CN108735411B - Lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material and preparation process thereof - Google Patents
Lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material and preparation process thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
- H01F1/015—Metals or alloys
-
- B22F1/0003—
-
- 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
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Hard Magnetic Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
A lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material and a preparation process thereof belong to the field of magnetic refrigeration materials in magnetic functional materials. The metal Gd particles are used as a second magnetic refrigeration material with a bonding effect, and the second magnetic refrigeration material and the La-Fe-Si alloy are subjected to hot-pressing sintering to obtain the La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance, and a preparation method and material application thereof. As the La-Fe-Si alloy and Gd are magnetic refrigeration materials with excellent performance, and the mechanical properties are complementary. The addition of the Gd simple substance particles not only greatly enhances the mechanical property of the La-Fe-Si alloy, but also avoids the damage of other binding agents to the magnetic refrigeration performance. The obtained magnet has good magnetic refrigeration performance, higher strength, simple equipment, simple and convenient operation, lower cost, easy large-scale production and high economic value in the implementation process, and has important application significance in the field of magnetic refrigeration.
Description
Technical Field
The invention discloses a lanthanum-iron-silicon/gadolinium (La-Fe-Si/Gd) composite magnetic refrigeration material and a preparation process thereof, belonging to the field of magnetic refrigeration materials in magnetic functional materials.
Background
Refrigeration technology has a wide and important application in today's society. However, refrigerants in the gas compression refrigeration technology that are currently in widespread use cause a greenhouse effect, destroy the ozone layer, and have low operating efficiency. The exploration of a novel environment-friendly, energy-saving and efficient refrigeration technology and the research and development of corresponding high-performance refrigeration working medium materials are problems which need to be solved urgently in the field and are research hotspots at home and abroad at present.
The magnetic refrigeration technology has the characteristics of environmental protection, high efficiency, energy conservation, stability and reliability, and has attracted extensive attention in recent years. Wherein lanthanum, iron and silicon (La (Fe, Si)13) The compound has giant magnetic entropy change effect in phase change process, and has low cost of raw materials, simple preparation, and various propertiesThe adjustability is high. Therefore, the material becomes one of the most potential working mediums in the practical application of the magnetic refrigeration technology. However, this material, as an intermetallic compound, is itself very brittle. When the characteristics are adjusted by C, H equal-gap atoms, more severe lattice expansion and chemical bond distortion occur, which causes strong internal stress and leads to pulverization, which is not favorable for practical use.
Chinese patent application CN103137281B provides a binder La (Fe, Si)13The invention relates to a base magnetocaloric effect material, a preparation method and application thereof, wherein the invention adopts a method of adhesive bonding thermosetting molding, and high-strength bonding La (Fe, Si) can be obtained by adjusting molding pressure, thermosetting temperature, thermosetting atmosphere and the like13A basic magnetocaloric effect material. The Chinese patent application CN103468226A provides a lanthanum-iron-silicon-based room-temperature magnetic refrigeration composite material, which is a composite material formed by uniformly mixing a lanthanum-iron-silicon-based compound, a high polymer material and an auxiliary agent and then performing mould pressing and heating, wherein the room-temperature magnetic refrigeration composite material can be isolated from a heat exchange fluid to prevent the magnetic refrigeration working medium from being oxidized in the using process; the composite material is pressed and molded at one time by a compression molding method, so that the magnetic refrigeration part with high specific surface area and low flow resistance channel is formed after assembly. Chinese patent application CN106906408A discloses a LaFeSi-based magnetic refrigeration composite material and a preparation method and application thereof. The invention adopts cheap and easily-obtained low-melting-point metal or alloy and LaFeSi-based alloy particles for composite hot pressing, and can obtain the LaFeSi-based magnetic refrigeration composite material with high thermal conductivity by selecting proper low-melting-point components and adjusting pressing pressure, hot pressing temperature, pressure maintaining time and the like.
However, these binders do not have magnetic refrigeration characteristics, so that the introduction of the binders inevitably reduces the effective content of the magnetic refrigeration working medium material, thereby affecting the refrigeration efficiency.
Disclosure of Invention
Therefore, the invention aims to provide a novel lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material which has high strength and high performance and is suitable for magnetic refrigeration application, a preparation method thereof, a magnetic refrigeration machine containing the material and application of the material in manufacturing the refrigeration material.
