CN109524190A - A kind of rare earth-iron-silicon substrate magnetic refrigeration composite material and preparation method thereof - Google Patents
A kind of rare earth-iron-silicon substrate magnetic refrigeration composite material and preparation method 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0264—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements the maximum content of each alloying element not exceeding 5%
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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Abstract
A kind of rare earth-iron-silicon substrate magnetic refrigeration composite material and preparation method thereof, it includes functive constituent elements and matrix constituent element, the functive constituent element includes rare earth-iron-silicon-base alloy particle, described matrix constituent element includes aluminum metal simple substance or aluminium alloy, and the rare earth-iron-silicon-base alloy particle is bonded by described matrix constituent element to form block materials or functive constituent element and matrix constituent element reactant bonds to form block materials.The composite material has keeps higher magnetothermal effect, heating conduction and mechanical property simultaneously, and molding easy to process, and hydrogenation treatment and not dusting when for refrigeration machine use, shape still keep complete advantage.
Description
Technical field
The present invention relates to a kind of magnetic refrigerating material more particularly to a kind of rare earth-iron-silicon substrate magnetic refrigeration composite material and its
Preparation method belongs to field of magnetic refrigeration material.
Background technique
Currently, Refrigeration Technique has penetrated into the every field of people's daily life and industrial production activities, from daily clothing,
Food, shelter, row all be unable to do without Refrigeration Technique to field of scientific study.In general cold technical field, vapor compression refrigeration is from 19 generation
It records and starts to develop the seventies, have nearly 150 years history so far, be to develop refrigeration that is fairly perfect, being most widely used at present
One of method.However, the efficiency of vapor compression refrigeration machine is only 40% of Carnot's cycle efficiency or so, and it is generally used
Freon class discharge refrigerant can destroy ozone layer into atmosphere and generate greenhouse effects, make global warming, endanger environment.
Under the increasingly prominent situation of energy and environmental problem, energy-saving and environment-friendly New Refrigerating technology is had been to be concerned by more and more people.
Magnetic refrigeration is a kind of environmentally protective, energy-efficient Refrigeration Technique, and development prospect is good by countries in the world.It should
Technology uses solid-state magnetic working medium, and entropy density is apparently higher than traditional chemical refrigerant, this can substantially reduce refrigeration machine volume, obtain
Obtain the refrigerating efficiency (can reach 60% of Carnot's cycle efficiency or more) of maximum possible；Importantly, magnetic refrigerating material will not
Generate the gas for such as destroying ozone layer and greenhouse effects；In addition, magnetic refrigerator also has, noise is small, the service life is long and high reliablity
Etc. advantages.As the heart of magnetic Refrigeration Technique, the performance of magnetic refrigerating material directly influences power and efficiency of magnetic refrigerator etc.
Performance.So far from 1997, the magnetic refrigerating material with giant magnetio-caloric effects is by Devoting Major Efforts To Developing and research extensively.It is several typical
Room temperature magnetic refrigerating material includes: Gd5(SixGe1-x)4Alloy, NaZn13La (the Fe of type structurexSi1-x)13Alloy, Fe2P-type structure
MnFeP (As, Ge, Si) alloy, Heusler type ferromagnetic shape memory alloys and perovskite-like type Mn oxide.Wherein, La
(Fe,Si)13The advantages such as based alloy is nontoxic with its, abundant raw material, low cost, narrow lag and low driving magnetic field are acknowledged as most
There is one of the magnetic refrigerating material of application prospect.So far, domestic and international many enterprises and scientific research institution are by La (Fe, Si)13Base magnetic system
Cold material is tested for Magnetic refrigerator.La(Fe,Si)13The Curie temperature of compound cannot be directly used to room in 200K or so
In temperature magnetic refrigerating machine.La (Fe, Si) is substituted with a small amount of Co13Fe atom in compound can be substantially by hydrogenation of compounds processing
Promote the Curie temperature of material.La(Fe,Co,Si)13Compound is intended to second-order phase transistion in the phase transformation of near room temperature, Entropy Changes compared with
It is low.La(Fe,Si)13HxCompound near room temperature still keeps stronger first order phase change, and Entropy Changes is higher.But this kind of hydrogeneous chemical combination
Object is easy to appear crackle or even dusting in hydrogenation treatment and refrigeration machine in the course of work.In practical applications, magnetic working medium is not only
There is big magnetothermal effect, it is necessary to can be with fluid effectively heat exchange.This requires magnetic refrigerating materials to have sufficiently high lead
Thermal energy power, and different shape (such as thin slice, spherical shape, porous media) can be processed to.Therefore, improve rare earth-iron-silicon substrate magnetic
Heating conduction, mechanical property and the processable forming ability of refrigerating material become scientific circles and the important research of engineering circles in recent years
Project.
Chinese patent application (publication No. CN103137281A) discloses a kind of with high-intensitive bonding La (Fe, Si)13
Base magnetothermal effect material and its preparation method and application, using the method for organic polymer adhesive bonds thermoset forming, passes through
Adjust the bonding La (Fe, Si) of the available high intensity such as typed pressure, thermoset temperature, thermosetting atmosphere13Base magnetothermal effect material, gram
The intrinsic property of magnetothermal effect material brittle is taken；Magnetic entropy becomes can be held essentially constant compared with before bonding.But due to organic
The presence of polymeric binder and hole, this kind of composite material capacity of heat transmission is generally very poor, corresponding even lower than before bonding to cause
Close block alloy several times.
