CN115109984A - Preparation method of La-Fe-Si-based magnetic refrigeration alloy - Google Patents

Preparation method of La-Fe-Si-based magnetic refrigeration alloy Download PDF

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CN115109984A
CN115109984A CN202210786336.XA CN202210786336A CN115109984A CN 115109984 A CN115109984 A CN 115109984A CN 202210786336 A CN202210786336 A CN 202210786336A CN 115109984 A CN115109984 A CN 115109984A
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magnetic refrigeration
based magnetic
refrigeration alloy
equal
alloy
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卢翔
刘剑
苗丽娅
张一飞
张朋娜
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Ningbo Institute of Material Technology and Engineering of CAS
Ningbo University of Technology
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Ningbo Institute of Material Technology and Engineering of CAS
Ningbo University of Technology
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Abstract

The invention discloses a preparation method of La-Fe-Si-based magnetic refrigeration alloy, which comprises the following steps: s1, designing components of the La-Fe-Si-based magnetic refrigeration alloy, and preparing raw materials according to the designed components; s2, smelting the prepared raw materials to obtain La-Fe-Si-based magnetic refrigeration alloy cast ingots; s3, plastically deforming the La-Fe-Si-based magnetic refrigeration alloy ingot obtained in the step S2 to obtain an La-Fe-Si-based magnetic refrigeration alloy blank; s4, carrying out homogenization heat treatment on the La-Fe-Si-based magnetic refrigeration alloy blank obtained in the step S3 to obtain La-Fe-Si-based magnetic refrigeration alloy; compared with the prior art, on the basis of the traditional casting of the La-Fe-Si-based alloy, the invention obtains the shape with large specific surface area through plastic deformation, simultaneously regulates and controls the microstructure of alpha-Fe and La-rich phase, accelerates the formation rate of the magnetocaloric phase in the heat treatment process, and forms a large amount of magnetocaloric phases in a short time to obtain the large magnetocaloric effect.

Description

Preparation method of La-Fe-Si-based magnetic refrigeration alloy
Technical Field
The invention relates to the field of magnetic material preparation, in particular to a preparation method of La-Fe-Si-based magnetic refrigeration alloy.
Background
Refrigeration technology is an indispensable part of modern life and plays an important role in energy and environment. In the traditional steam compression refrigeration mode, alkane substances with low boiling points are used as working media, and refrigeration is realized by volume compression and expansion of the working media. The mode has the defects of low refrigeration efficiency (20-40 percent of ideal Carnot cycle), large working noise, large equipment volume, greenhouse gas emission and the like. Magnetic refrigeration is a novel solid-state refrigeration technology based on the magnetocaloric effect of solid materials, and compared with air compression refrigeration, the magnetic refrigeration has the main advantages that: (1) the efficiency of the magnetic refrigeration technology can reach 60 percent of that of the Carnot cycle, which is far higher than that of the air compression mode; (2) the refrigerating working medium is a solid magnetic material, the entropy density is obviously higher than that of a gas working medium, and the miniaturization and the compaction of equipment are favorably realized; (3) the magnetic refrigeration utilizes a magnetic field to change the entropy value of a working medium, gas compression equipment is not needed, and moving parts are few, so that the working noise and vibration are small, and the running reliability of the equipment is high; (4) the use of solid refrigerating medium avoids the emission of greenhouse gas and has no environmental pollution.
As an important component of a magnetic refrigeration system, magnetic refrigeration materials determine the development and application of magnetic refrigeration technology. In a plurality of material systems with magnetocaloric effectSuch As Gd-Si-Ge, La-Fe-Si, Mn-Fe-P- (As, Ge, Si), Ni-Mn- (Ga, In, Sn) with NaZn 13 La (Fe, Si) of type structure 13 The compound (named as 1:13 phase) has low cost, obvious magnetocaloric effect and no toxic elements, and is one of the most widely accepted room temperature magnetic refrigeration materials. However, the La-Fe-Si material has a certain difference from an ideal magnetic refrigeration working medium, and one of the main reasons is that the 1:13 phase has intrinsic brittleness and cannot be processed and formed by a traditional method. The refrigerating medium used in magnetic refrigerating equipment is generally required to be processed into shapes with larger specific surface area, such as thin plates, filaments, microspheres, blocks with micro channels and the like, and aims to increase heat exchange with fluid and obtain high refrigerating efficiency. In order to solve the problem of processing and forming of La-Fe-Si-based magnetic materials, methods such as resin/metal composite bonding, powder metallurgy, additive manufacturing and the like are generally adopted at present. The method can reduce the magnetocaloric effect or the thermal conductivity, and is not beneficial to improving the refrigeration efficiency. More importantly, in the methods, the block material is prepared on the basis of powder, a powder preparation process is required, the process is complex and long, and the production efficiency is extremely low. The block material with large specific surface area prepared based on the common casting method has the advantages of simple process and high stability, and is an ideal solution.
