WO2008071829A1 - MATERIAL SUPERCONDUCTOR NANOESTRUCTURADO TIPO REBa2Cu3O7 (RE=TIERRA RARA O YTRIO) CON UNA ELEVADA DENSIDAD DE CENTROS DE ANCLAJE DE VÓRTICES Y SU MÉTODO DE PREPARACIÓN - Google Patents
MATERIAL SUPERCONDUCTOR NANOESTRUCTURADO TIPO REBa2Cu3O7 (RE=TIERRA RARA O YTRIO) CON UNA ELEVADA DENSIDAD DE CENTROS DE ANCLAJE DE VÓRTICES Y SU MÉTODO DE PREPARACIÓN Download PDFInfo
- Publication number
- WO2008071829A1 WO2008071829A1 PCT/ES2007/070204 ES2007070204W WO2008071829A1 WO 2008071829 A1 WO2008071829 A1 WO 2008071829A1 ES 2007070204 W ES2007070204 W ES 2007070204W WO 2008071829 A1 WO2008071829 A1 WO 2008071829A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- defects
- nanoparticles
- superconducting material
- metal
- superconducting
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 43
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 12
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 8
- 229910052727 yttrium Inorganic materials 0.000 title abstract description 10
- 238000004873 anchoring Methods 0.000 title abstract description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 77
- 230000007547 defect Effects 0.000 claims abstract description 49
- 229910052788 barium Inorganic materials 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims description 45
- 239000002105 nanoparticle Substances 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 39
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical class OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 26
- 241000954177 Bangana ariza Species 0.000 claims description 23
- 239000002887 superconductor Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 11
- 239000002086 nanomaterial Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- 229910004121 SrRuO Inorganic materials 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkali metal salts Chemical class 0.000 claims description 7
- 238000004320 controlled atmosphere Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 3
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical class CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000002082 metal nanoparticle Substances 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 241000894007 species Species 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims 3
- 239000003054 catalyst Substances 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 5
- 229910002761 BaCeO3 Inorganic materials 0.000 abstract 1
- 229910002929 BaSnO3 Inorganic materials 0.000 abstract 1
- 229910002353 SrRuO3 Inorganic materials 0.000 abstract 1
- 229910021523 barium zirconate Inorganic materials 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 abstract 1
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 13
- 238000000197 pyrolysis Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 229910002367 SrTiO Inorganic materials 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000004325 capillary sieving electrophoresis Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000399 optical microscopy Methods 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000000879 optical micrograph Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000006213 oxygenation reaction Methods 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000007737 ion beam deposition Methods 0.000 description 2
- 238000000608 laser ablation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- IQGAADOKZGEEQE-LNTINUHCSA-K gadolinium acetylacetonate Chemical compound [Gd+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O IQGAADOKZGEEQE-LNTINUHCSA-K 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009342 intercropping Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
- C01G45/1264—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing rare earth, e.g. La1-xCaxMnO3, LaMnO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
- C04B35/4504—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing rare earth oxides
- C04B35/4508—Type 1-2-3
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—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
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—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
- 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
- C04B35/6325—Organic additives based on organo-metallic compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/01—Manufacture or treatment
-
- 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
- H10N60/0324—Processes for depositing or forming copper oxide superconductor layers from a solution
-
- 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
- H10N60/0828—Introducing flux pinning centres
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
- H10N60/855—Ceramic superconductors
- H10N60/857—Ceramic superconductors comprising copper oxide
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- C01P2006/40—Electric properties
-
- 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
- C04B2235/32—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
-
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium 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
- 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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3225—Yttrium oxide 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3229—Cerium 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3248—Zirconates or hafnates, e.g. zircon
-
- 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
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
- C04B2235/3282—Cuprates
-
- 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
- C04B2235/3289—Noble metal oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
-
- 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
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
-
- 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
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention refers to sheets of superconducting material with high density of nanometric defects in its structure, suitable for effectively anchoring the vortices in an almost isotropic manner, and to the processes that effectively develop said defect structure.
