EP2828220A2 - Procédé de production de nanoparticules ainsi que leur utilisation pour la production de supraconducteurs à haute température - Google Patents

Procédé de production de nanoparticules ainsi que leur utilisation pour la production de supraconducteurs à haute température

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Publication number
EP2828220A2
EP2828220A2 EP13710432.9A EP13710432A EP2828220A2 EP 2828220 A2 EP2828220 A2 EP 2828220A2 EP 13710432 A EP13710432 A EP 13710432A EP 2828220 A2 EP2828220 A2 EP 2828220A2
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
phase
polar
htsc
precipitant
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.)
Withdrawn
Application number
EP13710432.9A
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German (de)
English (en)
Inventor
Thomas Freudenberg
Bernhard Holzapfel
Oliver Brunkahl
Michael BÄCKER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP13710432.9A priority Critical patent/EP2828220A2/fr
Publication of EP2828220A2 publication Critical patent/EP2828220A2/fr
Withdrawn legal-status Critical Current

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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
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/224—Oxides or hydroxides of lanthanides
    • C01F17/235—Cerium oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/32—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process
    • C01B13/328—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of elements or compounds in the liquid or solid state or in non-aqueous solution, e.g. sol-gel process by processes making use of emulsions, e.g. the kerosine process
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
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    • C01G3/006—Compounds containing copper, with or without oxygen or hydrogen, and containing two or more other elements
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    • 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
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    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • 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
    • H10N60/0324—Processes for depositing or forming copper oxide superconductor layers from a solution
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    • H10N60/80—Constructional details
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    • H10N60/855—Ceramic superconductors
    • H10N60/857—Ceramic superconductors comprising copper oxide
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3215—Barium oxides or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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Definitions

