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WO1997005669A1 - Procede de production de cuprate d'yttrium baryum fortement texture a utiliser dans les guides d'ondes et les lignes de transmission - Google Patents

Procede de production de cuprate d'yttrium baryum fortement texture a utiliser dans les guides d'ondes et les lignes de transmission Download PDF

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Publication number
WO1997005669A1
WO1997005669A1 PCT/US1996/012316 US9612316W WO9705669A1 WO 1997005669 A1 WO1997005669 A1 WO 1997005669A1 US 9612316 W US9612316 W US 9612316W WO 9705669 A1 WO9705669 A1 WO 9705669A1
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WO
WIPO (PCT)
Prior art keywords
superconductor
waveguide
atmosphere
yba2cu3θ7
constituents
Prior art date
Application number
PCT/US1996/012316
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English (en)
Inventor
James D. Hodge
Lori Jo Klemptner
Stephen K. Remillard
Original Assignee
Illinois Superconductor Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Illinois Superconductor Corporation filed Critical Illinois Superconductor Corporation
Publication of WO1997005669A1 publication Critical patent/WO1997005669A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P11/00—Apparatus or processes specially adapted for manufacturing waveguides or resonators, lines, or other devices of the waveguide type
    • H01P11/001—Manufacturing waveguides or transmission lines of the waveguide type
    • H01P11/002—Manufacturing hollow waveguides
    • 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
    • H10N60/0296—Processes for depositing or forming copper oxide superconductor layers
    • H10N60/0548—Processes for depositing or forming copper oxide superconductor layers by deposition and subsequent treatment, e.g. oxidation of pre-deposited material

