CN116612955A - Lanthanum iron silicon near-room temperature magnetic refrigeration material and rapid preparation method thereof - Google Patents
Lanthanum iron silicon near-room temperature magnetic refrigeration material and rapid preparation method thereof Download PDFInfo
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- PXELSXAIIUMJCA-UHFFFAOYSA-N [Si].[Fe].[La] Chemical compound [Si].[Fe].[La] PXELSXAIIUMJCA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000005057 refrigeration Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 56
- 239000000126 substance Substances 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 21
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 238000011282 treatment Methods 0.000 claims abstract description 14
- 238000010791 quenching Methods 0.000 claims abstract description 13
- 230000000171 quenching effect Effects 0.000 claims abstract description 13
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 11
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000005275 alloying Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000011112 process operation Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000008859 change Effects 0.000 description 16
- 229910019001 CoSi Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 230000005415 magnetization Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 229910005347 FeSi Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a lanthanum iron silicon near room temperature magnetic refrigeration material and a rapid preparation method thereof, wherein the material has NaZn 13 Cubic crystal structure with chemical general formula LaFe 11‑x Co x Si 2 X is more than or equal to 0 and less than or equal to 1, and the Curie temperature of the material is regulated by changing the component parameters, so that the magnetic refrigeration material can be conveniently applied to a near room temperature area. The preparation method comprises the following steps: configuration of LaFe in stoichiometric ratio 11‑x Co x Si 2 Forming raw materials into powder by adopting a mechanical alloying method; and carrying out high-temperature annealing treatment on the powder, quenching, grinding and sieving to obtain lanthanum iron silicon powder. The preparation method has simple process operation, energy conservation and time conservation; the solid solubility of alloying atoms is high; the obtained lanthanum-iron-silicon powder has good crystallinity, uniform components and high repetition rate, has higher magnetic entropy modification performance in a near room temperature area, and can be widely used for preparing magnetic refrigeration materials.
Description
Technical Field
The invention relates to a magnetic material, in particular to a lanthanum iron silicon near-room-temperature magnetic refrigeration material and a rapid preparation method thereof, belonging to the field of magnetic refrigeration materials.
Background
With the rapid development of society, the dependence of human life on refrigeration technology is gradually increased. At present, the most widely applied refrigeration technology is air compression refrigeration, but the technology has strong greenhouse effect and high energy consumption, so the search of a novel refrigeration technology which is environment-friendly, efficient and energy-saving has become a problem to be solved in the world.
The magnetic refrigeration technology developed based on the magnetocaloric effect of the magnetic material is a new technology with important application prospect, which is widely valued at home and abroad. The magnetocaloric effect is the intrinsic property of all magnetic materials, and is isothermal entropy change or adiabatic heating phenomenon generated in the magnetizing or demagnetizing process of the magnetic materials. Through long-term work accumulation, the exploration and research of a plurality of novel magnetic materials greatly promote the progress of magnetic refrigeration technology, in particular to the discovery of lanthanum iron silicon magnetic refrigeration materials with large magnetocaloric effect in a near room temperature area, which are generally regarded as one of the magnetic refrigeration working media with the most application prospect in the world, and are also magnetic refrigeration materials with independent intellectual property rights in China.
In 2000, la (Fe, M) with huge magnetic entropy change was reported for the first time by the institute of physics at the academy of sciences of China 13 (m=si, al) rare earth-iron based new material (reference Feng-Xia Hu et Al, chinese Physics 9 (2000) 550) which exhibits a huge magnetic entropy change value (La (Fe, co, si) at room temperature by substitution of Co atoms or introduction of interstitial sites 13 20.3J/(kg.K), laFe 11.5 Si 1.5 H 1.8 20.5J/(kg·k)), which is continuously adjustable between 127 and 340K, and which was successfully filed with chinese patents CN1450190a and CN102093850a. Subsequently, many researchers report on the series of work of improving the performance of lanthanum iron silicon materials and designing and processing magnetic refrigeration working media.