- the objects of the present invention are of special relevance in the following sectors:
- Chemical Sector Soluble complex metalorganic chemical precursors.
- Ceramic-metallurgical sector Deposition and growth of nanocomposite ceramic coatings on metal or ceramic substrates. Generation of functional nanostructures on ceramic or metal substrates
- Energy, Electromechanical and Transport Sector Improvement of the efficiency of existing electrical equipment for the generation, transport, distribution and use of electrical energy, development of new power electrical equipment, powerful magnets for diverse applications (including nuclear fusion), Powerful and light electric motors for Aeronautics or Nautical.
- Biomedicine and Pharmaceutical Sector New equipment, more powerful and capable of operating at higher temperatures, magnetic resonance imaging and new NMR spectrometers for molecular design.
- New devices passive or active, that work in the microwave range and that are of interest in the field of Telecommunications STATE OF THE TECHNIQUE
- High temperature superconducting materials have great potential to be used in very diverse technologies but for this it is an indispensable requirement to develop methodologies for obtaining conductors with high performance, in particular that they can transport high electrical currents without losses, even under high magnetic fields .
- the first high temperature drivers that were developed were based on phases type BiSrCaCuO and these were called conductors I to generation (IG).
- IG conductors I to generation
- Synthesis methodologies based on metallurgical chemical solutions have demonstrated their potential as low-cost techniques for manufacturing thin and multilayer sheets of functional oxides and superconducting tapes with good performance but have not yet been practically used to obtain nanocomposite systems.
- Recently thin film deposition techniques based on vacuum techniques laser ablation, sputtering, evaporation, ...) have shown that they can be used to obtain superconducting nanocomposites with second non-superconducting phases (JL Macmanus-Driscoll, SR Foltyn, QX Jia, H. Wang, A. Serquis, L. Civale, B.
- the second crystalline phase is segregated in the form of a textured nanoparticle and can be distributed randomly or forming nanopillars that cross perpendicularly to the sheet.
- a particular object of the invention is a system formed by the superconducting material of the invention and a substrate on which the superconducting material is deposited.
- a particular embodiment of the invention is a system formed by the superconducting material of the invention and a rigid monocrystalline substrate sheet substrate.
- Another particular object of the invention is the process for obtaining superconductors of the invention in which in step a) any anhydride corresponding to another organic acid that dissolves the oxide powders is used.
- a particular embodiment of the invention is the process for obtaining superconductors of the invention in which in step a) trifluoroacetic anhydride ((CFsCO) 2 O) and a small amount of trifluoro acetic acid (CF 3 COOH) are used (5 % by volume) as the reaction catalyst.
- step a) trifluoroacetic anhydride ((CFsCO) 2 O) and a small amount of trifluoro acetic acid (CF 3 COOH) are used (5 % by volume) as the reaction catalyst.
- Another particular object of the present invention is the process for obtaining superconductors of the invention in which the substrate used in step b) has previously been coated with a layer of metal oxide nanoparticles (BaZrO 3 ,
- Another object of the invention is the use of the superconducting material of the invention in electronic devices.
- Another object of the invention is the use of the superconducting material of the invention in electrical systems, improving the existing one for the generation, transport and distribution of the use of electrical energy.
- the performance of superconducting materials at high temperatures and low magnetic fields is determined by the ability to effectively anchor the vortices (quantum magnetic flux) existing in these materials and this process is optimal when there is a dense and homogeneous distribution of defects.
- Superconductors with nanometric dimensions The crystalline defects that can give rise to this beneficial effect of anchoring vortices can be of a very diverse nature and must be considered at least the secondary phase nanoparticles, dislocations, stacking defects, non-superconducting phase intercropping, twinning planes , the residual tensions generated by all of them, etc.
- the present invention refers to sheets of superconducting material with high density of nanometric defects in its structure, suitable for effectively anchoring the vortices almost isotropically, and to the processes that effectively develop said defect structure.