Definitions

  • the present invention relates generally to high temperature superconductor material structures useful in waveguides and transmission lines. More particularly, the invention relates to waveguides and transmission lines including reactive textured, high temperature superconductor ceramic ("HTSC”) materials and methods of use of such waveguides and transmission lines.
  • HTSC reactive textured, high temperature superconductor ceramic
  • High temperature superconducting ceramics are intrinsically weak and brittle materials.
  • conventional ceramic processing of these materials produces polycrystalline bodies which have low critical current densities (jc, in DC measurements) and high surface resistivities (R s , in RF measurements).
  • Commercial applications of these materials require components that exhibit high jc and/or low Rs values, as well as the capability of producing mechanically strong and easy to manufacture components. Due to the materials' low mechanical strength, commercially useful structures such as waveguides and transmission lines cannot be produced without the use of a substrate to impart strength and toughness to the superconductor. This is especially true for lower frequency RF devices that require the superconductor to be formed into relatively large, complex shapes.
  • HTSC thin films for example, (less than about 1 micron thickness) have been shown to have high current densities and low Rs values.
  • these films are not useful for low frequency RF applications because they require expensive single crystal substrates (typically, LaAl ⁇ 4 or SrTi ⁇ 4) and can only be formed into planar structures with dimensions under a few inches.
  • YBa2Cu3 ⁇ 7- x such textured microstructures are produced using a method called peritectic re crystallization or, more commonly, "melt-texturing".
  • "textured" YBa2Cu3 ⁇ 7- x is produced by crystallizing this compound out of its peritectic mixture of Y2BaCu ⁇ 5 plus a Ba/Cu-rich liquid.
  • the melt-texturing process typically involves heating a sample above the peritectic temperature (1015°C in air) to decompose the YBa2Cu3 ⁇ 7- ⁇ into Y2BaCu ⁇ 5 plus liquid. This mixture is cooled slowly through the peritectic temperature allowing YBa2Cu3 ⁇ 7- ⁇ to crystallize. When this cooling is performed in the presence of a thermal gradient, the YBa2Cu3 ⁇ 7- ⁇ grains preferentially grow parallel to the gradient and a "textured" microstructure results. The slow cooling keeps the nucleation rate of YBa2Cu3 ⁇ 7- ⁇ low, resulting in the formation of a small number of nuclei.
  • the YBa2Cu3 ⁇ 7- ⁇ grains can grow to very large sizes before impingement; and ifthe cooling is performed in a thermal gradient, the grains will be highly aligned.
  • samples were dete ⁇ nined to have critical currents of up to 17,000 A/cm2 in self-field with only a small magnetic field dependence. Improvements to this process (which have included the production of continuous lengths of melt-textured filaments) have resulted in measured current densities as high as 140,000 A/cm2 in self field and 44,000 A/cm2 in a 1 Tesla field at 77 K.
  • melt-texturing is essentially a crystal growth process in which the rate of material production is controlled by the velocity ofthe crystallization front.
  • the crystallization rate is extremely sluggish.
  • a second problem, of particular importance to texturing thick film structures, is the fact that the melt-texturing process requires processing at temperatures above 1000°C in the presence ofthe extremely reactive peritectic liquid.
  • HTSC high temperature superconductor
  • FIG. 1 illustrates a 40X magnification microstructure of reactively textured YBa2Cu3 ⁇ 7_ ⁇ on silver buffered stainless steel
  • FIG. 2 shows a reactively textured YBa2Cu3 ⁇ 7_ x on a silver substrate at 40X magmfication
  • FIG. 3 illustrates a conventional peritectic re crystallized thick film microstructure on a zirconia substrate
  • FIG. 4A illustrates an exemplary rocking angle X-ray diffraction curve showing the highly textured nature of an HTSC material prepared by one ofthe methods ofthe invention
  • FIG. 4B shows X-ray diffraction patterns for three crystalline YBa2Cu3 ⁇ 7_ x samples
  • FIG. 5 illustrates a pseudobinaiy phase diagram of Y2BaCu ⁇ 2 and 3BaO-5CuO;
  • FIG. 6 shows surface RF resistivity extrapolated to lGHz for YBa2Cu3 ⁇ 7_ x specimens ofthe invention, a prior art sintered YBa2Cu3 ⁇ 7_ x and Cu;
  • FIG. 7 illustrates a side view of a waveguide constructed in accordance with one form of the invention
  • FIG. 8 shows a front sectional view taken along lines 8-8 ofthe waveguide illustrated in FIG. 7;
  • FIG. 9A illustrates resonator Q versus surface resistance for a copper cylinder compared to a YBCO cylinder, each with a YBCO center conductor
  • FIG. 9B illustrates an unloaded resonator Q versus outer radius of a coaxial resonator with a copper outer wall and YBCO center conductor