Chinese patent application CN109023145a discloses a method for controlling curie temperature of LaFeSi-based magnetic refrigeration material and a preparation method thereof, which is to prepare the LaFeSi-based magnetic refrigeration material with required curie temperature after carrying out saturation hydrogen charging treatment on a thin strip obtained by high-temperature smelting of various solid-solution-atom lanthanum-iron-silicon raw materials. Chinese patent application CN109266951B discloses a LaFeSiCu magnetic refrigeration alloy and a preparation method thereof, which is to repeatedly smelt and cool raw materials in a vacuum arc furnace, and prepare lanthanum ferrosilicon magnetic refrigeration material after high-temperature heat treatment and cold water quenching. The Chinese patent application CN109378148A provides a lanthanum-iron-silicon-based magnetic refrigeration material and a preparation method thereof, wherein after smelting raw materials with various atoms replacing La and Fe, the raw materials are annealed at a high temperature in an inert atmosphere, and after rapid cooling, hydrogenation treatment is further carried out, so that the magnetic refrigeration material with Curie temperature close to room temperature and large adiabatic temperature change is obtained. Chinese patent application CN111755187a provides a method for expanding the magnetic refrigeration working temperature range of lanthanum-iron-silicon alloy, which comprises melting lanthanum-iron-silicon raw material to form alloy ingot, sequentially carrying out melt-spinning, annealing, quenching and grinding to obtain lanthanum-iron-silicon alloy powder, and then carrying out high-pressure annealing treatment to obtain the magnetic refrigeration material with wide working temperature range. Chinese patent application CN103468226a provides a lanthanum-iron-silicon-based room temperature magnetic refrigeration composite material and preparation method, which is a composite material formed by uniformly mixing lanthanum-iron-silicon-based compound, high polymer material and auxiliary agent, and then compression molding and heating, wherein the room temperature magnetic refrigeration composite material can be isolated from heat exchange fluid, and oxidation of magnetic refrigeration working medium in use is prevented. Chinese patent application CN106906408A discloses a LaFeSi-based magnetic refrigeration composite material, and preparation method and application thereof. The invention adopts low-cost and easily-obtained low-melting-point metal or alloy and LaFeSi-based alloy particles for composite hot pressing, and can obtain the high-thermal-conductivity LaFeSi-based magnetic refrigeration composite material by selecting proper low-melting-point components, adjusting pressing pressure, hot pressing temperature, dwell time and the like.
According to the literature and the patent, the multi-atom solid solution lanthanum iron silicon material becomes a solid magnetic refrigeration working medium with great application potential due to the advantages of low cost and no toxicity of raw materials, large magnetic entropy, adjustable Curie temperature and the like, but has some defects at the same time, so that the large-scale application of the multi-atom solid solution lanthanum iron silicon material is limited, and firstly, the traditional vacuum furnace is repeatedly smelted, and has the defects of complex operation, high equipment cost and high energy consumption; secondly, the molten cast ingot has uneven components and low main phase content, needs long-time high-temperature annealing, has high energy consumption and increases time cost; and thirdly, the preparation process has a plurality of procedures, so that solid solution atoms are easy to lose, and the effective solid solubility is reduced. Therefore, a simple and rapid preparation method is developed, energy and time are saved, and on the basis of improving the effective solid solubility of solid solution atoms, the lanthanum-iron-silicon magnetic refrigeration material with large magnetic entropy change in a near room temperature area is obtained, so that a key material is provided for the application of magnetic refrigeration technology.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art, which is the shortcomings of the prior art. Therefore, the invention discloses a lanthanum iron silicon near-room temperature magnetic refrigeration material and a rapid preparation method thereof, and the lanthanum iron silicon compound with large magnetic entropy change in a near-room temperature area and uniform components can be rapidly prepared by using the method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a lanthanum iron silicon magnetic refrigerating material near room temperature has a chemical general formula of LaFe 11-x Co x Si 2 Wherein, the value range of x is: x is more than or equal to 0 and less than or equal to 1.
a) The lanthanum-iron-silicon material is provided with NaZn 13 The space group is Fm3c.
The invention relates to a rapid preparation method of lanthanum iron silicon near-room temperature magnetic refrigeration material, which comprises the following steps:
1) La simple substance powder, fe simple substance powder, co simple substance powder and Si simple substance powder are taken as initial raw materials, and LaFe is taken as a raw material 11-x Co x Si 2 The stoichiometric ratio is configured, and a mechanical alloying method is adopted for treatment to obtain powder;
2) And annealing the powder, quenching, grinding and sieving to obtain lanthanum iron silicon powder.
According to a preferred embodiment of the preparation method of the present invention, specifically, the step 1) is: and (3) filling the raw materials with the stoichiometric ratio into a ball milling tank filled with protective gas, and then carrying out mechanical alloying reaction to obtain the powder.
