CN113373362A - Thulium-nickel material for magnetic refrigeration and preparation method thereof - Google Patents
Thulium-nickel material for magnetic refrigeration and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a method forThe thulium-nickel material for magnetic refrigeration and the preparation method thereof, the thulium-nickel material has the chemical formula: tm is3+xNi2+yWherein x is more than or equal to-0.1 and less than or equal to 0.1, y is more than or equal to-0.1 and less than or equal to 0.1, the crystal has a rhombohedral crystal structure, the space group of the crystal structure is R-3, the phase transition temperature is between 2 and 6K, and the magnetic entropy change peak value under the change of a 0-2T magnetic field is between 15 and 17J/(kg.K). The preparation method adopted by the invention comprises the modes of tabletting, crushing, grinding and the like, is clean and environment-friendly, and the obtained thulium-nickel material can be used for magnetic refrigeration in an extremely low temperature region under a low magnetic field.
Description
Technical Field
The invention belongs to the field of magnetic refrigeration, and particularly relates to a thulium-nickel material for magnetic refrigeration and a preparation method thereof.
Background
The modern society is more and more free from refrigeration technology, and the refrigeration technology is not available from daily life of people to industrial and agricultural production, medical treatment and health, national defense science and technology and the like. At present, the gas compression refrigeration technology is generally adopted to realize refrigeration, but the traditional gas compression refrigeration technology also has the problems of high energy consumption, damage to the atmospheric ozone layer by harmful gas discharged in the refrigeration process, greenhouse effect and the like. Therefore, it is of great significance to explore a novel refrigeration technology which is energy-saving and environment-friendly. Compared with the gas compression refrigeration technology, the magnetic refrigeration technology has the remarkable advantages of high efficiency, energy conservation, environmental protection, stable operation and the like, and is an ideal energy-saving and environment-friendly refrigeration technology. The magnetic refrigeration is a novel refrigeration technology using magnetic materials as refrigeration working media, and the basic principle is that the magnetic refrigeration materials are used as heat carrying media by means of the heat release and heat absorption physical effects generated when the magnetic field is enhanced and weakened by the magnetic materials, and heat is continuously transferred from one space to another space through proper work circulation so as to achieve the purpose of refrigeration.
The key point for realizing the magnetic refrigeration is to obtain a magnetic refrigeration material with excellent performance, the most important parameter of the magnetic refrigeration material is magnetic entropy change (delta S), and the larger the delta S of the material is, the higher the application value is. The magnetic entropy change of the magnetic refrigeration material generally has a maximum value near the phase-change temperature, and the magnetic refrigeration material used in different temperature regions can be obtained by regulating and controlling the phase-change temperature. According to the division of the working temperature area, the magnetic refrigeration materials can be divided into extremely low temperature (below 10K), low temperature (10K-80K), medium temperature (80K-250K) and high temperature (above 250K) magnetic refrigeration materials. ZL201110190323.8 discloses a rare earth-nickel material and a preparation method and application thereof, and the material of Ho or Er and Ni prepared by adopting an electric arc melting or induction melting method has the maximum magnetic entropy change under the magnetic field change of 0-5T and the phase change temperature of more than 10K, thereby achieving the best magnetic refrigeration effect.
However, the liquefaction of helium, which is widely concerned by research institutions and industrial departments at home and abroad, requires a magnetic refrigeration material in an extremely low temperature region, more specifically, an important temperature region of liquid helium is near 4K, and the research and development of a high-performance magnetic refrigeration material in the temperature region are of great significance for the liquefaction of helium. The phase-change temperature of the current magnetic refrigeration material is generally higher, and the current magnetic refrigeration material is not suitable for helium liquefaction.
In the investigation of magnetic refrigeration materials in general, the mentioned 0-5T magnetic field variations are usually referred to as high field variations, whereas magnetic field variations such as 0-2T may be considered low field variations. For magnetic refrigerators, the maximum magnetic field provided is generally not more than 2T, as is common knowledge, due to the limited size of the machine and the general use of permanent magnetic materials to provide the magnetic field.
In addition, the preparation method adopting arc melting or induction melting needs high temperature of 1500-1700 ℃, the required equipment is complex, the energy consumption is large, and the cost is high, so that the commercial application of the material is limited to a certain extent.
