Method for making Y123 superconducting material
11770983 · 2023-09-26
Assignee
Inventors
Cpc classification
International classification
Abstract
A superconducting material includes YBa.sub.2Cu.sub.3O.sub.7-δ and a nano-structured, preferably nanowires, WO.sub.3 dopant in a range of from 0.01 to 3.0 wt. %, preferably 0.075 to 0.2 wt. %, based on total material weight. Methods of making the superconductor may preferably avoid solvents and pursue solid-state synthesis employing Y, Ba, and/or Cu oxides and/or carbonates.
Claims
1. A method of synthesizing a superconducting material, comprising: heating an oxidized form of yttrium, an oxidized form of barium, and an oxidized form of copper in molar ratios of 1 (Y): 1.9 to 2.1 (Ba): 2.9 to 3.1 (Cu) in a range of from 850 to 1050° C. for a time in a range of from 8 to 16 hours, to obtain a Y-123; grinding a mixture comprising the Y-123 and 0.01 to 3.0 wt. %, relative to total mass of the mixture, of nano-structured WO.sub.3 to form a superconductor precursor; pressing the superconductor precursor at a pressure in a range of from 500 to 1000 MPa into a pre-sintered precursor; sintering the pre-sintered precursor at a temperature in a range of from 900 to 1000° C. for a period in a range of from 4 to 12 hours, to obtain a sintered product; and cooling the sintered product at a rate in a range of from 1 to 10° C./minute to obtain the superconducting material; wherein the superconducting material, comprises: a YBa.sub.2Cu.sub.3O.sub.7-δ matrix phase; and 0.05 to 0.2 wt. %, based on total superconductor weight, of particles of a dopant, wherein the dopant is the nano-structured WO.sub.3 in the form of WO.sub.3 nanowires and wherein the WO.sub.3 nanowires are disposed within voids between grain boundaries of the YBa.sub.2Cu.sub.3O.sub.7-δ matrix phase.
2. The method of claim 1, wherein the WO.sub.3 nanowires are present in the superconducting material in a range of from 0.075 to 0.2 wt. %.
3. The method of claim 1, further comprising: compressing the oxidized forms of yttrium, barium, and copper prior to the heating.
4. The method of claim 1, wherein the sintering is conducted in an atmosphere comprising air.
5. The method of claim 1, wherein the superconducting material has at least 97% YBa.sub.2Cu.sub.3O.sub.7-δ phase with orthorhombic crystal structure and Pmmm symmetry.
6. The method of claim 1, wherein the superconducting material comprises: no more than 0.5% of Y.sub.2BaCuO.sub.5 (Y-211); no more than 0.5% of YBaCu.sub.2O.sub.5-δ (Y-112); no more than 0.5% of YBa.sub.2Cu.sub.4O.sub.y (Y-124); no more than 0.5% of Y.sub.2Ba.sub.4Cu.sub.7O.sub.y (Y-247); and no more than 0.5% of BaCuO.sub.2, based on the total phases concentration.
7. The method of claim 1, wherein the superconducting material comprises no more than 1% of any further phases of YBCO than Y-123, based on the total phases concentration.
8. The method of claim 1, wherein the superconducting material has in its matrix a regular form of nanometer scale entities bright in contrast dispersed into grains.
9. The method of claim 1, wherein the superconducting material has a superconducting transition in a range of from 80 to 100 K.
10. The method of claim 1, wherein the superconducting material has a critical current density (J.sub.cm) in a range of from 1.0×10.sup.4 to 1.4×10.sup.4 A/cm.sup.2, in an applied magnetic field of 0 Tesla.
11. The method of claim 1, wherein the superconducting material has a critical current density (J.sub.cm) in a range of from 600 to 800 A/cm.sup.2, in an applied magnetic field of 1 Tesla.
12. The method of claim 1, wherein the superconducting material has a critical current density of at least 4×10.sup.3 to 10.sup.5 A/cm.sup.2 across a temperature range of from 60 to 10 K under a magnetic field in a range of from 0 to 6 Tesla.