It is noteworthy that the 1:13 phase is not directly available with conventional casting methods, and generally only alpha-Fe and La-rich phases are available. In order to obtain the 1:13 phase, the cast alloy is usually kept at 1173-1373K for several weeks so that the alpha-Fe and the La-rich phase are subjected to a eutectoid reaction to generate a magnetocaloric phase, and the development of a magnetic refrigeration technology is seriously hindered. It has been reported that the rapid ribbon quenching technique is used to change the solidification path of La-Fe-Si alloy, thereby promoting the formation of magnetocaloric phase. In addition, the rapid solidification can also obviously refine the solidification structure, which is beneficial to accelerating the diffusion rate of elements in the annealing process, and the final thin strip can obtain 96% of magnetocaloric phase only by annealing at 1273K for 20 minutes (J.appl.Phys.2005; 98(11): 113904.). Sichuan university reports a method of rapidly preparing a 1:13 phase (J.alloy.Compd. 2011; 509(34):8534-41.) by converting a La-rich phase into a liquid phase and carrying out a peritectic reaction with an a-Fe phase through annealing in a high temperature zone (1423-1573K). Recently, the addition of extra La or non-homogeneous element Cu to La-Fe-Si based alloy has been proposed to accelerate the formation of 1:13 phase (Acta mater. 2016; 118: 44-53; Chinese patent ZL 201811113587.1). The method can realize the high-efficiency preparation of the La-Fe-Si alloy to a certain degree, but generally has the problems of complex preparation process, reduction of the mechanical property or the magnetocaloric property of the alloy to a certain degree and is not beneficial to practical application.
Disclosure of Invention
The invention aims to provide a preparation method of La-Fe-Si-based magnetic refrigeration alloy, which is characterized in that on the basis of the traditional casting of La-Fe-Si-based alloy, the shape with large specific surface area is obtained through plastic deformation, the microstructure of alpha-Fe and La-rich phase is regulated and controlled, the formation rate of a magnetocaloric phase in the heat treatment process is accelerated, and a large amount of magnetocaloric phases are formed in a short time to obtain a large magnetocaloric effect.
The invention provides a preparation method of La-Fe-Si-based magnetic refrigeration alloy, which comprises the following steps:
s1, designing components of the La-Fe-Si-based magnetic refrigeration alloy, and preparing raw materials according to the designed components;
s2, smelting the prepared raw materials to obtain La-Fe-Si-based magnetic refrigeration alloy cast ingots;
s3, plastically deforming the La-Fe-Si-based magnetic refrigeration alloy ingot obtained in the step S2 to obtain an La-Fe-Si-based magnetic refrigeration alloy blank;
and S4, carrying out homogenization heat treatment on the La-Fe-Si-based magnetic refrigeration alloy blank obtained in the step S3 to obtain the La-Fe-Si-based magnetic refrigeration alloy.
Further, in the step S1, the chemical formula of the La-Fe-Si based magnetic refrigeration alloy is La 1-a RE a (Fe 1-b M b ) c (Si 1-d X d ) e Z f Wherein a is more than or equal to 0 and less than or equal to 0.5, B is more than or equal to 0 and less than or equal to 0.1, C is more than or equal to 11.0 and less than or equal to 15.0, d is more than or equal to 0 and less than or equal to 1.0, e is more than or equal to 1.0 and less than or equal to 1.6, RE is selected from one or more of rare earth elements Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, M is selected from one or more of transition metal elements Co, Ni, Mn, Cr, Cu, Zn, Ti, V, Zr and Nb, X is selected from one or more of Al, Ga, Sn and Ge, and Z is a non-metal element C and/or B.
Further, in the step S1, the purity of the prepared raw material is more than or equal to 99.9%.
Further, in step S2, the smelting method is induction smelting, and the induction smelting specifically includes: firstly, the vacuum of the vacuum induction furnace chamber is pumped to 1 x 10 -2 And Pa, washing with argon with the purity of more than 99.9% for 2 times, then filling argon again, electrifying and smelting, and slowly pouring molten metal into a water-cooled copper mold when the raw materials are completely melted and the temperature is 1400-1600 ℃ to obtain the La-Fe-Si-based magnetic refrigeration alloy ingot.