  • the invention relates to a process for the preparation of nano particles containing or preferably consisting of compounds of certain transition metals as well as the use of these particles in the production of high temperature superconductors (HTSC).
  • HTSC high temperature superconductors
  • particles of oxides of the metals can thus be obtained, which can be smaller than 1 ⁇ m.
  • a similar process for the production of nanoparticles for high-density ceramics is disclosed in DE 102 37 915 A1.
  • the formation of amorphous oxide particles is promoted by increasing the polarity of the O phase in the microemulsion.
  • a method for producing nanoparticles from cerium (IV) oxide is described by Masui et al. , Chem. Mat. 1997, 2197-2204.
  • a W / O microemulsion with hexane as the continuous phase, cerium nitrate solution as the aqueous phase, polyoxyethylene (10) octylphenyl ether as a surfactant and hexanol as a solubilizer for the surfactant is prepared.
  • This microemulsion is mixed with a second, which had been prepared in the same way with Ammoni ⁇ umhydroxidnaps as an aqueous phase.
  • particles could from cerium (IV) oxide 2-6 nm size, it ⁇ be generated.
  • the elaborate handle lo ⁇ environment is avoided by water-sensitive metal compounds such as alkoxides. It can not be transferred to other systems because mixing of the two emulsions can cause collision and breakup of individual micelles, thereby undesirably widening the particle size distribution.
  • DE 10 2006025 770 A1 discloses a method for producing a coating dispersion with nanoparticles, wherein a water-sensitive metal compound in alcoholic solution is mixed with an O / W microemulsion comprising a cationic surfactant.
  • the proportion of water in the microemulsion is preferably at least 5 to 15 percent by weight.
  • Such coating dispersions can be used to prepare thin ceramic coatings.
  • a molecular organometallic CSD solution can be added to the coating dispersion (hybrid solution).
  • HTSC high-temperature superconductors
  • the Lorenz force acts on the flow tubes and moves them through the superconductor. This movement is accompanied by an energy dissipation, which increases the resistance macroscopically and leads to the collapse of the superconducting phase.
  • the effect of energy dissipation by flow tube movement can be reduced or eliminated by incorporating pinning centers, allowing higher current densities.
  • the pinning centers can be placed in an yttrium-barium Copper oxide (YBCO) superconductors consist of, for example, barium-circonate (BZO) nanoparticles.
  • YBCO yttrium-barium Copper oxide
  • BZO barium-circonate
  • a method for producing thin HTSC layers of YBCO with built-in pinning centers from BZO is described by Molina-Luna (L. Molina-Luna, Dissertation, Tübingen 2010, p. 141). It is based on a solution of the trifluoroacetates of yttrium, barium and copper in methanol. BZO nanoparticles are prepared by adding alkoxides of barium and zirconium to a microemulsion of water in a mixture of cyclohexane and methanol with a cationic surfactant. This BZO dispersion is then mixed with the solution of the trifluoroacetates and used to coat a carrier.
  • the invention accordingly has for its object to provide a method by which nanoparticles of compounds of the Transition metals can be produced, which are largely free of interfering impurities and which are suitable for use in high-temperature superconductors with copper mixed oxides.
  • This object is achieved by a method according to claim 1, and by a method according to claim 12 for the production of a HTSC material.
  • the inventive method for producing Nanoteil- chen containing or consisting of compounds of transition metals Zr, Hf, Ti, Ta, Sc, Y, La, elements with the Trim ⁇ pay 58 (Ce) to 71 (Lu), and Mn Fe comprises the steps of: preparing a W / O microemulsion having at least one precursor of said metals in the disperse polar (W) phase with the aid of a surfactant,
  • a polar solvent having a water content of ⁇ 1 mol% and a precipitant in the nonpolar phase a base can be used.
  • microemulsion is meant here an emulsion whose inner disperse phase has a droplet size of less than 1 ⁇ m, preferably in the range of 1 to 100 nm, particularly preferably 2 to 30 nm. Since the droplets are separated from the continuous outer phase by a boundary layer of radially directed surfactant molecules, one also speaks of micelles.
  • the micelle size usually decreases with the Rw value.
  • suitable surfactant levels for example, correspond to a Rw 1 to 25, preferably Zvi ⁇ rule 2 and 15 °.
  • the polar solvent to be used according to the invention must not be miscible with the non-polar solvent of the outer phase of the microemulsion. On the other hand, it must have sufficient solvent power for the precursor. Furthermore, it must have only a very low miscibility with the surfactant, so that the formation of micelles with surfactant boundary layer is not prevented.
  • the choice of the polar solvent is thus determined by the type of precursor and the non-polar solvent. Suitable solvents and Rekurso ⁇ ren Maschinentube can be determined. Suitable examples of the polar solvent are ketones, e.g.
  • acetone lactones, for example, butyrolactone, nitriles, such as acetonitrile, nitro compounds such as nitromethane, dialkylcarboxamides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide.
  • Particularly preferred ⁇ are the ketones, lactones, nitro compounds, amides, sulfoxides alkyl or aryl compounds Cl to C8 or Cl to C6 compounds, preferably Cl to C4 or Cl to C3 compounds, in the case of nitro compounds also Cl or C2 connections.
  • nitriles in particular alkyl or aryl nitriles, in particular C 1 to C 7 nitriles or C 1 to C 6 alkylnitriles, preferably C 1 to C 4 or C 1 to C 2 alkylnitriles.
  • nitriles in particular alkyl or aryl nitriles, in particular C 1 to C 7 nitriles or C 1 to C 6 alkylnitriles, preferably C 1 to C 4 or C 1 to C 2 alkylnitriles.
  • the polar solvent must invention practically what his ⁇ serrile. This means a water content of at most 1-2% by weight, preferably at most 0.75% by weight or at most 0.5% by weight.
