CN114395718A - Preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles - Google Patents
Preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles Download PDFInfo
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Abstract
The invention provides a preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles, which comprises the following steps of (1) smelting a master alloy in a vacuum arc smelting furnace; (2) carrying out homogenization heat treatment on the mother alloy cast ingot under vacuum, and carrying out water quenching after heat preservation at 900 ℃ for 24 hours; (3) smashing the mother alloy by using an iron mortar to obtain initial particles; (4) adopting a high-speed vibration ball mill with the rotating speed of 1400 revolutions per minute, putting initial particles into a ball milling tank under the protection of argon before ball milling, putting grinding balls, adding an organic reagent, and carrying out ball milling to obtain micron-sized secondary particles; (5) annealing the secondary particles subjected to ball milling to obtain a solidified block; (6) the consolidated mass formed after annealing was ground in an agate mortar. The NiCoMnIn magnetic shape memory alloy prepared by the invention has uniform particle components, martensite phase change behavior and magnetic performance similar to those of a master alloy block material, and has the advantages of simple preparation method process, short preparation time and low cost.
Description
Technical Field
The invention relates to a preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles.
Background
The NiCoMnIn magnetic memory alloy is a novel functional material which has thermoelastic martensite phase transformation and can induce the martensite phase transformation by temperature, stress and magnetic field, has good shape memory effect, magnetocaloric effect, giant magnetoresistance effect and elasto-thermal effect, and can be used as a sensor, a driver and a room-temperature solid-state refrigeration working medium. However, as an intermetallic compound, NiCoMnIn polycrystalline alloy has a very high intrinsic brittleness, is easily broken along the crystal, cannot fully exhibit its functional characteristics, and has poor processability, which greatly limits the application of its polycrystalline material.
In order to overcome the polycrystalline brittleness and improve the mechanical property of the material, researchers propose a solution method which comprises the steps of preparing NiCoMnIn alloy into particles and preparing the particles and other materials into a composite material or sintering the alloy particles to form a block material. Both methods require that NiCoMnIn particles be obtained first, and the particles must have martensite transformation behavior and magnetic properties similar to those of bulk materials to ensure that the finally prepared composite material and sintered body have excellent functional characteristics. Mechanical ball milling is known as a common method for preparing NiMn-based Heusler alloy particles, and for example, in document 1, "preparation method of micron-sized particles of NiMnGa magnetic memory alloy" NiMnGa magnetic memory alloy particles with a particle size of less than 100 μm can be prepared by using a planetary ball mill. NiCoMnIn and NiMnGa belong to NiMn-based Heusler alloys, and therefore, the same method is attempted to prepare NiCoMnIn alloy micro-sized particles. However, according to the current published reports, although micron-sized particles are obtained by the mechanical ball milling method, the particles do not have martensite phase transformation and strong ferromagnetism, and lose the functional characteristics which are used as the magnetic shape memory alloy. As in document 2 "ferromagnetic shape memory alloy Ni51Mn27Ga22And Ni45Co5Mn36.6In13.4Study of organization and properties of its composite materials, 2009, university of northeastTo run over Ni45Co5Mn36.6In13.4After the alloy is ball-milled for 20 minutes, the alloy is annealed at 800 ℃/6 hours, and no martensitic transformation behavior is tested in the alloy particles. Document 3 "MicroStructure, Phase transformation and Mechanical Property of Ni-Co-Mn-In Alloy Prepared by Spark Plasma Sintering, Materials Science Forum 815(2015) 222-" reports Ni-45Co5Mn36.7In13.3The alloy was sintered at 800 c/5 min after ball milling for 20 min, and although a temperature sufficient to restore Heusler structure was provided, no martensitic transformation was detected in the sintered material.
Through literature retrieval, although a few reports are made on NiCoMnIn particles prepared by adopting a ball milling method at present, the prepared particles have no martensite phase transformation, so that the functional characteristics which should be possessed by the magnetic shape memory alloy, including the magnetocaloric effect, are lost. The literature search does not find the same composition as the material of the invention, and does not find the relevant report of the same preparation method as the invention.
Disclosure of Invention
The invention aims to overcome the problem that NiCoMnIn particles prepared by a ball milling method do not have martensite phase transformation, and provides a preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles by combining vibration ball milling and subsequent annealing, which can prepare NiCoMnIn magnetic shape memory alloy particles with uniform components and martensite phase transformation behavior and magnetic performance similar to those of a master alloy block material. The preparation method has the advantages of simple process, short preparation time and low cost. The micron-sized NiCoMnIn magnetic shape memory alloy particles can be used for preparing a NiCoMnIn composite material and can also be directly used as a magnetic refrigeration working medium.