How to prepare the magnetic refrigeration material with the magnetic phase transition temperature of about 4K by adopting a clean and environment-friendly method can realize high magnetic entropy change under low magnetic field change, meets the commercial application value of the magnetic refrigeration material, and is a technical problem to be solved urgently in the field.
Disclosure of Invention
The magnetic refrigeration material is used for solving the problems of commercial application of the magnetic refrigeration material in an extremely low temperature region and under the change of a low magnetic field and the like. The invention provides a thulium-nickel material for magnetic refrigeration, which comprises the following components in percentage by weight:
the thulium-nickel material has the chemical formula: tm is3+xNi2+yWherein-0.1 is less than or equal to x and less than or equal to 0.1, 0.1 is less than or equal to y and less than or equal to 0.1, the thulium-nickel material has a rhombohedral crystal structure, the space group of the rhombohedral crystal structure is R-3, the phase change temperature of the thulium-nickel material is between 2 and 6K, and the magnetic entropy change peak value of the thulium-nickel material under the magnetic field change of 0 to 2T is between 15 and 17J/(kg.K).
Further, the lattice parameter of the rhombohedral crystal structure is
A method of preparing the above thulium-nickel material, comprising the steps of:
step S1: weighing a powdery metal Ni raw material and an excessive Tm raw material according to the molecular formula ratio of the thulium-nickel material, and mixing;
wherein the particle size of the powdery metallic Ni raw material and the excessive Tm raw material is 10-100 μm;
step S2: putting the raw materials mixed in the step S1 into a tablet machine die, and performing tabletting treatment to obtain a flaky sample;
the inner diameter of the die is 1mm-2cm, the thickness of the flaky sample is 1mm-2cm, and the pressure applied by the tablet press is 1MPa-30 MPa;
step S3: subjecting the sheet-like sample in the step S2 to a vacuum annealing treatment;
the temperature of the vacuum annealing is 800-1200 ℃, and the annealing time is 1-5 days;
step S4: taking out the sample annealed in the step S3, crushing, grinding and obtaining a powdery sample again;
step S5: repeating the steps S2 to S4, and performing the last vacuum annealing;
the last vacuum annealing treatment is carried out at the temperature of 400 ℃ and the time of 200 h;
step S6: quenching the sample obtained after the step S5;
quenching is to quench the annealed sample into liquid nitrogen or water and cool the sample suddenly.
Further, the granularity of the powdery raw material is 40-80 μm.
Further, the inner diameter of the die is 5mm-1.5cm, and the pressure applied by the tablet press is 5MPa-20 MPa; and standing for 3-5min after the tabletting treatment in the step S2 to ensure that the raw materials in the obtained flaky sample are fully contacted.
Further, in the step S4, the sample size after the crushing is 1mm to 3mm by pressing and beating.
Further, in the step S4, an agate mortar is used for grinding and refining, a small amount of petroleum ether is added into the agate mortar before grinding, and the grinding time is 5-10 min.
Further, the size of the recovered powdery sample is 1 μm to 50 μm.
Further, the temperature of the vacuum annealing in the step S3 is 900-1100 ℃, the annealing time is 2-4 days, the heating rate of the vacuum annealing is 10K/min, and the temperature is reduced by adopting a natural cooling mode after the vacuum annealing.
The thulium-nickel material is used for magnetic refrigeration in an extremely low temperature region and low field magnetism.
Compared with the prior art, the thulium-nickel material for magnetic refrigeration and the preparation method thereof provided by the invention have the following advantages:
1. has extremely low magnetic phase transition temperature and working temperature, and is suitable for extremely low temperature refrigeration application in a liquid helium temperature zone.
2. Has huge low-field magnetocaloric effect and is suitable for practical application of the refrigerating machine.
3. The preparation method does not need high-temperature heating, and has low energy consumption and low cost compared with electric arc melting or induction melting.
4. The thulium-nickel material for magnetic refrigeration has good uniformity, the color inside the alloy material is uniform, and large particles with inconsistent color and luster with the periphery are not found.
5. The thulium-nickel material for magnetic refrigeration has stable magnetocaloric effect property, and the material can be stored for 4 years at normal temperature without changing the magnetocaloric effect property.