  • the solubility of the precursor in the polar solvent must be sufficient in order to be able to form sufficiently large nanoparticles in the individual micelles.
  • Geeig ⁇ designated Recaynesen have, for example concentrations of 0.025 to 2 mol / 1, preferably 0.05 to 0.75 mol / 1 or more preferably 0.1 to 0.5 mol / 1 with respect to the Rekur ⁇ sor.
  • non-polar solvents are for example those geeig ⁇ net, which have already been used in the art for micro-emulsions with aqueous micelles.
  • alkanes examples are alkanes, alkenes, benzene and other aromatics, carboxylic esters, ethers, such as diethyl ether, halogenated hydrocarbons, such as tetrachloromethane or hexafluorobenzene.
  • alkanes in particular C 2 - to C 14 -alkanes or C 4 - to C 12 -alkanes or in each case to mixtures thereof.
  • these are hexane, heptane, octane, or their technical mixtures in Erdöldestilla ⁇ th.
  • the nonpolar solvent must have sufficient solvency for the precipitant.
  • phase volume ratio of W / O according to the invention used ⁇ th microemulsions is preferably during preparation between 2/98 and 20/80, or preferably between 4/96 and 15/85.
  • the target compounds of the transition metals are primarily oxides in all oxidation states of the respective metal.
  • precursors can first be formed in the micelles from the precursors under the influence of the precipitating agent, which precursors are converted into the target compound during a subsequent heat treatment.
  • Such precursors may be, for example, hydroxides for oxides.
  • the compounds may also contain other metals.
  • the metals of the precursor may be those of ⁇ selected from the group consisting of Zr, Hf, Ti, Ta, Sc, Y and La, and ele- ments with atomic numbers 58 (Ce) to 71 (Lu), Mn and Fe, in each case individually or in combination, be.
  • Rare earth metals in the context of this invention are the elements Sc, Y, La and the elements with the atomic numbers 58 (Ce) to 71 (Lu), which can be used individually or in combination as metals of precursors.
  • the metals of the precursor can also be those selected from the group Zr, Hf, Ti, Ta, Sc, Y and La and Ce, Sm, Eu, Gd, Tb, Yb, Lu, in particular selected from the group Zr, Hf Ti, Ta, Sc, Y, La, Ce, Sm, Eu, Gd, in particular from the group Zr, Hf, Ti, Ta, Y, La, Ce, Sm, Eu, Gd; in especially special from the group Zr, Hf, Ce.
  • the jewei ⁇ time groups of the metals used can in each case at least substantially be free of Hf and / or Fe.
  • Precursors are compounds of the respective metals, which can form a polar solvent unlösli ⁇ che compound un- ter influence of a base.
  • These can be simple water-soluble inorganic or organic, neutral or basic salts such as nitrates, halides, in particular chlorides, oxyhalides or the corresponding transition metals, so-far they have sufficient solubility in the polar complementary and have ⁇ tel.
  • surfactants can be used in the prior Tech ⁇ technology.
  • the surfactant is a ceremoniioni ⁇ ULTRASONIC surfactant.
  • Such surfactants are composed of organic radicals and contain no inorganic counterions. They are used in the final heat treatment of the coating composition to form the HTSC or other ceramic mik removed without residue from the layer.
  • Nonionic surfactants include fatty alcohol alkoxylates, alkylphenyl alkoxylates, sugar surfactants (fatty alcohol glycosides.
  • Fatty alcohols here are aliphatic monohydric primary alcohols having 8 to 22, preferably 12 to 18 carbon atoms. Particular preference is given to alkylphenyl alkoxylates (alkylphenyl polyglycol ethers).
  • the surfactant must be sufficiently soluble in the outer phase. Also, the balance between the non-polar and the polar part of the surfactant molecule must be appropriate for the non-polar and polar-phase system.
  • the ge for aqueous systems ⁇ b syndromechliche HLB system can not be surely transmitted to the OF INVENTION ⁇ to the invention water-free systems.
  • suitable surfactant series with a graded ratio between polar and non-polar fractions are available to the person skilled in the art, for example the alkylphenyl polyoxyalkylene ethers.
  • the selection of a suitable surfactant can be done without difficulty by preliminary experiments.
  • nonylphenyl poly (5) oxyethylene ether is useful.
  • any agent which is soluble in the continuous outer phase of the microemulsion permeates the surfactant shell of the micelles and is capable of reacting with the precursor to form the desired compound of the transition metal or a precursor compound therefor.
  • Bases such as ammonia or organic amines are particularly suitable for the formation of precipitation products from metal salts for the preparation of oxides.
  • Short-chain organic amines are advantageous because they introduce little carbon into the system, for example C 1 - to C 10 -alkyl- or arylamines or C 1 - to C 6 -alkylamines or preferably C 1 - to C 4 -alkyl or in particular C 2 - to C 4 -alkylamines.
  • Particular preference is given to using propylamine as precipitant.
  • the precipitating agent for addition to the outer phase is dissolved and / or diluted with a suitable solvent, for example that of the outer phase.
  • the precipitating agent is advantageously used in relation to refkur ⁇ sor in excess.
  • Preference is given to molar ratios of precipitant / precursor between 1 and 10 or 1.05 and 10, preferably between 1.05 and 5.
  • the said molar ratio may in each case also be> 1.1 or> 1.2, for example also> 1.5.
  • the direct addition of the precipitant to the outer phase has the advantage that the micelles of the microemulsion are not affected by the addition of another surfactant or surfactant in a different concentration. As a result, their size distribution is unaffected and the resulting nanoparticles are almost monodisperse. The rate of precipitation and thus the structure of the nanoparticles can also be controlled by the addition.
  • the inventive method produces nanoparticles that are far ⁇ largely free from accompanying substances. Therefore, they can be used inter alia to form pinning centers in HTSC coatings, without the coating being adversely affected by the incorporation of nanoparticles.
