity is observed, namely x - x '0.1 - 0.2. Single phases have been obtained when xs 3, and x's 2. A sample with the composition La 38 K for 35 Lal, 8Sr0.2CuO4-y · DK 172938 B1 2 C. Michel et al., Z. Phys. B - Condensed Matter 68, I 421 (1987), describes a new family of superconductor oxides in • Bi-Sr -Cu-O system with a close composition
Bi2Sr2Cu207+g. En ren fase er blevet isoleret for sammensæt-, 5 ningen Bi2Sr2Cu207+g. Røntgenstrålediffraktionsmønsteret for dette materiale udviser en vis lighed med mønstret for J perovskit, og elektrondiffraktionsmønstret viser perovskitun- dercelle med de orthorhombiske celleparametre på a = 5,32 Å (0,53 2 nm), b = 26,6 Å (2,66 nm), og c = 48,8 Å (4,88 nm) .Bi2Sr2Cu207 + g. A pure phase has been isolated for the composition Bi2Sr2Cu2O7 + g. The X-ray diffraction pattern for this material shows some similarity to the pattern of J perovskite, and the electron diffraction pattern shows perovskit cell with the orthorhombic cell parameters of α = 5.32 Å (0.53 2 nm), b = 26.6 Å (2.66 nm ), and c = 48.8 Å (4.88 nm).
10 Materialet fremstillet ud fra ultrarene oxider har en superledende overgang med et midtpunkt på 22 K som bestemt ud fra målinger af specifik ledningsevne og modstanden nul - under 14 K. Materialet fremstillet ud fra oxider af kommerciel renhed har en superledende overgang med et midtpunkt " 15 på 7 K.10 The material made from ultra-pure oxides has a superconducting transition with a center of 22 K as determined from measurements of specific conductivity and resistance zero - below 14 K. The material made from oxides of commercial purity has a superconducting transition with a center "15 of 7 K.
Resume af opfindelsenSummary of the Invention
Den foreliggende opfindelse angår en superledende metaloxidfase, som er ejendommelig ved, at den har formlen - 20 Bi2Sr3.zCazCu2Og+w hvor z er et tal fra ca. 0,1 til ca. 0,9, fortrinsvis 0,4 - 0,8, især 0,6 - 0,7, og w er et tal større end 0 og mindre end l.The present invention relates to a superconducting metal oxide phase which is characterized in that it has the formula - 20 Bi2Sr3.zCazCu2Og + w where z is a number from 0.1 to approx. 0.9, preferably 0.4 - 0.8, especially 0.6 - 0.7, and w is a number greater than 0 and less than 1.
__ Den nominelle formel for superledende materialer, ^ 25 som indeholder væsentlige mængder af metaloxidfasen ifølge opfindelsen, som tilvejebringer superledningsevne, bliver derfor BiaSrj-)CacCu30x, hvor a er fra ca. 1 til ca. 3, b er fra ca. 3/8 til ca. 4, c er fra ca. 3/16 til ca. 2, og x = (l,5a+b + c + y), hvor y er fra ca. 2 til ca. 5, idet ^ 30 dog b + c er fra ca. 3/2 til ca. 5.Therefore, the nominal formula for superconducting materials containing substantial amounts of the metal oxide phase of the invention which provides superconductivity becomes BiaSrj-) CacCu30x, where a is from ca. 1 to approx. 3, b is from ca. 3/8 to approx. 4, c is from ca. 3/16 to approx. 2, and x = (1.5a + b + c + y), where y is from ca. 2 to approx. 5, however ^ 30 b + c is from ca. 3/2 to approx. 5th
_J Det superledende materiale, der indeholder metaloxid- "1 fasen ifølge opfindelsen kan fremstilles ved at opvarme en . J blanding, som udgøres af støkiometriske mængder af metalox ider, f.eks. Bi203, SrO eller Sr02, CaO og CuO, eller forsta-35 dier for metaloxiderne, f.eks. carbonater, såsom CaC03, eller nitrater, såsom Sr(N03)2, til fra 775°C til 900°C i p m DK 172938 B1 3 fra 8 til 48 timer eller mere i luft. Opvarmningstemperaturer fra 850°C til 900eC foretrækkes.The superconducting material containing the metal oxide phase of the invention can be prepared by heating a mixture made up of stoichiometric amounts of metal oxides, for example Bi 2 O 3, SrO or SrO 2, CaO and CuO, or solidification. 35 for the metal oxides, for example, carbonates such as CaCO 3, or nitrates such as Sr (NO 3) 2, to from 775 ° C to 900 ° C ipm DK 172938 B1 3 from 8 to 48 hours or more in air. 850 ° C to 900 ° C is preferred.
