CN114678181A - Aluminum-iron-boron magnetic refrigeration material and preparation method thereof - Google Patents

Aluminum-iron-boron magnetic refrigeration material and preparation method thereof Download PDF

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CN114678181A
CN114678181A CN202210294545.2A CN202210294545A CN114678181A CN 114678181 A CN114678181 A CN 114678181A CN 202210294545 A CN202210294545 A CN 202210294545A CN 114678181 A CN114678181 A CN 114678181A
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refrigeration material
magnetic refrigeration
aluminum
boron
iron
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韩昆
霍军涛
王军强
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01F1/015—Metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
    • B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26—Methods of annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/773—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material under reduced pressure or vacuum
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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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Abstract

The invention discloses a preparation method of an aluminum-iron-boron magnetic refrigeration material, which comprises the following steps ofxFe2B2Ingredient type preparationX is more than or equal to 1.0 and less than or equal to 1.35; smelting the raw materials into a master alloy ingot; heating the master alloy ingot by eddy current to obtain a master alloy melt; spraying the master alloy melt onto the surface of a copper roller rotating at a high speed to obtain an as-cast aluminum-iron-boron refrigeration material; and annealing the as-cast aluminum-iron-boron refrigeration material under a vacuum condition to obtain the aluminum-iron-boron magnetic refrigeration material. The method has the advantages of less Al consumption and shorter heat treatment time. The invention also discloses the ferro-aluminum boron magnetic refrigeration material prepared by the preparation method of the ferro-aluminum boron magnetic refrigeration material. The ferro-aluminum boron phase purity in the ferro-aluminum boron magnetic refrigeration material is higher, and the ferro-aluminum boron magnetic refrigeration material has higher magnetic entropy change.

Description

Aluminum-iron-boron magnetic refrigeration material and preparation method thereof
Technical Field
The invention belongs to the field of magnetic refrigeration materials, and particularly relates to an aluminum-iron-boron magnetic refrigeration material and a preparation method thereof.
Background
Magnetic refrigeration is a solid-state refrigeration technology which takes a magnetic material as a working medium and utilizes the magnetocaloric effect to realize refrigeration, and compared with the traditional gas compression type refrigeration, the solid-state refrigeration technology has remarkable advantages in the aspects of energy utilization efficiency and no gas refrigerant, and is beneficial to saving energy and protecting the environment.
Magnetic refrigeration technology is considered to be one of the most promising refrigeration technologies to replace the traditional gas compression refrigeration in the future. The rare earth magnetic refrigeration material has ideal performance, and the existing magnetic refrigeration material is mainly prepared from rare earth.
Chinese patent with the patent number CN113444966A discloses a mixed rare earth ferroboron magnetic refrigeration material and a preparation method thereof, and the material comprises the following chemical components: RExRE'1-x，Fe12B6(ii) a Wherein RE and RE' are one of the rare earth La, Y, Ce and Nd, and x is more than or equal to 0.2 and less than or equal to 0.8. The invention mixes the rare earth RExRE'1-x，Fe12B6The material belongs to
Figure BDA0003561410890000011
Space group of SrNi12B6A crystalline structure. The rare earth iron boron material is prepared by combining electric arc melting of raw materials under the protection of argon gas with a strip casting technology, has simple process, and is suitable for industrial production and application.
However, one of the keys that determine whether the magnetic refrigeration material technology can be taken out of a laboratory and is commercialized is to find a suitable magnetic refrigeration material in a room temperature region. On one hand, the high-performance magnetic refrigeration materials in the room temperature and temperature region are relatively few, and on the other hand, the high-performance magnetic refrigeration materials reported at present generally contain rare earth elements, and the rare earth elements are expensive and rare in content, so that the practical application of the materials is limited. The cost constraint is difficult to commercialize. Therefore, the search for high-performance non-rare earth magnetic refrigeration materials becomes the key of the application of the magnetic refrigeration technology.
It has been found that aluminoferroboron (AlFe)2B2) The intermetallic phase has a good magnetocaloric effect and is very cost-effective, and thus has received attention from researchers. But the traditional preparation method of the ferro-aluminum boron phase has the following defects that 1, 50-200% of excessive Al needs to be consumed to inhibit the FeB phase and improve the purity of the ferro-aluminum boron phase, so that waste is caused; 2. a long time of heat treatment is required; 3. the prepared Al-Fe-B phases have different properties, and the magnetic entropy of the Al-Fe-B phases prepared by a plurality of researchers is changed to 2-3J kg-1K-1(2T), well below 4J kg-1K-1The ideal value of (c).
