CN114597011A - Composite magnetic refrigeration material based on primary and secondary phase-change materials and preparation method thereof - Google Patents
Composite magnetic refrigeration material based on primary and secondary phase-change materials and preparation method thereof Download PDFInfo
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- CN114597011A CN114597011A CN202210266608.3A CN202210266608A CN114597011A CN 114597011 A CN114597011 A CN 114597011A CN 202210266608 A CN202210266608 A CN 202210266608A CN 114597011 A CN114597011 A CN 114597011A
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- 230000005291 magnetic effect Effects 0.000 title claims abstract description 61
- 238000005057 refrigeration Methods 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 47
- 239000012782 phase change material Substances 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 10
- 230000007704 transition Effects 0.000 claims description 4
- 238000009689 gas atomisation Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000003507 refrigerant Substances 0.000 claims 1
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002490 spark plasma sintering Methods 0.000 description 2
- 108010053481 Antifreeze Proteins Proteins 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/017—Compounds
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B30/00—Energy efficient heating, ventilation or air conditioning [HVAC]
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Hard Magnetic Materials (AREA)
Abstract
A composite magnetic refrigeration material based on primary and secondary phase-change materials and a preparation method thereof belong to the field of magnetic refrigeration materials in magnetic functional materials. One magnetic refrigeration material (A) based on a primary phase change magnetocaloric effect and the other magnetic refrigeration material (B) based on a secondary phase change magnetocaloric effect are selected, wherein the primary phase change magnetic refrigeration material (A) has strong brittleness, and the secondary phase change magnetic refrigeration material (B) has high mechanical property. The composite magnet of the primary phase-change material magnetic refrigeration material (A) and the secondary phase-change material magnetic refrigeration material (B) prepared according to the invention can improve the dilution of the non-phase-change material to the magnetocaloric property, and has higher mechanical property and heat conduction property.
Description
Technical Field
The patent discloses a design scheme of a composite magnetic refrigeration alloy based on a first-stage phase change material and a second-stage phase change material, and belongs to the field of magnetic refrigeration materials in magnetic functional materials.
Background
The magnetic refrigeration technology based on the magnetocaloric effect (MCE) is a technology for replacing the traditional refrigeration method, and has the advantages of high efficiency, high reliability, low noise, environmental friendliness and the like. The technology depends on a working medium with a larger magnetocaloric effect, and can effectively absorb heat when the magnetic field is reduced in the heat insulation process; in an isothermal process, heat is efficiently released when the magnetic field is increased. Therefore, solving the problems faced by various MCE materials is crucial to the development of magnetic refrigeration applications.
Magnetic refrigeration materials can be divided into primary and secondary phase change materials. In the first-order phase-change magnetic refrigeration material, the structure and magnetism can be changed simultaneously, and the huge magnetocaloric effect is accompanied. Common first-order phase change materials comprise Gd series compounds and NaZn13And MM' X compounds. Wherein, taking MM 'X compound as an example, M and M' represent transition group metal elements, and X represents main group elements. They have Ni2The In-type crystal structure generates a great magnetocaloric effect during the phase transition and is accompanied by a great expansion of volume, which usually causes the compound itself to be more brittle and even to be cracked. In the second-stage phase-change magnetocaloric material, only magnetic phase change occurs, for example, metal Gd is changed from a ferromagnetic state to a paramagnetic state, and the process hardly has thermal hysteresis, and volume change affecting mechanical properties is not generated. Meanwhile, Gd has extremely high strength and toughness, and can be processed into a rich shape for convenient use. In order to meet the application of magnetic refrigeration equipment, magnetic refrigeration materials have extremely high requirements on mechanical properties, so researchers usually adopt a non-magnetic material to be compounded with a primary phase-change material to improve brittleness, but the compounding can dilute the magnetocaloric properties of the primary phase-change material, so that the loss of the magnetocaloric properties is caused.
Disclosure of Invention
The invention provides a design scheme of a composite magnetic refrigeration alloy based on a primary phase-change material and a secondary phase-change material, which is characterized by solving the performance loss of the composite magnetic refrigeration alloy containing a non-phase-change material and simultaneously obtaining good mechanical property and heat conduction property.