Detaljeret beskrivelse af opfindelsen.Detailed description of the invention.
5 De superledende materialer med den nominelle formel5 The superconducting materials of the nominal formula
BiaSrbCacCu3°x bar superledende overgangstemperaturer på mindst 70 K og op til ca. 120 K. Foretrukket er de materialer, hvor a fra ca. 3/2 til ca. 3, b er fra ca. 3/2 til ca.BiaSrbCacCu3 ° x carried superconducting transition temperatures of at least 70 K and up to approx. 120 K. Preferred are the materials wherein a from about. 3/2 to approx. 3, b is from ca. 3/2 to approx.
4, c er fra ca. 1/2 til ca. 3/2, og b + c er ca. 3-5. Disse 10 foretrukne materialer har superledende overgangstemperaturer over 77 K, temperaturen af flydende nitrogen.4, c is from ca. 1/2 to approx. 3/2, and b + c is approx. 3-5. These 10 preferred materials have superconducting transition temperatures above 77 K, the temperature of liquid nitrogen.
De superledende materialer, der indeholder metaloxidfasen ifølge opfindelsen kan fremstilles ved følgende fremgangsmåde. Støkiometriske mængder af B12O3, SrO, CaO og CuO 15 blandes, f.eks. ved at de formales sammen i en morter. Forstadier for oxiderne, såsom carbonater, kan anvendes i stedet for et eller flere af oxiderne. Alternativt kan en inderlig, støkiometrisk blanding af forstadier for oxiderne fremstilles ud fra en opløsning af forstadier, som nitrater eller aceta-20 ter, enten ved udfældning fra en sådan opløsning eller ved tørring af en sådan opløsning ved afdampning af opløsningsmidlet eller ved forstøvnings- eller frysetørring. Blandingen af oxider eller forstadier i form af et pulver eller en presset perle anbringes derefter i en beholder fremstillet 25 af et ikke-reaktivt materiale, såsom aluminiumoxid eller guld. Derpå anbringes beholderen i en ovn og opvarmes til fra 775°C til 900°C i fra 8 til 48 timer i luft, fortrinsvis fra 850°C til 900°C. Den superledende overgangstemperatur er almindeligvis højere, hvis opvarmningstemperaturen er i 30 det foretrukne interval. Smeltning må undgås. Da smeltning indtræder ved opvarmningstemperaturer på ca. 900eC og derover, skal omsætningen ske under disse temperaturer.The superconducting materials containing the metal oxide phase of the invention can be prepared by the following process. Stoichiometric amounts of B12O3, SrO, CaO and CuO 15 are mixed, e.g. by grinding them together in a mortar. Precursors of the oxides, such as carbonates, may be used in place of one or more of the oxides. Alternatively, an inner, stoichiometric mixture of the precursors of the oxides can be prepared from a solution of precursors such as nitrates or acetates, either by precipitation from such a solution or by drying such a solution by evaporation of the solvent or by spraying or freeze-drying. The mixture of oxides or precursors in the form of a powder or pressed bead is then placed in a container made of a non-reactive material such as alumina or gold. Then, the container is placed in an oven and heated to from 775 ° C to 900 ° C for 8 to 48 hours in air, preferably from 850 ° C to 900 ° C. The superconducting transition temperature is generally higher if the heating temperature is in the preferred range. Melting must be avoided. As melting occurs at heating temperatures of approx. 900 ° C and above, the reaction must take place below these temperatures.
