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
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- 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
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- defects
- nanoparticles
- superconducting material
- metal
- superconducting
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- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- 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
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- C01G55/002—Compounds containing, besides ruthenium, rhodium, palladium, osmium, iridium, or platinum, two or more other elements, with the exception of oxygen or hydrogen
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- H10N60/0324—Processes for depositing or forming copper oxide superconductor layers from a solution
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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.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
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 |
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 |
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 |
Applications Claiming Priority (2)
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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. |
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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 |
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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) |
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US20140158950A1 (en) * | 2012-12-06 | 2014-06-12 | The Regents Of The University Of California | Surface chemical modification of nanocrystals |
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EP2565879B1 (en) * | 2010-04-26 | 2018-02-07 | Fujikura Ltd. | Oxide superconducting conductor and production method therefor |
WO2012060425A1 (ja) | 2010-11-02 | 2012-05-10 | 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 |
KR101429553B1 (ko) * | 2012-01-17 | 2014-09-22 | 주식회사 서남 | 초전도 선재 및 초전도 선재 형성방법 |
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 |
RU2753187C1 (ru) * | 2018-12-28 | 2021-08-12 | Фудзикура Лтд. | Сверхпроводящий оксидный провод и способ его изготовления |
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 |
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2006
- 2006-12-14 ES ES200603172A patent/ES2302637B1/es not_active Expired - Fee Related
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2007
- 2007-12-05 WO PCT/ES2007/070204 patent/WO2008071829A1/es active Application Filing
- 2007-12-05 EP EP20070858288 patent/EP2104151B1/en not_active Not-in-force
- 2007-12-05 US US12/519,359 patent/US20100144536A1/en not_active Abandoned
- 2007-12-05 JP JP2009540797A patent/JP2010513180A/ja active Pending
- 2007-12-05 KR KR1020097013571A patent/KR20090094121A/ko not_active Application Discontinuation
- 2007-12-05 CN CNA2007800507391A patent/CN101606249A/zh active Pending
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Cited By (2)
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---|---|---|---|---|
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 |
---|---|
EP2104151A4 (en) | 2011-12-21 |
US20100144536A1 (en) | 2010-06-10 |
KR20090094121A (ko) | 2009-09-03 |
ES2302637B1 (es) | 2009-06-05 |
EP2104151B1 (en) | 2013-07-17 |
EP2104151A1 (en) | 2009-09-23 |
JP2010513180A (ja) | 2010-04-30 |
ES2302637A1 (es) | 2008-07-16 |
CN101606249A (zh) | 2009-12-16 |
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