WO2004058638A1 - Procede de production de precurseurs a base de nitrate pour oxydes metalliques et oxocuprates supraconducteurs - Google Patents

Procede de production de precurseurs a base de nitrate pour oxydes metalliques et oxocuprates supraconducteurs Download PDF

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Publication number
WO2004058638A1
WO2004058638A1 PCT/EP2003/008861 EP0308861W WO2004058638A1 WO 2004058638 A1 WO2004058638 A1 WO 2004058638A1 EP 0308861 W EP0308861 W EP 0308861W WO 2004058638 A1 WO2004058638 A1 WO 2004058638A1
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nitrate
nitrates
oxide
multinary
composition
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PCT/EP2003/008861
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German (de)
English (en)
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Peter Ziegler
Katharina Gibson
H. Jürgen MEYER
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Universität Tübingen
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Priority to EP03813873A priority Critical patent/EP1578690A1/fr
Priority to AU2003253400A priority patent/AU2003253400A1/en
Publication of WO2004058638A1 publication Critical patent/WO2004058638A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/006—Compounds containing, besides copper, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/18—Methods for preparing oxides or hydroxides in general by thermal decomposition of compounds, e.g. of salts or hydroxides
    • C01B13/185—Preparing mixtures of oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/48—Methods for the preparation of nitrates in general
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4521—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing bismuth oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4521—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing bismuth oxide
    • C04B35/4525—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing bismuth oxide also containing lead oxide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • H10N60/0772—Processes including the use of non-gaseous precursors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • 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
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • 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
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • 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
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites

Definitions

  • the present invention relates to a method for producing defined, reproducible substances which are suitable for producing metal oxides and an oxocuprate superconductor or a nitrate-free precursor for the synthesis of oxocuprate superconductors.
  • the materials for the high-temperature superconductors must meet high requirements in terms of chemical purity, homogeneity, the defined phase composition and crystal size as well as reproducibility.
  • Some processes for producing precursors for superconductor materials are known.
  • EP522575, EP285392 and US5,298,654 describe the co-precipitation of metal compounds dissolved in water, for example nitrates.
  • the solutions with oxalic acid become water-insoluble or sparingly soluble .
  • Metal oxalate mixtures precipitated.
  • mixtures of aqueous salt solutions of the elements which are to be contained in the superconductor are spray dried or subjected to pyrolysis, as in WO89 / 02871, EP371211, EP681989 and DE19505133.
  • Another method for producing a one-piece, multinary metal oxide powder is the introduction of a mixture of metal salts and / or metal oxides and / or metals into a pulsation reactor with a pulsating gas flow, as described in WO02 / 072471.
  • the object of the present invention is to provide a process for the production of defined, reproducible substances which meet the high requirements for the superconductor materials, do not have the disadvantages of the substances produced by known processes and are therefore suitable for use as precursors for the Synthesis of oxocuprate superconductors or their nitrate-free precursors from nitrates or nitrate solutions are suitable.
  • a method in which a nitrogen oxide atmosphere is used.
  • This can be achieved, for example, in a nitrogen oxide stream or by using a reaction vessel in that a nitrogen oxide atmosphere is either added from the outside or is generated by stowage of the nitrogen oxides emerging from the mixture.
  • the starting batch consists of a) nitric acid solutions of the metal salts (e.g. nitrates, oxides, carbonates) or b) solid oxides and solid nitrates or c) other reactive materials that have already been subjected to pretreatment, e.g. drying or pyrolysis (Fig. 1). Undesired oxidic secondary phases can be converted into desired, defined substances in the nitrogen oxide atmosphere.
  • These desired substances which are stable in the multinary powders with the desired composition, could be represented and characterized.
  • the crystallographic data of the compounds BiCaO 2 NO 3 , BiSrO 2 N ⁇ 3 , BiBa0 2 NO 3 and BiPbO 2 NO 3 are listed below as examples of such multinary oxide nitrates.
  • Figures 2 and 3 show exemplary crystal structures of the compounds BiSrO 2 NO 3 and BiBaO 2 NO 3 .
  • Figures 4 and 5 show X-ray diffractograms of the compounds BiSrO 2 N ⁇ 3 and Bi-BaO 2 NO 3 .
  • the composition of the oxide nitrate according to the invention is (Bi u , Sr v , Ca w , Pb x ) 2 O 2 ⁇ y (N ⁇ 3) ⁇ ⁇ 2, where ⁇ means that the The number of the respective ions or ion groups with a positive or negative deviation can vary by the given value.
  • the phase mixture obtained by the process according to the invention contains Ca, Cu and / or Pb-containing phases, such as Ca 1 ⁇ x Cu ⁇ ⁇ y O z , CuO and Ca 2 PbO 4 .
  • the reactions preferably take place in a temperature range between room temperature and 850 ° C., preferably from 500 ° C. to 750 ° C. In principle, however, other temperatures are also conceivable.
  • the process according to the invention is therefore distinguished by the targeted formation of stable nitrate-containing precursors which contain the oxide nitrates mentioned, which is brought about by the use of a nitrogen oxide atmosphere.
  • the partial pressure of the nitrogen oxides is below 1.5 bar.
  • the type and composition of the oxide nitrates according to the invention depends only on the cation composition of the starting materials and not on the above-mentioned starting mixture according to a), b) or c) (Fig. 1).
  • the invention encompasses the use of the method described above for the production of a good superconductor.
  • the production of a superconductor takes place via the synthesis of a nitrate-free precursor.
  • this nitrate-free precursor can, for example, be the compound with the composition Bi 2 ⁇ u Pbo, 3 ⁇ Sr 2
  • the superconductor can be produced directly from the precursor according to the invention.
  • the oxide nitrates can also be contained in nitrate-containing precursors for numerous oxides or can themselves serve as precursors.
  • Starting mixtures which are used according to a), b) or c) and have the desired cation composition are thermally treated in a nitrogen oxide atmosphere and transferred to the nitrate-containing precursor which contains the oxide nitrates according to the invention.
  • the oxide nitrates are converted into the corresponding metal oxides (Fig. 1).
  • These can be any metal oxides, including superconducting materials such as Bao , 6 Ko , 4 Bi ⁇ 3 .
  • Fig. 1 Schematic course of the reaction of the method according to the invention.
  • Fig. 2 Crystal structure of BiSrO 2 NO 3 .
  • Fig. 3 Crystal structure of BiBaO 2 NO 3 .
  • Fig. 4 X-ray diffractogram of BiSrO 2 NO 3 .
  • Fig. 5 X-ray diffractogram of BiBaO 2 N ⁇ 3.
  • Fig. 6 X-ray diffractogram of the phase mixture after annealing at 660 ° C.
  • Fig. 7 X-ray diffractogram of the phase mixture after annealing at 820 ° C.
  • Fig. 8 X-ray diffractogram of (Bi, Pb) -2223 after annealing at 850 ° C.
  • Fig. 9 Schematic course of the reaction to form (Bi, Pb) -2223.
  • Fig. 10 X-ray diffractogram of the phase mixture after annealing at 650 ° C.
  • Fig. 11 X-ray diffractogram of (Bi, Pb) -2212 after annealing at 850 ° C.
  • Fig. 12 Schematic course of the reaction to form (Bi, Pb) -2212.
  • Fig. 13 X-ray diffractogram of the phase mixture after annealing at 650 ° C.
  • Fig. 14 X-ray diffractogram of Bi-2212 after annealing at 850 ° C.
  • Fig. 15 Schematic course of the reaction to form Bi-2212.
  • Fig. 16 X-ray diffractogram of the phase mixture after annealing at 650 ° C.
  • Fig. 17 X-ray diffractogram of Bi-2201 after annealing at 850 ° C.
  • Fig. 18 Schematic course of the reaction to form Bi-2201.
  • the powder which is the nitrate-containing precursor according to the invention, contains the phases (Bi, Pb, Sr, Ca) 2 O 2 NO 3 , Ca 2 PbO 4 , Ca 0 , 8 5CuO 2 and CuO (see Fig. 6) ,
  • the temperature is then increased to 820 ° C at a heating rate of 5 ° C / min.
  • the mixture is kept at this temperature for 1 h; then the nitrogen oxide atmosphere is slowly broken down by venting the reaction vessel.
  • the mixture is held at this temperature for an additional hour and then cooled at a rate of 5 ° C / min.