Afkøling kan foretages langsomt ved enten at afbryde strømmen til ovnen og tillade beholderen at køle af i ovnen 35 eller ved at programmere ovnen til at afkøle med en langsom hastighed, f.eks. med 2°C pr. minut. Når temperaturen er m- DK 172938 B1 4 j under 100°C, f.eks. stuetemperatur (ca. 20°C), udtages be holderen fra ovnen, og det sorte, krystallinske produkt udvindes. Afkøling kan også gennemføres ved afgysning ved stuetemperatur af det materiale, som er blevet opvarmet til 5 850-900°C. Et superledende materiale ifølge opfindelsen kan ? fremstilles, selv når de relative mængder af reaktanter i udvælges uden for de støkiometriske grænser, som er dikteret af de områder, som er angivet i formlen for metaloxid-fasen.Cooling can be done slowly by either switching off the power to the oven and allowing the container to cool in the oven 35 or by programming the oven to cool at a slow rate, e.g. at 2 ° C per day. minute. When the temperature is m-100 ° C below 100 ° C, e.g. room temperature (about 20 ° C), remove the container from the oven and recover the black crystalline product. Cooling can also be effected by shaking at room temperature of the material which has been heated to 5 850-900 ° C. A superconducting material according to the invention can? is prepared even when the relative amounts of reactants in are selected outside the stoichiometric limits dictated by the ranges specified in the metal oxide phase formula.
Det superledende materiale vil derefter være sammensat af t 10 mindst én superledende fase sammen med andre, ikke-super- - ledende faser.The superconducting material will then be composed of at least one superconducting phase together with other non-superconducting phases.
_ Superledningsevnen kan bekræftes ved iagttagelse af udelukkelsen af den magnetiske flux, dvs. Meissner-effekten.The superconductivity can be confirmed by observing the exclusion of the magnetic flux, ie. Meissner effect.
Denne effekt kan måles ved den metode, som er beskrevet i 15 en artikel af E. Polturak og B. Fisher in Physical Review B, 36, 5586 (1987).This effect can be measured by the method described in an article by E. Polturak and B. Fisher in Physical Review B, 36, 5586 (1987).
‘ De superledende materialer, der indeholder metaloxid fasen ifølge opfindelsen kan anvendes til at lede strøm ekstremt effektivt eller til tilvejebringelse af et magnetisk 20 felt til magnetisk billeddannelse til medicinske formål.The superconducting materials containing the metal oxide phase of the invention can be used to conduct power extremely efficiently or to provide a magnetic field for magnetic imaging for medical purposes.
Ved afkøling af materialet i form af en tråd eller stang til en temperatur under den superledende overgangstemperatur, f.eks. til eller under ca. 115 K, fortrinsvis til eller -- under ca. 85 K, ved at udsætte materialet for flydende nitro- 2 5 gen på en måde, som er velkendt af fagfolk på området, og ved at initiere en strømning af elektrisk strøm kan man derfor opnå en sådan strømning uden nogen elektriske modstandstab. Til tilvejebringelse af eksceptionelt høje magnetiske felter med minimale krafttab kan den ovenfor omtalte 30 tråd snos til dannelse af en spiral, som vil blive udsat for flydende helium, før nogen strøm frembringes i spiralen.By cooling the material in the form of a wire or rod to a temperature below the superconducting transition temperature, e.g. to or below approx. 115 K, preferably to or - below ca. 85 K, by exposing the material to liquid nitrogen in a manner well known to those skilled in the art, and by initiating a flow of electric current, such flow can therefore be obtained without any electrical resistance loss. To provide exceptionally high magnetic fields with minimal power loss, the above-mentioned 30 wire can be twisted to form a coil which will be exposed to liquid helium before any current is generated in the coil.
