CN112410596A - Method for preparing magnetic refrigeration alloy by using Spark Plasma Sintering (SPS) technology - Google Patents
Method for preparing magnetic refrigeration alloy by using Spark Plasma Sintering (SPS) technology Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- 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
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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Abstract
A method for preparing magnetic refrigeration alloy by using Spark Plasma Sintering (SPS) belongs to the field of magnetic refrigeration materials. The chemical general formula of the magnetic refrigeration alloy is Mn0.8Fe0.2NiSi1‑xGaxFe is used for doping Mn, Ga is used for doping Si, and x is more than or equal to 0.15 and less than or equal to 0.17. Proportioning according to a molar ratio, putting into a suspension smelting furnace, vacuumizing, and smelting under the protection of argon to obtain an alloy ingot; annealing the alloy ingot under the protection of pure inert gasFire, then directly quenching in ice water; grinding the magnetic alloy ingot into powder and grading the particle size; adding Mn0.8Fe0.2Ni Si1‑xGaxThe magnetic alloy powder is loaded into a mold and sintered into a block using a Spark Plasma Sintering (SPS) process. The alloy can generate structural phase change in a wider temperature range, is accompanied by a huge magnetocaloric effect, and can be used as a magnetic refrigeration working medium.
Description
Technical Field
The patent discloses a novel manganese-nickel-silicon (MnNiSi) magnetic refrigeration alloy and a preparation process thereof, 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 technology, 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 a magnetic field is reduced in the heat insulation process; in an isothermal process, heat is released efficiently when the magnetic field is increased. Therefore, solving the problems faced by various MCE materials is crucial to the development of magnetic refrigeration applications.
MM 'X (M and M' are transition group metals, and X is main group elements such as Si, Ge, Sn) compound is a new material group with martensite transformation. If the structure of the magnetic material can be phase-change modulated to be coupled with ferromagnetic ordered phase change, a series of large magnetocaloric effects can be realized in a wide temperature range. However, as with all other MM' X compounds, it still faces a significant obstacle to its use, namely its fragility. During the transformation of the primary hexagonal phase structure to the orthorhombic structure, the large magnetic volume effect due to the strong magnetic structure coupling can generate high levels of internal stress, which can cause the material to collapse into powder during the manufacturing process. This is disadvantageous in practical use, and thus the MM' X compound needs to be manufactured as a block having a certain shape.
SPS sintering is a novel technology for heating a sample by using a high-frequency instantaneous local high-temperature field generated in the whole sintering process by using pulse energy, spark impact pressure and Joule heating. The SPS has the advantages of high sintering speed, controllable grain growth, high size precision and high density.
Disclosure of Invention
Therefore, an object of the present invention is to provide a novel MnNiSi-based magnetic refrigeration material having a large magnetocaloric effect by SPS sintering, and a novel method for producing a magnetic refrigeration alloy.
The invention also aims to provide a magnetic refrigeration alloy which can be regulated and controlled in a larger particle size range, so that the effective magnetic refrigeration efficiency is greatly improved, and the magnetic refrigeration alloy has a wider application range.
In order to achieve the purpose of the invention, the invention provides an advanced method for preparing magnetic refrigeration alloy, namely Spark Plasma Sintering (SPS), which is characterized by high sintering speed, controllable grain growth, high dimensional precision and density and capability of further promoting the generation of hexagonal phase. The invention also provides a magnetic alloy with a chemical general formula of Mn0.8Fe0.2NiSi1-xGaxWherein, Fe is transition group metal to dope Mn, Ga is main group element to dope Si, and x is more than or equal to 0.15 and less than or equal to 0.17. The magnetic refrigeration alloy has the grain size range of 37-150 mu m, and is sintered into a compact block material at high temperature.
