CN108677078B - Mn-Ni-In-Co-Cu magnetic refrigeration material rich In Mn and preparation method thereof - Google Patents

Mn-Ni-In-Co-Cu magnetic refrigeration material rich In Mn and preparation method thereof Download PDF

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CN108677078B
CN108677078B CN201810576924.4A CN201810576924A CN108677078B CN 108677078 B CN108677078 B CN 108677078B CN 201810576924 A CN201810576924 A CN 201810576924A CN 108677078 B CN108677078 B CN 108677078B
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李宗宾
杨嘉晶
杨波
赵骧
左良
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Northeastern University China
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Abstract

The invention belongs to the technical field of magnetic refrigeration alloy materials and preparation processes of alloys thereof. The material can obtain excellent heat insulation temperature change near room temperature, and is an ideal near room temperature magnetic refrigeration working medium. The chemical molecular formula of the Mn-rich Mn-Ni-In-Co-Cu magnetic refrigeration alloy material is MnxNi37In9Co4CuyThe sum of the mole numbers of the elements in the alloy is 100, wherein x is more than or equal to 46 and less than or equal to 49, and y is more than or equal to 1 and less than or equal to 4. According to the invention, the Mn-Ni-In-Co-Cu magnetic refrigeration alloy block blank rich In Mn is prepared by proportioning raw materials, repeatedly melting by vacuum arc for many times, preparing a polycrystalline ingot, annealing under the protection of high-purity inert gas, and then rapidly cooling by water. The variation range of the magnetic entropy of the alloy block is 4.4-15.8 JKg under a 3T magnetic field‑1K‑1。

Description

Mn-Ni-In-Co-Cu magnetic refrigeration material rich In Mn and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation processes of magnetic refrigeration alloy materials and blocks thereof, and particularly relates to a near-room-temperature magnetic refrigeration alloy material and a preparation method of blocks thereof.
Background
Compared with the traditional gas compression type refrigeration technology, the magnetic refrigeration adopts magnetic substances as the refrigeration working medium, has no destructive effect on the ozone layer and no greenhouse effect, and the magnetic entropy density of the magnetic working medium is larger than that of gas, so that the refrigeration device can be more compact; because a compressor is not needed, the number of moving parts is small, the moving speed is low, the mechanical vibration and noise are low, the reliability is high, and the service life is long; in the aspect of heat efficiency, the gas compression type refrigeration technology can only reach 5-10% of Carnot cycle generally, and the magnetic refrigeration technology can reach 30-60%, so that high refrigeration efficiency is achieved. Based on the advantages, the room temperature magnetic refrigeration has great application prospect in magnetic refrigeration refrigerators, air conditioners, space technology, nuclear technology and the like, and becomes a high and new technical field which is strongly competitive in various countries at present.
In the development of magnetic refrigeration technology, ideal magnetic refrigeration materials contain at least 80% of transition group metal elements with large magnetic moment, such as Fe or Mn; also contains some elements of IIIA, IVA and VA groups, such as Al, Si, P, etc., which are mainly used to adjust the properties of the material. Therefore, the Cu element is doped to replace the Mn element to adjust the martensite phase transition temperature, so that the magnetocaloric effect of Mn-rich Mn-Ni-In-Co-Cu alloy is greatly improved, the Mn-rich Mn-Ni-In-Co-Cu alloy has good magnetocaloric effect near room temperature, and the excellent performance of Mn-rich Mn-Ni-In-Co-Cu magnetic refrigeration working media is greatly improved.
Disclosure of Invention
The invention mainly aims to provide a Mn-Ni-In-Co-Cu magnetic refrigeration material with giant magnetocaloric effect and a preparation method thereof, so as to overcome the defects In the prior art. In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the Mn-Ni-In-Co-Cu magnetic refrigeration alloy material is characterized In that the chemical molecular formula of elements In the alloy material is MnxNi37In9Co4CuyThe sum of the mole numbers of the elements in the alloy is 100, wherein x is more than or equal to 46 and less than or equal to 49, and y is more than or equal to 1 and less than or equal to 4.
Furthermore, the magnetic entropy change range of the Mn-rich Mn-Ni-In-Co-Cu magnetic refrigeration material under a 3T external magnetic field is 4.4-15.8 JKg-1K-1The phase-change temperature region is 240-306K.