Chinese patent application (publication No. CN105957672A) discloses a kind of lanthanum iron silicon substrate hydride magnetic working medium and its system
Preparation Method, provided lanthanum iron silicon substrate hydride magnetic working medium are shaped to block, and good mechanical properties using hot press forming technology,
Solve the problems, such as that dusting after the hydrogenation of lanthanum iron silicon base compound, the mechanical properties such as frangible are deteriorated.But the invention hot pressing magnetic working medium
There are still hole, heating conduction is difficult to be higher than before hot pressing compact block alloy accordingly.In addition, lanthanum iron silicon base compound is in height
It is easily decomposes when warm, cause the magnetothermal effect of the invention high temperature hot pressing magnetic working medium lower.
It reports in non-patent literature by block La (Fe, Si)13Magnetic refrigerating material is milled to particle, and in its surface chemistry side
Method plates a certain amount of copper, is then hot pressed into porous material at a certain temperature.Due to the elimination of crystal boundary, porous material magnetic field is circulated throughout
Mechanical property is better than block alloy in journey, but copper metal simple substance density itself is very big, in the composite shared volume fraction compared with
It is few, it is difficult to form continuous reticular structure, thermal conductivity is still significantly less than corresponding compact block alloy.
Summary of the invention
In view of the deficiencies of the prior art, it is compound to be to provide a kind of rare earth-iron-silicon substrate magnetic refrigeration for an object of the present invention
Material.The composite material keeps higher magnetothermal effect, heating conduction and mechanical property, and molding easy to process simultaneously, and
Hydrogenation treatment and not dusting when using for refrigeration machine, shape still keeps complete.
It is a further object to provide a kind of methods for preparing above-mentioned material.
First purpose to realize the present invention, the technical solution adopted by the present invention include: a kind of rare earth-iron-silicon substrate
Magnetic refrigeration composite material, it includes functive constituent element and matrix constituent element, the functive constituent element includes that rare earth-iron-silicon substrate is closed
Gold particle, described matrix constituent element include aluminum metal simple substance or aluminium alloy, and the rare earth-iron-silicon-base alloy particle is by the base
Body constituent element, which bonds, to form block materials or functive constituent element and matrix constituent element reactant bonds to form block materials.
Above-mentioned rare earth-iron-silicon-base alloy the particle of the present invention, chemical general formula are as follows: Rx(Fe1-a-bCoaMnb)13- ySiyAz；Wherein, the combination of any one or two kinds or more of A in H, B and C element, R are selected from La, Ce, Pr and Nd member
The combination of any one or two kinds or more in element, 1≤x≤2,1≤y≤2,0≤z≤4,0≤a≤0.1,0≤b≤
0.05；And the rare earth-iron-silicon-base alloy particle includes to have NaZn13The magnetothermal effect compound of type crystal structure.
Alloying element in the above-mentioned aluminium alloy of the present invention include Mg, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr,
The combination and inevitable impurity of any one or two kinds or more in Sn, Sb, Bi, Si.
Further, rare earth-iron of the present invention-silicon-base alloy particle partial size is no more than 300 μm, preferably 50
~150 μm.
Further, the partial size of aluminum metal simple substance or aluminium alloy of the present invention be not more than 200 μm, preferably 10~
150μm。
Further, aluminium alloy of the present invention has the characteristics that low-density and high heat conductance, and is convenient for rare earth-
Iron-silicon-base alloy grain forming, further preferably, aluminium alloy density are not more than 5g/cm3, thermal conductivity be not less than 10W/mK,
Purity is not less than 99% (weight percent content).
Further, the aluminum metal simple substance or aluminium alloy in rare earth-iron of the present invention-silicon substrate magnetic refrigeration composite material
Weight percent content be 1~30wt.%, preferably 10~20wt.%.
Further, rare earth-iron of the present invention-silicon substrate magnetic refrigeration composite material maximum Entropy Changes under 2T changes of magnetic field
Value is 4~30J/kg K, and transition temperature range is 180~350K；Room temperature uniaxial compressive strength is not less than 80MPa；Room temperature thermal conductivity
Rate is 2~100W/m K.
To make above content of the invention more clear and understandable, some terms are defined below.Term defined herein
The normally understood meaning of those of ordinary skill with technical field.Unless otherwise stated, the term as used herein
“NaZn13Type structure " refers to that space group is a kind of structure of Fm3c.LaFe13Compound is not present, and needs to add Al or Si
Stable compound is usually obtained Deng member.In imaginary LaFe13In compound, Fe occupies two different brilliant positions with the ratio of 1:12
FeIAnd FeII.La and FeIAtom forms CsCl structure, and La atom is by 24 FeIIAtom surrounds, FeIAtom is combined into 20 faces
12 Fe of bodyIIAtom surrounds, each FeIIThere is the Fe of 9 arest neighbors around atomIIAtom, 1 FeIAtom and 1 La
Atom.
Second purpose to realize the present invention, the technical solution adopted by the present invention are as follows: a kind of above-mentioned rare earth-iron-silicon
The preparation method of base magnetic refrigeration composite material comprising:
(1) raw material in addition to H element is prepared according to the rare earth-iron-silicon-base alloy particle chemical general formula；Such as press
According to following formula Rx(Fe1-a-bCoaMnb)13-ySiyAzAs rare earth-iron-silicon-base alloy particle chemical general formula preparation raw material；Wherein,
The combination of any one or two kinds or more of A in H, B and C element, R are any one in La, Ce, Pr and Nd element
Kind or two kinds or more of combination, 1≤x≤2,1≤y≤2,0≤z≤4,0≤a≤0.1,0≤b≤0.05；Described is dilute
Soil-iron-silicon-base alloy particle includes to have NaZn13The magnetothermal effect compound of type crystal structure；When the A in chemical formula includes
When H element, the raw material in addition to H element is prepared according to chemical formula；
(2) raw material is protected into lower progress melting in high purity inert gas, prepares master alloy；
(3) master alloy is annealed in vacuum environment or inert atmosphere, then quenching rapidly, acquisition contain NaZn13
Rare earth-iron-silicon-base alloy of type crystal structure compound；
(4) contain NaZn for described13That silicon-base alloy is broken into partial size to the rare earth-iron-of type crystal structure compound is little
Mixture is uniformly mixed to obtain in 300 μm of particle, and with aluminum metal simple substance or aluminium alloy；
(5) mixture is hot-forming in high vacuum environment or in inert gas, pressing pressure is not more than 1GPa,
Hot pressing temperature is not higher than 800 DEG C, and the dwell time is no more than 60min；
(6) it when the A in chemical formula includes H element, by material made from above-mentioned steps (5) or is further processed into
After type, the hydrogenation treatment in hydrogen atmosphere.