  • the invention also includes a process for producing HTSC materials comprising copper mixed oxides, wherein nanoparticles are incorporated into the copper mixed oxide of the HTSC phase, using the nanoparticles prepared according to the invention, and wherein the HTSC material is combined or separated by applying a solution of precursors of the mixed oxide components is formed with the nanoparticles on a support and heat treatment ⁇ treatment.
  • the copper mixed oxide is preferably produced in a third solvent on a support and heat treatment of the layer thus formed.
  • the mixed oxide is a rare earth-barium Kupfermischoxid, particularly preferably an yttrium-containing Kup ⁇ fermischoxid, in particular YBa 2 Cu 3 C> 7 (YBCO).
  • the precursor solution for the copper mixed oxide intended for the construction of the HTSC layer is mixed with the suspension of the nanoparticles in the non-polar phase to form a hybrid solution before application to the support.
  • a homogeneous distribution of the nano particles ⁇ in the HTSC layer is achieved, as is required for the effect of the particles as pinning centers.
  • the nonpolar solvent of the nanoparticle suspension is miscible with the third solvent of the coppermix oxide precursor solution.
  • the third solvent is preferably an aliphatic alcohol, a ketone and / or a carboxylic acid, each independently of ⁇ nen 4 to 12 carbon atoms, such as n-hexanol, n-heptanol, n-octanol, n-nonanol or n-decanol, individually or as a mixture used for the preparation of the precursor solution.
  • the precursor solution contains acid-reacting metal salts of strong acids such as trifluoroacetic acid
  • a base This can be, for example, diethanolamine.
  • the method according to the invention also includes that several different nanoparticle dispersions prepared according to the invention are incorporated in the HTSC layer of copper mixed oxide. This can be done, for example, by preparing different nanoparticle dispersions by the process according to the invention and adding to the coating solution. However, it is also possible to mix different microemulsions prior to the precipitation reaction so that a mixture of several nanoparticle dispersions is obtained after the precipitation.
  • the coating solution thus prepared is prepared by conventional methods (such as dipping, spinning, spraying, printing) used for coating carriers.
  • the layers are processed further as usual, for example by subjecting them to a stepwise heat treatment in which first the solvents are removed, then the organic salts are converted into oxides and finally the mixed oxide compound is produced. This may require a new optimization of the pro ⁇ program for heat treatment.
  • the so gewonne ⁇ NEN layer arrangements may still further layers, such as protective layers include adjacent the layer of HTSC material and the supporting layer.
  • the invention makes it possible to produce nanoparticles of transition metal compounds of narrow size distribution. These can be advantageously used for the production of HTSC layers based on copper mixed oxide. Such layers have excellent electrical properties. In contrast, unsatisfactory results are obtained by adding the metal compounds needed to form pinning centers directly to the coating solution. In contrast to the use of the prefabricated nanoparticles according to the invention, the size distribution of the pinning centers formed after the coating (eg during firing) can not be controlled and the formation of these precipitates can interfere with the epitaxial growth of the superconductor layer.
  • the invention relates to a process for the preparation of nanoparticles comprising or consisting of compounds of the transition metals Zr, Hf, Ti, Ta, Sc, Y, La, elements having the atomic numbers 58 (Ce) to 71 (Lu) and Fe, comprising the steps:
  • the embodiments of the invention thus also generally relate to a process for the preparation of nanoparticles containing or consisting of compounds of transition metals Zr, Hf, Ti, Ta, Sc , Y, La, ele ⁇ ments with the atomic numbers 58 (Ce) to 71 (Lu) and Fe.
  • the further features and measures of the invention, including selection of precursors also refer in particular to compounds of transition metals Zr, Hf, Ti, Ta, Sc, Y, La, elements having atomic numbers 58 (Ce) to 71 (Lu) and Fe.
  • n-heptane 50 g were mixed with the required amount of surfactant Marlophen NP5 (nonylphenol poly (5) ethylene glycol ether) to adjust the Rw value shown in Table 1.
  • the resulting mixture was stirred for 15 min by magnetic stirring at 600 rpm.
  • 5.0 g (1 mmol) of ent ⁇ speaking aqueous Cernitratandzugetropft were.
  • the preserver so ⁇ tene two-phase mixture was stirred for 60 min at 600 rev / min, as ⁇ homogenized with the micelles.
  • 1.59 g of an aqueous ammonia solution containing 2.5 percent by weight (2.3 mmol NH 3) as precipitant were added and stirred again at 600 rpm for 60 min.
  • Example 1 was repeated except that instead of water for the polar phase, acetonitrile having a water content of ⁇ 0.5 wt% was used.
  • the precipitant used was propylamine (10% by mass in n-heptane, 2.3 mmol). The results are also listed in Table 1.
  • Figure 2 shows the particle size distribution of IME at two different Rw.
  • Example 2 was repeated, but instead of cerium nitrate, either hafnium oxychloride or zirconium oxychloride was used in each case in the same molar amount.
  • the median values obtained at different ⁇ union Rw values D 5 o of the particle-size distribution are given in Table 2 below. Table 2
  • the solvents used were n-hexanol, n-heptanol or n-octanol to ensure miscibility with the outer phase (hexane) of the cerium-containing microemulsion.
  • the nanoparticle dispersion obtained in Example 2-1 was concentrated in vacuo and taken up with the YBCO precursor solution. With these solutions, layers of 80-400 nm thickness were applied to lanthanum aluminate support. The electrical properties of the layers are listed in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)