  • This composition (Bi-2212 with secondary phases containing Pb, Ca and Cu) corresponds to the precursor of the high-temperature superconductor (Bi, Pb) -2223.
  • the mixture is now pressed into a tablet and this is heated in an oven at a heating rate of 5 ° C / min to 850 ° C.
  • the powder now contains the high-temperature superconductor (Bi, Pb) -2223 (see Fig. 8).
  • Nitrates and oxides are used as starting materials (e.g. Bi 2 O 3 , PbO, Sr (N03) 2, Ca (NO 3 ) 2 • 4 H 2 O and CuO) and in a closed furnace with pressure relief valve (p ⁇ 1.5 bar) at a heating rate of 5 ° C / min to 660 ° C, so that a nitrogen oxide atmosphere is formed. The mixture is held at this temperature for 15 hours and then cooled at a rate of 5 ° C / min.
  • the nitrate-containing precursor according to the invention also forms here; the other reactions correspond to the reaction path described above.
  • a mixture of compounds with the cation composition Bi ⁇ , 8 Pbo, 3 3Sr 1 ⁇ 87 Ca ⁇ , oCu 2, oO x is produced.
  • Bi (NO 3 ) 3 - 5 H 2 O, PbO, Sr (NO 3 ) 2 , CaCO 3 and CuO are used.
  • the powders are weighed out and dissolved in 2N nitric acid HNO 3 .
  • the resulting mixture is concentrated on a heating stirrer, dried at 200 ° C. for 2 h and then triturated intimately.
  • a closed furnace with a pressure relief valve (p ⁇ 1.5 bar) the mixture is now heated to 650 ° C at a heating rate of 5 ° C / min, so that a nitrogen oxide atmosphere is formed.
  • the powder which is the nitrate-containing precursor according to the invention, contains the phases (Bi, Pb, Sr, Ca) 2 O 2 N ⁇ 3 and CuO (see Fig. 10).
  • the temperature is then increased to 850 ° C at a heating rate of 5 ° C / min.
  • the mixture is kept at this temperature for 1 h; then the nitrogen oxide atmosphere is slowly broken down by venting the reaction vessel.
  • the mixture is held at this temperature for 13 hours and then cooled at a rate of 5 ° C / min.
  • the product is the high-temperature superconductor (Bi, Pb) -2212 (see Fig. 11).
  • Nitrates and oxides eg B Ed 2 O 3 , PbO, Sr (NO 3 ) 2 , Ca (N0 3 ) 2 • 4 H 2 0 and CuO
  • Nitrates and oxides are used as starting materials and in a closed furnace with Pressure relief valve (p ⁇ 1.5 bar) heated to 650 ° C at a heating rate of 5 ° C / min, so that a nitrogen oxide atmosphere is formed.
  • the mixture is kept at this temperature for 14 hours and then cooled at a rate of 5 ° C./min.
  • the nitrate-containing precursor according to the invention also forms here; the other reactions correspond to the reaction path described above.
  • a mixture of compounds with the cation composition Bi 2, i 3 Sr ⁇ , 87 Ca ⁇ , oCu2, oO x is produced.
  • Bi (NOs) 3-5 H 2 O, Sr (NO 3 ) 2 , CaCO 3 and CuO are used as starting materials.
  • the powders are weighed out and dissolved in 2N nitric acid HNO 3 .
  • the resulting mixture is concentrated on a heating stirrer, dried at 200 ° C. for 2 hours and then sealed intimately. ben.
  • a pressure relief valve p ⁇ 1.5 bar
  • the mixture is now heated to 650 ° C at a heating rate of 5 ° C / min, so that a nitrogen oxide atmosphere is formed.
  • the mixture is kept at this temperature for 14 h.
  • the powder which is the nitrate-containing precursor according to the invention, contains the phases (Bi, Sr, Ca) 2 ⁇ 2 N ⁇ 3 and CuO (see Fig. 13).
  • the temperature is then increased to 850 ° C at a heating rate of 5 ° C / min.
  • the mixture is kept at this temperature for 1 h; then the nitrogen oxide atmosphere is slowly broken down by venting the reaction vessel.
  • the mixture is held at this temperature for 13 hours and then cooled at a rate of 5 ° C / min.
  • the product is the high-temperature superconductor Bi- 2212 (see Fig. 14).
  • nitrates and oxides are used as starting materials (e.g. Bi 2 ⁇ 3 , Sr (N ⁇ 3 ) 2, Ca (NO 3 ) 2 • 4 H 2 O and CuO) and in a closed furnace with pressure relief valve ( p ⁇ 1.5 bar) at a heating rate of 5 ° C / min to 650 ° C, so that a nitrogen oxide atmosphere is formed.
  • the mixture is kept at this temperature for 14 hours and then cooled at a rate of 5 ° C./min.
  • the nitrate-containing precursor according to the invention also forms here; the other reactions correspond to the reaction path described above.
  • a mixture of compounds with the cation composition Bi 2, oSr 2 ⁇ oCu ⁇ ⁇ oO x is produced.
  • Bi (NO 3) 3 - used 5 H 2 O, Sr (NO 3) 2 and CuO.
  • the powders are weighed out and dissolved in 2N nitric acid HNO 3 .
  • the resulting mixture is concentrated on a heating stirrer, dried at 200 ° C. for 2 h and then triturated intimately.
  • a closed furnace with pressure relief valve (p ⁇ 1.5 bar) the mixture is now heated to 650 ° C at a heating rate of 2 ° C / min, so that a nitrogen oxide atmosphere is formed.
  • the mixture is 4 h at this temperature held.
  • the powder which is the nitrate-containing precursor according to the invention, contains the phases BiSrO 2 NO 3 and CuO (see Fig. 16).
  • the temperature is then increased to 850 ° C at a heating rate of 2 ° C / min.
  • the mixture is kept at this temperature for 1 h; then the nitrogen oxide atmosphere is slowly broken down by venting the reaction vessel.
  • the mixture is kept at this temperature for 4 hours and then cooled at a rate of 5 ° C./min.
  • Bi-2201 is available as a product (see Fig. 17).
  • Nitrates and oxides e.g. Bi 2 ⁇ 3 , Sr (N0 3 ) 2 and CuO
  • a closed furnace with pressure relief valve p ⁇ 1.5 bar
  • p ⁇ 1.5 bar pressure relief valve
  • the nitrate-containing precursor according to the invention also forms here; the other reactions correspond to the reaction path described above.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne un procédé permettant de produire des précurseurs stables à base de nitrate, de composition définie, s'utilisant pour produire des oxydes métalliques, notamment des oxocuprates supraconducteurs ou leurs précurseurs exempts de nitrate. Selon l'invention, il est prévu à cet effet, qu'un mélange des sels métalliques utilisés comme produits de départ et/ou d'oxydes métalliques soit traité dans une atmosphère d'oxyde d'azote. Ce traitement s'effectue de préférence dans une plage de températures allant de la température ambiante à 850 DEG C, la température se situant de préférence entre 500 et 750 DEG C.
PCT/EP2003/008861 2002-12-23 2003-08-09 Procede de production de precurseurs a base de nitrate pour oxydes metalliques et oxocuprates supraconducteurs WO2004058638A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP03813873A EP1578690A1 (fr) 2002-12-23 2003-08-09 Procede de production de precurseurs a base de nitrate pour oxydes metalliques et oxocuprates supraconducteurs
AU2003253400A AU2003253400A1 (en) 2002-12-23 2003-08-09 Method for the production of nitrate-containing precursors for metal oxides and oxocuptrate superconductors