According to a further embodiment of the preparation method of the present invention, the shielding gas is argon, helium, argon-hydrogen mixed gas or helium-hydrogen mixed gas.
According to a further embodiment of the preparation method of the invention, the ball milling tank body is made of stainless steel or tungsten carbide, the grinding balls are made of zirconia or alumina, and the diameter of the grinding balls is 3-10 mm.
According to a further embodiment of the preparation method of the present invention, the conditions of the mechanical alloying reaction are: ball-material ratio is 10:1-40:1, rotation speed of planetary ball mill is 200-450 rpm, and reaction time is 12-96 h.
According to a preferred embodiment of the preparation method of the present invention, specifically, the step 2) is: and (3) filling the powder into a quartz tube filled with low-pressure protective gas, putting the quartz tube into a muffle furnace, performing high-temperature annealing treatment, and grinding and sieving after quenching to obtain lanthanum-iron-silicon powder.
According to a further embodiment of the preparation method of the present invention, the low pressure condition is a vacuum degree of less than 10Pa.
According to a further embodiment of the preparation method of the present invention, the high temperature annealing treatment conditions are: the temperature rising rate of the muffle furnace is less than 5 ℃/min, the annealing temperature is 1000-1200 ℃, and the annealing time is 1-10 days.
According to a further embodiment of the preparation method of the present invention, the quenching medium is an ice-water mixture.
According to a further embodiment of the preparation method of the invention, the quenched material is ground or mechanically crushed by an agate mortar, and is sieved by a 200-mesh standard sieve to obtain lanthanum iron silicon powder.
Compared with the prior art, the rapid preparation method of the lanthanum iron silicon near-room temperature magnetic refrigeration material has the advantages that:
3) The preparation method has the advantages of short process flow, simple operation, energy and time saving and high efficiency.
4) The prepared lanthanum-iron-silicon powder has the advantages of uniform component distribution, higher crystallinity and high repetition rate.
5) The loss is small when the polyatoms are in solid solution, and the effective solid solubility is improved.
6) The prepared lanthanum-iron-silicon powder has Curie temperature near room temperature and higher magnetic entropy change.
Therefore, the lanthanum iron silicon powder synthesized by the preparation method disclosed by the invention has the advantages of low cost, suitability for mass production and high economic value, and has a great application prospect in the field of magnetic refrigeration.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is an X-ray diffraction chart of lanthanum iron silicon samples with different Co doping amounts prepared in example 1 of the present invention.
FIG. 2 shows LaFe prepared in examples 1 and 4 of the present invention 11 Si 2 And LaFe 10 CoSi 2 Scanning electron microscope photographs of the samples.
FIG. 3 is a graph showing the magnetization intensity (M-T) of lanthanum iron silicon samples with different Co doping amounts prepared in examples 1 to 4 according to the invention under a magnetic field of 0.05T.
FIG. 4 is a plot (M-H) of magnetization of lanthanum iron silicon samples prepared in example 1 of the present invention at temperatures of 260-380K as a function of magnetic field strength.
FIG. 5 shows the magnetic entropy change (delta S-T) with temperature of lanthanum iron silicon samples with different Co doping amounts prepared in examples 1-4 according to the invention under a magnetic field of 2.0T.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout.
In the present invention, all the equipment and materials are commercially available or commonly used in the industry, and the methods in the examples described below are conventional in the art unless otherwise specified.
Example 1
a) In this example LaFe is obtained in nominal composition 11 Si 2 And (3) alloy.
La simple substance powder, fe simple substance powder and Si simple substance powder are taken as raw materials, and LaFe is carried out in a glove box (Ar atmosphere) 11 Si 2 The starting powder was weighed in a stoichiometric ratio to a total mass of 10g, charged into a stainless steel ball mill tank (volume 250 mL), and zirconia mill balls (total mass 400g, mass ratio 1:1) having diameters of 10mm and 6mm were added. The ball mill pot was filled with a high purity argon-hydrogen mixture (hydrogen content 5%) as a shielding gas, and ball-milled in a planetary ball mill (QM-3 SP2, university of south-Beijing) at a rotation speed of 200rpm for 24 hours. After ball milling, the intermediate compound powder was taken out in a glove box.
In a glove box, the intermediate compound powder was placed in a quartz tube and pumped to a low pressure (less than 10 Pa) state. And (3) placing the sealed quartz tube in a muffle furnace for high-temperature annealing treatment, preserving the heat for 2 days at 1050 ℃, and quenching by adopting ice water to obtain the lanthanum-iron-silicon powder with higher target phase content.