13. A method of synthesizing a superconducting material, comprising: heating an oxidized form of yttrium, an oxidized form of barium, and an oxidized form of copper in molar ratios of 1 (Y): 1.9 to 2.1 (Ba): 2.9 to 3.1 (Cu) in a range of from 850 to 1050° C. for a time in a range of from 8 to 16 hours, to obtain a Y-123; grinding a mixture comprising the Y-123 and 0.01 to 3.0 wt. %, relative to total mass of the mixture, of nano-structured WO.sub.3 to form a superconductor precursor; pressing the superconductor precursor at a pressure in a range of from 500 to 1000 MPa into a pre-sintered precursor; sintering the pre-sintered precursor at a temperature in a range of from 900 to 1000° C. for a period in a range of from 4 to 12 hours, to obtain a sintered product; and cooling the sintered product at a rate in a range of from 1 to 10° C./minute to obtain the superconducting material; wherein the WO.sub.3 nanowires are present in the superconducting material in a range of from 0.075 to 0.2 wt. % based on total superconductor weight.
14. The method of claim 13, further comprising: compressing the oxidized forms of yttrium, barium, and copper prior to the heating.
15. The method of claim 13, wherein the sintering is conducted in an atmosphere comprising air.
16. The method of claim 13, wherein the superconducting material has at least 97% YBa.sub.2Cu.sub.3O.sub.7-δ phase with orthorhombic crystal structure and Pmmm symmetry.
17. The method of claim 13, wherein the superconducting material comprises: no more than 0.5% of Y.sub.2BaCuO.sub.5 (Y-211); no more than 0.5% of YBaCu.sub.2O.sub.5-δ (Y-112); no more than 0.5% of YBa.sub.2Cu.sub.4O.sub.y (Y-124); no more than 0.5% of Y.sub.2Ba.sub.4Cu.sub.7O.sub.y (Y-247); and no more than 0.5% of BaCuO.sub.2, based on the total phases concentration.
18. The method of claim 13, wherein the superconducting material comprises no more than 1% of any further phases of YBCO than Y-123, based on the total phases concentration.
19. The method of claim 13, wherein the superconducting material has in its matrix a regular form of nanometer scale entities bright in contrast dispersed into grains.
20. The method of claim 13, wherein the superconducting material has a superconducting transition in a range of from 80 to 100 K.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(15) Aspects of the invention provide superconducting materials, comprising YBCO materials such as YBa.sub.2Cu.sub.3O.sub.7-δ (Y-123) and a nano-structured tungsten oxide dopant such as WO.sub.3 in a range of from 0.01 to 3.0 wt. %, based on total material weight. Herein, “superconductor” and “superconducting material” is treated identically and interchangeably, typically using “superconductor(s)” for brevity. The superconductor itself is not a nanostructure, and may be an amorphous or partially crystalline matrix, containing nano-structured WO.sub.3.
(16) Aspects of the invention provide methods of synthesizing a superconductor, comprising: heating an oxidized form of yttrium, an oxidized form of barium, and an oxidized form of copper in molar ratios of 1 (Y): 1.9 to 2.1 (Ba): 2.9 to 3.1 (Cu) in a range of from 850 to 1050, 900 to 1000, or 925 to 975° C. for a time in a range of from 8 to 16, 10 to 14, or 11 to 13 hours, to obtain a Y-123; grinding the Y-123 with 0.01 to 3.0, 0.02 to 1.0, 0.03 to 0.5, 0.05 to 0.2 wt. %, relative to total superconductor mass, of WO.sub.3 nano-structures to form a solid superconductor; pressing the solid superconductor at a pressure in a range of from 500 to 1000, 600 to 900, or 700 to 800 MPa into a pre-sintered form; sintering the pre-sintered form at a temperature in a range of from 900 to 1000, 915 to 985, 925 to 975, or 940 to 960° C. for a period in a range of from 4 to 12, 6 to 10, 7 to 9, or 7.5 to 8.5 hours, to obtain a sintered form; and cooling the sintered form at a rate in a range of from 1 to 10, 2 to 7.5, 2.5 to 6, 3 to 5, or 3.5 to 4.5° C./minute to obtain the superconductor. Any of the above permutations of superconductor may be made by such a method.
(17) The atomic ratio or stoichiometry of the YBCO precursor metal oxides may be 1 (Y): 1.9 to 2.1 (Ba): 2.9 to 3.1 (Cu), or 1 (Y): 2 (Ba):3 (Cu). The oxidized form of Y, Ba, and/or Cu, could be a nitrate, a halide, a carbonate, and/or a pure oxide, preferably including Y.sub.2O.sub.3, BaO, BaCO.sub.3, CuO, Cu.sub.2O, CuO.sub.2, and/or Cu.sub.2O.sub.3. The metal oxides may use only three, two, one, or no carbonates, but may preferably use one, or even two, most preferably only BaCO.sub.3, with non-carbonate Y and Cu, preferably Y.sub.2O.sub.3 and CuO.