Specifically, the invention provides a La-Fe-Si/Gd composite magnetic refrigeration material which is obtained by taking metal Gd particles as a second magnetic refrigeration material with a bonding effect through hot-pressing sintering, and a preparation method and material application thereof. As the La-Fe-Si alloy and Gd are magnetic refrigeration materials with excellent performance, and the mechanical properties are complementary. The addition of the Gd simple substance particles not only greatly enhances the mechanical property of the La-Fe-Si alloy, but also avoids the damage of other binding agents to the magnetic refrigeration performance. The obtained magnet has good magnetic refrigeration performance, higher strength, simple equipment, simple and convenient operation, lower cost, easy large-scale production and high economic value in the implementation process, and has important application significance in the field of magnetic refrigeration.
To facilitate an understanding of the present invention, certain terms are defined below. Terms defined herein have meanings as commonly understood by one of ordinary skill in the art to which the invention pertains.
As used herein, unless otherwise indicated, the terms La-Fe-Si, La (Fe, Si)13、La(Fe,Co,Si)13、(La1-x,Rx)(Fe1-y-z,My,Zz)13All mean having "NaZn13The compound system of the type structure or the phase structure 1:13 takes La, Fe and Si atoms as main elements and comprises a plurality of alternative elements.
The invention aims to provide a La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance.
The invention also aims to provide a preparation method of the La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance.
The invention further aims to provide application of the La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance in manufacturing refrigeration materials.
The purpose of the invention is realized by the following technical scheme.
The invention provides a high-strength and high-performance La-Fe-Si/Gd composite magnetic refrigeration material, which comprises La-Fe-Si-based magnetic refrigeration alloy particles and magnetic refrigeration elementary substance Gd particles with a bonding effect, wherein the La-Fe-Si-based magnetic refrigeration alloy particles and the magnetic refrigeration elementary substance Gd particles with the bonding effect are sintered into a compact block material at a low temperature.
Preferably, the La-Fe-Si-based magnetic refrigeration alloy is (La)1-x,Rx)(Fe1-y-z,My,Zz)13(R is rare earth elements such as Ce, Pr and the like; M is transition group elements such as Mn, Co and the like except Fe; Z is main group elements such as Si, Al, C and the like) (x is 0-0.5; y is 0-0.1; Z is 0-0.15; and x, y and Z are not 0 at the same time);
preferably, in some embodiments of the invention, the (La) is1-x,Rx)(Fe1-y-z,My,Zz)13Has the component of La0.5Pr0.5Fe10.7Co0.8Si1.5C0.2(x＝0.5,y＝0.062,zSi＝0.115,zC＝0.015)、LaFe10.58Co0.82Si1.6(x ═ 0, y ═ 0.063, z ═ 0.123) or La0.8Ce0.2Fe12.4Mn0.3Si1.3(x＝0.2,y＝0.023,z＝0.1)。
In the present invention, the composition of the magnetic refrigeration alloy is not particularly limited, and any magnetic refrigeration alloy effective at around room temperature such as La-Fe-Si may be used. The La-Fe-Si-based magnetic refrigeration alloy with the property of the primary phase change material has the characteristics of poor compressive strength, fragility, poor corrosion resistance and the like, and a second substance without magnetic refrigeration performance is inevitably introduced in a general method for forming by adding a binder, so that the technical scheme for solving the problems by adopting the Gd particles with the magnetic refrigeration performance has particularly excellent effect on the alloy.
Preferably, in the composite magnetic refrigeration material of the present invention, the content of the simple substance Gd particles for magnetic refrigeration having a binding effect may be 5 to 95 parts by weight, and preferably 10 to 50 parts by weight, with respect to 100 parts by weight of the La-Fe-Si based magnetic refrigeration alloy particles.
According to the magnetocaloric effect material provided by the invention, the particle size range of the La-Fe-Si-based magnetic refrigeration alloy particles is preferably 5-800 μm, and more preferably 15-200 μm.
According to the magnetocaloric effect material provided by the invention, the particle size range of the magnetic refrigeration elementary substance Gd particles playing a role in binding is preferably 5-800 μm, and more preferably 15-200 μm.