  • FIG. 9C illustrates unloaded Q values at 77°K versus dissipated power for a 1.5 inch diameter, 6 inch long halfwave coaxial resonator with 0.25 inch diameter HTSC center conductor fabricated by depositing a reactively textured YBCO thick film onto a stainless steel substrate.
  • FIG. 10 illustrates a high power coaxial transmission line having a high temperature YBCO superconductor thick film on a center conductor
  • FIG. 11 illustrates power dissipation versus input power for a copper center conductor compared to a YBCO center conductor power transmission line at 77°K and 1 GHz frequency.
  • a process of producing a waveguide in accordance with one form ofthe invention involves the crystallization of YBa2Cu3 ⁇ 7- x out of a metastable hquid formed by rapidly introducing a non-equilibrium mixture of Y-, Ba-and Cu-compounds (mixed in the appropriate stoichiometry) into a combination of temperature and a gas atmosphere in which YBa2Cu3 ⁇ 7- ⁇ is the thermodynamically stable phase (hereinafter generally referred to as "reactive texturing process"). Two general variations of this process have been successfully demonstrated.
  • Y2O3, CuO, and BaCO3 powders are mixed in a molar ratio of 0.5:3.0:2.0 and are heated in a CO2-rich atmosphere to approximately 850°C to 890°C. The atmosphere is then changed to 2 torr of pure oxygen.
  • the use of a CO2-rich atmosphere during heating suppresses the decomposition of BaCO3 and consequently prevents YBa2Cu3 ⁇ 7- x from forming prematurely.
  • the reaction mixture begins to decompose to a partially molten state out of which YBa2Cu3 ⁇ 7- x crystallizes.
  • a prereacted, phase-pure YBa2Cu3 ⁇ 7- x powder is heated to approximately 850°C to 890°C, also in a CO2-rich atmosphere.
  • the presence ofthe CO2 causes the YBa2Cu3 ⁇ 7- to decompose into a complex mixture of oxides and oxycarbonates.
  • the atmosphere is changed at temperature to a reduced pressure oxygen containing atmosphere, which causes this mixture to decompose into the partially molten state from which YBa2Cu3 ⁇ 7-. ⁇ can crystallize.
  • this reactive texturing process is preferably carried out on either a silver foil or a base metal, such as a stainless steel, which has been electroplated with either silver or silver with a nickel intermediate layer.
  • a silver foil or a base metal such as a stainless steel
  • the silver or silver/nickel buffer layers are necessary since YBa2Cu3 ⁇ 7_ x and its precursors are relatively active compounds which react strongly with most base metals.
  • silver is relatively inert with respect to YBa2Cu3 ⁇ 7_ x .
  • This silver or silver/nickel buffer layer is preferably at least 0.002" thick to protect the superconductor.
  • Base metals which have proven satisfactory include, for example, stainless steels, such as 302 stainless steel, 304 stainless steel, 316 stainless steel and also Inconel 600.
  • the substrate can be coated with the precursor slurry of appropriate stoichiometry using either painting, dipping, spraying, or any other technique currently used to apply thick film coatings or patterns. It has been determined that the preferred thickness of this applied coating is about 0.002" to 0.008".
  • the preferred thermal processing has three steps: 1. Binder/organic removal. Heating ofthe coating is preferably carried out in a reduced total pressure oxygen environment (e.g., 2 torr of oxygen) heated at a rate ofbetween 30°C/hr and 300°C/hr from room temperamre to a temperature between 350°C and 500°C which is sufficient to removal the volatile components ofthe precursor paint.
  • a reduced total pressure oxygen environment e.g., 2 torr of oxygen
  • Heating ofthe coating is preferably performed at a rate of about 300°C/hr. in a mtrogen atmosphere containing between at least about 0.8% and 2.8% CO2-
  • CO2 can be mixed with any inert gas, such as N2, argon or helium.
  • the temperature is preferably between the temperamre ofthe binder removal stage and the temperature ofthe crystallization stage. These temperatures are sufficient to suppress the formation of YBa2Cu3 ⁇ 7_ x in the case of an oxide/carbonate precursor or decompose the YBa2Cu3 ⁇ 7- x precursor to an appropriate mixture of oxides and oxycarbonates.
  • a preferred window for crystallization of YBa2Cu3 ⁇ 7- exists between about 850°C and 900°C in an atmosphere of about 1 to 3 torr of oxygen, although the oxygen pressure can range up to one atmosphere pressure. Below about 850°C, the grain sizes are greatly reduced in size. It should also be noted that at higher oxygen partial pressures, the process temperature increases such that at 0.21 atm. oxygen the temperature of treatment would be about 975°C. Preferably the process temperature is maintained below the melting point of the silver containing substrate. Most preferably, therefore, the pressure of oxygen is kept below about 50 torr to operate at a temperature below 925°C (the melting point of silver at 50 torr). One can choose to perform the process by slowly increasing the temperature within this window during the crystallization process as opposed to using a simple isothermal hold. Either procedure is acceptable.