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DE10261549.7 2002-12-23
DE10261549 2002-12-23

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103429093A (zh) * 2011-02-18 2013-12-04 杜邦营养生物科学有限公司 饲料添加剂组合物
CN104684408B (zh) * 2012-08-03 2018-08-31 杜邦营养生物科学有限公司 饲料添加剂组合物

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Publication number Priority date Publication date Assignee Title
JPH02145761A (ja) * 1988-11-28 1990-06-05 Matsushita Electric Ind Co Ltd 薄膜超電導体の製造方法
US5039502A (en) * 1989-02-02 1991-08-13 Hoechst Aktiengesellschaft Process for the preparation of metal nitrates
US5122505A (en) * 1990-10-01 1992-06-16 Sri International Carbonate-free inorganic nitrates or oxides and process thereof
US5219829A (en) * 1990-11-02 1993-06-15 Merck Patent Gesellschaft Mit Beschrankter Haftung Process and apparatus for the preparation of pulverulent metal oxides for ceramic compositions
EP0681989A1 (fr) * 1994-05-13 1995-11-15 MERCK PATENT GmbH Procédé pour la préparation de poudres d'oxydes métalliques multi éléments
DE10111938A1 (de) * 2001-03-13 2002-09-26 Merck Patent Gmbh Herstellung von Hochtemperatur-Supraleiter-Pulvern in einem Pulsationsreaktor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02145761A (ja) * 1988-11-28 1990-06-05 Matsushita Electric Ind Co Ltd 薄膜超電導体の製造方法
US5039502A (en) * 1989-02-02 1991-08-13 Hoechst Aktiengesellschaft Process for the preparation of metal nitrates
US5122505A (en) * 1990-10-01 1992-06-16 Sri International Carbonate-free inorganic nitrates or oxides and process thereof
US5219829A (en) * 1990-11-02 1993-06-15 Merck Patent Gesellschaft Mit Beschrankter Haftung Process and apparatus for the preparation of pulverulent metal oxides for ceramic compositions
EP0681989A1 (fr) * 1994-05-13 1995-11-15 MERCK PATENT GmbH Procédé pour la préparation de poudres d'oxydes métalliques multi éléments
DE10111938A1 (de) * 2001-03-13 2002-09-26 Merck Patent Gmbh Herstellung von Hochtemperatur-Supraleiter-Pulvern in einem Pulsationsreaktor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 014, no. 390 (C - 0751) 23 August 1990 (1990-08-23) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103429093A (zh) * 2011-02-18 2013-12-04 杜邦营养生物科学有限公司 饲料添加剂组合物
CN104684408B (zh) * 2012-08-03 2018-08-31 杜邦营养生物科学有限公司 饲料添加剂组合物

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AU2003253400A1 (en) 2004-07-22

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