The invention also provides a preparation method of the La-Fe-Si/Gd composite magnetic refrigeration material, which comprises the following steps:
firstly, preparing raw materials of a required simple substance or alloy such as La, Ce, Pr, Mn, Fe, Co, Si, Al and C according to the components of a chemical formula of the La-Fe-Si-based magnetic refrigeration alloy to obtain a La-Fe-Si-based magnetic refrigeration alloy ingot, namely (La)1-x,Rx)(Fe1-y-z,My,Zz)13(R is rare earth elements such as Ce, Pr and the like; M is transition group elements such as Mn, Co and the like; Z is main group elements such as Si, Al, C and the like) (x is 0-0.5; y is 0-0.1; Z is 0-0.15) ingot casting;
step two, annealing the ingot casting obtained in the step one in an inert atmosphere, and then quenching the ingot casting in liquid nitrogen or water to obtain the product with NaZn13The alloy with the structure is magnetically refrigerated, and the alloy with Curie temperature lower than room temperature is subjected to hydrogen absorption treatment;
step three, preparing pure Gd into powder particles and grading the particle size;
step four, crushing the alloy obtained in the step two and grading the granularity;
step five, uniformly mixing the alloy particles obtained in the step four and the Gd particles obtained in the step three in proportion;
and step six, filling the mixed powder obtained in the step five into a mould, and sintering the mixed powder into a block by using a Spark Plasma Sintering (SPS) method.
According to a preferred embodiment of the preparation method of the invention, the first step can specifically comprise the steps of putting the prepared raw materials into an electric arc melting furnace, and vacuumizing until the vacuum degree is less than 1 x 10-2Pa, cleaning the furnace chamber for 1-2 times by using high-purity argon with the purity of more than 99 percent, then filling the argon into the furnace chamber to 0.5-1.5 atmospheric pressure, and applying arc current of 150-200V to obtain the alloyAnd repeatedly smelting each alloy ingot for 1-6 times.
According to another preferred embodiment of the preparation method, specifically, the second step can comprise annealing the alloy ingot smelted in the first step at 1000-1400 ℃ for 1 hour to 60 days under the protection of inert gas, wherein the inert gas can be argon or nitrogen. And then quenched in liquid nitrogen or water.
According to an embodiment of the preparation method of the present invention, wherein in the third step, the method for preparing Gd particles may be melt quenching, ball milling, gas atomization, and the like. Preferably, in some embodiments of the present invention, the method of rapid quenching and ball milling is as follows:
selecting a Gd raw material, polishing oxide skin, putting the oxide skin into a quartz tube, and performing under the protection of inert gas, wherein the inert gas can be argon. The pressure difference in the rapid quenching furnace is 0.1-1 MPa, and the optimal pressure difference is 0.07 MPa. The rotation speed is selected to be 5 r/s-50 r/s, preferably 10-20 m/s. And (3) shearing the Gd thin strip prepared in the quick quenching process, and putting the Gd thin strip into a ball milling tank. Inert gas or liquid can be selected as a medium to avoid oxidation in the ball milling process. The inert gas may be argon or nitrogen and the liquid may be n-heptane, alcohol, gasoline, etc. The rotating speed in the ball milling process is selected to be 400-1000 r/min, preferably 600-700 r/min. The ball milling time is 10-120 min, preferably 30-60 min. And putting the ball-milled sample into a container for ultrasonic oscillation to form uniform turbid liquid, standing for natural sedimentation, and removing the supernatant when layering occurs. And (4) carrying out vacuum drying on the precipitate, and then screening to obtain powder with different size distribution ranges.
According to still another preferred embodiment of the preparation method of the present invention, in the sixth step, the mold may be a graphite or cemented carbide mold, the SPS hot pressing sintering temperature may be 400 ℃ to 1000 ℃, preferably 500 ℃ to 700 ℃, the SPS hot pressing sintering pressure may be 0 to 700MPa, preferably 50MPa to 500MPa, and the SPS hot pressing sintering time may be 1 to 30 minutes, preferably 2 to 20 minutes:
specifically, the mixture of La-Fe-Si and Gd particles can be pressed into the shape and size of the working medium required by the magnetic refrigerator: placing the mixture of La-Fe-Si and Gd particles into a mould (the shape and the size of the mould 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 the application of the magnetocaloric effect material or the magnetocaloric effect material prepared by the method in the preparation of a refrigerating material.
Compared with the prior art, the invention has the advantages that:
1. the addition of the Gd simple substance particles not only greatly enhances the mechanical property of the La-Fe-Si alloy, but also avoids the damage of common binders to the magnetocaloric property.
2. The method realizes the powdering of the high-plasticity Gd simple substance and can be conveniently used for sintering the composite magnet.
