CN116553913A - Preparation method of YbBCO superconducting block - Google Patents
Preparation method of YbBCO superconducting block Download PDFInfo
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- CN116553913A CN116553913A CN202310555991.9A CN202310555991A CN116553913A CN 116553913 A CN116553913 A CN 116553913A CN 202310555991 A CN202310555991 A CN 202310555991A CN 116553913 A CN116553913 A CN 116553913A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 239000011812 mixed powder Substances 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims 3
- 238000010792 warming Methods 0.000 claims 2
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000012071 phase Substances 0.000 description 33
- 238000002441 X-ray diffraction Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 239000002887 superconductor Substances 0.000 description 5
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical compound [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241000954177 Bangana ariza Species 0.000 description 1
- FFWQPZCNBYQCBT-UHFFFAOYSA-N barium;oxocopper Chemical compound [Ba].[Cu]=O FFWQPZCNBYQCBT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The invention provides a preparation method of a YbBCO superconducting block, which comprises the following steps: mixing Yb source, ba source and Cu source, and ball milling to obtain mixed powder; performing first heat treatment on the obtained mixed powder to obtain precursor powder; cold pressing the obtained precursor powder to obtain a block blank; and performing second heat treatment on the obtained block blank to obtain the YbBCO superconducting block. According to the preparation method of YbBCO provided by the invention, seed crystals are not needed, and YbBCO superconducting blocks can be prepared by two-step heat treatment, so that the process is simple and the operation is convenient; the prepared YbBCO superconducting block has high phase purity and strong texture.
Description
Technical Field
The invention belongs to the field of superconducting materials, relates to a preparation method of a superconducting block, and particularly relates to a preparation method of a YbBCO superconducting block.
Background
The superconducting material can be divided into low-temperature and high-temperature superconducting materials according to the critical temperature (Tc) (generally, tc is above 77K in a liquid nitrogen temperature region), the application of the superconducting material is greatly limited by the extremely low-temperature conditions required by the low-temperature superconductor, and the research of the high-temperature superconductor has great practical significance due to the fact that the high-temperature superconductor has a higher critical temperature. Wherein, rare earth barium copper oxygen high temperature superconductor (REBa 2 Cu 3 O 7-δ RE123 or REBCO, RE is rare earth elements such as Y, sm, nd or La, and the like, has a critical temperature (Tc) far higher than the liquid nitrogen temperature (77K), has a much lower commercial cost, has huge market potential in the aspect of practicality, and is an important research object in the superconducting field. In addition, because the REBCO superconductor still has higher critical current density under an external magnetic field, the material has wide application prospect in the aspects of superconducting magnetic suspension bearings, energy storage flywheels, magnetic suspension conveying systems, superconducting motors, superconducting magnets, superconducting magnetic separation devices and the like. REBCO superconducting materials can be classified into: (1) a superconducting film or tape for current transmission; (2) single crystals for studying physical mechanisms; (3) superconducting bulk material for generating a strong magnetic field. Among them, REBCO superconducting blocks can exhibit high critical current density (Jc) even at 77K and have strong magnetic field trapping ability, and thus, high performance superconducting blocks are important for basic research and practical application.
The current method for manufacturing REBCO superconducting bulk mainly comprises the following steps: sintering, powder melt texturing (PMP), quench-melt growth (QMG), liquid Phase Processing (LPP), melt Texturing (MTG), top Seed Melt Texturing (TSMTG) and top seed Infiltration Growth (IG) modified based on the above methods, and the like.
M Muralidhar et al obtained by IG method with a critical temperature Tc of 92K and a critical current density Jc of 225kA cm -2 Blocks (Physica C Superconductivity,1999,313 (3-4): 232-240) of YBCO of (B), the process first preparing Y 2 BaCuO 5 And Ba (beta) 3 Cu 5 O 8 Compacting, and then placing NdBCO seed crystal in Y 2 BaCuO 5 The material is heated by the process of heating and cooling for many times to obtainAnd YBCO blocks. This method requires the growth of a texture of a specific orientation by means of a seed; and the heat treatment process is complex, the cooling rate is slow, and the superconducting block with high purity can be obtained by sintering for many times and adopting extremely slow cooling rate. In a common preparation method, the superconducting block prepared usually contains a plurality of domains, and the existence of the domains enables a 'weak connection' to be formed between superconducting phases, so that the critical current density (Jc) of the block is reduced.