In the invention, the composition of the magnetic refrigeration alloy is not particularly limited, as long as one magnetic refrigeration material (A) based on the first-stage phase change magnetocaloric effect and the other magnetic refrigeration material (B) based on the second-stage phase change magnetocaloric effect are selected to be uniformly and very combined into a whole, wherein the first-stage phase change magnetic refrigeration material (A) has strong brittleness, and the second-stage phase change magnetic refrigeration material (B) has high mechanical property;
further preferably, the magnetic refrigeration material (A) is selected from Mn0.8Fe0.2NiSi0.84Ga0.16The magnetic refrigeration material (B) is selected from Gd. The relationship between the amounts of the magnetic refrigeration material (a) and the magnetic refrigeration material (B) is not limited, and is adjusted as needed.
The invention also provides a preparation method of the composite magnetic refrigeration material, which comprises the following steps:
preparing magnetic refrigeration material (A) particles with a primary phase change magnetocaloric effect;
preparing magnetic refrigeration material (B) particles with a secondary phase change magnetocaloric effect;
step three, uniformly mixing the particles (A) and (B) obtained in the step one and the step two;
step four, the mixed powder obtained in the step three is made into a block by a cold pressing or sintering mode;
according to an embodiment of the preparation method of the present invention, in the first step and the second step, the method for preparing the (a) and (B) particles may be vacuum melting, rotary electrode gas atomization, melt rapid quenching, ball milling, evaporation and condensation, and the like.
The invention also provides application of the composite magnetic refrigeration material prepared by any one of the methods.
Compared with the prior art, the invention has the following beneficial effects:
1. the composite magnet of the first-stage phase-change magnetic refrigeration material (A) and the second-stage phase-change magnetic refrigeration material (B) prepared according to the invention can improve the dilution of the non-phase-change material to the magnetocaloric performance.
2. The composite magnet of the first-stage phase-change magnetic refrigeration material (A) and the second-stage phase-change magnetic refrigeration material (B) prepared according to the invention has higher mechanical property.
3. The composite magnet of the first-stage phase-change magnetic refrigeration material (A) and the second-stage phase-change magnetic refrigeration material (B) prepared according to the invention has higher heat conduction performance.
Drawings
Embodiments of the invention are described below with reference to the accompanying drawings, in which:
fig. 1 is a graph of the change in magnetic entropy versus temperature of block magnets 1#, 2#, 3#, and 4# in embodiment 1 of the present invention;
fig. 2 is a graph of compressive strength versus temperature for bulk magnets 1#, 2#, 3#, 4# of example 1 of the present invention;
fig. 3 is a graph of thermal conductivity versus temperature for bulk magnets 1#, 2#, 3#, and 4# of example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1: this example selects the first order phase change alloy Mn0.8Fe0.2NiSi0.84Ga0.16Is sintered and compounded with a secondary phase change material Gd through discharge plasma sintering (SPS). The preparation method comprises the following specific steps:
step one, according to Mn: fe: ni: si: ga ═ 0.8: 0.2: 1: 0.84: raw materials of Mn, Fe, Ni, Si, Ga and the like with the purity of 99.9 percent are weighed respectively according to the molar ratio of 0.16; smelting the sample by a suspension smelting method for 4 times to ensure uniform components, annealing for 72 hours at 1000 ℃ under vacuum, and then throwing the sample into ice water at high temperature for quenching to obtain a quenched sample; preparing a particle sample with the particle size range of 75-150 mu m by a manual grinding method;
preparing Gd particles into particles within the range of 75-150 mu m by a rotary electrode gas atomization method;
step three, Mn obtained in the step one and the step two0.8Fe0.2NiSi0.84Ga0.16And Gd particles are mixed according to the mass ratio of 1: 1, uniformly mixing;
and step four, sintering the mixed powder obtained in the step three at 500 ℃, 550 ℃, 600 ℃ and 650 ℃ respectively in a Spark Plasma Sintering (SPS) mode, wherein the sintering pressure is 500MPa, and finally preparing the block.