3. The SPS technology is used for realizing the low-temperature dense sintering of the La-Fe-Si/Gd composite magnet, and the mutual diffusion between the two phases is effectively inhibited.
4. The refrigerating working medium material with any shape and size can be manufactured according to the actual requirement of the magnetic refrigerator on the refrigerating working medium material;
5. the obtained magnet has good magnetocaloric effect, higher strength, simple equipment in the implementation process, simple and convenient operation, lower cost, easy large-scale production and high economic value, and has great application prospect in the field of magnetic refrigeration.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a room temperature X-ray diffraction (XRD) pattern of the composite material samples # 1, # 2 and # 3 of example 1.
FIG. 2 is a graph showing the dependence of magnetic entropy change (. DELTA.S) on temperature under a 3T field for samples # 1, # 2 and # 3 composite materials of example 1.
FIG. 3 is a thermomagnetic (M-T) curve of the 4#, 5#, and 6# composite samples of example 2 under a 0.01T magnetic field.
FIG. 4 is a plot of Δ S as a function of temperature for the 3T field for the 4#, 5# and 6# composite samples of example 2.
FIG. 5Is La in example 30.8Ce0.2Fe12.4Mn0.3Si1.3Room temperature X-ray diffraction (XRD) pattern of the/Gd composite sample.
FIG. 6 shows La of example 30.8Ce0.2Fe12.4Mn0.3Si1.3Electron Probe (EPMA) analysis of the/Gd composite samples.
FIG. 7 is the magnetization curves (M-H curves) of the samples of composite materials # 2 and # 7 in example 4 during the processes of increasing the field and decreasing the field at different temperatures.
FIG. 8 is a plot of Δ S as a function of temperature for the 3T field for the 2# and 7# composite samples of example 4.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be exhaustive or to be limiting.
Example 1: the novel lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material and the preparation process thereof are implemented according to the following specific steps:
step one, mixing La, Fe, Co and Si simple substances in proportion to prepare LaFe10.58Co0.82Si1.6Casting ingots;
step two, the LaFe obtained in the step one10.58Co0.82Si1.6Annealing the cast ingot in an inert atmosphere to obtain uniform NaZn13Structural organization;
step three, preparing pure Gd into powder particles by a quick quenching and ball milling method;
screening the Gd powder particles in the third step to 75-125 mu m;
step five, crushing the alloy obtained in the step two and sieving the crushed alloy to 125-150 microns;
step six, the LaFe obtained in the step five is used10.58Co0.82Si1.6Uniformly mixing the particles and the Gd particles obtained in the step five according to a ratio of 9: 1;
and step seven, putting the mixed powder obtained in the step six into an alloy die, and preparing the mixed powder into a block by using a spark plasma sintering method under the conditions of 400 ℃, 550 ℃, 900 ℃ and 400MPa of pressure.
The blocks prepared by the spark plasma sintering method under the conditions of 400 ℃, 550 ℃, 900 ℃ and 400MPa pressure are respectively marked as No. 1, No. 2 and No. 3, and the sintered LaFe obtained in the embodiment10.58Co0.82Si1.6The thermal conductivity and compressive strength of the/Gd bulk magnets 1#, 2# and 3# are shown in Table 1. As can be seen from table 1, the density increased greatly as the sintering temperature increased. Along with the increase of the density of the sample, the compressive strength is also continuously improved, and the mechanical property is greatly improved. In addition, the thermal properties are also excellent.
TABLE 1 sintered LaFe10.58Co0.82Si1.6Thermal conductivity of/Gd bulk magnets 1#, 2#, and 3#
Fig. 1 is an XRD pattern of 1#, 2# and 3# in example 1. As can be seen from the figure, as the sintering temperature increases, a diffusion phenomenon occurs to form a diffusion phase. FIG. 2 is the dependence of the magnetic entropy change (Δ S) under a 3T field of 1#, 2# and 3# in example 1 on temperature. It can be seen from the figure that the maximum magnetic entropy change decreases with increasing sintering temperature, but also remains at a better level. This is because the degree of diffusion is increased by the increase in sintering temperature. It can be seen that the 550 c sintered magnet has the best overall performance.