CN104790036a discloses a method for growing nano composite yttrium barium copper oxide superconducting block by infiltration with ytterbium-based liquid phase source, which comprises the steps of preparing solid phase powder, preparing liquid phase source powder, pressing precursor block, assembling precursor block, infiltration growing nano composite yttrium barium copper oxide single domain block and oxygen infiltration treatment. The single domain yttrium barium copper oxide superconducting block is prepared by the method, but the adopted infiltration growth method has more complex process steps.
The peritectic reaction temperature of REBCO decreases with the decrease of the ionic radius, yb 3+ The YbBCO has a lower peritectic reaction temperature, about 960 ℃ in air, which is a significant advantage in REBCO superconducting bulk applications. However, in the preparation process of the YbBCO block, because of the competing reaction between the formation and decomposition of the YbBCO phase, the growth of YbBCO crystals is extremely sensitive to the heat treatment temperature and atmosphere, and the preparation difficulty of the YbBCO superconducting block with high phase purity is increased. Moreover, the YbBCO superconductive block prepared generally contains a plurality of domains, and the existence of the domains enables a 'weak connection' to be formed between superconductive phases, so that the critical current density (Jc) of the block is reduced.
Aiming at the defects of the prior art, a preparation method of a YbBCO superconducting block with high purity and strong texture needs to be provided.
Disclosure of Invention
The invention aims to provide a preparation method of a YbBCO superconducting block, which is simple in process and has the advantages of high phase purity and strong texture.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention provides a preparation method of a YbBCO superconducting block, which comprises the following steps:
(1) Mixing Yb source, ba source and Cu source, and ball milling to obtain mixed powder;
(2) Performing first heat treatment on the mixed powder obtained in the step (1) to obtain precursor powder;
(3) Cold pressing the precursor powder obtained in the step (2) to obtain a block blank;
(4) And (3) performing second heat treatment on the block blank obtained in the step (3) to obtain a YbBCO superconducting block.
The preparation method provided by the invention has simple process, no specific orientation texture is required to be grown through seed crystals, and the prepared YbBCO superconducting block has high phase purity and strong texture, and reduces 'weak connection of grain boundaries', so that the superconducting block with higher critical current density can be obtained.
Preferably, the Yb source, ba source and Cu source are used in the molar ratio of Yb, ba and Cu atoms in the step (1) is 1 (1.9-2.2) (2.9-3.3), for example, 1:2:3, 1:1.9:2.9, 1:1.9:3.3, 1:2.2:3.3 or 1:2.2:2.9, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the Yb source comprises Yb 2 O 3 。
Preferably, the Ba source comprises BaCO 3 。
Preferably, the Cu source comprises CuO.
Preferably, the ball milling time in the step (1) is 2-4h, for example, 2h, 2.5h, 3h, 3.5h or 4h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the ball milling in the step (1) has a rotation speed of 258-310r/min, for example 258r/min, 271r/min, 284r/min, 297r/min or 310r/min, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, ethanol is added during the ball milling in step (1).
Preferably, the ethanol is used in an amount of 30-50mL, for example, 30mL, 35mL, 40mL, 45mL or 50mL, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the ball-milling ball powder ratio in the step (1) is 4:1.
According to the invention, the raw materials can be uniformly mixed and the particle size is uniform by adopting ball milling.
Preferably, the mixed powder is dried after ball milling in the step (1).
Preferably, the temperature of the drying is 60-70 ℃, for example, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃ or 70 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying time is 10-15h, for example, 10h, 11h, 12h, 13h, 14h or 15h, but not limited to the recited values, and other non-recited values in the range are equally applicable.
Preferably, the first heat treatment of step (2) is performed in an oxygen atmosphere.
Preferably, the oxygen atmosphere has an oxygen purity of 99.5%.