- Nanometric defects are understood as nanoparticles, dislocations, partial dislocations surrounding some stacking defects, stacking defects or twinning planes.
- the fact that the average separation between the nanometric defects of these materailes is only a few tens of nm allows the superconducting vortices to be practically anchored continuously along their entire length in said defects.
- the high density of defects is what gives increased efficiency to the vortex anchoring process when high magnetic fields are applied in which its density is also high.
- the anisotropy values of the critical current depend above all on the magnetic field and more weakly on the temperature.
- the superconducting material of the invention at a magnetic field of 1 T when the orientation of the magnetic field is modified, shows variations of the critical current with a ratio between the maximum and the minimum of 1.5-1.8, which is a reduction of 100 % with respect to thin sheets of REBa 2 Cu 3 Oy prepared without secondary phases.
- a particular object of the invention is a system formed by the superconducting material of the invention and a substrate on which the first one has been deposited.
- a particular embodiment of the invention is the superconducting material of the invention deposited on rigid sheets of monocrystalline substrate.
- Another particular object of the invention is the process for obtaining superconductors of the invention in which the alkali metal, alkaline earth, rare earth and / or transition metal salts used in step a) are organic salts such as acetates, trifluoroacetates, acetylacetonates , soluble ethylhexanoates or propionates in the reaction medium to prevent the formation of precipitates.
- Another particular object of the invention is the process for obtaining superconductors of the invention in which in step a) complex anhydrous solutions of trifluoroacetates of RE, Ba and Cu are obtained, with various salts of Zr, Ce, Sn, Ru, La , Mn, Sr, Ca.
- Another particular object of the invention is the process for obtaining superconductors of the invention in which in step a) any anhydride corresponding to another organic acid that dissolves the oxide powders is used.
- a particular embodiment of the invention is the process for obtaining superconductors of the invention in which in step a) trifluoroacetic anhydride ((CFsCO) 2 O) and a small amount of trifluoro acetic acid (CF 3 COOH) are used (5 % by volume) as the reaction catalyst.
- step a) trifluoroacetic anhydride ((CFsCO) 2 O) and a small amount of trifluoro acetic acid (CF 3 COOH) are used (5 % by volume) as the reaction catalyst.
- step c) The choice of the maximum temperature during the heat treatment of step c) will be determined by the substrate used, as well as the minor secondary phase that is to be obtained in the material. Such heat treatment conditions will also be decisive for the generation of a suitable defect structure in the superconduct.
- Said nanoparticles will be used as templates and on which the solutions of metallic trifluoroacetates prepared under anhydrous or partially hydrolyzed conditions will be deposited and decomposed and the object of their introduction is that they act as nucleating centers of defects in the superconducting layers deposited on them.
- the process of formation of the nanoplantillas of oxides or metals consists of stages similar to those described above (deposition, pyrolysis and growth) but the concentrations of the metalorganic solutions of the oxides that are desired to be obtained are lower (0.003 to 0.02 M) with the so that they only partially cover the substrate.
- the duration of the heat treatment and the atmosphere and temperature at which it is carried out will determine the size and morphology of the nanoparticles obtained.
- the difference in crystalline lattice parameters between the oxide that grows in the form of a nanoparticle and the corresponding substrate constitutes a determining parameter.
- Such an approach to the formation of nanoparticles will lead to epitaxial structures with a well-determined crystalline orientation. On the contrary, the previously synthesized nanoparticles will be randomly oriented.
- the reason that explains the extraordinary improvement of superconducting performance lies in the formation of the high concentration of defects (10 3 -10 4 defects / ⁇ m 3 ) in the REBa 2 Cu 3 Oy matrix. This is because the secondary nanoparticles are randomly oriented, without any crystallographic relationship with the matrix, and therefore the interface has a high energy that acts as a driving force for the generation of defects.
- the reason that the secondary phases are randomized is that their formation is prior to the crystallization of REBa 2 Cu 3 Oy and consequently all those that are located outside the interface with the substrate do not have any reason to orient according to an orientation crystallographic determined. This characteristic distinguishes the materials obtained from all those previously prepared by vacuum deposition techniques in which both phases crystallize simultaneously.
