CN114775033A - Holmium-bismuth magnetic refrigeration material and preparation method and application thereof - Google Patents
Holmium-bismuth magnetic refrigeration material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 119
- 238000005057 refrigeration Methods 0.000 title claims abstract description 95
- ZENJQEGOGPMIBF-UHFFFAOYSA-N bismuth holmium Chemical compound [Ho].[Bi] ZENJQEGOGPMIBF-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 230000008859 change Effects 0.000 claims abstract description 31
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- 230000007704 transition Effects 0.000 claims abstract description 15
- 239000001307 helium Substances 0.000 claims abstract description 14
- 229910052734 helium Inorganic materials 0.000 claims abstract description 14
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000005347 demagnetization Effects 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000010453 quartz Substances 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 23
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Abstract
A holmium-bismuth magnetic refrigeration material and a preparation method and application thereof belong to the technical field of magnetic refrigeration, the holmium-bismuth magnetic refrigeration material is a holmium-bismuth single crystal material or a holmium-bismuth polycrystalline material, and the holmium-bismuth magnetic refrigeration material has the chemical formula: HoBi having a sodium chloride type cubic crystal structure with a space group ofFm‑3mThe phase transition temperature of the holmium-bismuth magnetic refrigeration material is 3.7K and 6K; both the holmium-bismuth monocrystal and the polycrystalline material can be used for multistage refrigeration and adiabatic demagnetization in a liquid helium temperature region, and the invention provides a preparation method of the holmium-bismuth monocrystal and the polycrystalline material. The holmium-bismuth magnetic refrigeration material provided by the invention has no hysteresis characteristic, can realize high magnetic entropy change in a liquid helium temperature region, has a larger low-field continuous positive and negative magnetocaloric effect under a high magnetic field condition, has a larger negative magnetocaloric effect under a high field condition, can be used for a common magnetic refrigeration technology, and can be applied to the aspects of multistage refrigeration and adiabatic demagnetization technologies.
Description
Technical Field
The invention belongs to the technical field of magnetic refrigeration, and particularly relates to a holmium-bismuth magnetic refrigeration material as well as a preparation method and application thereof.
Background
The refrigeration technology plays a very important role in the production and life of human beings, and the refrigeration technology cannot be separated from the daily life of people to industrial and agricultural production, medical treatment and health, national defense science and technology and the like. With the advance of industrialization process and the improvement of human living standard, people have greater and greater demands for refrigeration, and huge energy consumption and environmental pressure are inevitably brought. The refrigeration equipment commonly used at present, such as an air conditioner, a refrigerator and the like, adopts the conventional gas expansion and compression refrigeration, the refrigeration technology has low thermal efficiency, substances such as Freon and the like polluting the environment are used as refrigerant, the substances are the first culmination of destroying the ozone layer, the irreversible greenhouse effect is brought to the world, and the ecological stability and the human health are directly threatened. Under the concept of advocating environmental protection and energy conservation all over the world, product upgrading, material iteration and technical innovation are great trends.
Magnetic refrigeration technology based on the magnetocaloric effect (MCE) is a new type of refrigeration technology that has gradually moved from basic scientific research to application research in recent years. The magnetic refrigeration adopts solid magnetic substances as refrigeration working media, so that compression equipment is not needed, and environmental pollution is avoided, so that the magnetic refrigeration equipment is more small, convenient, stable, reliable, efficient, energy-saving and environment-friendly. The material which can be used as the magnetic refrigeration working medium is called as the magnetic refrigeration material, a proper refrigeration cycle mode is selected, and the refrigeration working medium and the external environment are subjected to heat exchange by adding a magnetic field and a demagnetizing field, so that the aim of refrigeration can be fulfilled.
The key to realizing magnetic refrigeration is to obtain a magnetic refrigeration material with excellent performance, wherein entropy change (Delta S) is the most important parameter for measuring the magnetic refrigeration material. The magnitude of the magnetic entropy change is directly related to the severity of the change in magnetic order, so the peak in magnetic entropy change occurs at a location near the phase transition temperature. Therefore, a magnetic refrigeration material required for a magnetic refrigeration technology is a material capable of generating a large magnetocaloric effect in the vicinity of a phase transition. However, these giant magnetocaloric effect (GMCE) materials are realized by first order magnetic phase transition (FOMT), accompanied by large thermal hysteresis and magnetic hysteresis, which means that a large amount of energy is lost in the refrigeration cycle, so that the refrigeration efficiency is reduced, adversely affecting the practical application of the magnetic refrigeration material. Therefore, thermomagnetic reversibility of the material is a prerequisite for excellent magnetic refrigeration performance, and reversibility of the effect of the material upon magnetic field and temperature oscillation must be ensured in the refrigeration cycle.