Preferably, the first heat treatment in step (2) includes sequentially performing first temperature-raising heating and first temperature-lowering heating.
Preferably, the heating rate of the first heating is 5-10deg.C/min, for example, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min or 10 deg.C/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the end temperature of the first heating temperature is 937-945 ℃, for example 937 ℃, 939 ℃, 940 ℃, 942 ℃, 944 ℃ or 945 ℃, but the method is not limited to the listed values, and other values not listed in the numerical range are equally applicable.
Preferably, the heating time of the first heating temperature is 10-12h, for example, 10h, 10.5h, 11h, 11.5h or 12h, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the cooling rate of the first cooling and heating is 1-2 ℃/min, for example, 1 ℃/min, 1.2 ℃/min, 1.4 ℃/min, 1.6 ℃/min, 1.8 ℃/min or 2 ℃/min, but the invention is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the end temperature of the first cooling and heating is 490-510 ℃, for example 490 ℃, 495 ℃, 500 ℃, 505 ℃, or 510 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the heating time of the first cooling heating is 1-3h, for example, 1h, 1.5h, 2h, 2.5h or 3h, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
In the invention, the first heat treatment causes the precursor powder to react to produce the target product.
Preferably, the pressure of the cold pressing in step (3) is 2-3t, for example, 2t, 2.2t, 2.4t, 2.6t, 2.8t or 3t, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the first heat treatment of step (4) is performed in an oxygen atmosphere.
Preferably, the oxygen atmosphere has an oxygen purity of 99.5%.
Preferably, the second heat treatment in step (4) includes sequentially performing a second temperature-raising heating and a second temperature-lowering heating.
Preferably, the heating rate of the second heating is 5-10deg.C/min, for example, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min or 10 deg.C/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the end temperature of the second heating is 937-945 ℃, for example 937 ℃, 939 ℃, 940 ℃, 942 ℃, 944 ℃ or 945 ℃, but the invention is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the heating time of the second heating temperature is 10-12h, for example, 10h, 10.5h, 11h, 11.5h or 12h, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the cooling rate of the second cooling and heating is 1-2 ℃/min, for example, 1 ℃/min, 1.2 ℃/min, 1.4 ℃/min, 1.6 ℃/min, 1.8 ℃/min or 2 ℃/min, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the end temperature of the second cooling and heating is 490-510 ℃, for example 490 ℃, 495 ℃, 500 ℃, 505 ℃, or 510 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the heating time of the second cooling and heating is 1-3h, for example, 1h, 1.5h, 2h, 2.5h or 3h, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
In the present invention, the second heat treatment can further improve the purity and allow the green compact having a strong texture to be grown.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of YbBCO provided by the invention, seed crystals are not needed, and YbBCO superconducting blocks can be prepared by two-step heat treatment, so that the process is simple and the operation is convenient; the prepared YbBCO superconducting block has high phase purity and strong texture.
Drawings
FIG. 1 is an X-ray diffraction pattern of a YbBCO superconducting block prepared in example 1 of the present invention.
Fig. 2 is an SEM micro morphology of the YbBCO superconducting bulk prepared in example 1 of the present invention.
FIG. 3 is a chart showing the superconducting performance test of YbBCO superconducting blocks prepared in example 1 of the present invention.
FIG. 4 is an X-ray diffraction pattern of the YbBCO superconducting block prepared in example 2 of the present invention.
FIG. 5 is an X-ray diffraction pattern of a YbBCO superconducting block prepared in example 3 of the present invention.
FIG. 6 is an X-ray diffraction pattern of a YbBCO superconducting block prepared in example 4 of the present invention.
FIG. 7 is an X-ray diffraction pattern of YbBCO superconducting bulk prepared in example 5 of the present invention.
FIG. 8 is an X-ray diffraction pattern of a YbBCO superconducting block prepared in example 6 of the present invention.
FIG. 9 is an X-ray diffraction pattern of a YbBCO superconducting block prepared in example 7 of the present invention.