Preferably, pressing pressure described in step (5) is 50~500MPa, and hot pressing temperature is 300~600 DEG C, when pressure maintaining
Between be 0.5~30min.
Preferably, hydrogenation treating conditions described in step (6) include: Hydrogen Vapor Pressure no more than 5MPa, preferably 0.05~
2MPa；Hydrotreating temperatures are not higher than 600 DEG C, preferably 200~400 DEG C；Hydrogenation time is no more than 5 hours.
Compared with prior art, the invention has the advantages that
(1) present invention is using low-density, the aluminum metal simple substance of high heat conductance or aluminium alloy as matrix constituent element and rare earth-
Hot pressing obtains the magnetic refrigeration composite material of block after the mixing of iron-silicon-base alloy particle, constituent element abundant raw material used, low in cost,
Product is conducive to commercialization；More importantly hot pressing combination process of the present invention by optimization, aluminum metal simple substance or aluminium alloy are made
Rare earth-iron-silicon-base alloy particle bonding is got up for the second constituent element, two matrix constituent elements, which are easy to mutually overlap, forms netted knot
Structure so that heating conduction and mechanical property are remarkably reinforced, as long as composite material have aluminium simple substance or aluminum alloy materials there are equal
Above-mentioned technical effect may be implemented.
(2) the particle ruler of considered critical of the present invention rare earth-iron-silicon-base alloy particle and aluminum metal simple substance or aluminium alloy
It is very little.Why in this way limit be because are as follows: if mixing first two constituent element particle size it is too big, two class particles can be made to be difficult to press
Densification, it is bad so as to cause gained block mechanical property and heating conduction improvement；If rare earth-iron-silicon-base alloy
Particle size is too small (such as partial size is less than 10 μm), and magnetothermal effect will be substantially reduced, or even disappears；If aluminum metal simple substance or aluminium
Alloying pellet is undersized, is not only easy to aoxidize, and grain boundary face thermal resistance can greatly increase, and lead to heating conduction not
It is good.Therefore, the present invention passes through the particle size for limiting two kinds of constituent elements, to efficiently solve above-mentioned technical problem.
(3) present invention also defines the concrete content ranges of aluminum metal simple substance or aluminium alloy, and why limiting the range is
Cause are as follows: aluminum metal simple substance or aluminium alloy do not have magnetic heat function, only improve mechanical property in the resulting composite material of the present invention
And heating conduction, and the effect that the aluminum metal simple substance of 20wt.% content generates has substantially met requirement.Aluminium alloy is because of thermal conductivity
Can be poorer than aluminum metal simple substance, it needs slightly to be further added by content.Certainly, if its content is too many, the magnetic heat of function phase will be diluted
Effect.
(4) present invention also defines the density of aluminium alloy, the second constituent element forms reticular structure ability in gained composite material
Heating conduction and mechanical property is remarkably reinforced.Under equal quality, aluminium alloy density more small size is bigger, more easy to form netted
Structure, heating conduction and mechanical property improvement become apparent from.
(5) present invention using heat pressing process by rare earth-iron-silicon-base alloy and aluminum metal simple substance or aluminium alloy compound at
Type, later hydrogenation treatment.Can get by technological parameters such as optimization pressing pressure, hot pressing temperature, dwell times has superiority
Rare earth-iron-silicon substrate magnetic refrigeration composite material of energy.Gained heat conductivity of the invention is existing resin-bonded magnetic refrigeration
3 times or more of material, and mechanical property is obviously improved, convenient for being reprocessed into complicated shape.It can also be according to magnetic refrigeration working substance
Actual needs, selects different molds to be directly prepared into required shape and size.
(6) considered critical of the present invention rare earth-iron-silicon-base alloy particle and aluminum metal simple substance or aluminium alloy hot pressing are compound
Molding condition.Pressing pressure it is too small so that molding after composite material hole it is too many, cause thermal conductivity not high；Pressing pressure is excessive
Rare earth-iron-silicon-base alloy particle is caused to generate a large amount of crackles or broken, magnetothermal effect reduces.Press temperature is too low or keeps the temperature
So that composite material porosity is too many, thermal conductivity is not high for time too short meeting；Press temperature is excessively high or the too long meeting of soaking time so that
Rare earth-iron-silicon-base alloy particle is reacted with aluminum metal simple substance or aluminium alloy generates cenotype, also results in magnetothermal effect reduction.
The specific pressure of hot pressing of the present invention, temperature and time substantially overcome above-mentioned technological deficiency and deficiency.
(7) present invention uses aluminum metal simple substance or aluminium alloy as the second constituent element, since its softening transform temperature is lower, heat
NaZn can be effectively avoided in pressure compound tense13Type structure mutually itself is decomposed.Therefore, the Entropy Changes of gained composite material is still higher.Separately
Outside, composite material has certain hole after compacting, is not only convenient for rapid hydrogenation, promotes Curie temperature, and when in use will not
Because of function phase lattice dilatation contraction and dusting.