The technical scheme of the invention is as follows:
(1) smelting a master alloy in a vacuum arc smelting furnace;
(2) carrying out homogenization heat treatment on the mother alloy cast ingot under vacuum, and carrying out water quenching after heat preservation at 900 ℃ for 24 hours;
(3) smashing the mother alloy by using an iron mortar to obtain initial particles;
(4) adopting a high-speed vibration ball mill with the rotation speed of 1400 revolutions per minute, putting initial particles into a ball milling tank under the protection of argon before ball milling, putting grinding balls, adding an organic reagent, screwing an upper cover of the ball milling tank, and carrying out ball milling for a certain time to obtain micron-sized secondary particles;
(5) annealing the secondary particles subjected to ball milling to obtain a solidified block;
(6) the consolidated mass formed after annealing was ground in an agate mortar.
Further, step (1), the master alloy consists of 45-45.5% of Ni, 5.3-4.8% of Co, 36.7% of Mn and the balance of In atomic fraction, and the sum of the atomic fractions of the components is 100%;
further, in the step (3), the initial particle size is less than 0.25 mm. (ii) a
Further, in the step (4), a stainless steel grinding ball with the diameter of 10mm is placed;
further, in the step (4), the ball-to-material ratio is 4;
further, in the step (4), the added organic reagent is absolute ethyl alcohol;
further, in the step (4), the ball milling time is 2-8 minutes;
further, in the step (5), the secondary particles were first annealed at 800 ℃ for 1 hour in an argon atmosphere, then annealed at 550 ℃ for 10 minutes in a vacuum, and quenched into water.
Compared with the prior art, the invention has the beneficial effects that:
the NiCoMnIn magnetic shape memory alloy prepared by the invention has uniform particle components and has martensite phase change behavior and magnetic performance similar to those of a master alloy block material. The preparation method has the advantages of simple process, short preparation time and low cost. The micron-sized NiCoMnIn magnetic shape memory alloy particles can be used for preparing a NiCoMnIn composite material and can also be directly used as a magnetic refrigeration working medium.
Drawings
FIG. 1 is a schematic diagram of a method for preparing NiCoMnIn magnetic shape memory alloy micron-sized particles;
FIG. 2 Ni after high energy ball milling45.2Co5.1Mn36.7In13Alloy particles are subjected to 800 DEG CRoom temperature X-ray diffraction spectrum after annealing for 1 hour and then annealing treatment at 550 ℃/10 minutes;
FIG. 3 Ni after high energy ball milling45.2Co5.1Mn36.7In13The magnetization-temperature curve of the alloy particles after annealing at 800 ℃/1 hour and then annealing at 550 ℃/10 minutes.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
A preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles comprises the following process steps:
1. vacuum arc melting furnace for melting Ni45.2Co5.1Mn36.7In13A master alloy;
2. carrying out homogenization heat treatment on the mother alloy cast ingot under vacuum, and carrying out water quenching after heat preservation at 900 ℃ for 24 hours;
4. smashing the mother alloy by using an iron mortar to form initial particles, wherein the particle size is less than 0.25 mm;
5. adopting a high-speed vibration ball mill with the rotation speed of 1400 revolutions per minute, putting initial particles into a ball milling tank under the protection of argon atmosphere before ball milling, putting stainless steel grinding balls with the diameter of 10mm, adding absolute ethyl alcohol, screwing an upper cover of the ball milling tank, and carrying out ball milling for 2-8 minutes to obtain secondary particles, wherein the ball milling ratio is 4;
6. annealing the secondary particles at 800 ℃ for 1 hour in an argon atmosphere, annealing at 550 ℃ for 10 minutes in vacuum, and quenching into water to obtain a solidified block;
7. grinding and annealing the mixture by using an agate mortar to form a solidified block;
8. measuring the granularity by a laser granularity analyzer, wherein the granularity range is 10-40 mu m;
9. measuring the crystal structure by X-ray diffractometer, wherein the martensite structure of the alloy particle is modulated at 10M at room temperature, as shown in FIG. 2;
10. the magnetization of the alloy particles was measured with a vibrating sample magnetometer as a function of temperature, as shown in FIG. 3. The alloy particles are seen to undergo a typical thermoelastic martensitic transformation, the martensite start temperature (M)s) In 3The phase change behavior characteristics of the alloy are basically consistent with those of the master alloy block material with the same composition at the temperature of about 6 ℃; the difference (Delta M) between the saturation magnetization of martensite and austenite is as high as 84.2emu/g, and the magnetic performance is close to that of a master alloy bulk material.