Example 2: the novel lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material and the preparation process thereof are implemented according to the following specific steps:
step one, mixing La, Pr, Fe-C, Co and Si simple substances in proportion to prepare La0.5Pr0.5Fe10.7Co0.8Si1.5C0.2Casting ingots;
step two, the La obtained in the step one is used0.5Pr0.5Fe10.7Co0.8Si1.5C0.2Annealing the cast ingot in an inert atmosphere to obtain uniform NaZn13Structural organization;
step three, pure Gd is prepared into powder particles by an air atomization method;
screening the Gd powder particles in the third step to 37-75 mu m;
step five, crushing the alloy obtained in the step two and sieving the crushed alloy to 180-425 micrometers;
step six, the La obtained in the step five is used0.5Pr0.5Fe10.7Co0.8Si1.5C0.2Uniformly mixing the particles and the Gd particles obtained in the step five according to the proportion of 7:3, 5:5 and 1:9 respectively;
and step seven, putting the mixed powder obtained in the step six into an alloy die, and preparing the mixed powder into a block by using a spark plasma sintering method under the conditions of 550 ℃ sintering temperature and 500MPa pressure.
La prepared by a spark plasma sintering method under the conditions of 550 ℃ sintering temperature and 500MPa pressure0.5Pr0.5Fe10.7Co0.8Si1.5C0.2The blocks with Gd ratios of 7:3, 5:5, 1:9 are respectively marked as 4#, 5#, 6#, and the sintered La obtained in this example0.5Pr0.5Fe10.7Co0.8Si1.5C0.2The thermal conductivity and compressive strength of the/Gd bulk magnets No. 4, No. 5 and No. 6 are shown in Table 2. As can be seen from Table 2, the density increased with increasing Gd content. Along with the increase of the density of the sample, the compressive strength is also continuously improved, and the mechanical property is greatly improved. In addition, with the increase of Gd content, the thermal diffusion coefficient is continuously improved, the heat capacity is continuously reduced, the thermal conductivity is kept at a higher level, and the thermal performance is more excellent.
TABLE 2 sintered La0.5Pr0.5Fe10.7Co0.8Si1.5C0.2Thermal conductivity of/Gd bulk magnets No. 4, No. 5 and No. 6
FIG. 3 shows thermomagnetic (M-T) curves of No. 4, No. 5 and No. 6 in example 2 under a 0.01T magnetic field. It can be seen from the graph that the curie temperature of each Gd-containing sintered sample was almost the same and the thermal hysteresis was reduced. FIG. 4 is the dependence of the magnetic entropy change (Δ S) under a 3T field of example 2 in No. 4, No. 5 and No. 6 on the temperature. As can be seen from the figure, the maximum magnetic entropy change of each Gd-containing sintered sample is basically kept at the same level, and the Gd-containing sintered sample has larger magnetic entropy change and better magnetic refrigeration performance.
Example 3: the novel lanthanum-iron-silicon/gadolinium composite magnetic refrigeration material and the preparation process thereof are implemented according to the following specific steps:
step one, La, Ce, Fe, Mn and Si are mixed according to a proportion to prepare La0.8Ce0.2Fe12.4Mn0.3Si1.3Casting ingots;
step two, the La obtained in the step one is used0.8Ce0.2Fe12.4Mn0.3Si1.3Annealing the cast ingot in an inert atmosphere to obtain uniform NaZn13Structural organization, subjecting it to a hydrogenation treatment to obtain La0.8Ce0.2Fe12.4Mn0.3Si1.3H particles;
step three, preparing pure Gd into powder particles by a ventilation atomization method;
screening the Gd powder particles in the third step to 125-150 mu m;
step five, the La obtained in the step two0.8Ce0.2Fe12.4Mn0.3Si1.3Sieving H particles to 150-180 mu m;
step six, the La obtained in the step five is used0.8Ce0.2Fe12.4Mn0.3Si1.3And the Gd particles obtained in the step five are mixed according to the weight ratio of 9:1, uniformly mixing in proportion;
and step seven, putting the mixed powder obtained in the step six into an alloy die, and preparing the mixed powder into a block by using a spark plasma sintering method under the conditions of the sintering temperature of 550 ℃ and the pressure of 400 MPa.