Therefore, a preparation method of an aluminum-iron-boron magnetic refrigeration material which can reduce heat treatment time, consume less Al and obtain higher aluminum-iron-boron phase purity and higher magnetic entropy change is needed.
Disclosure of Invention
The invention provides a preparation method of an aluminum-iron-boron magnetic refrigeration material, which has the advantages of less Al consumption, shorter heat treatment time, higher aluminum-iron-boron phase purity in the prepared aluminum-iron-boron magnetic refrigeration material and higher magnetic entropy change.
A preparation method of an aluminum-iron-boron magnetic refrigeration material comprises the following steps:
(1) according to AlxFe2B2Preparing raw materials in a component mode, wherein x is more than or equal to 1.0 and less than or equal to 1.35;
(2) smelting the raw materials into a master alloy ingot;
(3) heating the master alloy ingot by vortex to obtain a master alloy melt, and rapidly solidifying the master alloy melt to obtain an as-cast aluminum-iron-boron refrigeration material;
(4) and annealing the as-cast aluminum-iron-boron refrigeration material under a vacuum condition to obtain the final aluminum-iron-boron magnetic refrigeration material.
By adding Al with proper content and combining with the rapid quenching of the rapid solidification process, the size of the FeB phase precipitated first is smaller, and the FeB phase with smaller size passes through the ladle more completelyConversion to AlFe by crystal reaction2B2Phase, thereby obtaining AlFe with higher purity2B2And the components of the finally prepared aluminum-iron-boron magnetic refrigeration material are uniform through an annealing process, so that high magnetic refrigeration performance is obtained.
Lower Al content results in AlFe2B2The phase mass fraction decreases and the non-contributing phase FeB mass fraction increases, impairing performance.
In the step (1), the purity of Al, Fe or B in the raw materials is not less than 98 wt.%.
In the step (2), the smelting process is carried out under the condition of argon or vacuum.
In the step (3), the rapid solidification process parameters are as follows: the cooling rate is as follows: 105–106K/s。
In the step (3), the rapid solidification process comprises the following steps: and spraying the master alloy melt onto the surface of a copper roller rotating at high speed.
In the step (3), the linear speed of the copper roller is 10-50 m/s.
If the linear velocity is too low, the effect of the copper roller rapid quenching method is insufficient, and the prepared material cannot be sufficiently cooled. This will result in peritectic transformation of the prepared material to AlFe2B2The phase process is not thorough enough, the fraction of impure phase is increased, the micro-components of the prepared material are more uneven, and the subsequent homogenization heat treatment effect is poor.
In the step (4), the annealing process parameters are as follows: the annealing temperature is 800-1050 ℃, and the annealing time is 1-24 h.
The intermetallic phase generally requires higher heat treatment temperatures. If the annealing temperature is insufficient, homogenization annealing is insufficient, and the material performance is weakened. If the annealing temperature is higher, excessive burning will be caused, and because the B element is an element with certain volatility, the problem of material oxidation will become serious.
Further, said AlxFe2B2In the formula, x is more than or equal to 1.0 and less than or equal to 1.2, the rotating speed of the copper roller is 12-15 m/s, the annealing temperature is 900-1050 ℃, and the annealing time is 20-24 h.
The Al-Fe-B magnetic refrigeration material is prepared according to the preparation method of the Al-Fe-B magnetic refrigeration material, and the magnetic entropy change of the Al-Fe-B magnetic refrigeration material is not less than 3.5J kg under a 0-2T external magnetic field-1K-1。
Compared with the prior art, the invention has the following excellent effects:
the invention consumes the secondary phase FeB phase by the technical means of copper roller rapid quenching, and converts the FeB phase into AlFe2B2Phase, the growth of FeB phase is not inhibited by a large amount of Al, and AlFe with higher purity is obtained due to the large consumption of FeB phase2B2And then, the components of the obtained aluminum-iron-boron magnetic refrigeration material are uniform through an annealing process, so that higher magnetic refrigeration performance is obtained.
Drawings
FIG. 1 shows Al prepared in examples 1 to 2 of the present invention1.0Fe2B2、Al1.2Fe2B2High performance magnetocaloric samples and Al prepared in comparative examples 1-21.4Fe2B2And Al1.8Fe2B2X-ray diffraction XRD pattern of magnetocaloric samples.
FIG. 2 shows Al obtained in example 2 of the present invention1.2Fe2B2Scanning back-scattered BSE images of high performance magnetocaloric samples in the as-cast state before annealing.
FIG. 3 shows Al obtained in comparative example 1 of the present invention1.4Fe2B2Scanning back-scattered BSE images of magnetocaloric samples in the as-cast state before annealing.