Abstract

Des procédés connus de production de nanoparticules à partir de composés des métaux de transition Zr, Ti, Ta, terres rares (RE), Mn et Fe en passant par des microémulsions débouchent sur des produits qui contiennent des impuretés provenant des substances de départ, en particulier de l'eau, qui compliquent l'utilisation ultérieure des nanoparticules par exemple dans des supraconducteurs à haute température (HTSC). Il est proposé de produire les nanoparticules en passant par des microémulsions sans eau comprenant une phase extérieure composée d'un solvant non polaire et une phase intérieure composée d'un solvant polaire sans eau. Les nanoparticules obtenues ont une bonne monodispersité et peuvent être utilisées lors de la production de supraconducteurs REBa2Cu307 par incorporation à la solution de revêtement de précurseur.
EP13710432.9A 2012-03-21 2013-03-20 Procédé de production de nanoparticules ainsi que leur utilisation pour la production de supraconducteurs à haute température Withdrawn EP2828220A2 (fr)

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EP0280292A2 (fr) * 1987-02-26 1988-08-31 Sumitomo Electric Industries Limited Procédé de la fabrication d'une couche en matériau d'oxyde supraconducteur
US5112802A (en) * 1987-08-20 1992-05-12 Sumitomo Electric Co., Ltd. Superconducting ceramics elongated body and method of manufacturing the same

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EP0383927A4 (en) 1988-05-19 1990-10-24 Institut Gornogo Dela Sibirskogo Otdelenia Akademii Nauk Sssr Method and electrolyzer for softening water
DE10237915A1 (de) 2002-08-14 2004-03-11 Forschungszentrum Jülich GmbH Hochdichte Keramiken sowie Verfahren zur Herstellung derselben
DE102006025770A1 (de) 2006-05-31 2007-12-13 Jürgen Dr. Dornseiffer Herstellung von Beschichtungslösungen nebst hergestellten Produkten
DE102008004818B4 (de) 2008-01-17 2010-07-15 Zenergy Power Gmbh Nasschemisches Verfahren zur Herstellung eines Hochtemperatursupraleiters

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EP0280292A2 (fr) * 1987-02-26 1988-08-31 Sumitomo Electric Industries Limited Procédé de la fabrication d'une couche en matériau d'oxyde supraconducteur
US5112802A (en) * 1987-08-20 1992-05-12 Sumitomo Electric Co., Ltd. Superconducting ceramics elongated body and method of manufacturing the same

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CHHABRA VISHAL ET AL: "Nanophase BaFe12O19 synthesized from a nonaqueous microemulsion with Ba- and Fe-containing surfactants", JOURNAL OF MATERIALS RESEARCH, MATERIALS RESEARCH SOCIETY, WARRENDALE, PA, US, vol. 10, no. 11, 1 November 1995 (1995-11-01), pages 2689 - 2692, XP008161844, ISSN: 0884-2914, [retrieved on 20110303], DOI: 10.1557/JMR.1995.2689 *
See also references of WO2013139843A2 *

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US20150072863A1 (en) 2015-03-12
KR20140143154A (ko) 2014-12-15
WO2013139843A3 (fr) 2014-03-20
WO2013139843A2 (fr) 2013-09-26

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