The blocks with sintering temperature of 500 deg.C, 550 deg.C, 600 deg.C and 650 deg.C are respectively designated as No. 1, No. 2, No. 3 and No. 4. The curves of the magnetic entropy changes and the temperature of the block magnets 1#, 2#, 3#, and 4# obtained in the present embodiment are shown in fig. 1. As can be seen from FIG. 1, the maximum magnetic entropy of the 1# composite magnet became 6.0J/kg.K, the magnetic entropy of the sample became gradually lower as the sintering temperature increased, and the maximum magnetic entropy of the 4# composite magnet became 4.7J/kg.K. The compressive strength versus strain curves of the block magnets 1#, 2#, 3#, and 4# obtained in the present example are shown in fig. 2. As can be seen from fig. 2, the fracture modes of the four composite samples belong to brittle fracture, but the strength is higher, the maximum compressive strength is increased from 309MPa of the 1# sintered sample to 456MPa of the 4# sintered sample, and the strain is increased from 4% to 5.5%, which indicates that the bulk magnets 1#, 2#, 3#, and 4# obtained by the embodiment have better mechanical properties, and the maximum compressive strength of the samples is increased along with the increase of the sintering temperature. The thermal conductivity vs. temperature curves of the block magnets 1#, 2#, 3#, and 4# obtained in this example are shown in fig. 3. As can be seen from FIG. 3, the thermal conductivities of the 1#, 2#, 3#, and 4# composite magnets at the phase transition temperature 291K are 4.77W/m.K, 4.87W/m.K, 4.93W/m.K, and 5.36W/m.K, respectively, and the thermal conductivities of the curves tend to increase with increasing temperature. In addition, as the sintering temperature is increased from 500 ℃ to 650 ℃, the thermal conductivity change interval of the magnet gradually moves to a high position, namely, the thermal conductivity of the sample is gradually increased as the sintering temperature is increased.
Claims (5)
1. A composite magnetic refrigeration material based on a primary phase-change material and a secondary phase-change material is characterized in that a magnetic refrigeration material (A) based on a primary phase-change magnetocaloric effect and another magnetic refrigeration material (B) based on a secondary phase-change magnetocaloric effect are uniformly and very combined into a whole, wherein the primary phase-change magnetic refrigeration material (A) has strong brittleness, and the secondary phase-change magnetic refrigeration material (B) has high mechanical property.
2. The composite magnetic refrigeration material based on the primary and secondary phase change materials as claimed in claim 1Characterized in that the refrigerant material (A) is selected from Mn0.8Fe0.2NiSi0.84Ga0.16The magnetic refrigeration material (B) is selected from Gd.
3. The method for preparing the composite magnetic refrigeration material based on the primary and secondary phase-change materials according to the claim 1 or 2, which is characterized by comprising the following steps:
preparing magnetic refrigeration material (A) particles with a primary phase change magnetocaloric effect;
preparing magnetic refrigeration material (B) particles with a second-stage phase transition magnetocaloric effect;
step three, uniformly mixing the particles (A) and (B) obtained in the step one and the step two;
and step four, preparing the mixed powder obtained in the step three into a block by a cold pressing or sintering mode.
4. The method of claim 3, wherein in the first and second steps, the method for preparing the particles (A) and (B) can be vacuum melting, rotary electrode gas atomization, melt rapid quenching, ball milling, evaporation and condensation, and the like.
5. Use of a composite magnetic refrigeration material based on primary and secondary phase change materials according to claim 1 or 2 as a magnetic refrigeration material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210266608.3A CN114597011A (en) | 2022-03-16 | 2022-03-16 | Composite magnetic refrigeration material based on primary and secondary phase-change materials and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210266608.3A CN114597011A (en) | 2022-03-16 | 2022-03-16 | Composite magnetic refrigeration material based on primary and secondary phase-change materials and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865391A (en) * | 2006-05-19 | 2006-11-22 | 北京工业大学 | Preparation method of multiple units composite room temperature magnetic cooling medium possessing laminated structure |
| CN108735411A (en) * | 2018-06-12 | 2018-11-02 | 北京工业大学 | A kind of lanthanum iron silicon/compound magnetic refrigerating material of gadolinium and its preparation process |
| CN112410596A (en) * | 2020-10-19 | 2021-02-26 | 北京工业大学 | Method for preparing magnetic refrigeration alloy by using Spark Plasma Sintering (SPS) technology |
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- 2022-03-16 CN CN202210266608.3A patent/CN114597011A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865391A (en) * | 2006-05-19 | 2006-11-22 | 北京工业大学 | Preparation method of multiple units composite room temperature magnetic cooling medium possessing laminated structure |
| CN108735411A (en) * | 2018-06-12 | 2018-11-02 | 北京工业大学 | A kind of lanthanum iron silicon/compound magnetic refrigerating material of gadolinium and its preparation process |
| CN112410596A (en) * | 2020-10-19 | 2021-02-26 | 北京工业大学 | Method for preparing magnetic refrigeration alloy by using Spark Plasma Sintering (SPS) technology |
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