Preferably, in some embodiments of the invention, Mn is0.8Fe0.2NiSi1-xGaxIs preferably Mn0.8Fe0.2NiSi0.85Ga0.15、Mn0.8Fe0.2NiSi0.84Ga0.16And Mn0.8Fe0.2NiSi0.83Ga0.17。
The preparation steps of the magnetic alloy are as follows:
step one, according to Mn: fe: ni: si: ga ═ 0.8: 0.2: 1: 1-x: x, respectively weighing Mn, Fe, Ni, Si and Ga raw materials;
secondly, putting the prepared raw materials into a suspension smelting furnace, vacuumizing, and smelting under the protection of argon to obtain an alloy ingot;
step three, annealing the smelted alloy ingot under the protection of pure inert gas, and then directly quenching in ice water to prepare the alloy ingotPreparation of Mn0.8Fe0.2NiSi1-xGaxAn alloy ingot;
step four, adding Mn0.8Fe0.2NiSi1-xGaxPreparing the magnetic alloy into powder and grading the particle size;
step five, the obtained Mn0.8Fe0.2NiSi1-xGaxThe magnetic alloy powder is loaded into a mold and sintered into a block using a Spark Plasma Sintering (SPS) process.
According to a preferred embodiment of the preparation method of the invention, in the third step, the obtained alloy ingot or the alloy ingot fine particles are wrapped by tantalum sheets, sealed in a quartz tube filled with pure argon, annealed for not less than 48 hours at 800-1100 ℃, preferably for 72 hours at 1000 ℃, and then thrown into ice water at high temperature and crushed rapidly to quench the quartz tube.
According to a preferred embodiment of the preparation method of the present invention, in the fourth step, the powder is prepared by manually grinding the ingot sample in an agate mortar, and using particles with a particle size range of 37-150 μm, and further preferably screening into three different particle size ranges, namely, P1 (74-150 μm), P2 (50-74 μm), and P3 (37-50 μm), wherein one or more of the three different particle sizes are used.
According to still another preferred embodiment of the preparation method of the present invention, in the step five, the mold may be a graphite or cemented carbide mold, the SPS hot pressing sintering temperature is preferably 700 ℃ to 900 ℃, and the SPS hot pressing sintering pressure is preferably 50Mpa to 100 Mpa. Specifically, the MnNiSi-based alloy can be pressed and formed into the shape and size of a working medium required by a magnetic refrigerator; putting MnNiSi-based alloy powder with different grain diameters into a die (the shape and the size of the die are prepared according to the actual requirement of a magnetic refrigerator on the material), pressing and forming at room temperature, then performing SPS sintering after pressing and forming, and cooling to room temperature and demoulding.
The invention also provides application of the magnetocaloric effect material prepared by the method in manufacturing magnetic refrigeration materials.
The maximum magnetic entropy change of the magnetic alloy can reach 11.14J/kg.K under the change of a 0-3T magnetic field, and the maximum phase change temperature can reach 328K. The components are modulated into combinations of different components according to the requirements to realize the requirements of different temperatures.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts conventional smelting and annealing equipment and an SPS sintering furnace, and the SPS technology has the advantages of high sintering speed, controllable grain growth, high dimensional precision and high density.
2. The magnetic alloy prepared according to the invention has large magnetic entropy change effect. Under the action of an external magnetic field, the magnetic alloy generates magnetic and structural transformation under the drive of the magnetic field, and shows large magnetic difference. Meanwhile, the directions of the structure entropy change and the magnetic entropy change of the magnetic alloy are always consistent, and the heat effects are mutually superposed, so that the magnetic refrigeration or energy conversion efficiency is greatly improved.
3. The magnetic alloy prepared according to the invention belongs to the same material system, and the needed raw materials of Mn, Fe, Ni, Si and Ga are transition group elements which are cheap, abundant and easy to store.
4. The phase change of the magnetic alloy prepared according to the present invention is continuously adjustable over a wide temperature range including room temperature. This allows the magnetic alloy to provide different solutions for different application requirements.
5. Magnetic alloy Mn prepared according to the invention0.8Fe0.2NiSi1-xGaxHas excellent comprehensive performance and is an ideal Mn-based non-rare earth magnetic refrigeration candidate material.
Drawings
Embodiments of the invention are described below with reference to the accompanying drawings, in which:
FIG. 1 is Mn alloy of example 1 of the present invention0.8Fe0.2NiSi0.85Ga0.15Room temperature X-ray diffraction pattern;
FIG. 2 is Mn alloy of example 1 of the present invention0.8Fe0.2NiSi0.84Ga0.16Magnetization versus temperature curve;
FIG. 3 is alloy M of example 2 of the present inventionn0.8Fe0.2NiSi0.84Ga0.16Magnetic entropy change versus temperature curve;
FIG. 4 is Mn alloy of example 3 of the present invention0.8Fe0.2NiSi0.83Ga0.17A back-scattered electron image of (a);
the present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
In the following examples, room temperature X-ray diffraction patterns, magnetization and magnetic field strength curves, magnetization and temperature curves, and scanning electron microscope images of the obtained samples were measured, respectively, to identify relevant properties of the materials involved in the present invention, and to determine phase transition temperatures and magnetic entropy changes. But for simplicity only the relevant curves for some of the samples are shown, the corresponding curves for the other samples being similar.