  • an intermediate product, or article of manufacture is obtained.
  • the peritectic zone (region P in FIG. 5) encompasses the region ofthe phase diagram involved in producing the desired YBa2Cu3 ⁇ 7- x .
  • the amount of liquid present is quite large throughout the processing temperature range (about 1015°C then cooled slowly through the peritectic temperature of 1013°C).
  • the intermediate product is primarily a solid and a small fraction of a eutectic liquid (not a peritectic liquid).
  • the liquid that forms is the lowest melting Uquid in the Y-Ba-Cu-O system, that is, the ternary eutectic.
  • Substantial advantages result from being able to prepare textured YBa2Cu3 ⁇ 7- x without excess liquid present.
  • One such advantage is the ability to cast well defined solid patterns without need of liquid barriers in place.
  • a desired pattern can be disposed on a substrate, such as by applying a thick film slurry in a desired pattern; and then the YBa2Cu3 ⁇ 7- x can be formed by the method ofthe invention without substantial liquid flowage causing loss ofthe shape ofthe desired pattern.
  • the intermediate product ofthe invention formed at about 850-900°C does not have the undesirable large liquid component present in the conventional intermediate product formed in the peritectic region.
  • a process has been described herein which produces textured YBa2Cu3 ⁇ 7- microstructures, as in the peritectic re crystallization method.
  • the instant method produces these microstructures at low temperatures (less than about 900°C) and in relatively short times (less than about 1 hr compared to 10-15 hours for conventional melt texturing).
  • This combination of low temperatures and short times enables the use of relatively inexpensive and easy to form base metal substrates that substantially reduce the potential cost ofthe component. This cost reduction makes this process much more attractive for the commercial application of HTSC components.
  • This process is especially attractive for the fabrication of three dimensional RF resonant structures which are the fundamental components of numerous RF devices such as filters, oscillators, combiners and radar units.
  • FIG. 6 illustrates a side elevation view of a waveguide 100 constructed in accordance with the invention.
  • the waveguide 100 is a two pole filter assembly having reactively textured thick film 102 of YBCO disposed on the inner walls ofthe waveguide 100.
  • FIG. 8 illustrates a cross sectional view ofthe waveguide 100. Further details of waveguide construction and other embodiments are set forth in a co-pending application 08/349,060, which is incorporated by reference here.
  • FIG. 9A The calculated resonator Q versus surface resistance behavior of a waveguide structure is illustrated in FIG. 9A which compares the Q values of a copper outer cylinder with a YBCO high temperature superconductor cylinder, each having a high temperature superconductor coated (or optionally a solid) center resonator ring. These values were obtained by using conventional, well known geometry factor measurements in which the geometrical features were removed, enabling determination ofthe effect ofthe YBCO material used, alone, versus the same geometry using copper or other conventional materials.
  • one can calculate Q values using conventional computer software for example, "Emenance” from AnSoft Corp., Pittsburgh, PA or "EMAS” from McNeil-Schcoenneller Corp., Milwaukee, WI.
  • FEA finite element analysis code
  • AnSoft can be used to simulate various features of RF filters. This type of code is accepted as accurately predicting resonator Q and frequency, given various input parameters, including resonator geometry and electrical conductivity (loss tangent). These types of codes also accurately calculate coupling between two or more adjacent waveguide resonators.
  • the AnSoft computer software code solves the known electromagnetic field equations ofthe three-dimensional waveguide structure, including performing a known asymptotic waveform evaluation to produce the frequency response of a waveguide.
  • Such conventional computer software code is divided into three parts: (1) a solid modeler section allows the user to input the geometry ofthe device and input/output couplers using a CAD interface, (2) a finite element solver determines the finite element matrix, and (3) a post processor section allows the user to view the electric and magnetic field patterns at user selected frequencies, as well as the insertion and return losses versus frequency.
  • FIG. 9A the geometry factor on toroid measurements for a copper cylinder geometry factor measurement show the typical flat plateau wherein losses are dominated by the presence of metal waveguide walls.