The preparation method of the Mn-rich Mn-Ni-In-Co-Cu magnetic refrigeration material comprises the following steps:
(1) the raw material ratio is as follows: according to the chemical formula MnxNi37In9Co4CuyThe molar ratio of the raw materials is 46-49, and 1-4;
(2) preparing a polycrystalline ingot: placing the raw materials weighed in the step (1) into a water-cooled copper crucible of a vacuum arc melting furnace, and vacuumizing the cavity of the arc melting furnace to 3 multiplied by 10-3～5×10-3And (3) introducing inert protective gas of 0.04-0.05 MPa after Pa, and repeatedly smelting for 4-5 times, wherein the smelting time is 2-2.5 hours. Carrying out electric arc melting under electromagnetic stirring to obtain polycrystalline mother alloy with uniform components;
(3) and (3) heat treatment:
and (3) carrying out heat preservation on the Mn-rich Mn-Ni-In-Co-Cu alloy ingot at the temperature of 750-800 ℃ for 15-24 h, and then carrying out water cooling to obtain the Mn-rich Mn-Ni-In-Co-Cu magnetic refrigeration material.
In a preferred embodiment, the preparation method comprises: in the step (1), Ni is 99.97 wt.% high-purity Ni, Mn is 99.9 wt.% high-purity Mn, In is 99.99 wt.% high-purity In, Co is 99.9 wt.% high-purity Co, and Cu is 99.9 wt.% high-purity Cu.
In a preferred embodiment, the preparation method comprises: the placing method of Ni, Mn, In, Co and Cu In the water-cooled copper crucible In the step (1) is that Mn is placed at the bottommost part of the water-cooled copper crucible, Co, Cu, In and Ni are placed above Mn In sequence, wherein Ni is placed at the topmost part.
Further, in the preparation method, in the step (2), the ingot is repeatedly smelted for 4-5 times.
Further, the preparation method comprises the step of (1) and the step of (2) using high-purity argon as the inert gas.
Compared with the prior art, the Mn-Ni-In-Co-Cu magnetic refrigeration material rich In Mn and the preparation method thereof have the beneficial effects that:
(1) by adjusting the proportion of alloy components, the Mn-Ni-In-Co-Cu alloy rich In Mn can show larger difference In magnetism of materials before and after martensite phase transformation, and can generate a magnetic field to drive martensite phase transformation under the drive of an external magnetic field to show a large magnetocaloric effect.
(3) The raw materials of Ni, Mn, In, Co and Cu required by the magnetic alloy provided by the invention are low In price and rich In reserves. Meanwhile, the alloy is non-toxic, good in heat conducting performance, good in refrigerating capacity and good in performance stability.
(3) The Cu element is used for replacing the Mn element to adjust the martensite phase transformation temperature and the Curie temperature, the method is simple and has good repeatability, and the near-room-temperature magnetic refrigeration material with narrow lag and high magnetocaloric effect can be obtained.
Drawings
FIG. 1 shows Mn in example of the present invention49Ni37In9Co4Cu1DSC curve of magnetic refrigeration material.
FIG. 2 shows Mn in example of the present invention48Ni37In9Co4Cu2DSC curve of magnetic refrigeration material.
FIG. 3 shows Mn in example of the present invention47Ni37In9Co4Cu3DSC curve of magnetic refrigeration material.
FIG. 4 shows Mn in example of the present invention46Ni37In9Co4Cu4DSC curve of magnetic refrigeration material.
FIG. 5 shows Mn in example of the present invention49Ni37In9Co4Cu1The Delta S-T curve of the magnetic refrigeration material.
FIG. 6 shows Mn in example of the present invention48Ni37In9Co4Cu2The Delta S-T curve of the magnetic refrigeration material.
FIG. 7 shows Mn in example of the present invention47Ni37In9Co4Cu3The Delta S-T curve of the magnetic refrigeration material.
FIG. 8 shows Mn in example of the present invention46Ni37In9Co4Cu4The Delta S-T curve of the magnetic refrigeration material.
Detailed Description
In the following examples, Ni is 99.97 wt.% high purity Ni, Mn is 99.9 wt.% high purity Mn, In is 99.99 wt.% high purity In, Co is 99.9 wt.% high purity Co, and Cu is 99.9 wt.% high purity Cu.
In the following examples, a vacuum arc melting furnace was purchased from Shenyang scientific instruments research center, Inc., of China academy of sciences, and the type of the vacuum arc melting furnace was DHL-400.