Grinding the quenched powder by an agate mortar, and sieving by a 200-mesh standard sieve to obtain lanthanum iron silicon powder with small particle size.
The obtained LaFe 11 Si 2 The powder adopts an X-ray diffraction analyzer to carry out phase test, adopts a field emission scanning electron microscope to carry out microscopic morphology test, and adopts a vibrating sample magnetometer to carry out magnetic property test
Analysis of the experimental results, FIG. 1 shows LaFe 11 Si 2 Sample X-ray diffraction pattern. FIG. 2 shows LaFe 11 Si 2 Scanning electron microscope photographs of the samples. FIG. 3 shows LaFe 11 Si 2 The magnetization of the sample under a magnetic field of 0.05T is plotted against temperature. FIG. 4 shows LaFe 11 Si 2 The magnetization of the sample at the temperature of 260-380K is changed along with the magnetic field intensity. FIG. 5 shows LaFe 11 Si 2 The magnetic entropy change of the sample under the magnetic field of 2.0T is changed along with the temperature.
As can be seen from FIG. 1, the alloy can be rapidly prepared by mechanical alloying and high-temperature annealingTo the main phase (La (FeSi) 13 ) Lanthanum iron silicon sample with higher content. From FIG. 2, it can be reflected that LaFe 11 Si 2 The powder particle size, average particle size, was 2. Mu.m. From FIG. 3, laFe can be obtained 11 Si 2 The curie temperature (magnetic transition temperature) of the sample was 311K. FIG. 4 shows the LaFe effect as the test temperature increases gradually 11 Si 2 The magnetization of the sample gradually decreases and reaches saturation magnetization under a high magnetic field. FIG. 5 shows LaFe 11 Si 2 The highest magnetic entropy change value of 0.8J/(kg K) is obtained at 315K when the sample is subjected to a 2.0T magnetic field.
Example 2
b) In this example LaFe is obtained in nominal composition 10.6 Co 0.4 Si 2 And (3) alloy.
La simple substance powder, fe simple substance powder, co simple substance powder and Si simple substance powder are taken as raw materials, and LaFe is carried out in a glove box (Ar atmosphere) 10.6 Co 0.4 Si 2 The starting powder was weighed in a stoichiometric ratio to a total of 10g, charged into a stainless steel ball mill tank (volume 250 mL), and zirconia mill balls (total mass 200g, mass ratio 1:1) having diameters of 10mm and 6mm were added. The ball mill pot was filled with a high purity argon-hydrogen mixture (hydrogen content 5%) as a shielding gas, and ball-milled in a planetary ball mill (QM-3 SP2, university of south-Beijing) at a rotation speed of 200rpm for 24 hours. After ball milling, the intermediate compound powder was taken out in a glove box.
In a glove box, the intermediate compound powder was placed in a quartz tube and pumped to a low pressure (less than 10 Pa) state. And (3) placing the sealed quartz tube in a muffle furnace for high-temperature annealing treatment, preserving the heat for 2 days at 1050 ℃, and quenching by adopting ice water to obtain the lanthanum-iron-silicon powder with higher target phase content.
Grinding the quenched powder by an agate mortar, and sieving by a 200-mesh standard sieve to obtain lanthanum iron silicon powder with small particle size.
The obtained LaFe 10.6 Co 0.4 Si 2 The powder was subjected to phase testing using an X-ray diffraction analyzer and to magnetic properties testing using a vibrating sample magnetometer.
Analysis of the experimental results, FIG. 1 shows LaFe 10.6 Co 0.4 Si 2 Sample X-ray diffraction pattern. FIG. 3 shows LaFe 10.6 Co 0.4 Si 2 The magnetization of the sample under a magnetic field of 0.05T is plotted against temperature. FIG. 5 shows LaFe 10.6 Co 0.4 Si 2 The magnetic entropy change of the sample under the magnetic field of 2.0T is changed along with the temperature.
As can be seen from FIG. 1, the main phase (La (FeSi)) can be rapidly prepared by mechanical alloying and high temperature annealing 13 ) Lanthanum iron silicon sample with higher content. From FIG. 3, laFe can be obtained 10.6 Co 0.4 Si 2 The curie temperature (magnetic transition temperature) of the sample was 322K. FIG. 5 shows LaFe 10.6 Co 0.4 Si 2 The sample obtained the highest magnetic entropy change value of 0.7J/(kg K) at 324K under 2.0T magnetic field.