  • FIG. 9B shows the results of a conventional analytic solution for the unloaded behavior of Q for a coaxial resonator versus outer radius of a copper cylinder with YBCO center conductor.
  • FIG. 9C shows direct measurements of copper with a YBCO reactively textured unloaded Q versus dissipated power for a coaxial resonator thick film layer on a stainless steel base. Changing from copper to aluminum or any other metal will only move the plateau in FIGS. 9 A or 9B shghtly up or down.
  • the utilization ofthe YBCO walls for the coaxial resonator results in substantial improvement of performance over conventional metal waveguide walls.
  • a superconductor thick film transmission line can be constructed to carry high RF power, such as 50-1000W.
  • the transmission line 104 further includes an outer housing 105 and a superconductor thick film 106 is disposed on a substrate 108.
  • the thick film 106 preferably is a reactive texture process thick film, although other embodiments can comprise thick films prepared by other methods, such as peritectic recrystallization.
  • the reactively textured film 106 preferably is deposited on the substrate 108, such as stainless or silver.
  • a peritectic recrystallized film can be deposited on a substrate 108 of zirconia.
  • the losses in a transmission line can be determined using conventional methodologies. Using known R s versus surface field data for such resonant structures, one can generate functional behavior of dissipated power versus input power for a coaxial transmission line (see FIG. 11).
  • This transmission line has a 0.125 inch diameter 123 YBCO coated stainless steel center conductor in a 1.68 inch diameter copper outer housing, producing a 50 ⁇ impedance.
  • the space between the inner and outer conductors was filled with MgO with an epsilon of 9.72 and loss tangent of 3 x 10 "6.
  • the 123 YBCO geometry shows a substantial advantage over copper in the power range of at least about 1000W and less.
  • the power range is generally limited by the limitations on dissipating heat from a ceramic material.
  • Semi-continuous lengths ofthe transmission line 104, shown in FIG. 10 can be produced by a variety of techmques, such as continuous firing ofthe high temperature superconductor in a commercial off-the-shelf belt furnace.
  • the superconductor is in the form of fine filaments of 123 YBCO formed using a known thermoplastic extrusion technique. The filaments are fed to the furnace from a supply spool.
  • the YBCO thick film can be deposited using various continuous printing techniques on a continuous ribbon of zirconia which can subsequently be fed onto a belt furnace for firing and then spooled.
  • a silver-plated stainless steel wire can be coated with a 123 YBCO thick film slurry, dried and then fed into a belt furnace. After firing, the center conductor can be swaged using the copper outer housing 105 and an appropriate dielectric, such as quartz, Teflon (registered trademark of DuPont Corp.), MgO and pressurized nitrogen.
  • a mixture of Y2O3, CuO, and BaCO3 was mixed in turn with an acrylic binder, a sorbitan trioleate dispersant, and an n-butanol/xylene solvent to make precursor 'paint'.
  • Other suitable carrier formulations can also be used as understood in the art.
  • This paint was then applied to a silver foil using a paint brush. The resultant dried coating was 0.008" thick.
  • This sample was then placed in a controlled atmosphere furnace, heated in 2 torr of oxygen at 60° C/hr to 350°C to insure adequate removal ofthe organic components ofthe paint.
  • the atmosphere ofthe furnace was then changed to 0.9% CO2 in nitrogen, and the sample was heated to 900°C at a rate of about 300°C hr.
  • the atmosphere ofthe furnace was again changed to 2 torr of oxygen, and the sample was held at temperature for 1 hour. This treatment resulted in a textured, crystallized YBa2Cu3 ⁇ 7- x microstructure.
  • a commercial YBa2Cu3 ⁇ 7- ⁇ powder was mixed with an acrylic binder, a sorbitan trioleate dispersant, and an n-butanol/xylene solvent to make a precursor 'paint'.
  • This paint was applied to a 304 stainless steel disc, a 316 stainless steel disc, and an Inconel 600 disc (all 1.125" diameter and previously electroplated with 0.002" of silver) with a paint brush.
  • the resultant dried coating was, in all cases, about 0.004 to 0.005" thick. All three samples were then placed in a controlled atmosphere furnace, and heated in 2 torr of oxygen at 60°C/hr to 350°C to insure proper removal ofthe organic components ofthe paint.
  • a variety of starting materials different from those used in Examples 1 and 2 also proved satisfactory. These starting materials included: (1) phase pure YBa2Cu3 ⁇ 7- x with 22% Y2BaCu ⁇ 5, (2) YBaSrCu3 ⁇ 7_ x with 22% Y2BaCuOs, (3) a CuO rich commercially available YBa2Cu3 ⁇ 7_ x and stoichiometric YBa2Cu3 ⁇ 7_ x . All of these starting materials were used successfully in implementing the methods described in Examples 1 and 2.