Detailed description of the invention
Fig. 1 is the LaFe of the hot pressing at 400 DEG C, 500 DEG C, 600 DEG C and 700 DEG C in the embodiment of the present invention 111Co0.8Si1.2/Al
The backscatter mode scanning electron microscope (SEM) photograph of (Al content 10wt.%) block composite material.
Fig. 2 is the LaFe of the hot pressing at 500 DEG C in the embodiment of the present invention 111Co0.8Si1.2/ Al (Al content 10wt.%) block
Isothermal magnetization (M-H) curve of field process is risen under composite material different temperatures.
Fig. 3 is the LaFe of the hot pressing at 400 DEG C, 500 DEG C and 600 DEG C in the embodiment of the present invention 111Co0.8Si1.2/ Al (Al content
10wt.%) Entropy Changes of the block composite material under 2T changes of magnetic field varies with temperature curve.
Fig. 4 is LaFe in the embodiment of the present invention 111Co0.8Si1.2Under/Al (Al content 10wt.%) block composite material 300K
Thermal conductivity with hot pressing temperature change curve.
Fig. 5 is the LaFe of the hot pressing at 400 DEG C, 500 DEG C, 600 DEG C and 700 DEG C in the embodiment of the present invention 111Co0.8Si1.2/Al
Room temperature single compressing stress-the strain curve of (Al content 10wt.%) block composite material.
Fig. 6 is the LaFe of the hot pressing at 500 DEG C in the embodiment of the present invention 211Co0.8Si1.2/ Al (Al content 20wt.%) block
Isothermal magnetization (M-H) curve of field process is risen under composite material different temperatures.
Fig. 7 is the LaFe of the hot pressing at 500 DEG C in the embodiment of the present invention 211Co0.8Si1.2/ Al (Al content 20wt.%) block
The Entropy Changes of composite material varies with temperature curve.
Fig. 8 is the LaFe of the hot pressing at 500 DEG C in the embodiment of the present invention 211Co0.8Si1.2/ Al (Al content 20wt.%) block
Room temperature single compressing stress-strain curve of composite material.
Fig. 9 is the LaFe of the hot pressing at 500 DEG C in the embodiment of the present invention 311.6Si1.4/ Al (Al content 20wt.%) block is multiple
Condensation material hydride LaFe11.6Si1.4H1.7Field is risen under/Al different temperatures and drops isothermal magnetization (M-H) curve of field process.
Figure 10 is the LaFe of the hot pressing at 500 DEG C in the embodiment of the present invention 311.6Si1.4/ Al (Al content 20wt.%) block is multiple
Condensation material hydride LaFe11.6Si1.4H1.7The Entropy Changes of/Al varies with temperature curve.
Figure 11 is the LaFe of the hot pressing at 500 DEG C in the embodiment of the present invention 311.6Si1.4/ Al (Al content 20wt.%) block is multiple
Condensation material hydride LaFe11.6Si1.4H1.7Room temperature single compressing stress-strain curve of/Al.
Figure 12 is the La of the hot pressing at 500 DEG C in the embodiment of the present invention 40.7Ce0.3Fe11.4Mn0.2Si1.4/ Al (Al content
20wt.%) block composite material hydride La0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7Field and drop field process are risen under/Al different temperatures
Isothermal magnetization (M-H) curve.
Figure 13 is the La of the hot pressing at 500 DEG C in the embodiment of the present invention 40.7Ce0.3Fe11.4Mn0.2Si1.4/ Al (Al content
20wt.%) block composite material hydride La0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7The Entropy Changes of/Al varies with temperature curve.
Figure 14 is the La of the hot pressing at 500 DEG C in the embodiment of the present invention 40.7Ce0.3Fe11.4Mn0.2Si1.4/ Al (Al content
20wt.%) block composite material hydride La0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7Room temperature single compressing stress-strain of/Al
Curve.
Figure 15 is the La of the hot pressing at 500 DEG C in the embodiment of the present invention 51.7Fe11.6Si1.4/ Al (Al content 20wt.%) block
Composite material hydride La1.7Fe11.6Si1.4H2.9Field is risen under/Al different temperatures and drops isothermal magnetization (M-H) curve of field process.
Figure 16 is the La of the hot pressing at 500 DEG C in the embodiment of the present invention 51.7Fe11.6Si1.4/ Al (Al content 20wt.%) block
Composite material hydride La1.7Fe11.6Si1.4H2.9The Entropy Changes of/Al varies with temperature curve.
Figure 17 is the La of the hot pressing at 500 DEG C in the embodiment of the present invention 51.7Fe11.6Si1.4/ Al (Al content 20wt.%) block
Composite material hydride La1.7Fe11.6Si1.4H2.9Room temperature single compressing stress-strain curve of/Al.
Specific embodiment
It is with reference to the accompanying drawing and specific real in order to make those skilled in the art more fully understand technical solution of the present invention
Applying example, the present invention is described in further detail.These embodiments are merely to illustrate the purpose of the present invention, not with any side
Formula limits the scope of the invention.
The present invention provides a kind of rare earth-iron-silicon substrate magnetic refrigeration composite materials, include functive constituent element and matrix group
Member, the functive constituent element include rare earth-iron-silicon-base alloy particle, and described matrix constituent element includes low-density, high heat conductance
Aluminum metal simple substance or aluminium alloy, the rare earth-iron-silicon-base alloy particle are bonded to block or functive by described matrix constituent element
Constituent element and matrix constituent element reactant are bonded to block, and (such as Fig. 1 works as in 600 DEG C of hot pressed samples, and it is micro- number occur between two class particles at this time
The thick conversion zone of rice is the phenomenon that functive constituent element is bonded to block with matrix constituent element reactant at this time).The rare earth-
Iron-silicon-base alloy particle, chemical general formula are (i.e. configuration rare earth-iron-silicon-base alloy particulate material matches general formula): Rx
(Fe1-a-bCoaMnb)13-ySiyAz；Wherein, the combination of any one or two kinds or more of A in H, B and C element, R are selected from
The combination of any one or two kinds or more in La, Ce, Pr and Nd element, 1≤x≤2,1≤y≤2,0≤z≤4,0≤a≤
0.1,0≤b≤0.05；The rare earth-iron-silicon-base alloy particle includes to have NaZn13The magnetothermal effect of type crystal structure
Compound.