Drawings
The above and other objects, features and advantages of exemplary embodiments of the present disclosure will become readily apparent from the following detailed description read in conjunction with the accompanying drawings. Several embodiments of the present disclosure are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which like reference numerals refer to similar or corresponding parts and in which:
FIG. 1 shows Tm prepared by the present invention2.97Ni2.02Thermomagnetic profile of (example one);
FIG. 2 shows Tm prepared by the present invention3.02Ni1.96Thermomagnetic curves of (example two);
FIG. 3 shows Tm prepared by the present invention2.97Ni2.02Thermomagnetic curve of (comparative example one);
FIG. 4 is a graph comparing the magnetic entropy change curves of the first embodiment and the first comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in the examples of the present invention and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise, and "a plurality" typically includes at least two.
It is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such article or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in the article or device in which the element is included.
Alternative embodiments of the present invention are described in detail below with reference to the accompanying drawings.
Example one
This example is for the purpose of illustrating Tm2.97Ni2.02Materials and methods for their preparation.
Tm2.97Ni2.02The preparation method comprises the following steps:
step S1: weighing powdery metal Tm and Ni raw materials according to a molecular formula ratio, and mixing, wherein the amount of the Ni raw material is weighed according to a chemical formula, the amount of the Tm raw material is weighed according to a specific chemical formula, the excess ratio is 2%, the granularity of the powder is 50 microns, and the purity of the raw material is 99.99%;
step S2: and (4) putting the raw materials mixed in the step S1 into a die of a tablet press, and tabletting. Wherein the inner diameter of the die is 1cm, the applied pressure is 10MPa, and the die is kept still for 3-5min after tabletting treatment, so that the raw materials in the flaky sample are fully contacted;
step S3: carrying out vacuum annealing treatment on the flaky sample obtained in the step S2, wherein the annealing temperature is 1000 ℃, the annealing time is 3 days, the heating rate of the vacuum annealing is 10K/min, and the temperature is reduced by adopting a natural cooling mode after the vacuum annealing;
the initial time point of the annealing time is calculated when the temperature of the furnace body reaches the annealing temperature;
step S4: taking out the annealed sample obtained in the step S3, crushing the annealed sample in a semi-closed steel mortar by squeezing and beating, wherein the size of the crushed sample is 1-3 mm, grinding and refining the crushed sample by using an agate mortar, adding a small amount of petroleum ether into the agate mortar before grinding for 5-10min, and then obtaining a powdery sample again;
the steel mortar has high hardness and stable chemical property so as to ensure that no impurity phase is introduced in the beating and crushing process; adding a small amount of petroleum ether into the mortar before grinding, so as to avoid the damage of partial crystal grains of the synthesized phase in the further grinding process and further ensure the obtainment of a high-performance target material;
step S5: repeating the steps S2 to S4, and then performing the final annealing and quenching, and then obtaining the target material. Wherein the annealing temperature of the last annealing is 600 ℃, and the annealing time is 150 h.
The preparation method comprises the steps of firstly realizing sufficient contact of two raw material particles through a tabletting process in step S2, then heating in a vacuum annealing process in step S3 to enable surface parts of the two raw materials to form an alloy, and finally separating the alloy part on the surface from the rest of the raw material particles through a crushing and grinding process in step S4. And repeating the steps, wherein all the simple substance metal raw materials form alloy after twice circulation, and thus the target material is obtained.
The annealing temperature in the step S3 is relatively high, and at this temperature, the two metal materials are allowed to interact with each other to form an alloy; the final annealing temperature of step S5 is relatively low, so as to eliminate the residual stress in the sample, thereby obtaining a target material with balanced performance and uniform structure.
Tm measurement Using X-ray diffractometer2.97Ni2.02Room temperature X-ray diffraction line (XRD) of the material. The following results, Tm, can be obtained2.97Ni2.02The material has rhombohedral crystal structure with space group R-3 and lattice parameter
Tm of the present example was determined on a magnetic measurement System (SQUID-VSM)2.97Ni2.02The thermomagnetic (M-T) curve of the material at a magnetic field strength H of 100Oe is shown in fig. 1. Tm can be determined from the zero field cooling M-T curve2.97Ni2.02Is the phase transition temperature (i.e. Curie temperature) TCAbout 4.3K, which belongs to the liquid helium temperature zone.
In addition, Tm of the present example was measured on SQUID-VSM2.97Ni2.02MaterialIsothermal magnetization curve around curie temperature. According to maxwell's relationship:
the magnetic entropy change can be calculated from the isothermal magnetization curve. Calculated Tm of this example2.97Ni2.02The magnetic entropy change peak value of the material appears near the Curie temperature, and under the change of a 0-2T magnetic field, the magnetic entropy change peak value is as high as 15.8J/(kg.K).