The detection technical means of the following embodiment is as follows:
and measuring the martensite phase transformation temperature and the inverse transformation temperature of the sample by adopting a Differential Scanning Calorimetry (DSC). The temperature rise and the temperature drop rate of the sample are both 10K/min during measurement, and the phase change temperature is determined on a DSC curve by a tangent method.
The M-H curve of the sample was measured using an MPMS magnetic measurement system. According to isothermal magnetization curve and by using Maxwell relation
Figure BDA0001687481350000041
Calculating, namely cooling the sample to 140K in a zero field manner, heating the sample to a measurement temperature in the zero field manner, and then starting to measure; M-H curves including rising and falling fields: 0 → 3T and 3T → 0T, one spot per 1000G. Before each temperature point is measured, the sample needs zero field cooling to 140K, and then is heated to the next temperature to be measured for measurement. The magnetic field direction is parallel to the plane of the lamella.
Example 1
The Mn-Ni-In-Co-Cu magnetic refrigeration alloy material is rich In Mn, the sum of the mole numbers of elements In the alloy material is 100, and the mole ratio of the elements is Mn, Ni, In, Co and Cu is 49, 37, 9, 4 and 1.
The preparation method of the Mn-Ni-In-Co-Cu magnetic refrigeration alloy material rich In Mn comprises the following steps:
step 1, preparing a polycrystalline mother alloy:
(1) the raw material ratio is as follows: according to the chemical formula Mn49Ni37In9Co4Cu1Preparing the materials according to the molar ratio of (A);
(2) preparing a polycrystalline ingot: placing the raw materials weighed in the step (1) into a water-cooled copper crucible of a vacuum arc melting furnace, and vacuumizing the cavity of the arc melting furnace to 3 multiplied by 10-3～5×10-3And (3) introducing inert protective gas of 0.04-0.05 MPa after Pa, and repeatedly smelting for 4-5 times, wherein the smelting time is 2-2.5 hours. Carrying out electric arc melting under electromagnetic stirring to obtain polycrystalline mother alloy with uniform components;
(3) and (3) heat treatment:
carrying out heat preservation on Mn-Ni-In-Co-Cu alloy cast ingot rich In Mn at 750-800 ℃ for 15-24 h, and then carrying out water cooling to obtain Mn49Ni37In9Co4Cu1A magnetic refrigeration material.
Mn prepared in this example was analyzed by Differential Scanning Calorimetry (DSC)49Ni37In9Co4Cu1Phase transformation behavior of the alloy. As shown in FIG. 1, Mn49Ni37In9Co4Cu1The magnetic refrigeration material is directly transformed from weak magnetic martensite to ferromagnetic austenite in the process of increasing the temperature from 278K to 305K, and the magnetic transformation and the structural transformation occur simultaneously (namely, the magnetic-structural transformation).
The M-H curve of the sample was measured using an MPMS magnetic measurement system. Firstly, zero-field cooling the sample to 140K, then zero-field heating to a measurement temperature, and starting measurement; M-H curves including rising and falling fields: 0 → 3T and 3T → 0T, one spot per 1000G. Before each temperature point is measured, the sample needs zero field cooling to 140K, and then is heated to the next temperature to be measured for measurement. The measurement temperature range is 250-318K. The magnetic field direction is parallel to the plane of the lamella. The magnetic entropy becomes 4.5JKg calculated by the Maxwell relation according to the isothermal magnetization curve-1K-1。
Example 2
The Mn-Ni-In-Co-Cu magnetic refrigeration alloy material rich In Mn has the sum of the mole numbers of elements In the alloy material of 100, and the mole ratio of the elements is Mn to Ni to In to Co to Cu to 48 to 37 to 9 to 4 to 2.
The preparation method of the Mn-Ni-In-Co-Cu magnetic refrigeration alloy material rich In Mn comprises the following steps:
step 1, preparing a polycrystalline mother alloy:
(1) the raw material ratio is as follows: according to the chemical formula Mn48Ni37In9Co4Cu2Preparing the materials according to the molar ratio of (A);
(2) preparing a polycrystalline ingot: placing the raw materials weighed in the step (1) into a water-cooled copper crucible of a vacuum arc melting furnace, and vacuumizing the cavity of the arc melting furnace to 3 multiplied by 10-3～5×10-3And (3) introducing inert protective gas of 0.04-0.05 MPa after Pa, and repeatedly smelting for 4-5 times, wherein the smelting time is 2-2.5 hours. Carrying out electric arc melting under electromagnetic stirring to obtain polycrystalline mother alloy with uniform components;
(3) and (3) heat treatment:
carrying out heat preservation on Mn-Ni-In-Co-Cu alloy cast ingot rich In Mn at 750-800 ℃ for 15-24 h, and then carrying out water cooling to obtain Mn48Ni37In9Co4Cu2A magnetic refrigeration material.