FIG. 10 is an X-ray diffraction pattern of YbBCO superconducting bulk prepared in comparative example 1 of the present invention.
FIG. 11 is an X-ray diffraction pattern of YbBCO superconducting blocks prepared in comparative example 2 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the examples of the present invention, yb was used 2 O 3 And BaCO 3 The purity of (2) was 99.99% and the purity of CuO was 99.5% independently.
Example 1
The embodiment provides a preparation method of a YbBCO superconducting block, which comprises the following steps:
(1) Yb is mixed with Yb, ba and Cu in a molar ratio of 1:2:3 2 O 3 、BaCO 3 And CuO, putting the mixture into a ball milling tank, adding 30mL of absolute ethyl alcohol, ball milling the mixture in a planetary ball mill at a rotating speed of 258r/min for 2 hours, putting the mixture into a baking oven, and drying the mixture at 70 ℃ for 12 hours to obtain mixed powder;
(2) Placing the mixed powder obtained in the step (1) in a corundum crucible, placing the crucible in a tubular furnace, heating to 937 ℃ at a heating rate of 10 ℃/min under flowing oxygen atmosphere, and preserving heat for 10 hours; then cooling to 500 ℃ at a cooling rate of 1 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace after finishing to obtain precursor powder;
(3) Grinding the precursor powder obtained in the step (2), putting the ground precursor powder into a cold pressing mold, pressurizing by using a hydraulic press, wherein the pressure is 2t, and demolding to obtain a block blank with the diameter of 10mm and the height of 2.12 mm;
(4) Placing the block blank obtained in the step (3) in a corundum crucible, placing the crucible in a tubular furnace, heating to 937 ℃ at a heating rate of 10 ℃/min under flowing oxygen atmosphere, and preserving heat for 10 hours; then cooling to 500 ℃ at a cooling rate of 1 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with a furnace after finishing to obtain the YbBCO superconducting block.
X-ray diffraction analysis, SEM microcosmic appearance characterization and superconducting performance test are respectively carried out on the YbBCO superconducting block obtained in the embodiment; the resulting XRD diffractogram is shown in figure 1; SEM microtopography is shown in fig. 2, and superconducting performance test (critical temperature Tc) is shown in fig. 3.
As can be seen from the XRD diffraction pattern and the SEM microscopic morphology pattern, the block prepared by the embodiment is YbBCO phase, the phase purity is high, and the superconducting phase with the crystal phase of (001) forms a very strong texture; as can be seen from the critical temperature Tc chart, the critical temperature of the block reaches 89.97K, which is the critical temperature value of YbBCO, and YbBCO prepared in this example has superconductivity.
Example 2
The embodiment provides a preparation method of a YbBCO superconducting block, which comprises the following steps:
(1) Yb is mixed with Yb, ba and Cu in a molar ratio of 1:1.9:2.9 2 O 3 、BaCO 3 And CuO, putting the mixture into a ball milling tank, adding 50mL of absolute ethyl alcohol, ball milling the mixture for 3 hours in a planetary ball mill at a rotating speed of 310r/min, and then putting the mixture into a baking oven to dry the mixture for 15 hours at 65 ℃ to obtain mixed powder;
(2) Placing the mixed powder obtained in the step (1) in a corundum crucible, placing the crucible in a tubular furnace, heating to 940 ℃ at a heating rate of 5 ℃/min under the flowing oxygen atmosphere, and preserving heat for 12 hours; then cooling to 510 ℃ at a cooling rate of 1.5 ℃/min, preserving heat for 1h, and cooling to room temperature along with a furnace after finishing to obtain precursor powder;
(3) Grinding the precursor powder obtained in the step (2), putting the ground precursor powder into a cold pressing mold, pressurizing the ground precursor powder by using a hydraulic press, and demolding the ground precursor powder to obtain a block blank with the diameter of 10mm and the height of 2.12mm, wherein the pressure is 2.5 t;
(4) Placing the block blank obtained in the step (3) in a corundum crucible, placing the crucible in a tubular furnace, heating to 940 ℃ at a heating rate of 5 ℃/min under flowing oxygen atmosphere, and preserving heat for 12 hours; then cooling to 490 ℃ at a cooling rate of 2 ℃/min, preserving heat for 3 hours, and cooling to room temperature along with a furnace after finishing to obtain the YbBCO superconducting block.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 4.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example has high phase purity, and the superconducting phase with the crystalline phase (001) forms a very strong texture.