It should be noted that the composition of the rare earth-iron-silicon-base alloy is not limited specifically mutually in the present invention,
In addition to that must include with NaZn13Outside the magnetothermal effect phase of type crystal structure, it is also possible to have a certain amount of miscellaneous phase, such as α-Fe, richness
Rare-earth phase etc., the phenomenon are the conventional known phenomenon of industry.
In some embodiments, in the rare earth-iron-silicon substrate magnetic refrigeration composite material, described matrix constituent element is low
The aluminum metal simple substance of density, mass fraction are 10wt.% and 20wt.%.But not limited to this, it can be selected from normal in the prior art
Density is not higher than 5g/cm3And thermal conductivity is not less than the Al alloy powder of 10W/mK, mass fraction is not higher than 30wt.%,
As long as convenient for making rare earth-iron-silicon-base alloy grain forming.
Another aspect of the present invention provides the rare earth-iron-silicon substrate magnetic refrigeration composite material preparation method, main
If suppressing aluminum metal simple substance or aluminium alloy and the mixed uniformly powder of rare earth-iron-silicon-base alloy at a certain temperature, pass through
Optimize the technological parameters such as hot pressing temperature, pressing pressure and soaking time, obtain while having big magnetothermal effect, high heat conductance and
The magnetic refrigerating material of well processed forming ability.
Rare earth-iron of the present invention-silicon-base alloy particle partial size is not more than 300 μm, preferably 50~150 μm；
The partial size of the aluminum metal simple substance or aluminium alloy is not more than 200 μm, preferably 10~150 μm；Using above-mentioned when the two mixes
The particle form of particle size range mixes, and it is hot-forming to be then placed in mold progress.
In some more specific embodiments, the preparation method includes the following steps:
(1) its chemical general formula R is pressedx(Fe1-a-bCoaMnb)13-ySiyAzAlloy atom percentage (is converted into matter by preparation raw material
Percentage is measured, raw material is then weighed).When A includes protium, the raw material in addition to protium is prepared by chemical general formula；
(2) prepared raw material is placed in smelting furnace, carries out melting under high purity inert gas protection, obtains alloy
Ingot；Or raw material is placed in vacuum induction rapid hardening furnace, aluminium alloy is poured onto rotary copper roller under high purity inert gas protection
Prepare rapid-hardening flake；
(3) material prepared in step (2) is annealed in vacuum or inert gas, then quenching rapidly, is had
NaZn13The operation of rare earth-iron-silicon-base alloy of type crystal structure, the step (2) and step (3) is those skilled in the art
Member realizes according to scheme known in the art；
(4) alloy breaks down obtained in step (3) is not more than 300 μm of alloying pellet at partial size, and with aluminum metal list
Matter or aluminium alloy are uniformly mixed, and obtain mixture；
(5) mixture obtained in step (4) is poured into mold, mold is placed in the induction heating line of vacuum hotpressing machine
Circle center, pumping high vacuum to 8 × 10-2Pa or less carries out hot pressing into block materials；
(6) it when the A in chemical general formula includes H element, by block materials made from step (5) or is further processed
After molding, the hydrogenation treatment in hydrogen atmosphere.
In some embodiments, the rare earth-iron-silicon-base alloy particle partial size is no more than 300 μm, preferably 50
~150 μm.In some embodiments, the aluminium simple substance or Al alloy powder partial size are not more than 200 μm, preferably 10~150 μm.
In some embodiments, the hot-forming operation can carry out in inert gas or vacuum environment, the item of hot pressing
Part includes: that pressing pressure can be selected as 200MPa, hot pressing temperature can be selected as 600 DEG C hereinafter, the dwell time can be selected as 2min,
Forming shape is depending on mold shape.In the implementation process of scheme, rare earth-iron-silicon-base alloy can be advanced optimized
The technological parameters such as the size and proportional amount and hot pressing temperature of grain and aluminium simple substance or Al alloy powder, pressure, time.
Argon gas etc. of the purity 99.99% or more can be selected in inert gas above-mentioned, but not limited to this.
With reference to the accompanying drawing and several preferred embodiments further description of the technical solution of the present invention.It needs to illustrate
, in the following example, used material purity is as follows: La, Ce, Fe, Co, Mn, Si purity are 99% (weight hundred
Divide than content) more than.
Embodiment 1LaFe11Co0.8Si1.2/ Al (Al content 10wt.%) magnetic refrigeration composite material
(1) LaFe is pressed11Co0.8Si1.2La, Fe, Co, Si raw material prepared is packed into vacuum induction rapid hardening by chemical formula ingredient
In furnace crucible, it is evacuated to 5 × 10-2Pa, after be filled with high-purity argon gas (99.999% or more) to 0.05MPa.Intermediate frequency power supply is opened,
Heating a period of time, start smelting metal, be completely melt to raw material and keep the temperature 5 minutes, it is 1.7m/s that aluminium alloy, which is poured onto revolving speed,
Rotary copper roller on obtain LaFe11Co0.8Si1.2Rapid-hardening flake；
(2) rapid-hardening flake obtained step (1) is broken, is then put into quartz ampoule with Mo piece cladding, it is evacuated to 1 ×
10-4Pa is filled with the argon gas of 0.05MPa, by the quartzy seal of tube；
(3) quartz ampoule sealed in step (2) is put into Muffle furnace and is warming up to 1050 DEG C, taken out after heat preservation 24 hours fast
Speed is put into ice water and is cooled to room temperature；
(4) by the LaFe after step (3) heat treatment11Co0.8Si1.2Rapid-hardening flake filters out 74~150 μm of powder of partial size after grinding
End uniformly mixes it with 54~74 μm of partial size of Al powder, embodiment LaFe11Co0.8Si1.2Powder and Al powder weight ratio are 9:
1；
(5) mixed powder of step (4) is poured into mold, mold is placed in the load coil of vacuum hotpressing machine
Centre, is evacuated to 6 × 10-2Pa is hereinafter, respectively in 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C of progress hot pressing, pressing pressure is
200MPa, heat-insulation pressure keeping time are 2min, obtain block LaFe11Co0.8Si1.2/ Al magnetic refrigeration composite material.