De superledende materialer, der indeholder metaloxidfasen ifølge opfindelsen kan også anvendes til tilvejebrin-“ ‘ gelse af diamagnetiske felter, som er yderst vedvarende.The superconducting materials containing the metal oxide phase of the invention can also be used to provide diamagnetic fields which are highly renewable.
1 35 Sådanne felter opnås, ved at materialerne i form af et ark eller en tilsvarende konstruktion udsættes for et ydre, DK 172938 B1 5 magnetisk felt, idet arket er afkølet til en temperatur under den superledende overgangstemperatur, f.eks. afkølet til mellem 77°C og 115 K ved udsættelse for flydende nitrogen. Sådanne felter kan anvendes til at løfte genstande så 5 store som jernbanevogne. Disse superledende materialer kan også anvendes i Josephson-apparaturer, såsom SQUIDS (superledende kvantuminterferensapparaturer), og i instrumenter, som er baseret på Josephson-effekten, såsom høj hastighedprø-vekredsløb og spændingsstandarder. Disse materialer ser ud 10 til at være mere stabile, især i nærvær af vand, end kendte, superledende materialer med overgangstemperaturer i samme interval. Materialerne er ligeledes lettere at behandle end kendte materialer.Such fields are obtained by exposing the materials in the form of a sheet or similar structure to an outer magnetic field, the sheet being cooled to a temperature below the superconducting transition temperature, e.g. cooled to between 77 ° C and 115 K upon exposure to liquid nitrogen. Such fields can be used to lift objects as large as 5 lorries. These superconducting materials can also be used in Josephson devices, such as SQUIDS (superconducting quantum interference devices), and in instruments based on the Josephson effect, such as high speed test circuits and voltage standards. These materials appear to be more stable, especially in the presence of water, than known superconducting materials with transition temperatures in the same range. The materials are also easier to process than known materials.
15 EksempelExample
Et materiale med den nominelle formel Bi2Sr2CaCu30x fremstilles på følgende måde. Bi203 (4,6596 g), Sr02 (2,3924 g), CaC03 (1,0009 g) og CuO (2,3865 g) blandes og formales sammen i en agatmorter i tredive minutter. Pulver-20 blandingen anvendes til presning af 10 pellets, hver med en diameter på 10 mm og en tykkelse på ca. 2 mm.A material of the nominal formula Bi2Sr2CaCu30x is prepared as follows. Bi 2 O 3 (4.6596 g), SrO 2 (2.3924 g), CaCO 3 (1,0009 g) and CuO (2.3865 g) are mixed and ground together in an agate mortar for thirty minutes. The powder-20 mixture is used for pressing 10 pellets, each with a diameter of 10 mm and a thickness of approx. 2 mm.
En af de pressede pellets anbringes på en guldbakke, og bakken anbringes i en ovn og opvarmes i luft med en hastighed på 10°C pr. minut til 875°C og holdes derefter ved 25 875°C i 36 timer. Derefter afkøles ovnen med en hastighed på 1°C pr. minut til en temperatur under ca. 100°C, før bakken tages ud.One of the pressed pellets is placed on a gold tray and the tray is placed in an oven and heated in air at a rate of 10 ° C per minute. per minute to 875 ° C and then kept at 25 875 ° C for 36 hours. The oven is then cooled at a rate of 1 ° C per hour. per minute to a temperature below approx. 100 ° C before removing the tray.
Pladeagtige krystaller, som udviser spaltning i basisplanet, er dominerende i smelten. De adskilles mekanisk og 30 anvendes til yderligere karakterisering og strukturbestemmelse. Både fluxudelukkelse og måling af specifik elektrisk modstand på de enkelte krystaller afslører en skarp, superledende overgang ved Tc ved på ca. 95 K.Plate-like crystals exhibiting cleavage in the base plane are dominant in the melt. They are mechanically separated and used for further characterization and structure determination. Both the flux exclusion and the measurement of specific electrical resistance on the individual crystals reveal a sharp, superconducting transition at Tc of approx. 95 K.