According to the division of the working temperature zone, the magnetic refrigeration materials can be divided into extremely low temperature (below 10K), low temperature (10K-80K), medium temperature (80K-250K) and high temperature (above 250K) magnetic refrigeration materials. At present, the development of high, precise and sharp is scientifically realized without the low temperature and extremely low temperature environment, and helium can be liquefied by using a magnetic refrigeration technology, so that magnetic refrigeration materials near the temperature of liquid helium (4.2K) are more and more concerned. The phase-change temperature of the known magnetic refrigeration material is generally higher, so that the material is not suitable for helium liquefaction. In order to meet the increasing low-temperature requirement of China, the exploration of novel materials with low-temperature large magnetocaloric effect has important practical significance for the application of low-temperature magnetic refrigeration technology.
The magnetocaloric effect is classified as negative MCE (Δ S) according to the positive and negative values of the magnetic entropy changeM<0) And positive MCE (. DELTA.S)M>0) Recently, it has been found that the continuous positive and negative magnetocaloric effect of the material is of great value in realizing adiabatic magnetization and multi-stage refrigeration of a refrigerator. Materials with continuous positive and negative magnetic entropy changes exist only in first-order phase change materials, most positive magnetocaloric effect phenomena reported to date show smaller magnetic entropy change values, and can only be kept under a low magnetic field condition, and with the increase of a magnetic field, antiferromagnetic coupling is weakened, so that positive MCE disappears.
The development and application of the magnetic refrigeration technology depend on the continuous improvement of the performance of the magnetic refrigeration material, how to prepare the hysteresis-free magnetic refrigeration material with the magnetic phase transition temperature of about 4K, and the high continuous positive and negative magnetic entropy change can be realized, so that the method not only has important commercial value for the low-temperature magnetic refrigeration technology, but also has potential effect on the development and design of a novel magnetic refrigerator.
Disclosure of Invention
The currently known continuous positive and negative magnetic entropy change materials only exist in a first-stage phase change magnetic refrigeration material, and energy loss in thermomagnetic circulation can be caused due to the lag problem; the phase change temperature of the known magnetic refrigeration material is generally higher, so that the material is not suitable for helium liquefaction; the positive magnetocaloric effect generally disappears under high magnetic field conditions. The present invention is to overcome the above-mentioned drawbacks of the prior art, and aims to provide a low-temperature magnetic refrigeration material which has no hysteresis, can realize high magnetic entropy change in an extremely low temperature region, has a large magnetocaloric effect in a low field, and can maintain continuous positive and negative magnetocaloric effects in a high magnetic field.
The invention is realized by the following technical scheme:
a holmium-bismuth magnetic refrigeration material has a chemical formula as follows: HoBi having a sodium chloride type cubic crystal structure with a space group ofFm-3m(ii) a The holmium-bismuth magnetic refrigeration material is a single crystal material or a polycrystalline material, has the phase transition temperature of 3.7K and 6K, and is suitable for refrigeration of a liquid helium temperature zone; the lattice parameter of the holmium-bismuth single crystal material isa= b = c =6.223 ± 0.02 a, the lattice parameter of the holmium-bismuth polycrystalline material beinga=b=c=6.234±0.02 Å。
Further, the size of the holmium-bismuth magnetic refrigeration material is 3-5 mm.
Furthermore, the holmium-bismuth magnetic refrigeration material has magnetic reversibility below 6K and thermal reversibility in the whole temperature range of 2K-300K.
Further, the [100] is positioned in the holmium-bismuth single crystal material]The direction is as follows: under the condition of 0-2T magnetic field change, the positive magnetic entropy changes to a peak value deltaS M 13.1J/kgK; under the condition of 0-5T magnetic field change, the negative magnetic entropy changes to peak value-deltaS M is-18J/kgK.
Further, under the condition of 0-2T magnetic field change, the positive magnetic entropy change peak value delta of the holmium-bismuth polycrystalline materialS M Is 6J/kgK, and the negative magnetic entropy changes to peak value-deltaS M Is 3J/kgK; under the condition of 0-5T magnetic field change, the negative magnetic entropy changes to peak value-deltaS M is-15J/kgK.