FIG. 5 shows La in example 30.8Ce0.2Fe12.4Mn0.3Si1.3The ratio of H to Gd is 9:1 XRD pattern of the composite block. As can be seen from the figure, the composite sampleMainly contains LaCo13The phases and Gd phases did not form a diffused phase. FIG. 6 shows La of example 30.8Ce0.2Fe12.4Mn0.3Si1.3The ratio of H to Gd is 9:1, EPMA image of the composite mass. FIG. 6(a) is a scanning electron microscope image, (b) is an EPMA result of Fe element, (c) is an EPMA result of Gd element, and it can be seen from the figure that the spherical structure is morphology after sintering of Gd particles prepared by gas atomization, and the matrix phase is La0.8Ce0.2Fe12.4Mn0.3Si1.3H, as can be seen from FIG. 6(b), the matrix phase contains a large amount of iron, and the Gd grains contain almost no iron element, and the same phenomenon can be seen in FIG. 6(c), but a thin diffused phase is formed at the boundary portion, but the diffusion phenomenon is not significant.
Comparative example: the lanthanum-iron-silicon/copper composite magnetic refrigeration material and the preparation process thereof are implemented according to the following specific steps:
step one, mixing La, Fe, Co and Si simple substances in proportion to prepare LaFe10.58Co0.82Si1.6Casting ingots;
step two, the LaFe obtained in the step one10.58Co0.82Si1.6Annealing the cast ingot in an inert atmosphere to obtain uniform NaZn13Structural organization;
step three, preparing pure Cu into powder particles by an evaporation and condensation method;
step four, screening the Cu powder particles in the step three to about 2 microns;
step five, crushing the alloy obtained in the step two, and screening particles to 125-150 microns;
step six, the LaFe obtained in the step five is used10.58Co0.82Si1.6Uniformly mixing the particles and the Cu particles obtained in the step five according to a certain ratio of 9: 1;
and step seven, putting the mixed powder obtained in the step six into an alloy die, and preparing the mixed powder into a block by using a spark plasma sintering method under the conditions of the sintering temperature of 550 ℃ and the pressure of 400 MPa.
Sintering at 550 ℃ under 500MPaLaFe prepared by using spark plasma sintering method under condition10.58Co0.82Si1.6Gd ratio of 9:1 was compared with 2# in example one. Mixing LaFe10.58Co0.82Si1.6The block with a ratio of 9:1 Gd is designated as 7#, and the compressive strength, density and thermal diffusivity of the samples 7# and 2# obtained in this example are shown in Table 3. As can be seen from Table 3, the mechanical properties and thermal properties of the 2# composite sample are slightly reduced compared to the 7# composite. This is mainly because on the one hand the Cu particles in this embodiment are smaller than the Gd particles in the # 2 magnet and therefore a higher density is easier to obtain; on the other hand, Cu has a thermal conductivity much higher than Gd, and therefore the thermal diffusivity of the 7# magnet is also high.
TABLE 3LaFe10.58Co0.82Si1.610% Cu blocks and LaFe10.58Co0.82Si1.6Compressive strength, density and thermal diffusivity of/10% Gd samples # 7, # 8
FIG. 7 is the magnetization curves (M-H curves) of example 4 in the processes of increasing and decreasing the field at different temperatures in No. 2 and No. 7. As can be seen from the figure, the magnetic transitions of the two samples are substantially identical and the hysteresis loss is reduced. Fig. 8 is a graph showing the dependence of magnetic entropy change (Δ S) on temperature for magnets # 2 and # 7 at a 3T field. As can be seen from the figure, the magnetic entropy change of the sample No. 2 is much larger than that of the sample No. 7, and the magnetic refrigeration capacity of the sample No. 2 is more excellent. The comprehensive performance of the La-Fe-Si/Gd composite material is better than that of the La-Fe-Si/Cu composite material.
Claims (14)
1. The La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance is characterized by comprising La-Fe-Si-based magnetic refrigeration alloy particles and magnetic refrigeration elementary substance Gd particles with a bonding effect, wherein the La-Fe-Si-based magnetic refrigeration alloy particles and the magnetic refrigeration elementary substance Gd particles with the bonding effect are sintered into a compact block material at a low temperature.
2. The La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance according to claim 1, wherein the La-Fe-Si based magnetic refrigeration alloy is (La)1-x,Rx)(Fe1-y-z,My,Zz)13R is a rare earth element; m is a transition group element other than Fe; z is Si, and x is 0-0.5; y is 0-0.1; z is 0 to 0.15 and is not 0.
3. The La-Fe-Si/Gd composite magnetic refrigerant material with high strength and high performance as claimed in claim 2, wherein R is Ce or Pr; m is Mn or Co.