Den superledende metaloxidfase i dette materiale er 35 blevet identificeret som Bi2Sr3.2CazCu208 +w 6 DK 172938 B1 ; hvor "z" er ca. 0,65, og "w" er under 1, men større end 0. Strukturen baseret på en A-centreret, orthorhombisk celle med a = 5,409Å, b = 5,414Å og c = 30,914Å er blevet bestemt ved anvendelse af enkeltkrystalrøntgenstrålediffrak- - 5 tionsdata.The superconducting metal oxide phase in this material has been identified as Bi2Sr3.2CazCu208 + w 6 DK 172938 B1; where "z" is approx. 0.65, and "w" is less than 1 but greater than 0. The structure based on an A-centered, orthorhombic cell with a = 5.409Å, b = 5.414Å and c = 30.914Å has been determined using single crystal X-ray diffraction. - 5 tions data.
Strukturen udgøres af afvekslende, dobbelte kobber-: -oxygen-lag og dobbelte bismuth-oxygen-lag. Der er Ca2+ ogThe structure is composed of alternating double copper: oxygen layers and double bismuth oxygen layers. There is Ca 2+ and
Sr2+-kationen mellem de tilstødende Cu-O-lag, og Sr2+-katio- - ner findes også mellem Cu-0 og Bi-O-lagene. Transmissions- r; 10 elektromikroskopistudier med høj opløsning viser, at b-aksen rent faktisk er 27,07Å, en forøgelse med en faktor på fem i forhold til undercelledimensionen. Denne superstruktur kan også iagttages ved røntgenstrålediffraktion på enkeltkry- - staller, men tvillingdannelse kan få det til at se ud, som 15 om der er superstruktur langs både a- og b-aksen.The Sr2 + cation between the adjacent Cu-O layers and Sr2 + cations are also found between the Cu-0 and Bi-O layers. Transmission; 10 high-resolution electromicroscopy studies show that the b-axis is actually 27.07Å, an increase of a factor of five relative to the subcell size. This superstructure can also be observed by X-ray diffraction on single crystals, but twin formation may make it appear as if there is superstructure along both the a and b axes.
Når "z" i formlen for den superledende metaloxidfase er hvor som helst fra 0,1 til 0,9, må det forstås, at "a" og "b" begge er ca. 5,4Å, og "c" er ca. 31Å, medens a, β og nr (de vinkler, som er forbundet med enhedscellen, således 20 som det er kendt af fagfolk på området) er ca. 90°. Endvidere ... kan, således som det er vist i dette eksempel, en eller to af underdimensionerne (a eller b eller c) multipliceres med et helt tal fra ca. 2 til 10 til opnåelse af en celle, som udviser superstrukturen af den superledende fase ifølge 25 opfindelsen.When "z" in the formula for the superconducting metal oxide phase is anywhere from 0.1 to 0.9, it should be understood that "a" and "b" are both approx. 5.4Å and "c" is approx. 31A, while α, β, and no (the angles associated with the unit cell, as known by those skilled in the art) are approx. 90 °. Furthermore, as shown in this example, one or two of the subdimensions (a or b or c) can be multiplied by an integer from ca. 2 to 10 to obtain a cell exhibiting the superstructure of the superconducting phase of the invention.