Mn prepared in this example was analyzed by Differential Scanning Calorimetry (DSC)48Ni37In9Co4Cu2Phase transformation behavior of the alloy. As shown in FIG. 2, Mn48Ni37In9Co4Cu2The magnetic refrigeration material is directly transformed from weak magnetic martensite to ferromagnetic austenite in the process of increasing the temperature from 288K to 303K, and the magnetic transformation and the structural transformation occur simultaneously (namely, the magnetic-structural transformation).
The M-H curve of the sample was measured using an MPMS magnetic measurement system. Firstly, zero-field cooling the sample to 140K, then zero-field heating to a measurement temperature, and starting measurement; M-H curves including rising and falling fields: 0 → 3T and 3T → 0T, one spot per 1000G. Before each temperature point is measured, the sample needs zero field cooling to 140K, and then is heated to the next temperature to be measured for measurement. The measurement temperature range is 268-308K. The magnetic field direction is parallel to the plane of the lamella. The value of the magnetic entropy change is 11.8JKg calculated by using Maxwell relation according to the isothermal magnetization curve-1K-1。
Example 3
The Mn-Ni-In-Co-Cu magnetic refrigeration alloy material is rich In Mn, the sum of the mole numbers of elements In the alloy material is 100, and the mole ratio of the elements is Mn, Ni, In, Co and Cu is 47:37:9:4: 3.
The preparation method of the Mn-Ni-In-Co-Cu magnetic refrigeration alloy material rich In Mn comprises the following steps:
step 1, preparing a polycrystalline mother alloy:
(1) the raw material ratio is as follows: according to the chemical formula Mn47Ni37In9Co4Cu3Preparing the materials according to the molar ratio of (A);
(2) preparing a polycrystalline ingot: placing the raw materials weighed in the step (1) into a water-cooled copper crucible of a vacuum arc melting furnace, and vacuumizing the cavity of the arc melting furnace to 3 multiplied by 10-3～5×10-3And (3) introducing inert protective gas of 0.04-0.05 MPa after Pa, and repeatedly smelting for 4-5 times, wherein the smelting time is 2-2.5 hours. Carrying out electric arc melting under electromagnetic stirring to obtain polycrystalline mother alloy with uniform components;
(3) and (3) heat treatment:
carrying out heat preservation on Mn-Ni-In-Co-Cu alloy cast ingot rich In Mn at 750-800 ℃ for 15-24 h, and then carrying out water cooling to obtain Mn47Ni37In9Co4Cu3A magnetic refrigeration material.
Mn prepared in this example was analyzed by Differential Scanning Calorimetry (DSC)47Ni37In9Co4Cu3Phase transformation behavior of the alloy. As shown in FIG. 3, Mn47Ni37In9Co4Cu3The magnetic refrigeration material is directly transformed from weak magnetic martensite to ferromagnetic austenite in the process of increasing the temperature from 286K to 303K, and the magnetic transformation and the structural transformation occur simultaneously (namely, the magnetic-structural transformation).
The M-H curve of the sample was measured using an MPMS magnetic measurement system. Firstly, zero-field cooling the sample to 140K, then zero-field heating to a measurement temperature, and starting measurement; M-H curves including rising and falling fields: 0 → 3T and 3T → 0T, one spot per 1000G. Before each temperature point is measured, the sample needs zero field cooling to 140K, and then is heated to the next temperature to be measured for measurement. The measurement temperature range is 270-310K. The magnetic field direction is parallel to the plane of the lamella. The value of the magnetic entropy change is 15.2JKg calculated by using Maxwell relation according to the isothermal magnetization curve-1K-1。
Example 4
The Mn-Ni-In-Co-Cu magnetic refrigeration alloy material is rich In Mn, the sum of the mole numbers of elements In the alloy material is 100, and the mole ratio of the elements is Mn, Ni, In, Co and Cu is 46:37:9:4: 4.