Example 3
c) In this example LaFe is obtained in nominal composition 10.2 Co 0.8 Si 2 And (3) alloy.
La simple substance powder, fe simple substance powder, co simple substance powder and Si simple substance powder are taken as raw materials, and LaFe is carried out in a glove box (Ar atmosphere) 10.2 Co 0.8 Si 2 The starting powder was weighed in a stoichiometric ratio to a total of 10g, charged into a stainless steel ball mill tank (volume 250 mL), and zirconia mill balls (total mass 200g, mass ratio 1:1) having diameters of 10mm and 6mm were added. The ball mill pot was filled with a high purity argon-hydrogen mixture (hydrogen content 5%) as a shielding gas, and ball-milled in a planetary ball mill (QM-3 SP2, university of south-Beijing) at a rotation speed of 200rpm for 24 hours. After ball milling, the intermediate compound powder was taken out in a glove box.
In a glove box, the intermediate compound powder was placed in a quartz tube and pumped to a low pressure (less than 10 Pa) state. And (3) placing the sealed quartz tube in a muffle furnace for high-temperature annealing treatment, preserving the heat for 2 days at 1050 ℃, and quenching by adopting ice water to obtain the lanthanum-iron-silicon powder with higher target phase content.
Grinding the quenched powder by an agate mortar, and sieving by a 200-mesh standard sieve to obtain lanthanum iron silicon powder with small particle size.
The obtained LaFe 10.2 Co 0.8 Si 2 The powder is obtained by X-ray diffractionThe analyzer performs phase testing and the magnetic property testing is performed by using a vibrating sample magnetometer.
Analysis of the experimental results, FIG. 1 shows LaFe 10.2 Co 0.8 Si 2 Sample X-ray diffraction pattern. FIG. 3 shows LaFe 10.2 Co 0.8 Si 2 The magnetization of the sample under a magnetic field of 0.05T is plotted against temperature. FIG. 5 shows LaFe 10.2 Co 0.8 Si 2 The magnetic entropy change of the sample under the magnetic field of 2.0T is changed along with the temperature.
As can be seen from FIG. 1, the main phase (La (FeSi)) can be rapidly prepared by mechanical alloying and high temperature annealing 13 ) Lanthanum iron silicon sample with higher content. From FIG. 3, laFe can be obtained 10.2 Co 0.8 Si 2 The curie temperature (magnetic transition temperature) of the sample was 342K. FIG. 5 shows LaFe 10.2 Co 0.8 Si 2 The sample obtained a maximum magnetic entropy change value of 0.51J/(kg K) at 347K under a 2.0T magnetic field.
Example 4
d) In this example LaFe is obtained in nominal composition 10 CoSi 2 And (3) alloy.
La simple substance powder, fe simple substance powder, co simple substance powder and Si simple substance powder are taken as raw materials, and LaFe is carried out in a glove box (Ar atmosphere) 10 CoSi 2 The starting powder was weighed in a stoichiometric ratio to a total of 10g, charged into a stainless steel ball mill tank (volume 250 mL), and zirconia mill balls (total mass 200g, mass ratio 1:1) having diameters of 10mm and 6mm were added. The ball mill pot was filled with a high purity argon-hydrogen mixture (hydrogen content 5%) as a shielding gas, and ball-milled in a planetary ball mill (QM-3 SP2, university of south-Beijing) at a rotation speed of 200rpm for 24 hours. After ball milling, the intermediate compound powder was taken out in a glove box.
In a glove box, the intermediate compound powder was placed in a quartz tube and pumped to a low pressure (less than 10 Pa) state. And (3) placing the sealed quartz tube in a muffle furnace for high-temperature annealing treatment, preserving the heat for 2 days at 1050 ℃, and quenching by adopting ice water to obtain the lanthanum-iron-silicon powder with higher target phase content.
Grinding the quenched powder by an agate mortar, and sieving by a 200-mesh standard sieve to obtain lanthanum iron silicon powder with small particle size.
The obtained LaFe 10 CoSi 2 The powder is subjected to phase test by an X-ray diffraction analyzer, microscopic morphology test by a field emission scanning electron microscope, and magnetic property test by a vibrating sample magnetometer.