Microstructure characterization:
One, each in the block composite material obtained using scanning electron microscope back-scattered electron mode observation of steps (5)
The composition of phase and distribution.It will be seen from figure 1 that the LaFe of 400 DEG C and 500 DEG C hot pressing11Co0.8Si1.2In/Al composite material,
LaFe11Co0.8Si1.2Almost without conversion zone between particle and Al particle, and occur a few micrometers between 600 DEG C of two class particles of hot pressed samples
Thick conversion zone further increases hot pressing temperature to 700 DEG C, and Al particle almost disappears because of reaction；But in 600 DEG C of hot pressed samples
In the presence of the conversion zone for occurring several microns thick between two class particles, Al particle, which is still susceptible to mutually overlap, forms netted knot
Structure.
Performance test:
One, using superconducting quantum interference device (SQUID) vibrating specimen magnetometer (Quantum Design, SQUID-VSM) determination step
(5) the block LaFe obtained11Co0.8Si1.2The isothermal magnetization curve of/Al magnetic refrigeration composite material.Fig. 2 provides 500 DEG C of hot pressing
LaFe11Co0.8Si1.2Isothermal magnetization (M-H) curve of field process is risen under/Al (Al content 10wt.%) sample different temperatures.From
Within the temperature range of paramagnetic becomes magnetic transition to ferrimagnetic state, all samples magnetization curve does not occur inflection point, shows to be intended to second level
The M-H curve of phase transformation, 400 DEG C and 600 DEG C hot pressed samples also has similar characteristics.According to the relationship based on Maxwell equation
Formula:
Entropy Changes is calculated from the isothermal magnetization curve tested.From figure 3, it can be seen that 400 DEG C, 500 DEG C and 600 DEG C hot pressing
LaFe11Co0.8Si1.2/ Al composite material have wide operating temperature range, externally-applied magnetic field from 0 increase to 2T when, maximum entropy variation
Not Wei 5.9J/kg K, 5.5J/kg K and 5.1J/kg K, show excessively high hot pressing temperature will lead to Entropy Changes reduction.
Two, using LaFe made from laser analysis of thermal conductivity instrument (NETZSCH, LFA457) testing procedure (5)11Co0.8Si1.2/
The thermal diffusion coefficient α and specific heat C of Al composite materialp, according to relational expression λ=α ρ CpCalculate material thermal conductivity.Fig. 4 provides 400
DEG C, under the 300K of 500 DEG C, 600 DEG C and 700 DEG C hot pressed samples thermal conductivity with hot pressing temperature variation relation.It can from Fig. 4
Out, with the raising of hot pressing temperature, thermal conductivity takes the lead in reducing after increasing, wherein the thermal conductivity of 500 DEG C of hot pressed samples is maximum, about
17W/m K。
Three, the LaFe made from electronic universal tester testing procedure (5)11Co0.8Si1.2The compression of/Al composite material room temperature
Intensity.Fig. 5 provides 400 DEG C, 500 DEG C, the 600 DEG C and 700 DEG C typical stress-strain curves of hot pressed samples, can from Fig. 5
Out, each sample load pre-stress-strain curve approximation meet linear relationship, be in elastic deformation area, subsequent stress with
Strain very slowly rises, and shows a very narrow approximate stage area, then declines, sample is destroyed.Sample breaks
Resistance to spalling increases first increases and then decreases with hot pressing temperature, wherein the breaking strength of 600 DEG C of hot pressed samples is maximum, reaches
186MPa.The high intensity of the hot pressed samples is probably derived from the humidification of small thickness conversion zone.Embodiment
2LaFe11Co0.8Si1.2/ Al (Al content 20wt.%) magnetic refrigeration composite material
(1) LaFe is pressed11Co0.8Si1.2La, Fe, Co, Si raw material prepared is packed into vacuum induction rapid hardening by chemical formula ingredient
In furnace crucible, it is evacuated to 5 × 10-2Pa, after be filled with high-purity argon gas to 0.05MPa.Intermediate frequency power supply is opened, a period of time is heated,
Start smelting metal, be completely melt to raw material and keep the temperature 5 minutes, aluminium alloy is poured onto the rotary copper roller that revolving speed is 1.7m/s and is made
Standby LaFe11Co0.8Si1.2Rapid-hardening flake；
(2) rapid-hardening flake in step (1) is broken, it is coated with Mo piece, is put into quartz ampoule, is evacuated to 1 × 10-4Pa fills
The argon gas for entering 0.05MPa, by the quartzy seal of tube；
(3) quartz ampoule sealed in step (2) is put into Muffle furnace and is warming up to 1050 DEG C, after taking out after heat preservation 24 hours
It is quickly put into ice water and is cooled to room temperature；
(4) by the LaFe after heat treatment in step (3)11Co0.8Si1.2Rapid hardening slice lapping filters out 74~150 μm of powder of partial size
End uniformly mixes it with 54~74 μm of partial size of Al powder, embodiment LaFe11Co0.8Si1.2Powder and Al powder weight ratio are 8:
2；
(5) step (4) mixed powder is poured into mold, mold is placed in the load coil center of vacuum hotpressing machine,
It is evacuated to 6 × 10-2For Pa hereinafter, in 500 DEG C of progress hot pressing, pressing pressure 200MPa, the heat-insulation pressure keeping time is 2min, is obtained
Block LaFe11Co0.8Si1.2/ Al magnetic refrigeration composite material.