The preparation method of the Mn-Ni-In-Co-Cu magnetic refrigeration alloy material rich In Mn comprises the following steps:
step 1, preparing a polycrystalline mother alloy:
(1) the raw material ratio is as follows: according to the chemical formula Mn46Ni37In9Co4Cu4Preparing the materials according to the molar ratio of (A);
(2) preparing a polycrystalline ingot: placing the raw materials weighed in the step (1) into a water-cooled copper crucible of a vacuum arc melting furnace, and vacuumizing the cavity of the arc melting furnace to 3 multiplied by 10-3～5×10-3And (3) introducing inert protective gas of 0.04-0.05 MPa after Pa, and repeatedly smelting for 4-5 times, wherein the smelting time is 2-2.5 hours. Carrying out electric arc melting under electromagnetic stirring to obtain polycrystalline mother alloy with uniform components;
(3) and (3) heat treatment:
carrying out heat preservation on Mn-Ni-In-Co-Cu alloy cast ingot rich In Mn at 750-800 ℃ for 15-24 h, and then carrying out water cooling to obtain Mn46Ni37In9Co4Cu4A magnetic refrigeration material.
Mn prepared in this example was analyzed by Differential Scanning Calorimetry (DSC)46Ni37In9Co4Cu4Phase transformation behavior of the alloy. As shown in FIG. 4, Mn46Ni37In9Co4Cu4The magnetic refrigeration material is directly transformed from weak magnetic martensite to ferromagnetic austenite in the process of increasing the temperature from 301K to 323K, and the magnetic transformation and the structural transformation occur simultaneously (namely, the magnetic-structural transformation).
The M-H curve of the sample was measured using an MPMS magnetic measurement system. Firstly, zero-field cooling the sample to 140K, then zero-field heating to a measurement temperature, and starting measurement; M-H curves including rising and falling fields: 0 → 3T and 3T → 0T, one spot per 1000G. Before each temperature point is measured, the sample needs zero field cooling to 140K, and then is heated to the next temperature to be measured for measurement. The measurement temperature range is 284-320K. The magnetic field direction is parallel to the plane of the lamella. The value of the magnetic entropy change is 15.8JKg calculated by using Maxwell relation according to the isothermal magnetization curve-1K-1。

Claims (6)

1. The Mn-Ni-In-Co-Cu magnetic refrigeration alloy material is characterized In that the chemical molecular formula of elements In the alloy material is MnxNi37In9Co4CuyThe sum of the mole numbers of the elements in the alloy is 100, wherein x is more than or equal to 46 and less than or equal to 49, and y is more than or equal to 1 and less than or equal to 4;
the Mn-Ni-In-Co-Cu magnetic refrigeration alloy material rich In Mn has the magnetic entropy change range of 4.4-15.8 JKg under a 3T magnetic field-1K-1The phase-change temperature region is 252-313K.
2. The preparation method of the Mn-rich Mn-Ni-In-Co-Cu magnetic refrigeration alloy material of claim 1, characterized by comprising the following steps:
(1) the raw material ratio is as follows: according to the chemical formula MnxNi37In9Co4CuyThe molar ratio of the raw materials is 46-49, and 1-4;
(2) preparing a polycrystalline ingot: placing the raw materials weighed in the step (1) into a water-cooled copper crucible of a vacuum arc melting furnace, and vacuumizing the cavity of the arc melting furnace to 3 multiplied by 10-3～5×10-3After Pa, introducing inert protective gas of 0.04-0.05 MPa, repeatedly smelting for 4-5 times, wherein the smelting time is 2-2.5 hours, and carrying out arc smelting under electromagnetic stirring to obtain polycrystalline master alloy with uniform components;
(3) and (3) heat treatment:
and (3) carrying out heat preservation on the Mn-Ni-In-Co-Cu alloy ingot rich In Mn for 15-24 h at 750-800 ℃, and then carrying out water cooling to obtain the Mn-Ni-In-Co-Cu magnetic refrigeration material rich In Mn.
3. The method according to claim 2, wherein In the step (1), Ni is 99.97 wt.% high purity Ni, Mn is 99.9 wt.% high purity Mn, In is 99.99 wt.% high purity In, Co is 99.9 wt.% high purity Co, and Cu is 99.9 wt.% high purity Cu.
4. The production method according to claim 2 or 3, wherein In the step (2), Ni, Mn, In, Co and Cu are placed In the water-cooled copper crucible by placing Mn at the lowermost part of the water-cooled copper crucible and placing Cu, Co, In and Ni above Mn In this order, with Ni at the uppermost part.
5. The preparation method according to claim 4, wherein the ingot is repeatedly melted 4-5 times in the step (2).
6. The method according to claim 4, wherein the inert shielding gas in step (2) is high purity argon.
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