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Claims (3)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15310788A | 1988-02-08 | 1988-02-08 | |
| US15310788 | 1988-02-08 | ||
| PCT/US1989/000355 WO1989007087A1 (en) | 1988-02-04 | 1989-02-03 | SUPERCONDUCTING Bi-Sr-Ca-Cu OXIDE COMPOSITONS AND PROCESS FOR MANUFACTURE |
| US8900355 | 1989-02-03 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK188190D0 DK188190D0 (en) | 1990-08-07 |
| DK188190A DK188190A (en) | 1990-08-07 |
| DK172938B1 true DK172938B1 (en) | 1999-10-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK199001881A DK172938B1 (en) | 1988-02-08 | 1990-08-07 | Superconducting metal oxide phase |
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|---|---|
| JP (1) | JP2850310B2 (en) |
| KR (1) | KR970000482B1 (en) |
| AU (1) | AU617765B2 (en) |
| CA (1) | CA1341237C (en) |
| DK (1) | DK172938B1 (en) |
| HU (1) | HU217018B (en) |
| NO (1) | NO180043C (en) |
| RU (1) | RU2056068C1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE58908712D1 (en) * | 1988-02-05 | 1995-01-19 | Hoechst Ag | Superconductor and process for its manufacture. |
| JPH01212227A (en) * | 1988-02-17 | 1989-08-25 | Nippon Telegr & Teleph Corp <Ntt> | Oxide superconducting material |
| DE4108869A1 (en) * | 1991-03-19 | 1992-09-24 | Hoechst Ag | METHOD FOR PRODUCING A SUPRAL-CONDUCTIVE MATERIAL CONTAINING BISMUT |
| RU2460175C1 (en) * | 2011-05-12 | 2012-08-27 | Учреждение Российской академии наук Институт металлургии и материаловедения им. А.А. Байкова РАН | Superconducting composite material based on hts compounds and method of producing said material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2506892B2 (en) | 1988-02-05 | 1996-06-12 | 松下電器産業株式会社 | Oxide superconducting material |
| JP2629771B2 (en) | 1988-02-05 | 1997-07-16 | 松下電器産業株式会社 | Oxide superconducting material |
| US5181481A (en) * | 1991-03-25 | 1993-01-26 | Foster Wheeler Energy Corporation | Fluidized bed combustion system and method having multiple furnace sections |
| JPH0643268A (en) * | 1992-07-27 | 1994-02-18 | Casio Comput Co Ltd | Stop watch device |
-
1989
- 1989-02-03 RU SU894830651A patent/RU2056068C1/en not_active IP Right Cessation
- 1989-02-03 KR KR1019890701845A patent/KR970000482B1/en not_active IP Right Cessation
- 1989-02-03 HU HU891437A patent/HU217018B/en not_active IP Right Cessation
- 1989-02-03 JP JP1502391A patent/JP2850310B2/en not_active Expired - Fee Related
- 1989-02-03 AU AU30689/89A patent/AU617765B2/en not_active Ceased
- 1989-02-03 CA CA000590128A patent/CA1341237C/en not_active Expired - Fee Related
-
1990
- 1990-07-13 NO NO903160A patent/NO180043C/en not_active IP Right Cessation
- 1990-08-07 DK DK199001881A patent/DK172938B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| HUT57939A (en) | 1991-12-30 |
| AU617765B2 (en) | 1991-12-05 |
| DK188190D0 (en) | 1990-08-07 |
| CA1341237C (en) | 2001-05-22 |
| JP2850310B2 (en) | 1999-01-27 |
| AU3068989A (en) | 1989-08-25 |
| NO180043B (en) | 1996-10-28 |
| NO903160D0 (en) | 1990-07-13 |
| KR970000482B1 (en) | 1997-01-13 |
| RU2056068C1 (en) | 1996-03-10 |
| NO180043C (en) | 1997-02-05 |
| JPH03502918A (en) | 1991-07-04 |
| HU891437D0 (en) | 1991-11-28 |
| DK188190A (en) | 1990-08-07 |
| KR900700390A (en) | 1990-08-13 |
| NO903160L (en) | 1990-07-13 |
| HU217018B (en) | 1999-11-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| B1 | Patent granted (law 1993) | ||
| PBP | Patent lapsed |
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