Example 3
The embodiment provides a preparation method of a YbBCO superconducting block, which comprises the following steps:
(1) Yb is mixed with Yb, ba and Cu in a molar ratio of 1:2.2:3.3 2 O 3 、BaCO 3 And CuO, putting the mixture into a ball milling tank, adding 40mL of absolute ethyl alcohol, ball milling the mixture in a planetary ball mill at a rotating speed of 284r/min for 4 hours, putting the mixture into a baking oven, and drying the mixture at 70 ℃ for 10 hours to obtain mixed powder;
(2) Placing the mixed powder obtained in the step (1) in a corundum crucible, placing the crucible in a tubular furnace, heating to 945 ℃ at a heating rate of 8 ℃/min under a flowing oxygen atmosphere, and preserving heat for 11h; then cooling to 490 ℃ at a cooling rate of 2 ℃/min, preserving heat for 3 hours, and cooling to room temperature along with a furnace after finishing to obtain precursor powder;
(3) Grinding the precursor powder obtained in the step (2), putting the ground precursor powder into a cold pressing mold, pressurizing the ground precursor powder by using a hydraulic press, demolding the ground precursor powder to obtain a block blank with the diameter of 10mm and the height of 2.12mm, wherein the pressure is 3 t;
(4) Placing the block blank obtained in the step (3) in a corundum crucible, placing the crucible in a tubular furnace, heating to 945 ℃ at a heating rate of 8 ℃/min under flowing oxygen atmosphere, and preserving heat for 11h; then cooling to 510 ℃ at a cooling rate of 1.5 ℃/min, preserving heat for 1h, and cooling to room temperature along with the furnace after finishing to obtain the YbBCO superconducting block.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 5.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example has high phase purity, and the superconducting phase with the crystalline phase (001) forms a very strong texture.
Example 4
The present example provides a method for preparing a YbBCO superconducting block, which is similar to example 1 except that the temperature is raised to 927 ℃ in step (4) compared with example 1.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 6.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example has high phase purity, and the texture of the superconducting phase having the crystal phase (001) is weak.
Example 5
The present example provides a method for preparing a YbBCO superconducting block, which is similar to example 1 except that the temperature is increased to 950 ℃ in step (4) compared with example 1.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 7.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example has high phase purity, and the texture of the superconducting phase having the crystal phase (001) is weak.
Example 6
The present example provides a method for preparing a YbBCO superconducting block, and compared with example 1, the method controls the temperature in step (4) to be reduced to 450 ℃, and the rest is the same as example 1.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 8.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example has high phase purity, and the texture formed by the superconducting phase having the crystal phase (001) is strong.
Example 7
The present example provides a method for preparing a YbBCO superconducting block, and compared with example 1, the method controls the temperature in step (4) to be reduced to 550 ℃, and the rest is the same as example 1.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 9.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example has high phase purity, and the texture formed by the superconducting phase having the crystal phase (001) is strong.
Comparative example 1
This comparative example provides a method for preparing a YbBCO superconducting block, which does not perform the heat treatment process of step (2) compared to example 1, and the rest is the same as example 1.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 10.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example forms a strong superconducting phase texture with the crystalline phase (001), but has poor purity.
Comparative example 2
This comparative example provides a method for preparing a YbBCO superconducting block, which does not perform the heat treatment process of step (4) as compared with example 1, and the rest is the same as example 1.
The XRD diffraction pattern of the YbBCO superconducting bulk obtained in this example is shown in FIG. 11.
As can be seen from the XRD diffractogram, the YbBCO superconducting bulk obtained in this example formed powder with YbBCO as the main phase, and no texture was formed.