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  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un guide d'ondes (10) et d'une ligne de transmission (104) supraconducteurs. Le procédé consiste à préparer un mélange de constituants en matière supraconductrice, à disposer sous la forme souhaitée pour le guide d'ondes (100) les constituants sur un substrat contenant de l'argent, à chauffer le mélange de constituants sur le substrat contenant de l'argent, à chauffer le mélange sous une première atmosphère à pression partielle de CO2 de façon à réguler la décomposition de l'un au moins des constituants en matière supraconductrice et à remplacer la première atmosphère par une seconde atmosphère essentiellement composée d'un gaz oxydant susceptible de permettre la décomposition de l'un au moins des constituants en matière supraconductrice. Le procédé réactif de texturation peut s'utiliser pour disposer de la matière supraconductrice sur des constituants sélectionnés de guides d'ondes (100) et de lignes de transmission (104).
PCT/US1996/012316 1995-07-26 1996-07-26 Procede de production de cuprate d'yttrium baryum fortement texture a utiliser dans les guides d'ondes et les lignes de transmission WO1997005669A1 (fr)

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US08/507,775 1995-07-26

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Cited By (11)

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Publication number Priority date Publication date Assignee Title
WO2001026164A3 (fr) * 1999-07-23 2002-01-17 American Superconductor Corp Commande des vitesses de reaction de couches d'oxyde
US6436317B1 (en) 1999-05-28 2002-08-20 American Superconductor Corporation Oxide bronze compositions and textured articles manufactured in accordance therewith
US6562761B1 (en) 2000-02-09 2003-05-13 American Superconductor Corporation Coated conductor thick film precursor
US6673387B1 (en) 2000-07-14 2004-01-06 American Superconductor Corporation Control of oxide layer reaction rates
US6730410B1 (en) 1999-08-24 2004-05-04 Electronic Power Research Institute, Incorporated Surface control alloy substrates and methods of manufacture therefor
US6765151B2 (en) 1999-07-23 2004-07-20 American Superconductor Corporation Enhanced high temperature coated superconductors
US6828507B1 (en) 1999-07-23 2004-12-07 American Superconductor Corporation Enhanced high temperature coated superconductors joined at a cap layer
US6974501B1 (en) 1999-11-18 2005-12-13 American Superconductor Corporation Multi-layer articles and methods of making same
US7326434B2 (en) 2000-10-23 2008-02-05 American Superconductor Corporation Precursor solutions and methods of using same
CN103086709A (zh) * 2013-01-31 2013-05-08 西安理工大学 钇钡铜氧超导薄膜的制备方法
EP2506324A3 (fr) * 2011-03-31 2014-01-15 Korea Electrotechnology Research Institute Bande supraconducteur haute température

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6436317B1 (en) 1999-05-28 2002-08-20 American Superconductor Corporation Oxide bronze compositions and textured articles manufactured in accordance therewith
US6765151B2 (en) 1999-07-23 2004-07-20 American Superconductor Corporation Enhanced high temperature coated superconductors
WO2001026164A3 (fr) * 1999-07-23 2002-01-17 American Superconductor Corp Commande des vitesses de reaction de couches d'oxyde
US6669774B1 (en) 1999-07-23 2003-12-30 American Superconductor Corporation Methods and compositions for making a multi-layer article
US6893732B1 (en) 1999-07-23 2005-05-17 American Superconductor Corporation Multi-layer articles and methods of making same
US6828507B1 (en) 1999-07-23 2004-12-07 American Superconductor Corporation Enhanced high temperature coated superconductors joined at a cap layer
US6730410B1 (en) 1999-08-24 2004-05-04 Electronic Power Research Institute, Incorporated Surface control alloy substrates and methods of manufacture therefor
US6974501B1 (en) 1999-11-18 2005-12-13 American Superconductor Corporation Multi-layer articles and methods of making same
US6562761B1 (en) 2000-02-09 2003-05-13 American Superconductor Corporation Coated conductor thick film precursor
US6673387B1 (en) 2000-07-14 2004-01-06 American Superconductor Corporation Control of oxide layer reaction rates
US7326434B2 (en) 2000-10-23 2008-02-05 American Superconductor Corporation Precursor solutions and methods of using same
US7939126B2 (en) 2000-10-23 2011-05-10 American Superconductor Corporation Precursor solutions and methods of using same
EP2506324A3 (fr) * 2011-03-31 2014-01-15 Korea Electrotechnology Research Institute Bande supraconducteur haute température
CN103086709A (zh) * 2013-01-31 2013-05-08 西安理工大学 钇钡铜氧超导薄膜的制备方法
CN103086709B (zh) * 2013-01-31 2014-06-04 西安理工大学 钇钡铜氧超导薄膜的制备方法

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Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

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Free format text: PAT.BUL.08/97 UNDER INID (22) "INTERNATIONAL FILING DATE",REPLACE "960725" BY "960726"

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