- an added advantage of the described invention objects is that they have a reduced anisotropy of the critical currents. This is due to the fact that the defects generated have an isotropic character and because the angular distribution of the mosaic structure of the layers increases. Said decrease in anisotropy will allow greater flexibility in the design of superconducting coils based on the tapes that are manufactured based on the new process described in the present invention.
- Another object of the invention is the use of the superconducting material of the invention in electronic devices.
- Another object of the invention is the use of the superconducting material of the invention in electrical systems, improving the existing one for the generation, transport and distribution of the use of electrical energy.
- Figure 1 Transversal image of transmission electron microscopy of a layer of YBa 2 Cu 3 O 7 with 5% by weight of BaZrO 3 nanoparticles.
- Figure 2 Transmission electron microscopy image of a layer of YBa 2 Cu 3 O 7 with BaZrO 3 nanoparticles in which the large concentration of defects generated by them in the YBa 2 Cu 3 O 7 matrix can be observed.
- Figure 6 Optical microscopy image of a layer of YBa 2 Cu 3 O 7 with 5% by weight of BaZrO 3 nanoparticles after the pyrolysis process.
- Figure 7. X-ray diffraction spectrum ⁇ -2 ⁇ of a layer of YBa 2 Cu 3 O 7 with 5% by weight of BaZrO 3 nanoparticles.
- Figure 8 Angular dependence of the critical current density at 77K as a function of the angle formed between the applied magnetic field and the substrate for a standard TFA-YBCO layer and a TFA-YBCO layer with BZO nanoparticles.
- Figure 9. Optical microscopy image of a YBa 2 Cu 3 O 7 layer with 5% by weight of Y 2 O 3 nanoparticles after the pyrolysis process.
- Figure 12 X-ray diffraction spectrum ⁇ -2 ⁇ of a layer of YBa 2 Cu 3 O 7 with 5% by weight of nanoparticles of Gd 2 O 3 .
- Figure 13 Optical microscopy image of a layer of YBa 2 Cu 3 O 7 with 5% by weight of Au nanoparticles after the pyrolysis process.
- Figure 16 Images obtained by Atomic Forces Microscopy of (a) nanpoints and (b) self-assembled nanobars of CeO 2 oxide grown on a monocrystalline substrate.
- the mixture was heated at 5O 0 C for 72 hours under an inert atmosphere (Ar). It was then cooled to room temperature and filtered through a 0.45 ⁇ m filter. The resulting solution was then evaporated under pressure reduced using a rotary evaporator, first at room temperature (2 hours) and then progressively heating to 8O 0 C, obtaining the trifluoroacetates of Y, Ba and Cu. A part of the solid obtained was dissolved in acetone and another in methanol, both solutions being kept in closed vials and in an inert atmosphere. This solution was deposited by a spin coating technique on a monocrystalline substrate of SrTiO 3 of dimensions 5mm * 5mm, thickness 0.5mm and orientation (100).
- Said humidity is achieved by passing the gas through some washing jars provided with a porous plate in its inner lower part, to divide the gas into small drops, thus increasing the surface of contact with the water.
- the sample was stored in a desiccator.
- the sample was characterized by scanning electron microscopy and X-ray diffraction ( Figure 10) where it is observed that Y 2 O 3 nanoparticles have been formed.
- Example I From the solution of example I of the trifluoroacetates of Y, Ba and Cu to which 5% by weight of HAuCl 4 was added, it was deposited (14 ⁇ l) on a substrate of LaAlO 3 (of dimensions 5mm * 5mm, thickness 0.5 mm and orientation (100)) using the Spin-coating technique.
- the deposited sample was decomposed following a pyrolysis process as described in Example I.
- the sample thus pyrolized was characterized by Optical Microscopy to verify that it is homogeneous and free of cracks and roughness. ( Figure 13).