Example 1: this example prepares a compound of the formula Mn0.8Fe0.2NiSi0.85Ga0.15In the magnetic alloy bulk of (1), wherein Mn0.8Fe0.2NiSi0.85Ga0.15The alloy shows that 20% (mol ratio) of Mn is replaced by Fe and 15% (mol ratio) of Si is replaced by Ga in the MnNiSi alloy. The same explanation is also made for other embodiments. The preparation method comprises the following specific steps:
step one, according to Mn: fe: ni: si: ga ═ 0.8: 0.2: 1: 0.85: 0.15, respectively weighing raw materials of Mn, Fe, Ni, Si, Ga and the like with the purity of 99.9%;
secondly, putting the weighed raw materials into a water-cooled copper crucible, vacuumizing by using a mechanical pump, introducing argon for gas washing, repeating the steps for 4 times, smelting polycrystalline sample ingots by a suspension smelting method, turning each sample for 3 times, smelting for 4 times in total to ensure uniform components, and preparing alloy ingots;
step three, wrapping the obtained spindle or the obtained fine crushed particles with tantalum sheets, sealing the wrapped spindle or the fine crushed particles in a quartz tube filled with high-purity argon, annealing the wrapped spindle or the fine crushed particles for 72 hours at 1000 ℃ to perform homogenization annealing treatment, then throwing the wrapped spindle or the fine crushed particles into ice water at high temperature and quickly crushing the quartz tube to perform quenching to obtain a quenched sample;
step four, preparing the sample obtained in the step three into powder particles by a manual grinding method, and screening the sample with the particle size range of P2 (50-74 mu m);
and step five, putting the sample obtained in the step four into a mould, and sintering the sample into a block by using a Spark Plasma Sintering (SPS) method under the environment condition of 700 ℃ and 100 Mpa.
FIG. 1 shows Mn in this example at room temperature0.8Fe0.2NiSi0.85Ga0.15The X-ray diffraction pattern of the alloy shows that the main phase is a TiNiSi type orthogonal structure phase, and the Curie temperature is higher than the room temperature. FIG. 2 shows Mn in the present example0.8Fe0.2NiSi0.85Ga0.15The magnetization intensity and the temperature curve of the alloy have Curie temperature of 328K.
Example 2: this example prepares a compound of the formula Mn0.8Fe0.2NiSi0.84Ga0.16The preparation method of the magnetic alloy block is similar to that of the embodiment 1, except that the four-step screening uses samples with three particle size ranges, namely P1 (74-150 μm), P2 (50-74 μm) and P3 (37-50 μm); and step five, sintering at 900 ℃ and 50 Mpa.
Mn prepared in this example0.8Fe0.2NiSi0.84Ga0.16The alloy has the same crystal structure and similar change law with the first embodiment. FIG. 3 shows Mn0.8Fe0.2NiSi0.84Ga0.16The magnetic entropy change and temperature dependence curve of the alloy reduces with the reduction of the particle size, and the maximum magnetic entropy becomes as high as 11.14J/kg.K.
Example 3: this example prepares a compound of the formula Mn0.8Fe0.2NiSi0.83Ga0.17The preparation method of the magnetic alloy block is similar to that of the magnetic alloy block in the embodiment 1, except that in the step four, a sample with the particle size range of P3 (37-50 μm) is screened and used; and step five, sintering at 800 ℃ and 80 Mpa.
Mn prepared in this example0.8Fe0.2NiSi0.83Ga0.17The alloy is different from that of the embodiment 1 and the embodiment 2A crystal structure. FIG. 4 shows Mn0.8Fe0.2NiSi0.83Ga0.17Back-scattered electron images of the alloy, from which it can be seen that a large number of micro-cracks exist inside a single particle, indicating that the particle size is further reduced by the destruction of the particle during hot pressing, and the defects of the particle are introduced, thereby lowering the phase transition temperature of the alloy.