The NiCoMnIn magnetic shape memory alloy prepared by the method has uniform particle components and has martensite phase change behavior and magnetic performance similar to those of a master alloy block material. The preparation method has the advantages of simple process, short preparation time and low cost. The micron-sized NiCoMnIn magnetic shape memory alloy particles can be used for preparing a NiCoMnIn composite material and can also be directly used as a magnetic refrigeration working medium.
Claims (8)
1. A preparation method of NiCoMnIn magnetic shape memory alloy micron-sized particles is characterized by comprising the following steps: the method comprises the following steps:
(1) smelting a master alloy in a vacuum arc smelting furnace;
(2) carrying out homogenization heat treatment on the mother alloy cast ingot under vacuum, and carrying out water quenching after heat preservation at 900 ℃ for 24 hours;
(3) smashing the mother alloy by using an iron mortar to obtain initial particles;
(4) adopting a high-speed vibration ball mill with the rotation speed of 1400 revolutions per minute, putting initial particles into a ball milling tank under the protection of argon before ball milling, putting grinding balls, adding an organic reagent, screwing an upper cover of the ball milling tank, and ball milling to obtain micron-sized secondary particles;
(5) annealing the secondary particles subjected to ball milling to obtain a solidified block;
(6) the consolidated mass formed after annealing was ground in an agate mortar.
2. The method of claim 1, wherein the NiCoMnIn magnetic shape memory alloy micron-sized particles are prepared by a method comprising the following steps: step (1), the master alloy consists of 45-45.5% of Ni, 5.3-4.8% of Co, 36.7% of Mn and the balance of In by atomic fraction, and the sum of the atomic fractions of the components is 100%.
3. The method of claim 1, wherein the NiCoMnIn magnetic shape memory alloy micron-sized particles are prepared by a method comprising the following steps: in step (3), the initial particle size is less than 0.25 mm.
4. The method of claim 1, wherein the NiCoMnIn magnetic shape memory alloy micron-sized particles are prepared by a method comprising the following steps: in the step (4), a stainless steel grinding ball with the diameter of 10mm is placed.
5. The method of claim 1, wherein the NiCoMnIn magnetic shape memory alloy micron-sized particles are prepared by a method comprising the following steps: in the step (4), the ball-to-material ratio is 4.
6. The method of claim 1, wherein the NiCoMnIn magnetic shape memory alloy micron-sized particles are prepared by a method comprising the following steps: in the step (4), the added organic reagent is absolute ethyl alcohol.
7. The method of claim 1, wherein the NiCoMnIn magnetic shape memory alloy micron-sized particles are prepared by a method comprising the following steps: in the step (4), the ball milling time is 2-8 minutes.
8. The method of claim 1, wherein the NiCoMnIn magnetic shape memory alloy micron-sized particles are prepared by a method comprising the following steps: in the step (5), the secondary particles are first annealed at 800 ℃ for 1 hour in an argon atmosphere, then annealed at 550 ℃ for 10 minutes in a vacuum, and quenched into water.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116083774A (en) * | 2023-04-10 | 2023-05-09 | 成都先进金属材料产业技术研究院股份有限公司 | High magnetic entropy change non-equilibrium state Ni-Co-Mn-In alloy and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007353A (en) * | 2007-01-25 | 2007-08-01 | 哈尔滨工程大学 | Preparation method of micrometer grade NiMnCa magnetic memory alloy grain |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007353A (en) * | 2007-01-25 | 2007-08-01 | 哈尔滨工程大学 | Preparation method of micrometer grade NiMnCa magnetic memory alloy grain |
Non-Patent Citations (1)
| Title |
|---|
| 赵文儒: "热变形对Ni45Co5Mn36.7In13.3组织与磁性能的影响", 《中国优秀硕士学位论文全文数据库 (》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116083774A (en) * | 2023-04-10 | 2023-05-09 | 成都先进金属材料产业技术研究院股份有限公司 | High magnetic entropy change non-equilibrium state Ni-Co-Mn-In alloy and preparation method and application thereof |
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