- the heat treatment described in Example III was carried out from the pyrolized sample to achieve the formation of the YBa 2 Cu 3 O 7 and Au phases.
- the sample was characterized by scanning electron microscopy ( Figure 14) and X-ray diffraction ( Figure 15) where it is observed that Au nanoparticles have been formed.
- the resulting layer may have thicknesses in the range 300-800
- a solution of Ce and Gd propionates was prepared, with molar proportions between 0 and 15% Gd, in isopropanol in concentrations between 0.02 M and 0.003 M and 14 ⁇ l were deposited on SrTiO 3 or LaAlO 3 substrates (orientation ( 100)) by spin coating.
- a solution of Ba acetate and Zr acetylacetonate in stoichiometric 1: 1 molar ratios was also prepared. The deposited samples were decomposed following a pyrolysis process followed by a high temperature growth process (900 0 C-IOOO 0 C) with varying durations (5-30 minutes).
- the atmosphere during growth can be O 2 or an Ar-5% H 2 mixture and the temperature rise ramp was set at ° C / h.
- the morphology and size of the resulting self-assembled nanostructures were controlled by Atomic Forces Microscopy and some typical examples are shown in Figure 16. In these figures the nanometric dimensions of the structures generated from the Cei -x Gd x óxido2 oxide can be observed, thus as important modifications of its morphology (nanpoints, nanobars). These substrates constitute excellent templates for the deposition of superconducting sheets with improved performance.
- Example II From the solution of example I of the trifluoroacetates of Y, Ba and Cu, (14 ⁇ l) was deposited in LaAlO 3 or SrTiO 3 substrates with self-assembled nanostructures obtained according to Example VII (dimensions 5mm * 5mm, thickness 0.5mm and orientation (10O)) by Spin-coating technique.
- the deposited sample was decomposed following a pyrolysis process as described in Example I.
- the sample thus pyrolized was characterized by Optical Microscopy to verify that it is homogeneous and free of cracks and roughness. From the pyrolized layers, heat treatment was performed to achieve the formation of the YBa 2 Cu 3 O 7 phase.
- the carrier gas was changed to dry O 2 1 bar pressure and maintained at this temperature for 90 minutes. Then a ramp was made at 300 ° C / h to room temperature. The resulting layer is approximately 200-300 nm thick.
- the sample was characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy and its critical currents were measured by inductive or transport techniques.
- a typical TEM image is shown in Figure 17, showing that a BaZrO 3 nanoparticle induces defects in the REBa 2 Cu 3 O 7 matrix.
- Figure 18 shows the dependence of critical currents with the 77K magnetic field on two samples grown on a nanostructured and a normal substrate. As can be seen there is an improvement in the critical current at high magnetic fields due to the defects induced in the REBa 2 Cu 3 O 7 matrix.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Structural Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/519,359 US20100144536A1 (en) | 2006-12-14 | 2007-12-05 | NANOSTRUCTURED SUPERCONDUCTING MATERIAL OF TYPE REBa2Cu3O7 (RE = RARE EARTH OR YTTRIUM) WITH A HIGH DENSITY OF VORTEX ANCHORING CENTRES AND PREPARATION METHOD THEREOF |
JP2009540797A JP2010513180A (ja) | 2006-12-14 | 2007-12-05 | 高密度の渦固定中心を有するREBa2Cu3O7(RE=希土類元素またはイットリウム)型のナノ構造超伝導材料およびその調製方法 |