FIG. 4 shows Al obtained in comparative example 2 of the present invention1.8Fe2B2Scanning back-scattered BSE images of magnetocaloric samples in the as-cast state before annealing.
FIG. 5 shows Al prepared in examples 1 to 2 of the present invention1.0Fe2B2、Al1.2Fe2B2High performance magnetocaloric samples and Al prepared in comparative examples 1-21.4Fe2B2And Al1.8Fe2B2Magnetic entropy curve of magnetocaloric samples.
FIG. 6 shows Al prepared in examples 1 to 2 of the present invention1.0Fe2B2、Al1.2Fe2B2High performance magnetocaloric samples and Al prepared in comparative examples 3 to 41.0Fe2B2And Al1.2Fe2B2Magnetic entropy curve of magnetocaloric samples.
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples, which are intended to facilitate the understanding of the invention and are not intended to limit the invention in any way.
Example 1
Preparation of Al1.0Fe2B2High-performance ferro-aluminum boron magnetic refrigeration material:
al, Fe and B with the purity of more than 99.5 wt.% are mixed according to a chemical formula, and the mixture ratio of the Al, Fe and B elements is 1: 2: 2, after the preparation, melting the mixture into a melt in an induction melting furnace (firstly vacuumizing, then backfilling high-purity argon to 0.05MPa), keeping the temperature for a short time, and then pouring the melt into a cylindrical copper mold to obtain a master alloy ingot. The mother alloy cast ingot is inductively melted in the argon atmosphere, and after the mother alloy cast ingot is completely melted, the metal melt is sprayed onto a copper wheel with the rotating speed of 15m/s through the instantaneous pressure difference of 0.045MPa, so that as-cast strip Al is obtained1.0Fe2B2The sample was rapidly solidified. Wrapping the sample with Mo foil, annealing at 900 deg.C for 24 hr in vacuum, and quenching to obtain annealed Al1.0Fe2B2High magnetocaloric properties of the samples. In this example, the width of the strip is about 2mm and the thickness of the strip is about 70 μm.
Example 2
Preparation of Al1.2Fe2B2High-performance ferro-aluminum boron magnetic refrigeration material:
al, Fe and B with the purity of more than 99.5 wt.% are mixed according to a chemical formula, and the mixture ratio of Al, Fe and B is 1.2: 2: 2, after the preparation, melting the mixture into a melt in an induction melting furnace (firstly vacuumizing, then backfilling high-purity argon to 0.05MPa), keeping the temperature for a short time, and then pouring the melt into a cylindrical copper mold to obtain a master alloy ingot. The mother alloy cast ingot is inductively melted in argon atmosphere, and gold is melted completely through instantaneous pressure difference of 0.045MPaThe metal melt is sprayed on a copper wheel with the rotating speed of 15m/s to obtain as-cast strip Al1.2Fe2B2The sample was rapidly solidified. Wrapping the sample with Mo foil, annealing at 900 deg.C for 24 hr in vacuum, and quenching to obtain annealed Al1.2Fe2B2High magnetocaloric properties of the samples. In this example, the width of the strip is about 2mm and the thickness of the strip is about 70 μm.
Comparative example 1
Preparation of Al1.4Fe2B2Aluminum-iron-boron magnetic refrigeration material:
al, Fe and B with the purity of more than 99.5 wt.% are mixed according to a chemical formula, and the mixture ratio of Al, Fe and B is 1.4: 2: 2, after the preparation, melting the mixture into a melt in an induction melting furnace (firstly vacuumizing, then backfilling high-purity argon to 0.05MPa), keeping the temperature for a short time, and then pouring the melt into a cylindrical copper mold to obtain a master alloy ingot. The mother alloy cast ingot is inductively melted in the argon atmosphere, and after the mother alloy cast ingot is completely melted, the metal melt is sprayed onto a copper wheel with the rotating speed of 15m/s through the instantaneous pressure difference of 0.045MPa, so that as-cast strip Al is obtained1.4Fe2B2The sample was rapidly solidified. Wrapping the sample with Mo foil, annealing at 900 deg.C for 24 hr in vacuum, and quenching to obtain annealed Al1.4Fe2B2And (3) magnetically refrigerating the sample with the aluminum, iron and boron. Before testing magnetic properties, the samples were soaked in a 20wt. NaOH solution for about 6 hours to remove Al13Fe4A second phase. In this comparative example, the width of the strip was about 2mm and the thickness of the strip was about 70 μm.
Comparative example 1 is different from the examples in the composition, and Al is more abundant in comparative example 113Fe4The second phase was removed by soaking in a 20wt. NaOH solution prior to magnetic property testing.