Analysis of the experimental results, FIG. 1 shows LaFe 10 CoSi 2 Sample X-ray diffraction pattern. FIG. 2 shows LaFe 10 CoSi 2 Scanning electron microscope photographs of the samples. FIG. 3 shows LaFe 10 CoSi 2 The magnetization of the sample under a magnetic field of 0.05T is plotted against temperature. FIG. 5 shows LaFe 10 CoSi 2 The magnetic entropy change of the sample under the magnetic field of 2.0T is changed along with the temperature.
As can be seen from FIG. 1, the main phase (La (FeSi)) can be rapidly prepared by mechanical alloying and high temperature annealing 13 ) Lanthanum iron silicon sample with higher content. From FIG. 2, it can be reflected that LaFe 10 CoSi 2 The powder particle size, average particle size, was 1. Mu.m. From FIG. 3, laFe can be obtained 10 CoSi 2 The curie temperature (magnetic transition temperature) of the sample was 351K. FIG. 5 shows LaFe 10 CoSi 2 The highest magnetic entropy change value of 0.38J/(kg K) is obtained at 354K when the sample is subjected to a 2.0T magnetic field.
The lanthanum iron silicon near room temperature region magnetic refrigeration material is prepared by the rapid preparation method of the lanthanum iron silicon near room temperature region magnetic refrigeration material in any embodiment of the invention. In the description of the present specification, reference to the term "one preferred embodiment," "a further embodiment," "an embodiment," or "one embodiment" etc. means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments.
It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (12)
1. A lanthanum iron silicon near room temperature magnetic refrigeration material is characterized in that: the chemical general formula is LaFe 11-x Co x Si 2 Wherein x is more than or equal to 0 and less than or equal to 1, and the lanthanum-iron-silicon material is provided with NaZn 13 Cubic crystal structure.
2. A rapid preparation method of a lanthanum iron silicon near room temperature magnetic refrigeration material as claimed in claim 1, which is characterized by comprising the following steps:
1) La simple substance powder, fe simple substance powder, co simple substance powder and Si simple substance powder are taken as initial raw materials, and LaFe is taken as a raw material 11-x Co x Si 2 The stoichiometric ratio is configured, and a mechanical alloying method is adopted for treatment to obtain powder;
2) And annealing the powder, quenching, grinding and sieving to obtain lanthanum iron silicon powder.
3. The rapid preparation method of lanthanum iron silicon near room temperature magnetic refrigeration material according to claim 2, wherein step 1) specifically comprises: and (3) filling the raw materials with the stoichiometric ratio into a ball milling tank filled with protective gas, and then carrying out mechanical alloying reaction to obtain the powder.
4. A rapid preparation method according to claim 3, wherein the shielding gas is argon, helium, argon-hydrogen mixed gas or helium-hydrogen mixed gas.
5. The rapid preparation method according to claim 3, wherein the ball milling tank body is made of stainless steel or tungsten carbide, the grinding balls are made of zirconia or alumina, and the diameter of the grinding balls is 3-10 mm.
6. A rapid preparation method according to claim 3, wherein the conditions of the mechanical alloying reaction are: ball-material ratio is 10:1-40:1, rotation speed of planetary ball mill is 200-450 rpm, and reaction time is 12-96 h.
7. The rapid preparation method of lanthanum iron silicon near room temperature magnetic refrigeration material according to claim 2, wherein the step 2) is specifically as follows: and (3) filling the powder into a quartz tube filled with low-pressure protective gas, putting the quartz tube into a muffle furnace, performing high-temperature annealing treatment, and grinding and sieving after quenching to obtain lanthanum-iron-silicon powder.
8. The rapid manufacturing method according to claim 7, wherein the low pressure condition is a vacuum degree of less than 10Pa.
9. The rapid manufacturing method according to claim 7, wherein the high temperature annealing treatment conditions are: the temperature rising rate of the muffle furnace is less than 5 ℃/min, the annealing temperature is 1000-1200 ℃, and the annealing time is 1-10 days.
10. The rapid preparation method according to claim 7, wherein the quenching medium is an ice-water mixture.
11. The rapid preparation method according to claim 7, wherein the quenched material is subjected to agate mortar grinding or mechanical crushing, and is sieved by a 200-mesh standard sieve to obtain lanthanum iron silicon powder.
12. A lanthanum iron silicon near room temperature magnetic refrigeration material, characterized in that the lanthanum iron silicon near room temperature magnetic refrigeration material is prepared by a rapid preparation method of the lanthanum iron silicon near room temperature magnetic refrigeration material according to any one of claims 2-11.
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