EP20070858288 EP2104151B1 (en) | 2006-12-14 | 2007-12-05 | Nanostructured superconducting material of type reba2cu3o7 (re=rare earth or yttrium) with a high density of vortex anchoring centres and preparation method thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ESP200603172 | 2006-12-14 | ||
ES200603172A ES2302637B1 (es) | 2006-12-14 | 2006-12-14 | Material superconductor nanoestructurado tipo reba2cu3o7(re=tierra rara o ytrio) con una elevada densidad de centros de anclaje de vortices y su metodo de preparacion. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008071829A1 true WO2008071829A1 (es) | 2008-06-19 |
Family
ID=39511296
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/ES2007/070204 WO2008071829A1 (es) | 2006-12-14 | 2007-12-05 | MATERIAL SUPERCONDUCTOR NANOESTRUCTURADO TIPO REBa2Cu3O7 (RE=TIERRA RARA O YTRIO) CON UNA ELEVADA DENSIDAD DE CENTROS DE ANCLAJE DE VÓRTICES Y SU MÉTODO DE PREPARACIÓN |
Country Status (7)
Country | Link |
---|---|
US (1) | US20100144536A1 (es) |
EP (1) | EP2104151B1 (es) |
JP (1) | JP2010513180A (es) |
KR (1) | KR20090094121A (es) |
CN (1) | CN101606249A (es) |
ES (1) | ES2302637B1 (es) |
WO (1) | WO2008071829A1 (es) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140158950A1 (en) * | 2012-12-06 | 2014-06-12 | The Regents Of The University Of California | Surface chemical modification of nanocrystals |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102834879B (zh) * | 2010-04-26 | 2014-10-15 | 株式会社藤仓 | 氧化物超导导体及其制造方法 |
JP5981346B2 (ja) | 2010-11-02 | 2016-08-31 | 古河電気工業株式会社 | 超電導線材用基材、超電導線材及び超電導線材の製造方法 |
US9059371B2 (en) * | 2011-02-18 | 2015-06-16 | Solar-Tectic Llc | Enhancing critical current density of cuprate superconductors |
WO2013109065A1 (en) * | 2012-01-17 | 2013-07-25 | Sunam Co., Ltd. | Superconducting wire and method of forming the same |
CN102627453B (zh) * | 2012-04-23 | 2014-08-13 | 清华大学 | 非水基化学溶液制备钇钡铜氧高温超导膜的方法 |
RU2580213C1 (ru) * | 2015-02-02 | 2016-04-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Омский государственный университет им. Ф.М. Достоевского" | Способ формирования сверхпроводящей тонкой пленки с локальными областями переменной толщины |
WO2017193011A1 (en) * | 2016-05-05 | 2017-11-09 | The Florida State University Research Foundation, Inc. | Defect-irrelevant high temperature superconductor (hts) magnet |
JP6788152B1 (ja) * | 2018-12-28 | 2020-11-18 | 株式会社フジクラ | 酸化物超電導線材及びその製造方法 |
CN115417441B (zh) * | 2022-08-29 | 2023-11-21 | 兰州大学 | 一种热分解法制备片状纳米氟化钡的方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050159298A1 (en) | 2004-01-16 | 2005-07-21 | American Superconductor Corporation | Oxide films with nanodot flux pinning centers |
WO2006103303A1 (es) | 2005-04-01 | 2006-10-05 | Consejo Superior De Investigaciones Científicas | Preparación de precursores metalorgánicos anhidros y su uso para la deposición y crecimiento de capas y cintas superconductoras |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3556586B2 (ja) * | 2000-09-05 | 2004-08-18 | 株式会社東芝 | 酸化物超電導体の製造方法、酸化物超電導体用原料、および酸化物超電導体用原料の製造方法 |
US7687436B2 (en) * | 2005-12-02 | 2010-03-30 | University Of Dayton | Flux pinning enhancements in superconductive REBa2CU3O7-x (REBCO) films and method of forming thereof |
-
2006
- 2006-12-14 ES ES200603172A patent/ES2302637B1/es not_active Expired - Fee Related
-
2007
- 2007-12-05 EP EP20070858288 patent/EP2104151B1/en not_active Not-in-force
- 2007-12-05 WO PCT/ES2007/070204 patent/WO2008071829A1/es active Application Filing
- 2007-12-05 US US12/519,359 patent/US20100144536A1/en not_active Abandoned
- 2007-12-05 CN CNA2007800507391A patent/CN101606249A/zh active Pending