Further, in step S2, the smelting method is arc smelting, and the arc smelting specifically includes: firstly, the vacuum of the electric arc smelting furnace chamber is pumped to 8 multiplied by 10 -4 And Pa, washing with argon with the purity of more than 99.9% for 2 times, then introducing argon again, and electrifying and smelting for 3-4 times to obtain the La-Fe-Si-based magnetic refrigeration alloy ingot.
Further, in the step S3, the plastic deformation is selected from one of rolling, drawing, extruding, and swaging.
Further, in the step S3, the plastic deformation temperature range is 20 to 1200 ℃, and the deformation amount range is 0.1% to 99.9%. .
Further, in the step S4, the homogenization heat treatment is performed under the protection of high-purity inert gas, and the temperature of the homogenization heat treatment is 950 to 1200 ℃ for 0.01 to 720 hours.
Further, the method also comprises the following steps: and S5, carrying out hydrogenation treatment on the La-Fe-Si-based magnetic refrigeration alloy.
Further, in the step S5, the temperature of the hydrogenation treatment is 100-500 ℃, the time is 0.5-10 h, and the hydrogen pressure is 0.01-3.0 MPa.
Compared with the prior art, the invention has the following advantages:
(1) on the basis of the traditional casting of the La-Fe-Si-based alloy, the invention obtains the shape with large specific surface area through plastic deformation, simultaneously regulates and controls the microstructure of alpha-Fe and La-rich phase, accelerates the formation rate of the magnetocaloric phase in the heat treatment process, forms a large amount of magnetocaloric phases in a short time and obtains the large magnetocaloric effect.
(2) In the method, different plastic deformation modes are selected according to the shape requirements of the magnetic refrigeration working medium, and plate, sheet, rod and filiform materials can be directly prepared, so that the preparation process is simple and efficient, the operation is easy, the product yield is high, the method is suitable for large-scale production, and the economic value is high. The method has wide application prospect in the field of magnetic refrigeration;
(3) the deformation precursor used in the invention contains a large amount of ductile alpha-Fe phases which can be used as a plastic deformation network to coordinate deformation, thereby ensuring the integrity of a deformation sample;
(4) in the invention, the alpha-Fe and the La-rich phase of the ingot are flattened or elongated in the deformation process, on one hand, the contact area of the two phases is increased, more nucleation sites are provided for the inclusion reaction during heat treatment, and the nucleation process of the 1:13 phase is promoted; on the other hand, the refined alpha-Fe and the La-rich phase are easier to be swallowed by the 1:13 phase, the growth process of the 1:13 phase is facilitated, the two effects enable the phase forming speed in the deformation sample to be faster, and further the heat treatment time is obviously shortened;
(5) in the invention, the magnetocaloric effect of the La-Fe-Si-based alloy can be adjusted by controlling parameters such as deformation amount, deformation temperature, deformation rate and the like, and the La-Fe-Si-based alloy can be used for developing magnetic working media required by different service conditions.
Drawings
FIG. 1 shows LaFe obtained in example 1 of the present invention 11 Co 0.8 Si 1.2 A physical diagram of the magnetic refrigeration alloy;
FIG. 2 shows LaFe obtained in example 1 of the present invention 11 Co 0.8 Si 1.2 Microstructure diagram of magnetic refrigeration alloy;
FIG. 3 shows LaFe obtained in example 1 of the present invention 11 Co 0.8 Si 1.2 The magnetic entropy change of the magnetic refrigeration alloy is shown as a change graph with temperature.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1:
LaFe 11 Co 0.8 Si 1.2 The magnetic refrigeration alloy is prepared by the following preparation method:
(1) weighing simple substances of La, Fe, Co and Si according to the component proportion, wherein the purity of each raw material is more than or equal to 99.9%;
(2) placing the raw materials in a medium-frequency induction smelting furnace, firstly vacuumizing to 1 x 10 -2 Pa, then washing with argon with the purity of more than 99.9 percent for 2 times, then filling argon again, electrifying and smelting, and slowly pouring molten metal into a water-cooled copper mold to obtain LaFe when the raw materials are completely molten and the temperature is about 1400 DEG C 11 Co 0.8 Si 1.2 Magnetically refrigerating alloy ingot casting;
(3) mixing LaFe 11 Co 0.8 Si 1.2 Placing the magnetic refrigeration alloy cast ingot in a heating furnace, heating to 1000 ℃, and then carrying out multi-pass hot rolling deformation to obtain LaFe 11 Co 0.8 Si 1.2 The thickness deformation of the magnetic refrigeration alloy blank is 31 percent, and the heating and deformation processes are carried out in the air;
(4) removal of LaFe by wire-electrode cutting 11 Co 0.8 Si 1.2 Performing homogenization heat treatment on the surface area of the magnetic refrigeration alloy blank in argon atmosphere, wherein the heat treatment temperature is 1050 ℃, the time is 72 hours, and quenching in water after the heat treatment is finished to obtain LaFe 11 Co 0.8 Si 1.2 Magnetic refrigeration alloy.