In conclusion, the preparation method of YbBCO provided by the invention does not need seed crystals, and YbBCO superconducting blocks can be prepared by two steps of heat treatment, so that the process is simple and the operation is convenient; the prepared YbBCO superconducting block has high phase purity and strong texture.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. A method for preparing a YbBCO superconducting block, comprising the steps of:
(1) Mixing Yb source, ba source and Cu source, and ball milling to obtain mixed powder;
(2) Performing primary heat treatment on the mixed powder obtained in the step (1) to obtain precursor powder;
(3) Cold pressing the precursor powder obtained in the step (2) to obtain a block blank;
(4) And (3) performing a second heat treatment on the block blank obtained in the step (3) to obtain a YbBCO superconducting block.
2. The method according to claim 1, wherein the amounts of the Yb source, the Ba source and the Cu source used in the step (1) are 1 (1.9-2.2): 2.9-3.3) in terms of the molar ratio of Yb, ba and Cu atoms;
preferably, the Yb source comprises Yb 2 O 3 ；
Preferably, the Ba source comprises BaCO 3 ；
Preferably, the Cu source comprises CuO.
3. The method according to claim 1 or 2, wherein the ball milling time in step (1) is 2 to 4 hours;
preferably, the rotating speed of the ball milling in the step (1) is 258-310r/min;
preferably, ethanol is added during the ball milling in step (1).
4. The method according to any one of claims 1 to 3, wherein the mixed powder is dried after the ball milling in step (1);
preferably, the temperature of the drying is 60-70 ℃;
preferably, the drying time is 10-15 hours.
5. The method according to any one of claims 1 to 4, wherein the first heat treatment of step (2) is performed in an oxygen atmosphere.
6. The method according to any one of claims 1 to 5, wherein the first heat treatment in step (2) comprises sequentially performing first warming heating and first cooling heating;
preferably, the heating rate of the first heating is 5-10 ℃/min;
preferably, the end temperature of the first heating temperature is 937-945 ℃;
preferably, the heating time of the first temperature rising heating is 10-12h;
preferably, the cooling rate of the first cooling and heating is 1-2 ℃/min;
preferably, the end temperature of the first cooling and heating is 490-510 ℃;
preferably, the heating time of the first cooling heating is 1-3h.
7. The method of any one of claims 1-6, wherein the cold pressing in step (3) is performed at a pressure of 2-3t.
8. The method according to any one of claims 1 to 7, wherein the second heat treatment of step (4) is performed in an oxygen atmosphere.
9. The method according to any one of claims 1 to 8, wherein the second heat treatment in step (4) comprises sequentially performing a second warming heating and a second cooling heating;
preferably, the temperature rising rate of the second temperature rising heating is 5-10 ℃/min;
preferably, the end temperature of the second heating temperature is 937-945 ℃;
preferably, the heating time of the second heating temperature is 10-12h;
preferably, the cooling rate of the second cooling and heating is 1-2 ℃/min;
preferably, the end temperature of the second cooling and heating is 490-510 ℃;
preferably, the heating time of the second cooling and heating is 1-3h.
10. The preparation method according to any one of claims 1 to 9, characterized in that the preparation method comprises the steps of:
(1) Mixing Yb source, ba source and Cu source in the molar ratio of 1 (1.9-2.2) (2.9-3.3), ball milling at 258-310r/min for 2-4 hr, and stoving at 60-70 deg.c for 10-15 hr to obtain mixed powder;
(2) Heating the mixed powder obtained in the step (1) to 937-945 ℃ at a heating rate of 5-10 ℃/min under an oxygen atmosphere, heating for 10-12h, and then cooling to 490-510 ℃ at a cooling rate of 1-2 ℃/min for heating for 1-3h to obtain precursor powder;
(3) Cold pressing the precursor powder obtained in the step (2) at the pressure of 2-3t, and demoulding to obtain a block blank;
(4) Heating the block blank obtained in the step (3) to 937-945 ℃ at a heating rate of 5-10 ℃/min under an oxygen atmosphere, heating for 10-12h, and then cooling to 490-510 ℃ at a cooling rate of 1-2 ℃/min for heating for 1-3h to obtain the YbBCO superconducting block.
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