- 2007-12-05 KR KR1020097013571A patent/KR20090094121A/ko not_active Application Discontinuation
- 2007-12-05 JP JP2009540797A patent/JP2010513180A/ja active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050159298A1 (en) | 2004-01-16 | 2005-07-21 | American Superconductor Corporation | Oxide films with nanodot flux pinning centers |
WO2005081710A2 (en) * | 2004-01-16 | 2005-09-09 | American Superconductor Corporation | Oxide films with nanodot flux pinning centers |
WO2006103303A1 (es) | 2005-04-01 | 2006-10-05 | Consejo Superior De Investigaciones Científicas | Preparación de precursores metalorgánicos anhidros y su uso para la deposición y crecimiento de capas y cintas superconductoras |
ES2259919A1 (es) | 2005-04-01 | 2006-10-16 | Consejo Superior Investig. Cientificas | Preparacion de precursores metalorganicos anhidros y su uso para la deposicion y crecimiento de capas y cintas superconductoras. |
Non-Patent Citations (10)
Title |
---|
A. GOYAL ET AL.: "Irradiation-free, columnar defects comprised of self- assembled nanodots and nanorods resulting in strongly enhanced flux-pinning in YBa2Cu307-x films", SUPERCOND. SCI. TECHNOL., vol. 18, 2005, pages 1533, XP020088024, DOI: doi:10.1088/0953-2048/18/11/021 |
A. GUPTA ET AL.: "Superconducting oxide films with high transition temperature prepared from metal trifluoroacetate precursors", APPL. PHYS. LETT., vol. 52, 1988, pages 2077 |
GUTIERREZ J. ET AL.: "Strong isotropic flux pinning in solution-derived YBA2Cu2O7_X nanocomposite superconductor films", NATURE MATERIALS, vol. 6, 22 April 2007 (2007-04-22), pages 367 - 373, XP008110110 * |
J.L. MACMANUS-DRISCOLL ET AL.: "Strongly enhanced current densities in superconducting coated conductors of YBa2Cu307-x + BaZr03", NATURE MAT., vol. 3, 2004, pages 439, XP002629385, DOI: doi:10.1038/nmat1156 |
N. ROMA ET AL.: "Acid anhydrides: a simple route to highly pure organometallic solutions for superconducting films", SUPERCOND. SCI. TECHNOL., vol. 19, 2006, pages 521, XP020100972, DOI: doi:10.1088/0953-2048/19/6/019 |
OBRADORS X. ET AL.: "Progress towards all-chemical superconducting YBa2CuO7-coated conductors", SCIENCE AND TECHNOLOGY, vol. 19, 20 January 2006 (2006-01-20), pages S13 - S26, XP020100846 * |
P.C. MCINTYRE; M.J. CIMA; M.F. NG: "Metalorganic deposition of high-J Ba2YCu307 thin films from trifluoroacetate precursors onto (100) SrTi03", J. APPL. PHYS., vol. 68, 1990, pages 4183, XP001032053, DOI: doi:10.1063/1.346233 |
See also references of EP2104151A4 |
X. OBRADORS ET AL.: "Progress towards all chemical superconducting YBCO coated conductors", SUPERCOND. SCI. TECHNOL., vol. 19, 2006, pages S13 |
Y. YAMADA ET AL.: "Epitaxial nanostructure and defects effective for pinning in (Y,RE)Ba2Cu307-x coated conductors", APPLIED PHYSICS LETTERS, vol. 87, 2005, pages 132502, XP012075802, DOI: doi:10.1063/1.2061874 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140158950A1 (en) * | 2012-12-06 | 2014-06-12 | The Regents Of The University Of California | Surface chemical modification of nanocrystals |
US9595363B2 (en) * | 2012-12-06 | 2017-03-14 | The Regents Of The University Of California | Surface chemical modification of nanocrystals |
Also Published As
Publication number | Publication date |
---|---|
ES2302637A1 (es) | 2008-07-16 |
EP2104151A1 (en) | 2009-09-23 |
US20100144536A1 (en) | 2010-06-10 |
CN101606249A (zh) | 2009-12-16 |
EP2104151B1 (en) | 2013-07-17 |
ES2302637B1 (es) | 2009-06-05 |
EP2104151A4 (en) | 2011-12-21 |
KR20090094121A (ko) | 2009-09-03 |
JP2010513180A (ja) | 2010-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