(18) The WO.sub.3 dopant may present in the range of from 0.01 to 3.0, 0.025 to 2.0, 0.025 to 1.0, 0.05 to 0.5, 0.075 to 0.2 wt. %, based on the total superconductor weight. Because the superconductor may be used for a variety of applications, a desirable doping endpoint may be any of the preceding values as a lower and/or upper end point or at least 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, or 0.08 wt. %, and/or no more than 0.5, 0.45, 0.4, 0.35, 0.3, 0.25, 0.2, or 0.15
(19) The dopant maybe in a form that includes wire(s), tube(s), sphere(s), prism(s), or a mixture of two or more of any of these nano-structures, preferably at least including nanowires. Preferably at least 99, 99.5, 99.9, 99.98, 99.99 or 100% of the dopant have a nano-wire structure.
(20) Inventive methods may further comprise compressing, such as pelletizing, the oxidized forms of yttrium, barium, and copper into a precursor form prior to the heating. The sintering may be conducted in an atmosphere comprising air, e.g., in at least 50, 60, 75, 85, 90, 95, 97.5, 99, or 100%. The WO.sub.3 nano-structures may comprise 99, 99.5, 99.8, 99.9, 99.99, or 100% nanowires, based on the total number of WO.sub.3 nano-structures, which is also applicable to the superconductors discussed above, and the nanostructure properties discussed above may be applied to the starting material and final, incorporated dopant(s) in inventive methods. The starting material and product dopant(s) will preferably have identical structural properties, ignoring the incorporation of and any particular YBCO-dopant interaction forces.
(21) Inventive superconductors may comprise at least 97, more preferably 98, more preferably 99, more preferably 99.5, more preferably 99.6, more preferably 99.7% YBa.sub.2Cu.sub.3O.sub.7-δ (Y-123), relative to other yttrium-based compounds, wherein, measured volumetrically and/or mass-wise, the Y-123 superconducting material has orthorhombic crystal structure having Pmmm symmetry. The superconductors may contain small amounts, e.g., no more than 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3% of Y.sub.2BaCuO.sub.5 (Y-211).
(22) Inventive superconductors may have at least 97, more preferably 98, more preferably 99, more preferably 99.5, more preferably 99.6, more preferably 99.7% of Y-123 phase having orthorhombic crystal structure and Pmmm symmetry. The superconductor generally comprises single-phase Y-123. Inventive superconductors may comprise no further phases of YBCO than Y-123, or no more than 3, 2.5, 2, 1, 0.5, 0.4, 0.3%, based on a total weight of any phase beyond Y-123. Inventive superconductors preferably comprise no more than 0.5, 0.25, 0.1, 0.05, 0.01, 0.001 or 0.0001%, or even none to detectable limits, of any further phases of YBCO than Y-123, based on the total material weight. Inventive superconductors may comprise no more than 0.5, 0.25, 0.1, 0.05, 0.01, 0.001 or 0.0001% of Y.sub.2BaCuO.sub.5 (Y-211), and/or YBaCu.sub.2O.sub.5-δ (Y-112), and/or YBa.sub.2Cu.sub.4O.sub.y (Y-124), and/or Y.sub.2Ba.sub.4Cu.sub.7O.sub.y (Y-247), BaCuO.sub.2, based on the total material weight, either individually, or combined. Inventive superconductors, however, under some circumstances, may not desirably contain any of these or further phases.
(23) The superconductors within the scope of the invention preferably do not have additional phases beyond the normal YBCO phase and defined WO.sub.3 dopant, i.e., has no more than 1, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3% of Y-211. Preferably, the inventive superconductors maintain nanowires of WO.sub.3 that do not react with YBa.sub.2Cu.sub.3O.sub.7-δ, but instead keep their size and preferably contribute with their volume, interfaces, and/or generated defects that may enhance the critical current density J.sub.cm.
(24) In addition or alternatively, the inventive superconductors are made without chelating ligands on the metals, particularly acetate or acetylacetone (acac). The YBCO used may also be produced from only solids, rather than involving solubilized starting materials, thereby leading to crystal structures as described herein and illustrated in the drawings. The synthesis of superconductors within the invention may be made by any method leading to the claimed structure, but preferably avoids solution phase reactions, particularly avoiding ethylene glycol (glycols generally), ethanol (alcohols generally), and/or water, and can eschew the use of bases, such as ammonia, hydroxides, and the like. Superconductors herein may avoid sustaining temperatures for longer than 1 hour, 45, 30, 15, 10, 5, or 1 minute after the 900+° C. calcining, i.e., an annealing step such as sustained heating in a range of 300 to 600° C. after formation of the YBCO and/or doped YBCO may be avoided.