Performance test:
One, using superconducting quantum interference device (SQUID) vibrating specimen magnetometer (Quantum Design, SQUID-VSM) determination step
(5) the block LaFe obtained11Co0.8Si1.2The isothermal magnetization curve of/Al magnetic refrigeration composite material.Fig. 6 provides 500 DEG C of hot pressing
LaFe11Co0.8Si1.2Isothermal magnetization (M-H) curve of field process is risen under/Al (Al content 20wt.%) sample different temperatures；From figure
6 can be seen that within the temperature range of becoming magnetic transition from paramagnetic to ferrimagnetic state, and all samples magnetization curve does not occur inflection point,
Show to be intended to second-order phase transistion, this and LaFe11Co0.8Si1.2The M-H curvilinear characteristic of/Al (Al content 10wt.%) sample is similar.
According to the relational expression based on Maxwell equation:
Entropy Changes is calculated from the isothermal magnetization curve tested.From figure 7 it can be seen that 500 DEG C of hot pressing
LaFe11Co0.8Si1.2/ Al composite material have wide operating temperature range, externally-applied magnetic field from 0 increase to 2T when, maximum entropy becomes
4.4J/kg K。
Two, using LaFe made from laser analysis of thermal conductivity instrument (NETZSCH, LFA457) testing procedure (5)11Co0.8Si1.2/
The thermal diffusion coefficient α and specific heat C of Al composite materialp, according to relational expression λ=α ρ CpCalculate material thermal conductivity.Test result shows
Thermal conductivity reaches 55W/m K under sample 300K, which is the LaFe of 500 DEG C of hot pressing in embodiment 111Co0.8Si1.2/ Al (Al content
10wt.%) 3 times of sample, its capacity of heat transmission can be remarkably reinforced by illustrating to optimize Al content in composite material of the present invention.
Three, the LaFe made from electronic universal tester testing procedure (5)11Co0.8Si1.2The compression of/Al composite material room temperature
Intensity.Fig. 8 provides 500 DEG C of typical stress-strain curves of hot pressed samples.As can be seen that with 500 DEG C of hot pressing samples in embodiment 1
Condition ratio, the sample stress-strain curves show a very wide approximate stage area after linear approximate relationship, and
Breaking strength significantly increases, and reaches 182MPa.
Embodiment 3LaFe11.6Si1.4H1.7/ Al magnetic refrigeration composite material
(1) LaFe is pressed11.6Si1.4La, Fe, Si raw material prepared is packed into vacuum induction rapid hardening furnace crucible by chemical formula ingredient
In, it is evacuated to 5 × 10-2Pa, after be filled with high-purity argon gas to 0.05MPa.Intermediate frequency power supply is opened, heating a period of time, starts to melt
Gold metallurgy category is completely melt to raw material and keeps the temperature 5 minutes, and aluminium alloy is poured onto the rotary copper roller that revolving speed is 1.7m/s and is prepared
LaFe11.6Si1.4Rapid-hardening flake；
(2) rapid-hardening flake in step (1) is broken, it is coated with Mo piece, is put into quartz ampoule, is evacuated to 1 × 10-4Pa fills
The argon gas for entering 0.05MPa, by the quartzy seal of tube；
(3) quartz ampoule sealed in step (2) is put into Muffle furnace and is warming up to 1050 DEG C, after taking out after heat preservation 24 hours
It is quickly put into ice water and is cooled to room temperature；
(4) by LaFe after annealing in step (3)11.6Si1.4Rapid hardening slice lapping filters out 74~150 μm of powder of partial size, will
It is uniformly mixed with 54~74 μm of partial size of Al powder, embodiment LaFe11.6Si1.4Powder and Al powder weight ratio are 8:2；
(5) step (4) mixed powder is poured into mold, mold is placed in the load coil center of vacuum hotpressing machine,
It is evacuated to 6 × 10-2For Pa hereinafter, in 500 DEG C of progress hot pressing, pressing pressure 200MPa, the heat-insulation pressure keeping time is 2min, is obtained
Block LaFe11.6Si1.4/ Al magnetic refrigeration composite material.
(6) by the LaFe after hot pressing in step (5)11.6Si1.4/ Al block sample, is put into hydrogenation treatment furnace cavity, takes out
Vacuum is to 5Pa or less and is filled with argon gas, and gas washing three times, is then charged with 0.2MPa hydrogen repeatedly, and is heated to 300 DEG C, and heat preservation 5 is small
When, obtain LaFe11.6Si1.4H1.7/ Al magnetic refrigeration composite material.