The performance index has great advantages compared with other materials, and is detailed in table 1.
Example two
This example is for the purpose of illustrating Tm3.02Ni1.96Materials and methods for their preparation.
Tm3.02Ni1.96The preparation method comprises the following steps:
step S1: weighing powdery metal Tm and Ni raw materials according to a molecular formula ratio, and mixing, wherein the amount of the Ni raw material is weighed according to a chemical formula, the amount of the Tm raw material is weighed according to a specific chemical formula, the excess ratio is 2%, the granularity of the powder is 50 microns, and the purity of the raw material is 99.99%;
step S2: and (4) putting the raw materials mixed in the step S1 into a die of a tablet press, and tabletting. Wherein the inner diameter of the die is 1cm, the applied pressure is 10Mpa, and the die is kept still for 3-5min after tabletting treatment, so that the raw materials in the flaky sample are fully contacted;
step S3: carrying out vacuum annealing treatment on the flaky sample obtained in the step S2, wherein the annealing temperature is 1000 ℃, the annealing time is 3 days, the heating rate of the vacuum annealing is 10K/min, and the temperature is reduced by adopting a natural cooling mode after the vacuum annealing;
step S4: taking out the annealed sample obtained in the step S3, crushing the annealed sample in a semi-closed steel mortar by squeezing and beating, wherein the size of the crushed sample is 1-3 mm, grinding and refining the crushed sample by using an agate mortar, adding a small amount of petroleum ether into the agate mortar before grinding for 5-10min, and then obtaining a powdery sample again;
step S5: repeating the steps S2 to S4, and then performing the final annealing and quenching, and then obtaining the target material. Wherein the annealing temperature of the last annealing is 600 ℃, and the annealing time is 150 h.
Tm measurement Using X-ray diffractometer3.02Ni1.96Room temperature X-ray diffraction line (XRD) of the material. The following results, Tm, can be obtained3.02Ni1.96The material has rhombohedral crystal structure with space group R-3 and lattice parameter
Tm of the present example was determined on a magnetic measurement System (SQUID-VSM)3.02Ni1.96The thermomagnetic (M-T) curve of the material at a magnetic field strength H of 100Oe is shown in fig. 2. Tm can be determined from the zero field cooling M-T curve3.02Ni1.96Is the phase transition temperature (i.e. Curie temperature) TCAbout 3.8K, belonging to the liquid helium temperature zone.
In addition, Tm of the present example was measured on SQUID-VSM3.02Ni1.96Isothermal magnetization curve of the material around curie temperature. According to maxwell's relationship:
the magnetic entropy change can be calculated from the isothermal magnetization curve. Calculated Tm of this example3.02Ni1.96The magnetic entropy change peak value of the material appears near the Curie temperature, and under the change of a 0-2T magnetic field, the magnetic entropy change peak value is as high as 16.1J/(kg.K).
The performance index has great advantages compared with other materials, and is detailed in table 1.
Comparative example 1
This comparative example is used to illustrate the procedure for simplified preparation of Tm2.97Ni2.02The effect of the material.
Tm2.97Ni2.02The preparation method comprises the following steps:
step S1: weighing powdery metal Tm and Ni raw materials according to a molecular formula ratio, and mixing, wherein the amount of the Ni raw material is weighed according to a chemical formula, the amount of the Tm raw material is weighed according to a specific chemical formula, the excess ratio is 2%, the granularity of the powder is 50 microns, and the purity of the raw material is 99.99%;
step S2: and (4) carrying out vacuum annealing treatment on the raw material mixed in the step S1, wherein the annealing temperature is 600 ℃, and the annealing time is 150 hours.
Tm measurement Using X-ray diffractometer2.97Ni2.02Room temperature X-ray diffraction line (XRD) of the material. The following results, Tm, can be obtained2.97Ni2.02The material contains 3 sets of diffraction peaks, being a mixture of three phases, respectively: 1. a metallic Tm phase; 2. a metallic Ni phase; 3. a target alloy material phase.
Tm of the present example was determined on a magnetic measurement System (SQUID-VSM)2.97Ni2.02The thermomagnetic (M-T) curve of the material under the magnetic field strength H-100 Oe. From the M-T curve, there are several phase transition temperatures of the compound, and in addition to the magnetic phase transition around 4K, the magnetic phase transition is also observed around 57K.