Example 2:
la 0.7 Ce 0.3 Fe 11.4 Mn 0.2 Si 1.4 The magnetic refrigeration alloy is prepared by the following preparation method:
(1) weighing simple substances of La, Ce, Fe, Mn and Si according to the component proportion, wherein the purity of each raw material is more than or equal to 99.9%;
(2) putting the raw materials into an electric arc melting furnace, and vacuumizing to 8 x 10 -4 Pa, then washing with argon with the purity of more than 99.9% for 2 times, then introducing argon again, electrifying and smelting, wherein the smelting current is 10-150A, the smelting time is about 60s, smelting is repeated for 4 times, turning over the sample before remelting every time, and after smelting is finished, obtaining cylindrical La with the diameter of 10mm by using a vacuum suction casting system 0.7 Ce 0.3 Fe 11.4 Mn 0.2 Si 1.4 Magnetically refrigerating alloy ingot casting;
(3) la 0.7 Ce 0.3 Fe 11.4 Mn 0.2 Si 1.4 Placing the magnetic refrigeration alloy cast ingot in an extrusion die, heating the cast ingot and the die to 800 ℃ under the protection of argon gas, completing extrusion to obtain a bar with the diameter of 1mm, and cooling an extrusion sample to room temperature along with a furnace to obtain La 0.7 Ce 0.3 Fe 11.4 Mn 0.2 Si 1.4 A magnetic refrigeration alloy blank;
(4) la 0.7 Ce 0.3 Fe 11.4 Mn 0.2 Si 1.4 Heating the magnetic refrigeration alloy blank to 1000 ℃ in the protection of argon, and preserving heat for 24h to complete homogenization heat treatment and water quenching;
(5) placing the heat-treated sample into an atmosphere furnace, replacing air with argon, filling hydrogen to finish hydrogenation treatment, and setting the hydrogen pressure at 0.1MPa, the heating temperature at 300 ℃ and the heating time at 5h to obtain La 0.7 Ce 0.3 Fe 11.4 Mn 0.2 Si 1.4 H x Magnetic refrigeration alloy.
Example 3:
LaFe 13.92 Si 1.4 The magnetic refrigeration alloy is prepared by the following preparation method:
(1) weighing the simple substances of La, Fe and Si according to the component proportion, wherein the purity of each raw material is more than or equal to 99.9 percent
(2) Placing the raw materials in a medium-frequency induction smelting furnace, firstly vacuumizing to 1 x 10 -2 Pa, then washing with argon with the purity of more than 99.9 percent for 2 times, then filling argon again, electrifying and smelting, and slowly pouring molten metal into a water-cooled copper mold when the raw materials are completely melted and the temperature is about 1400 ℃ to obtain platy LaFe 13.92 Si 1.4 Magnetically refrigerating alloy ingot casting;
(3) mixing LaFe 13.92 Si 1.4 The magnetic refrigeration alloy cast ingot is placed in a heating furnace to be heated to 1000 ℃, and then is subjected to multi-pass hot rolling deformation to obtain LaFe 13.92 Si 1.4 The total deformation of the magnetic refrigeration alloy blank is about 50 percent, and the heating and deformation processes are carried out in the air;
(4) removal of LaFe by wire-electrode cutting 13.92 Si 1.4 And (3) magnetically refrigerating the surface area of the alloy blank, then performing homogenization heat treatment in an argon atmosphere, wherein the heat treatment temperature is 1050 ℃, the time is 72 hours, and after the heat treatment is finished, quenching the sample in water.
(5) Putting the heat-treated sample into an atmosphere furnace, replacing air with argon, and filling hydrogen to complete hydrogenation treatment to obtain LaFe 13.92 Si 1.4 H x The magnetic refrigeration alloy is set with hydrogen pressure of 0.1MPa, heating temperature of 350 ℃ and heating time of 5 h.
The inventors examined the preparation process of example 1, and FIG. 1 shows 1mm thick plate-like LaFe prepared in example 1 11 Co 0.8 Si 1.2 The magnetic refrigeration alloy has a corresponding microstructure shown in FIG. 2, as can be seen from FIG. 2, the microstructure mainly consists of a 1:13 phase, a small amount of alpha-Fe and a 1:1:1 La-rich phase, FIG. 3 shows entropy change curves of heat-treated samples in example 1 under different temperature conditions, and the hot-rolled deformation La-Fe-Co-Si alloy has a large magnetic entropy change of 6.1J/kg K under 2T conditions.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure, and such changes and modifications will fall within the scope of the present invention.