The holmium-bismuth monocrystal material and the holmium-bismuth polycrystal material have large positive magnetocaloric effect under low field and large negative magnetocaloric effect under high field, and the excellent performance can be used for multistage refrigeration and adiabatic demagnetization.
A preparation method of a holmium-bismuth magnetic refrigeration material (monocrystal) comprises the following steps:
s1, weighing a block Ho raw material and a granular metal Bi raw material according to an atomic ratio of 1: 10-1: 15;
s2, firstly, mixing the raw materials weighed in the step S1, putting the mixture into an alumina crucible, and covering quartz wool above the alumina crucible; then, placing the alumina crucible in a tantalum tube, and tightly covering a cover of the tantalum tube by using external pressure, wherein the thickness of the wall of the tantalum tube has no requirement, and the size of the tantalum tube is matched with that of the alumina crucible; finally, vacuumizing and filling argon into the quartz tube, sealing the quartz tube by oxyhydrogen flame, and sealing the alumina crucible in the vacuum quartz tube to protect the sample from being oxidized in the next heat treatment process;
s3, single crystal growth: heating the vacuum quartz tube sealed in the step S2 from room temperature to 900 +/-50 ℃, preserving heat for 5-10 hours, and then slowly cooling to 400 +/-10 ℃ at a cooling speed of 4 +/-1K/h;
and S4, taking out the vacuum quartz tube cooled in the step S3, and then quickly putting the vacuum quartz tube into a centrifuge to separate the sample from the Bi liquid to prepare the holmium-bismuth single crystal material.
The application of the holmium-bismuth monocrystal cold material prepared by the preparation method comprises the following steps: the liquid helium temperature zone is used for hysteresis-free low-field magnetic refrigeration, and is used for hysteresis-free multi-stage refrigeration and adiabatic demagnetization under a high field.
A preparation method of a holmium-bismuth magnetic refrigeration material (polycrystal) comprises the following steps:
s1, weighing a granular metal Bi raw material and a blocky Ho raw material according to the atomic ratio of 1: 1; wherein the purity of the blocky Ho raw material is 99.99%;
s2, firstly, mixing the raw materials weighed in the step S1, putting the mixture into an alumina crucible, then, putting the alumina crucible into a quartz tube, vacuumizing and filling argon into the quartz tube, sealing the quartz tube by oxyhydrogen flame, and sealing the alumina crucible in a vacuum quartz tube;
s3, polycrystalline growth: heating the sealed vacuum quartz tube obtained in the step S2 from room temperature to 900 +/-50 ℃, preserving heat for 5-10 hours, and then slowly cooling to room temperature at a cooling speed of 4 +/-1K/h;
s4, taking out the vacuum quartz tube cooled in the step S3 to obtain a holmium-bismuth polycrystalline powder material;
s5, putting the powder sample obtained in the step S4 into an agate mortar for extrusion grinding for 5-10min to obtain a refined powder sample;
s6, putting the sample obtained in the step S5 into a die of a tablet press for tabletting, wherein the inner diameter of the die is 1cm, the applied pressure is 20MPa, and standing for 3-10min after tabletting treatment to obtain the holmium-bismuth polycrystalline material.
The application of the holmium-bismuth polycrystalline material prepared by the preparation method comprises the following steps: the liquid helium temperature zone is used for hysteresis-free multistage refrigeration and adiabatic demagnetization in a low field.
Compared with the prior art, the invention has the beneficial effects that:
1. the holmium-bismuth magnetic refrigeration material has extremely low magnetic phase transition temperature and working temperature, and is suitable for extremely low temperature refrigeration application of a liquid helium temperature zone.
2. For holmium-bismuth single crystal materials: the high-temperature-resistant high-temperature-resistant medium has a large low-field magnetocaloric effect, can keep a large continuous positive and negative magnetocaloric effect under a high field, and can be applied to a general low-temperature magnetic refrigeration technology and can be applied to a multi-stage refrigeration and adiabatic demagnetization technology;
for holmium-bismuth polycrystalline materials: the magnetic refrigeration system has larger continuous positive and negative magnetocaloric effect in low field and larger negative magnetocaloric effect in high field, can be used for common magnetic refrigeration technology, and can be applied to the aspects of multistage refrigeration and adiabatic demagnetization technology.
3. The holmium-bismuth monocrystal material and the holmium-bismuth polycrystalline material provided by the invention are special first-stage phase change materials with no hysteresis characteristic, and do not cause energy loss in the magnetocaloric cycle.
4. High-temperature heating is not needed in the preparation process of the holmium-bismuth magnetic refrigeration material, and compared with electric arc melting or induction melting, the holmium-bismuth magnetic refrigeration material has the advantages of low energy consumption and low cost.