ES2302637B1 (es) | Material superconductor nanoestructurado tipo reba2cu3o7(re=tierra rara o ytrio) con una elevada densidad de centros de anclaje de vortices y su metodo de preparacion. | |
US8536098B2 (en) | High performance superconducting devices enabled by three dimensionally ordered nanodots and/or nanorods | |
KR100815000B1 (ko) | 나노도트 플럭스 피닝 센터가 있는 산화물 막 | |
EP1198847B1 (en) | Method of making a multi-layer superconductor article | |
US7902120B2 (en) | High temperature superconductors having planar magnetic flux pinning centers and methods for making the same | |
Cayado et al. | Large critical current densities and pinning forces in CSD-grown superconducting GdBa2Cu3O7− x-BaHfO3 nanocomposite films | |
US20130196856A1 (en) | Iron based superconducting structures and methods for making the same | |
WO2011017439A1 (en) | Critical current density enhancement via incorporation of nanoscale ba2renbo6 in rebco films | |
Shi et al. | Deposition of REBCO with different rare earth elements on CeO2 buffered technical substrates by fluorine-free metal organic decomposition route | |
US20110034338A1 (en) | CRITICAL CURRENT DENSITY ENHANCEMENT VIA INCORPORATION OF NANOSCALE Ba2(Y,RE)TaO6 IN REBCO FILMS | |
Piperno et al. | CeO2-based buffer layers via chemical solution deposition: Critical issues and latest developments | |
ES2259919B1 (es) | Preparacion de precursores metalorganicos anhidros y su uso para la deposicion y crecimiento de capas y cintas superconductoras. | |
Rijckaert et al. | Superconducting YBa 2 Cu 3 O 7− δ Nanocomposite Films Using Preformed ZrO 2 Nanocrystals via Chemical Solution Deposition | |
Miura et al. | Magnetic Field Dependence of Critical Current and Microstructure in TFA-MOD ${\rm Y} _ {1-x}{\rm Sm} _ {x}{\rm Ba} _ {2}{\rm Cu} _ {3}{\rm O} _ {y} $ With Nanoparticles for Coated Conductors | |
ES2259564B1 (es) | Cintas superconductoras multicapa preparadas mediante deposicion de disoluciones quimicas. | |
Tang | Development of a fluorine-free chemical solution deposition route for rare-earth cuprate superconducting tapes and its application to reel-to-reel processing | |
Rijckaert et al. | Superconducting Nanocomposite Films YBa2 Using Cu3O Preformed | |
ES2355222B1 (es) | Cintas superconductoras formadas a partir de soluciones metalorgánicas que contienen dos metales de transición. | |
JP2011201712A (ja) | 配向酸化物膜の製造方法および配向酸化物膜、酸化物超電導体 | |
Amemiya et al. | Preparation of Y-Ba-Cu-O superconducting tape by pyrolysis of organic acid salts | |
WO2016059264A1 (es) | Cintas, capas o láminas superconductoras y su método de fabricación a partir de disoluciones precursoras sin flúor con elevadas velocidades de crecimiento | |
Takahashi et al. | Development of large scale YBa2Cu3O7-x superconductor with plastic forming | |
Liu et al. | YBCO Films With ${\rm Zr}^{4+} $ Doping Grown by MOD Method | |
Vandaele | YBa2Cu3O7 coatings based on trifluoro-acetic acid precursors | |
Wang | Chemical solution deposition for YBCO superconducting films and Sm2O3 buffer layers on single crystal and biaxially textured metallic substrates |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200780050739.1 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07858288 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2009540797 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020097013571 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2007858288 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12519359 Country of ref document: US |