4. The La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance according to claim 1, wherein the content of said magnetic refrigeration simple substance Gd particles having a binding effect is 5 to 95 parts by weight with respect to 100 parts by weight of said La-Fe-Si based magnetic refrigeration alloy particles.
5. The La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance according to claim 4, characterized in that the content of the simple substance Gd particles for magnetic refrigeration is 10 to 50 parts by weight.
6. The La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance according to claim 1, wherein the particle size range of the La-Fe-Si based magnetic refrigeration alloy particles is 5 to 800 μm; the particle size range of the magnetic refrigeration elementary substance Gd particles with the bonding effect is 5-800 mu m.
7. The La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance according to claim 6, wherein the particle size range of the La-Fe-Si based magnetic refrigeration alloy particles is 15 to 200 μm; the particle size range of the magnetic refrigeration elementary substance Gd particles with the bonding effect is 15-200 mu m.
8. The method for preparing the La-Fe-Si/Gd composite magnetic refrigeration material with high strength and high performance according to any one of claims 1 to 7, characterized by comprising the following steps:
preparing raw materials of a required simple substance or alloy according to the La-Fe-Si-based magnetic refrigeration alloy and chemical formula components to obtain an La-Fe-Si-based magnetic refrigeration alloy ingot;
step two, annealing the ingot casting obtained in the step one in an inert atmosphere, and then quenching the ingot casting in liquid nitrogen or water to obtain the product with NaZn13The alloy with the structure is magnetically refrigerated, and the alloy with Curie temperature lower than room temperature is subjected to hydrogen absorption treatment;
step three, preparing pure Gd into powder particles and grading the particle size;
step four, crushing the alloy obtained in the step two and grading the granularity;
step five, uniformly mixing the alloy particles obtained in the step four and the Gd particles obtained in the step three in proportion;
and step six, filling the mixed powder obtained in the step five into a mould, and sintering the mixed powder into a block by using a Spark Plasma Sintering (SPS) method.
9. The method of claim 8, wherein step one comprises placing the prepared raw materials into an electric arc melting furnace, and vacuumizing to a vacuum degree of less than 1 x 10-2And Pa, cleaning the furnace chamber for 1-2 times by using high-purity argon with the purity of more than 99%, then filling the argon into the furnace chamber to 0.5-1.5 atmospheric pressure, applying arc current of 150-200V to obtain alloy ingots, and repeatedly smelting each alloy ingot for 1-6 times.
10. The method according to claim 8, wherein the second step comprises annealing the alloy ingot smelted in the first step at 1000-1400 ℃ for 1 hour to 60 days under the protection of inert gas, wherein the inert gas is argon or nitrogen; and then quenched in liquid nitrogen or water.
11. The method according to claim 8, wherein in step three, the method for preparing Gd particles comprises melt quenching, ball milling or aerosolization.
12. The method according to claim 11, wherein the method of preparing Gd particles: selecting a Gd raw material, polishing oxide skin, putting the polished oxide skin into a quartz tube, and performing under the protection of inert gas, wherein the pressure difference in a rapid quenching furnace is 0.1-1 MPa; selecting the rotating speed of 5 r/s-50 r/s; shearing a Gd thin strip prepared in the quick quenching process, and putting the Gd thin strip into a ball milling tank, wherein an inert gas or liquid is selected as a medium in the ball milling process to avoid oxidation, the inert gas is argon or nitrogen, and the liquid is n-heptane, alcohol or gasoline; the rotating speed is selected to be 400-1000 r/min in the ball milling process; the ball milling time is 10-120 min; putting the ball-milled sample into a container, performing ultrasonic oscillation to form uniform turbid liquid, standing for natural sedimentation, and removing supernatant when layering occurs; and (4) carrying out vacuum drying on the precipitate, and then screening to obtain powder with different size distribution ranges.
13. The method according to claim 8, wherein in the sixth step, the mold is a graphite or hard alloy mold, the SPS hot pressing sintering temperature is 400-1000 ℃, the SPS hot pressing sintering pressure is 0-700 MPa and does not include 0, and the SPS hot pressing sintering time is 1-30 minutes.
14. The method as claimed in claim 13, wherein in the sixth step, the mold is a graphite or hard alloy mold, the SPS hot pressing sintering temperature is 500 ℃ to 700 ℃, the SPS hot pressing sintering pressure is 50MPa to 500MPa, and the SPS hot pressing sintering time is 2 minutes to 20 minutes.
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