Comparative example 2
Preparation of Al1.8Fe2B2Aluminum-iron-boron magnetic refrigeration material:
al, Fe and B with the purity of more than 99.5 wt.% are mixed according to a chemical formula, and the mixture ratio of Al, Fe and B is 1.8: 2: 2 after being prepared, the mixture is melted into a melt in an induction melting furnace (firstly vacuumized, and then backfilled with high-purity argon to 0.05MPa) and is temporarily kept warmAnd then pouring the melt into a cylindrical copper mold to obtain a master alloy ingot. The mother alloy cast ingot is inductively melted in argon atmosphere, and after the mother alloy cast ingot is completely melted, the metal melt is sprayed onto a copper wheel with the rotating speed of 15m/s through the instantaneous pressure difference of 0.045MPa, so that as-cast strip Al is obtained1.8Fe2B2The sample was rapidly solidified. Wrapping the sample with Mo foil, annealing at 900 deg.C for 24 hr in vacuum, and quenching to obtain annealed Al1.8Fe2B2And (3) magnetically refrigerating the sample with the aluminum, iron and boron. Before testing magnetic properties, the samples were soaked in a 20wt. NaOH solution for about 6 hours to remove Al13Fe4A second phase. In this comparative example, the width of the strip was about 2mm and the thickness of the strip was about 70 μm.
Comparative example 2 is different from the examples in the composition, and Al is more abundant in comparative example 213Fe4The second phase was removed by soaking in a 20wt. NaOH solution prior to magnetic property testing.
Comparative example 3
Preparation of Al1.0Fe2B2Aluminum-iron-boron magnetic refrigeration material:
al, Fe and B with the purity of more than 99.5 wt.% are mixed according to a chemical formula, and the mixture ratio of the Al, Fe and B elements is 1: 2: 2, after the preparation, melting the mixture into a melt in an induction melting furnace (firstly vacuumizing, then backfilling high-purity argon to 0.05MPa), keeping the temperature for a short time, and then pouring the melt into a cylindrical copper mold to obtain a master alloy ingot. The mother alloy cast ingot is inductively melted in the argon atmosphere, and after the mother alloy cast ingot is completely melted, the metal melt is sprayed onto a copper wheel with the rotating speed of 15m/s through the instantaneous pressure difference of 0.045MPa, so that as-cast strip Al is obtained1.0Fe2B2The sample was rapidly solidified. In this comparative example, the width of the strip was about 2mm and the thickness of the strip was about 70 μm.
Comparative example 3 differs from example 1 in that comparative example 3 was not subjected to a homogenizing anneal.
Comparative example 4
Preparation of Al1.2Fe2B2Aluminum-iron-boron magnetic refrigeration material:
al, Fe and B with the purity of more than 99.5 wt.% are mixed according to a chemical formula, and the mixture ratio of Al, Fe and B is 1.2: 2: 2 after being prepared, sensingMelting into a melt in a smelting furnace (firstly vacuumizing, then backfilling high-purity argon to 0.05MPa), keeping the temperature for a short time, and then pouring the melt into a cylindrical copper mold to obtain a master alloy ingot. The mother alloy cast ingot is inductively melted in the argon atmosphere, and after the mother alloy cast ingot is completely melted, the metal melt is sprayed onto a copper wheel with the rotating speed of 15m/s through the instantaneous pressure difference of 0.045MPa, so that as-cast strip Al is obtained1.2Fe2B2The sample was rapidly solidified. In this comparative example, the tape width was about 2mm and the tape thickness was about 70 μm.
Comparative example 4 differs from example 2 in that comparative example 4 was not subjected to a homogenizing anneal.
Microstructure and performance testing
The microstructures and the magnetocaloric properties of examples 1 to 2 and comparative examples 1 to 4 were tested.
FIG. 1 is an X-ray diffraction (XRD) pattern of examples 1 to 2 of the present invention and comparative examples 1 to 2, to which AlFe is added2B2Phase standard diffraction peaks. With reference to FIG. 1, Al corresponding to examples 1 to 21.0Fe2B2And Al1.2Fe2B2The main phase of the high-performance magnetocaloric sample is AlFe2B2Phase, with a small amount of FeB secondary phase. While comparative example Al with different Al content1.4Fe2B2And Al1.8Fe2B2The main phase of the Al-Fe-B magnetic refrigeration material is AlFe2B2Phase with a small amount of Al13Fe4And (4) a secondary phase.
FIG. 2 is an as-cast scanning back-scatter (BSE) image of example 2 of the present invention. A and b in FIG. 2 are Al at different magnifications1.2Fe2B2Microstructure of as-cast band, picture showing presence of FeB phase in AlFe2B2Typical peritectic reaction microstructure within the grains.