Claims (10)

1. A preparation method of La-Fe-Si-based magnetic refrigeration alloy is characterized by comprising the following steps:
s1, designing components of the La-Fe-Si-based magnetic refrigeration alloy, and preparing raw materials according to the designed components;
s2, smelting the prepared raw materials to obtain La-Fe-Si-based magnetic refrigeration alloy cast ingots;
s3, plastically deforming the La-Fe-Si-based magnetic refrigeration alloy ingot obtained in the step S2 to obtain an La-Fe-Si-based magnetic refrigeration alloy blank;
and S4, carrying out homogenization heat treatment on the La-Fe-Si-based magnetic refrigeration alloy blank obtained in the step S3 to obtain the La-Fe-Si-based magnetic refrigeration alloy.
2. The method for preparing the La-Fe-Si based magnetic refrigeration alloy according to claim 1, wherein the La-Fe-Si based magnetic refrigeration alloy has a chemical formula of La 1 1-a RE a (Fe 1-b M b ) c (Si 1-d X d ) e Z f Wherein a is more than or equal to 0 and less than or equal to 0.5, B is more than or equal to 0 and less than or equal to 0.1, C is more than or equal to 11.0 and less than or equal to 15.0, d is more than or equal to 0 and less than or equal to 1.0, e is more than or equal to 1.0 and less than or equal to 1.6, RE is selected from one or more of rare earth elements Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, M is selected from one or more of transition metal elements Co, Ni, Mn, Cr, Cu, Zn, Ti, V, Zr and Nb, X is selected from one or more of Al, Ga, Sn and Ge, and Z is a non-metal element C and/or B.
3. The method for preparing La-Fe-Si based magnetic refrigeration alloy according to claim 1, wherein in step S1, the purity of the prepared raw material is not less than 99.9%.
4. The preparation method of the La-Fe-Si-based magnetic refrigeration alloy according to claim 1, wherein the melting in the step S2 is induction melting, and the specific steps of the induction melting are as follows: firstly, the vacuum of the vacuum induction furnace chamber is pumped to 1 x 10 -2 And Pa, washing with argon with the purity of more than 99.9% for 2 times, then filling argon again, electrifying and smelting, and slowly pouring molten metal into a water-cooled copper mold when the raw materials are completely melted and the temperature is 1400-1600 ℃ to obtain the La-Fe-Si-based magnetic refrigeration alloy ingot.
5. The method for preparing the La-Fe-Si based magnetic refrigeration alloy according to claim 1, wherein the melting in the step S2 is arc melting, and the arc melting comprises the following specific steps: firstly, the vacuum of the electric arc melting furnace chamber is pumped to 8 multiplied by 10 -4 And Pa, washing with argon with the purity of more than 99.9% for 2 times, then introducing argon again, and electrifying and smelting for 3-4 times to obtain the La-Fe-Si-based magnetic refrigeration alloy ingot.
6. The method for preparing an La-Fe-Si-based magnetic refrigeration alloy according to claim 1, wherein in the step S3, the plastic deformation is one selected from rolling, drawing, extruding, and swaging.
7. The method for preparing La-Fe-Si based magnetic refrigeration alloy according to claim 6, wherein in the step S3, the plastic deformation temperature is 20 to 1200 ℃ and the deformation amount is 0.1 to 99.9%.
8. The method for preparing the La-Fe-Si based magnetic refrigeration alloy according to claim 1, wherein the homogenization heat treatment is performed under the protection of high purity inert gas in the step S4, and the temperature of the homogenization heat treatment is 950 to 1200 ℃ for 0.01 to 720 hours.
9. The method for preparing the La-Fe-Si based magnetic refrigeration alloy according to claim 1, further comprising the steps of: and S5, carrying out hydrogenation treatment on the La-Fe-Si-based magnetic refrigeration alloy.
10. The method for preparing the La-Fe-Si based magnetic refrigeration alloy according to claim 9, wherein the temperature of the hydrogenation treatment in the step S5 is 100 to 500 ℃, the time is 0.5 to 10 hours, and the hydrogen pressure is 0.01 to 3.0 MPa.
CN202210786336.XA 2022-07-04 2022-07-04 Preparation method of La-Fe-Si-based magnetic refrigeration alloy Pending CN115109984A (en)

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