Tm was also determined on SQUID-VSM2.97Ni2.02Isothermal magnetization curve of the material around curie temperature. According to maxwell's relationship:
the magnetic entropy change can be calculated from the isothermal magnetization curve. Calculated Tm of this example2.97Ni2.02The material has a peak value of magnetic entropy change near 4K. Under the change of a 0-2T magnetic field, the peak value of the magnetic entropy change near 4K is only 4.1J/(kg K). The performance index is obviously different from the performance of the material obtained by the standard process. As shown in fig. 4, compared with the examples, the material prepared in the comparative example is not a pure phase and contains a large amount of Tm and Ni phases as raw materials, and thus the magnetic entropy change value of the material prepared in the comparative example is very small and has no commercial application value.
TABLE 1
The foregoing describes preferred embodiments of the present invention, and is intended to provide a clear and concise description of the spirit and scope of the invention, and not to limit the same, but to include all modifications, substitutions, and alterations falling within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A thulium-nickel material for magnetic refrigeration, which is characterized in that,
the thulium-nickel material has the chemical formula: tm is3+xNi2+yWherein-0.1 is less than or equal to x and less than or equal to 0.1, 0.1 is less than or equal to y and less than or equal to 0.1, the thulium-nickel material has a rhombohedral crystal structure, the space group of the rhombohedral crystal structure is R-3, the phase change temperature of the thulium-nickel material is between 2 and 6K, and the magnetic entropy change peak value of the thulium-nickel material under the magnetic field change of 0 to 2T is between 15 and 17J/(kg.K).
2. The material of claim 1, wherein said rhombohedral crystal structure has a lattice parameter of
3. A method of preparing a thulium-nickel material according to any of claims 1 to 2, comprising the steps of:
step S1: weighing a powdery metal Ni raw material and an excessive Tm raw material according to the molecular formula ratio of the thulium-nickel material, and mixing;
wherein the particle size of the powdery metallic Ni raw material and the excessive Tm raw material is 10-100 μm;
step S2: putting the raw materials mixed in the step S1 into a tablet machine die, and performing tabletting treatment to obtain a flaky sample;
the inner diameter of the die is 1mm-2cm, the thickness of the flaky sample is 1mm-2cm, and the pressure applied by the tablet press is 1MPa-30 MPa;
step S3: subjecting the sheet-like sample in the step S2 to a vacuum annealing treatment;
the temperature of the vacuum annealing is 800-1200 ℃, and the annealing time is 1-5 days;
step S4: taking out the sample annealed in the step S3, crushing, grinding and obtaining a powdery sample again;
step S5: repeating the steps S2 to S4, and performing the last vacuum annealing;
the last vacuum annealing treatment is carried out at the temperature of 400 ℃ and the time of 200 h;
step S6: quenching the sample obtained after the step S5;
quenching is to quench the annealed sample into liquid nitrogen or water and cool the sample suddenly.
4. The method of claim 3, wherein the particle size of the powdered feedstock is 40-80 μm.
5. The method of claim 3, wherein the inner diameter of the die is sized from 5mm to 1.5cm, and the pressure applied by the tablet press is from 5MPa to 20 MPa;
and standing for 3-5min after the tabletting treatment in the step S2 to ensure that the raw materials in the obtained flaky sample are fully contacted.
6. The method according to claim 3, wherein the crushing is performed in step S4 by impact beating in a semi-closed steel mortar, and the sample size after the crushing is 1mm to 3 mm.
7. The method according to claim 6, wherein the grinding refinement in the step S4 is performed by using an agate mortar, a small amount of petroleum ether is added into the agate mortar before the grinding, and the grinding time is 5-10 min.
8. The method of claim 7, wherein the size of the recovered powdered sample is from 1 μ ι η to 50 μ ι η.
9. The method as claimed in claim 3, wherein the temperature of the vacuum annealing in step S3 is 900-1100 ℃, and the annealing time is 2-4 days;
the heating rate of the vacuum annealing is 10K/min, and the temperature is reduced by adopting a natural cooling mode after the vacuum annealing.
10. Use of a thulium-nickel material according to any of claims 1 to 2 for magnetic refrigeration in the very low temperature region under low field magnetism.
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