FIG. 3 is an as-cast scanning back-scatter (BSE) image of comparative example 1 of the present invention. A and b in FIG. 3 are Al at different magnifications1.4Fe2B2The microstructure of the as-cast strip, which has undergone a very large change, is not observed for the presence of the FeB phase, but shows a needle-like crystal structure with direct crystal growth.
FIG. 4 is an as-cast scanning back-scatter (BSE) image of comparative example 2 of the present invention. A and b in FIG. 4 are Al at different magnifications1.8Fe2B2As-cast strip microstructure, similarly to the microstructure of comparative example 1, the presence of FeB phase was not observed, and Al was observed in intergranular regions13Fe4The secondary phase as a whole shows an acicular crystal structure in which crystals are directly grown.
FIG. 5 is a magnetic entropy curve of examples 1 to 2 of the present invention and comparative examples 1 to 2. Compared to comparative example Al which underwent direct crystalline growth1.4Fe2B2And Al1.8Fe2B2Ferro-Al magnetic refrigeration material, example Al undergoing peritectic transformation1.0Fe2B2And Al1.2Fe2B2The high-performance aluminum-iron-boron magnetic refrigeration material has more excellent magnetic thermal performance.
FIG. 6 is a magnetic entropy curve of examples 1 to 2 of the present invention and comparative examples 3 to 4. Example Al after homogenizing annealing compared to the comparative example without homogenizing annealing1.0Fe2B2And Al1.2Fe2B2The magnetocaloric property of the high-performance aluminum-iron-boron magnetic refrigeration material is obviously improved.
TABLE 1 magnetic transition temperature and magnetic entropy transition Peak (2T) of examples and comparative examples
Figure BDA0003561410890000071
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (10)

1. The preparation method of the aluminum-iron-boron magnetic refrigeration material is characterized by comprising the following steps:
(1) according to AlxFe2B2Preparing raw materials in a component mode, wherein x is more than or equal to 1.0 and less than or equal to 1.35;
(2) smelting the raw materials into a master alloy ingot;
(3) heating the master alloy ingot by vortex to obtain a master alloy melt, and rapidly solidifying the master alloy melt to obtain an as-cast aluminum-iron-boron refrigeration material;
(4) and annealing the as-cast aluminum-iron-boron refrigeration material under a vacuum condition to obtain the final aluminum-iron-boron magnetic refrigeration material.
2. The method for preparing an Al-Fe-B magnetic refrigeration material as claimed in claim 1, wherein in step (1), the purity of Al, Fe or B in the raw materials is not lower than 98 wt.%.
3. The method for preparing an aluminum-iron-boron magnetic refrigeration material according to claim 1, wherein in the step (2), the smelting process is carried out under argon or vacuum conditions.
4. The preparation method of the ferro-aluminum boron magnetic refrigeration material according to claim 1, wherein in the step (3), the rapid solidification process parameters are as follows: cooling rate of 105–106K/s。
5. The preparation method of the ferro-aluminum boron magnetic refrigeration material according to claim 1, wherein in the step (3), the rapid solidification process is as follows: and spraying the master alloy melt onto the surface of a copper roller rotating at high speed.
6. The method for preparing an Al-Fe-B magnetic refrigeration material as claimed in claim 5, wherein in step (3), the linear speed of rotation of the copper roller is 10-50 m/s.
7. The preparation method of the Al-Fe-B magnetic refrigeration material according to claim 1, wherein in the step (4), the annealing process parameters are as follows: the annealing temperature is 800-1050 ℃, and the annealing time is 1-24 h.
8. The method for preparing Al-Fe-B magnetic refrigeration material according to claim 1, wherein the Al isxFe2B2In the composition formula, x is more than or equal to 1.0 and less than or equal to 1.2, the rotating speed of the copper roller is 12-15 m/s, the annealing temperature is 900-1050 ℃, and the annealing time is 20-24 h.
9. An alumino-ferro-boron magnetic refrigeration material prepared by the method for preparing an alumino-ferro-boron magnetic refrigeration material according to any one of claims 1 to 7.
10. The Al-Fe-B magnetic refrigeration material prepared by the preparation method of the Al-Fe-B magnetic refrigeration material according to claim 9, characterized in that the magnetic entropy change of the Al-Fe-B magnetic refrigeration material is not less than 3.5J kg under the external magnetic field of 0-2T-1K-1。
CN202210294545.2A 2022-03-23 2022-03-23 Aluminum-iron-boron magnetic refrigeration material and preparation method thereof Pending CN114678181A (en)

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