5. A sealing sintering preparation technology is adopted in the preparation process of the holmium-bismuth magnetic refrigeration material, the mass loss caused by element volatilization does not need to be considered, and the impure phase is not introduced.
Drawings
FIG. 1 is a topographical view of a holmium-bismuth single-crystal material prepared in example 1;
fig. 2 is an XRD pattern of the holmium-bismuth single-crystal material prepared in example 1;
FIG. 3 is a thermomagnetic graph of a holmium-bismuth single-crystal material prepared in example 1;
FIG. 4 is a hysteresis loop diagram of the holmium-bismuth single-crystal material prepared in example 1 at a temperature of 2K and with a magnetic field parallel to the [100] direction;
FIG. 5 is a graph showing the magnetic entropy change of the holmium-bismuth single-crystal material prepared in example 1 in a direction in which the magnetic field is parallel to [100 ].
Fig. 6 is an XRD pattern of the holmium-bismuth polycrystalline material prepared in example 2;
fig. 7 is a graph of the magnetic entropy change of the holmium-bismuth polycrystalline material prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A preparation method of a holmium-bismuth magnetic refrigeration material comprises the following steps:
s1, weighing a blocky Ho raw material and a granular metal Bi raw material according to an atomic ratio of 1: 10; wherein the purity of the block Ho raw material is 99.99%;
s2, firstly, selecting a proper cylindrical alumina crucible according to the raw materials weighed in the step S1, mixing the raw materials weighed in the step S1, putting the mixture into the alumina crucible, and covering quartz wool above the alumina crucible, wherein the purpose of the quartz wool is to ensure that a HoBi sample obtained in centrifugation is separated from redundant cosolvent Bi; then, placing the alumina crucible in a tantalum tube, and tightly covering the tantalum tube by using external pressure; finally, vacuumizing and filling argon into the quartz tube, sealing the quartz tube by oxyhydrogen flame, and sealing the alumina crucible in the vacuum quartz tube;
s3, single crystal growth: heating the vacuum quartz tube sealed in the step S2 from room temperature to 900 ℃, preserving heat for 5 hours, and then slowly cooling to 400 ℃ at a cooling speed of 4K/h;
s4, taking out the vacuum quartz tube cooled in the step S3, then quickly putting the vacuum quartz tube into a centrifuge, separating the sample from the Bi liquid, and making the redundant Bi liquid flow into the tantalum tube through quartz wool at the moment to prepare the holmium-bismuth single crystal material, wherein the shape and appearance of the holmium-bismuth single crystal material are shown in figure 1, and the sizes of the holmium-bismuth single crystal material are respectively 3mm and 5 mm.
The holmium-bismuth monocrystal material prepared by the preparation method in the embodiment 1 is used for multistage refrigeration and adiabatic demagnetization in a liquid helium temperature region, and has a chemical formula as follows: HoBi, it can be seen from FIG. 2 that the holmium-bismuth single-crystal material prepared in this example 1 hasA sodium chloride type cubic crystal structure having a lattice parameter ofa= b = c = 6.234A, spatial groupFm-3m(ii) a The holmium-bismuth single crystal material obtained in this example 1 was measured for a thermomagnetic (M-T) curve at a magnetic field strength H of 100Oe using a magnetic measurement system (SQUID-VSM), and the result is shown in fig. 3. Two phase transition temperatures of the holmium-bismuth single crystal material can be determined from a zero field cooling M-T curve, wherein the two phase transition temperatures are respectively 3.7K and 6K, the phase transition temperature of the holmium-bismuth single crystal material belongs to a liquid helium temperature region, the phase transition temperature of the holmium-bismuth single crystal material is a first-level antiferromagnetic-paramagnetic phase transition, and the holmium-bismuth single crystal material has thermal reversibility in a phase transition temperature range of 3.7K-6K; a hysteresis loop (shown in figure 4) of the holmium-bismuth single crystal material prepared in the embodiment 1 at the temperature of 2K is measured on the SQUID-VSM, the holmium-bismuth single crystal material shows multi-stage phase change induced by a magnetic field, the holmium-bismuth single crystal material has magnetic reversibility below the phase change temperature, M-T curves of zero field cooling and band field cooling are completely overlapped in the whole temperature interval, and no thermal hysteresis is generated.