While particular embodiments of the present invention have been described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (8)
1. A magnetic alloy is characterized in that the chemical general formula is Mn0.8Fe0.2Ni Si1-xGaxWherein Fe is a transition group metal to dope Mn, Ga is a main group element to dope Si, x is more than or equal to 0.15 and less than or equal to 0.17, the particle size range of the magnetic refrigeration alloy is 37-150 mu m, and the particle size of the magnetic refrigeration alloy is sintered at high temperature to form a compact block material.
2. A magnetic alloy as claimed in claim 1, characterised in that Mn0.8Fe0.2NiSi1-xGaxComponent (C) is Mn0.8Fe0.2NiSi0.85Ga0.15、Mn0.8Fe0.2Ni Si0.84Ga0.16And Mn0.8Fe0.2Ni Si0.83Ga0.17。
3. A method of making a magnetic alloy as claimed in claim 1 or claim 2, including the steps of:
step one, according to Mn: fe: ni: si: ga ═ 0.8: 0.2: 1: 1-x: x, respectively weighing Mn, Fe, Ni, Si and Ga raw materials;
secondly, putting the prepared raw materials into a suspension smelting furnace, vacuumizing, and smelting under the protection of argon to obtain an alloy ingot;
step three, annealing the smelted alloy ingot under the protection of pure inert gas, and then directly quenching in ice water to prepare Mn0.8Fe0.2Ni Si1-xGaxAn alloy ingot;
step four, adding Mn0.8Fe0.2Ni Si1-xGaxPreparing the magnetic alloy into powder and grading the particle size;
step five, the obtained Mn0.8Fe0.2Ni Si1-xGaxThe magnetic alloy powder is loaded into a mold and sintered into a block using a Spark Plasma Sintering (SPS) process.
4. The method according to claim 3, wherein the alloy ingot or the alloy ingot fine crushed particles obtained in the third step are wrapped by tantalum sheets, sealed in a quartz tube filled with pure argon gas, subjected to homogenization annealing treatment, annealed at 800-1100 ℃ for not less than 48 hours, preferably at 1000 ℃ for 72 hours, then dropped into ice water at high temperature and rapidly crushed into the quartz tube for quenching.
5. The method according to claim 3, wherein in step four, the powder is prepared by manually grinding the ingot sample in an agate mortar, using particles with a particle size range of 37-150 μm, further preferably by screening into three different particle size ranges, namely P1 (74-150 μm), P2 (50-74 μm), P3 (37-50 μm), using one or more of the three different particle sizes.
6. The method as claimed in claim 3, wherein the mold in the fifth step can be a graphite or hard alloy mold, the SPS hot pressing sintering temperature is preferably 700-900 ℃, and the SPS hot pressing sintering pressure is preferably 50-100 Mpa; specifically, the MnNiSi-based alloy can be pressed and formed into the shape and size of a working medium required by a magnetic refrigerator; putting the MnNiSi-based alloy powder with different grain diameters into a die, pressing the powder into a mold at room temperature, performing SPS sintering after pressing, and cooling to room temperature for demolding.
7. Use of a magnetic alloy as claimed in claim 1 or claim 2 in the manufacture of a magnetic refrigeration material.
8. The use of claim 7, wherein the magnetic entropy change of the alloy is up to 11.14J/kg-K and the phase transition temperature is up to 328K under the change of 0-3T magnetic field.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113471355A (en) * | 2021-06-28 | 2021-10-01 | 深圳大学 | Method, device and system for preparing p-type bismuth telluride and computer readable storage medium |
| CN113471355B (en) * | 2021-06-28 | 2024-05-31 | 深圳大学 | Method, device, system and computer readable storage medium for preparing p-type bismuth telluride |
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| CN102931334A (en) * | 2012-06-28 | 2013-02-13 | 北京工业大学 | High-manganese silicon compound thermoelectric material and preparation method thereof |
| JP2014095486A (en) * | 2012-11-07 | 2014-05-22 | Denso Corp | Method of producing magnetic refrigeration material |
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| CN113471355B (en) * | 2021-06-28 | 2024-05-31 | 深圳大学 | Method, device, system and computer readable storage medium for preparing p-type bismuth telluride |
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