(25) Inventive superconductors may have in their matrices a regular form of nanometer scale entities bright in contrast dispersed into grains. The nanosized entities may have an average size of 100, 60, 50, 40, 30, or 20 nm in diameter. The nanosized entities are generally well-dispersed, i.e., only 1 in 5, 1 in 10, or 1 in 20 is agglomerated. Inventive superconductors may have in their matrices WO.sub.3 nanowires taking place within the grains boundaries by filling the voids among the grains.
(26) Inventive superconductors may have a superconducting transition in a range of from 80 to 100, 85 to 98, 88 to 97, 91 to 96 K, or at least 85, 87, 89, 90, 91, 92, 93, 94, 95, or even 96 K.
(27) Inventive superconductors may have a critical current density (J.sub.cm) in a range of from 1.0×10.sup.4 to 1.4×10.sup.4, 1.1×10.sup.4 to 1.35×10.sup.4, 1.2×10.sup.4 to 1.3×10.sup.4 A/cm.sup.2, or at least 1, 1.05, 1.1, 1.15, or 1.2×10.sup.4 A/cm.sup.2, in an applied magnetic field of 0 Tesla, and/or a critical current density (J.sub.cm) in a range of from 600 to 800, 650 to 780, or 700 to 750 A/cm.sup.2, or at least 600, 625, 650, 675, or 700 A/cm.sup.2, in an applied magnetic field one of 1 Tesla. Alternatively, or in addition, inventive superconductors may have a critical current density of at least 4×10.sup.3, 10.sup.4, 2×10.sup.4, 3×10.sup.4, 5×10.sup.4, or 10.sup.5 A/cm.sup.2 at temperature range 60, 50, 40, 30, 20, or 10 K, under a magnetic field in a range of from 0 to 6 Tesla. The critical current density of inventive superconductors enhanced in WO.sub.3 added Y-123 compared to non-added Y-123 by factors more than 25, 15, 10, 5, or 2%, at temperature range 77, 70, 60, 50, 40, 30, 20, or 10 K, over the magnetic field range of 0 to 6 Tesla.
Example
(28) Pure YBCO samples and WO.sub.3 nanowire-doped YBCO samples were synthesized through the solid-state reaction method under identical conditions. The single phase YBCO was synthesized by thoroughly mixing high purity of Y.sub.2O.sub.3, BaCO.sub.3, and CuO according to the stoichiometric formula of Y:Ba:Cu=1:2:3. This mixture of powders was pelletized and then calcined at 950° C. for 12 h in air. WO.sub.3 nanowires were added to the precursor powder Y-123 in the final processing stage, by mixing and hand grinding both powders in an agate mortar. The amount of added WO.sub.3 nanowire varied from x=0 to 3 wt. % of the total mass of sample. The mixed powders were pressed into pellets at 750 MPa in the form of circular disks having 13 mm in diameter. The pellets were sintered at 950° C. for 8 hours in air and then cooled to room temperature at a rate of 4° C./min. The non-doped (0 wt. % WO.sub.3) sample was used as a reference, then it was hand ground in the same manner as the WO.sub.3-doped samples to ensure identical physical conditions for all of the samples.
(29) The resulting samples were characterized using x-ray powder diffraction (XRD), scanning electron microscopy (SEM), electrical resistivity versus temperature, and magnetization versus fields M(H) hysteresis loops.
(30) Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views.
(31)
(32) As seen in
(33)
(34)
(35) The intra-granular critical current density (J.sub.cm) versus magnetic field for various amounts of WO.sub.3 nanowires were estimated from the experiments of M vs. H using Bean's critical-state model are shown in
(36) As seen in
(37)
(38)
wherein J.sub.cm is intra-granular critical current density, NW is the nanowire-doped superconductor, WO.sub.3 is the pure nanowire, and 0.0 wt. % is the pure Y-123.
(39) The superconducting materials described herein may be used for application that function to transport higher current densities with very low loss of energy such as in low-loss power and electrical transmission cables; enhance power stability for energy storage such as in fuel cells; improve electromagnetic performance such as in superconducting electromagnets; to generate high magnetic fields for several practical applications. Products, devices and systems may include the superconducting materials for service in transport of higher current densities with very low loss of energy and the generation of high magnetic fields for practical applications.
(40) Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.