Further, the isothermal magnetization curve of the HoBi material prepared in the example 1 was measured on SQUID-VSM, and the magnetic entropy change was calculated from the isothermal magnetization curve according to maxwell's relationship, as shown in fig. 4, with two continuous positive and negative magnetic entropy change peaks, wherein the positive magnetic entropy change peak Δ was observed under the condition of 0-2T magnetic field changeS M Is 13.1J/kgK which is larger than other magnetic refrigeration materials; under the condition of 0-5T magnetic field change, the positive magnetic entropy changes to peak value deltaS M Can still maintain 5.6J/kgK, and the negative magnetic entropy changes to peak value-deltaS M is-18J/kgK. Therefore, the holmium-bismuth single crystal material prepared in the embodiment 1 has a large positive magnetocaloric effect under a low field, can maintain a continuous large positive and negative magnetocaloric effect under a high field, and can be used for multistage refrigeration and adiabatic demagnetization.
Example 2
A preparation method of a holmium-bismuth polycrystalline material comprises the following steps:
s1, weighing a granular metal Bi raw material and a blocky Ho raw material according to an atomic ratio of 1: 1; wherein the purity of the block Ho raw material is 99.99%;
s2, firstly, selecting a proper cylindrical alumina crucible according to the raw materials weighed in the step S1, mixing the raw materials weighed in the step S1 and then putting the mixture into the alumina crucible, then, placing the alumina crucible into a quartz tube, vacuumizing the quartz tube and filling argon, and sealing the quartz tube by oxyhydrogen flame;
s3, polycrystalline growth: heating the vacuum quartz tube sealed in the step S2 from room temperature to 900 ℃, preserving heat for 5 hours, and then slowly cooling to room temperature at a cooling speed of 4K/h;
s4, taking out the vacuum quartz tube cooled in the step S3 to obtain a holmium-bismuth polycrystalline powder material;
s5, putting the powder sample obtained in the step S4 into an agate mortar, extruding and grinding for 5min to obtain a refined powder sample;
and S6, putting the sample obtained in the step S5 into a die of a tablet press for tabletting, wherein the inner diameter of the die is 1cm, the applied pressure is 20MPa, and standing for 3min after tabletting treatment to obtain the holmium-bismuth polycrystalline material.
The holmium-bismuth polycrystalline material prepared by the preparation method of the embodiment 2 has a chemical formula: HoBi having a sodium chloride type cubic crystal structure with a lattice parameter ofa= b = c =6.234 ± 0.02 a, the spatial group beingFm-3mAs in fig. 6.
The holmium-bismuth polycrystalline material has magnetic reversibility at a neel temperature of below 6K, and has thermal reversibility in a whole range from low temperature of 2K-300K to room temperature.
Under the condition of 0-2T magnetic field change of the holmium-bismuth polycrystalline material, the positive magnetic entropy change peak value deltaS M The flux density is 6J/kgK, and the negative magnetic entropy variation peak value is 3J/kgK; under the condition of 0-5T magnetic field change, the negative magnetic entropy changes to peak value-deltaS M The magnetic field strength is-15J/kgK, and the magnetic field strength has large positive magnetocaloric effect under a low field and large negative magnetocaloric effect under a high field, and can be used for multi-stage refrigeration and adiabatic demagnetization as shown in figure 7.
The performance pairs of the holmium-bismuth magnetic refrigeration materials prepared in the examples 1 and 2 and other low-temperature continuous positive and negative magnetocaloric effect materials are shown in the table below.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. A holmium-bismuth magnetic refrigeration material is characterized in that: the holmium-bismuth magnetic refrigeration material has the chemical formula as follows: HoBi having a sodium chloride type cubic crystal structure with a space group ofFm-3m(ii) a The holmium-bismuth magnetic refrigeration material is a monocrystalline material or a polycrystalline material, and the phase transition temperature is 3.7K and 6K; the lattice parameter of the holmium-bismuth single crystal material isa= b = c =6.223 ± 0.02 a, the lattice parameter of the holmium-bismuth polycrystalline material beinga=b=c=6.234±0.02 Å。
2. The holmium-bismuth magnetic refrigeration material according to claim 1, characterized in that: the size of the holmium-bismuth magnetic refrigeration material is 3-5 mm.
3. The holmium-bismuth magnetic refrigeration material according to claim 1, characterized in that: the holmium-bismuth magnetic refrigeration material has magnetic reversibility below the phase transition temperature of 6K, and has thermal reversibility in the whole temperature range of 2K-300K.
4. The holmium-bismuth magnetic refrigeration material according to claim 1, characterized in that: is positioned in [100] of the holmium-bismuth single crystal material]Direction: under the condition of 0-2T magnetic field change, the positive magnetic entropy changes to a peak value deltaS M 13.1J/kgK; under the condition of 0-5T magnetic field change, the negative magnetic entropy changes to peak value-deltaS M is-18J/kgK.
5. The holmium-bismuth magnetic refrigeration material according to claim 1, characterized in that: under the condition of 0-2T magnetic field change, the positive magnetic entropy change peak value delta of the holmium-bismuth polycrystalline materialS M Is 6J/kgK, and the negative magnetic entropy changes to peak value-deltaS M is-3J/kgK; under the condition of 0-5T magnetic field changeNegative magnetic entropy variation peak value-deltaS M is-15J/kgK.
6. A method for preparing the holmium-bismuth magnetic refrigeration material as claimed in claim 1, which is characterized by comprising the following steps of:
s1, weighing a block Ho raw material and a granular metal Bi raw material according to an atomic ratio of 1: 10-1: 15;
s2, firstly, mixing the raw materials weighed in the step S1, putting the mixture into an alumina crucible, and covering quartz wool above the alumina crucible; then, the alumina crucible is placed in the tantalum tube, and the cover of the tantalum tube is tightly covered by using external pressure; finally, vacuumizing and filling argon into the quartz tube, sealing the quartz tube by oxyhydrogen flame, and sealing the alumina crucible in the vacuum quartz tube;
s3, single crystal growth: heating the vacuum quartz tube sealed in the step S2 from room temperature to 900 +/-50 ℃, preserving heat for 5-10 hours, and then slowly cooling to 400 +/-10 ℃ at a cooling speed of 4 +/-1K/h;
s4, taking out the vacuum quartz tube cooled in the step S3, and then quickly putting the vacuum quartz tube into a centrifuge to separate the sample from the Bi liquid to obtain the holmium-bismuth monocrystal material.
7. Use of the holmium-bismuth single-crystal material produced by the production method according to claim 6, characterized in that: the magnetic refrigeration system is used for reversible low-field magnetic refrigeration in a liquid helium temperature region and reversible multi-stage refrigeration and adiabatic demagnetization in a high field.
8. A method for preparing the holmium-bismuth magnetic refrigeration material as claimed in claim 1, which is characterized by comprising the following steps of:
s1, weighing a granular metal Bi raw material and a blocky Ho raw material according to the atomic ratio of 1: 1;
s2, firstly, mixing the raw materials weighed in the step S1, putting the mixture into an alumina crucible, then, putting the alumina crucible into a quartz tube, vacuumizing and filling argon into the quartz tube, sealing the quartz tube by oxyhydrogen flame, and sealing the alumina crucible in a vacuum quartz tube;
s3, polycrystalline growth: heating the vacuum quartz tube sealed in the step S2 from room temperature to 900 +/-50 ℃, preserving the heat for 5-10 hours, and then slowly cooling to room temperature at a cooling speed of 4 +/-1K/h;
s4, taking out the vacuum quartz tube cooled in the step S3 to obtain a holmium-bismuth polycrystalline powder material;
s5, putting the powder sample obtained in the step S4 into an agate mortar, extruding and grinding for 5-10min to obtain a refined powder sample;
and S6, putting the sample obtained in the step S5 into a die of a tablet press for tabletting, wherein the inner diameter of the die is 1cm, the applied pressure is 20MPa, and standing for 3-10min after tabletting treatment to obtain the holmium-bismuth polycrystalline material.
9. Use of the holmium-bismuth polycrystalline material prepared by the preparation method according to claim 8, characterized in that: the liquid helium temperature zone is used for reversible multistage refrigeration and adiabatic demagnetization under a low field.
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| US20030051774A1 (en) * | 2001-03-27 | 2003-03-20 | Akiko Saito | Magnetic material |
| CN105347797A (en) * | 2015-10-10 | 2016-02-24 | 东北大学 | R2Cu2O5 oxide material used for low-temperature magnetic refrigeration and preparation method thereof |
| JPWO2021157735A1 (en) * | 2020-02-05 | 2021-08-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030051774A1 (en) * | 2001-03-27 | 2003-03-20 | Akiko Saito | Magnetic material |
| CN105347797A (en) * | 2015-10-10 | 2016-02-24 | 东北大学 | R2Cu2O5 oxide material used for low-temperature magnetic refrigeration and preparation method thereof |
| JPWO2021157735A1 (en) * | 2020-02-05 | 2021-08-12 |
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