Performance test:
One, using superconducting quantum interference device (SQUID) vibrating specimen magnetometer (Quantum Design, SQUID-VSM) determination step
(6) the block LaFe obtained11.6Si1.4H1.7The isothermal magnetization curve of/Al magnetic refrigeration composite material.Fig. 9 is given at 500 DEG C of hot pressing
LaFe11.6Si1.4/ Al (Al content 20wt.%) block composite material hydride LaFe11.6Si1.4H1.7It is risen under/Al different temperatures
Isothermal magnetization (M-H) curve of field and drop field process.Within the temperature range of becoming magnetic transition from paramagnetic to ferrimagnetic state, the magnetic sample
Change curve and inflection point occur near Curie temperature, and magnetic hysteresis occur, there is more obvious first order phase change feature.According to based on wheat
The relational expression of Ke Siwei equation:
Entropy Changes is calculated from the isothermal magnetization curve tested.From fig. 10 it can be seen that relative to 500 DEG C of heat in embodiment 2
The LaFe of pressure11Co0.8Si1.2/ Al composite material, composite material work temperature range narrows, but Entropy Changes is remarkably reinforced, additional magnetic
From 0 increase to 2T when, Entropy Changes be 11.9J/kg K.
Two, using LaFe made from laser analysis of thermal conductivity instrument (NETZSCH, LFA457) testing procedure (6)11.6Si1.4H1.7/
The thermal diffusion coefficient α and specific heat C of Al composite materialp, according to relational expression λ=α ρ CpCalculate material thermal conductivity.Test result shows
Thermal conductivity reaches 52W/m K under sample 300K, which is and LaFe in embodiment 211Co0.8Si1.2/ Al sample is suitable, at hydrogenation
Reason operation does not significantly affect the thermal conductivity of the composite material.
Three, the LaFe made from electronic universal tester testing procedure (6)11.6Si1.4H1.7The compression of/Al composite material room temperature
Intensity.Figure 11 provides 500 DEG C of typical stress-strain curves of hot pressed samples.As can be seen that between the sample stress-strain
After linear approximate relationship, a wider approximate stage area is showed, breaking strength reaches 147MPa.
Embodiment 4La0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7/ Al magnetic refrigeration composite material
(1) La is pressed0.7Ce0.3Fe11.4Mn0.2Si1.4La, Ce, Fe, Mn, Si raw material prepared is packed into true by chemical formula ingredient
In sky induction rapid hardening furnace crucible, it is evacuated to 5 × 10-2Pa, after be filled with high-purity argon gas to 0.05MPa.Open intermediate frequency power supply, heating
For a period of time, start smelting metal, be completely melt to raw material and keep the temperature 5 minutes, aluminium alloy is poured onto the rotation that revolving speed is 1.7m/s
Turn to prepare La on copper roller0.7Ce0.3Fe11.4Mn0.2Si1.4Rapid-hardening flake；
(2) rapid-hardening flake in step (1) is broken, it is coated with Mo piece, is put into quartz ampoule, is evacuated to 1 × 10-4Pa fills
The argon gas for entering 0.05MPa, by the quartzy seal of tube；
(3) quartz ampoule sealed in step (2) is put into Muffle furnace and is warming up to 1050 DEG C, after taking out after heat preservation 24 hours
It is quickly put into ice water and is cooled to room temperature；
(4) by La after annealing in step (3)0.7Ce0.3Fe11.4Mn0.2Si1.4Rapid hardening slice lapping filters out partial size 74~150
μm powder, it is uniformly mixed with 54~74 μm of partial size of Al powder, embodiment La0.7Ce0.3Fe11.4Mn0.2Si1.4Powder and Al
Powder weight ratio is 8:2；
(5) step (4) mixed powder is poured into mold, mold is placed in the load coil center of vacuum hotpressing machine,
It is evacuated to 6 × 10-2For Pa hereinafter, in 500 DEG C of progress hot pressing, pressing pressure 200MPa, the heat-insulation pressure keeping time is 2min, is obtained
Block La0.7Ce0.3Fe11.4Mn0.2Si1.4/ Al magnetic refrigeration composite material.
(6) by the La after hot pressing in step (5)0.7Ce0.3Fe11.4Mn0.2Si1.4/ Al block sample, is put into Hydrotreat Stove
It in cavity, is evacuated to 5Pa or less and is filled with argon gas, gas washing three times, is then charged with 0.2MPa hydrogen, and be heated to 300 repeatedly
DEG C, 5 hours are kept the temperature, La is obtained0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7/ Al magnetic refrigeration composite material.
Performance test:
One, using superconducting quantum interference device (SQUID) vibrating specimen magnetometer (Quantum Design, SQUID-VSM) determination step
(6) the block La obtained0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7The isothermal magnetization curve of/Al magnetic refrigeration composite material.Figure 12 is provided
The La of the hot pressing at 500 DEG C0.7Ce0.3Fe11.4Mn0.2Si1.4/ Al (Al content 20wt.%) block composite material hydride
La0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7Field is risen under/Al different temperatures and drops isothermal magnetization (M-H) curve of field process.From suitable
Within the temperature range of magnetic becomes magnetic transition to ferrimagnetic state, which there is inflection point near Curie temperature, and occurs
Magnetic hysteresis has more obvious first order phase change feature.According to the relational expression based on Maxwell equation:
Entropy Changes is calculated from the isothermal magnetization curve tested.As can be seen from Figure 13, relative to 500 DEG C of heat in embodiment 2
The LaFe of pressure11Co0.8Si1.2/ Al composite material, composite material work temperature range narrows, but Entropy Changes is remarkably reinforced, additional magnetic
From 0 increase to 2T when, Entropy Changes be 9.5J/kg K.
Two, obtained using laser analysis of thermal conductivity instrument (NETZSCH, LFA457) testing procedure (6)
La0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7The thermal diffusion coefficient α and specific heat C of/Al composite materialp, according to relational expression λ=α ρ CpIt calculates
Material thermal conductivity out.Test result shows that thermal conductivity reaches 45W/m K under sample 300K.
Three, the La made from electronic universal tester testing procedure (6)0.7Ce0.3Fe11.4Mn0.2Si1.4H1.7/ Al composite wood
Expect room temperature compressive strength.Figure 14 provides 500 DEG C of typical stress-strain curves of hot pressed samples.As can be seen that the sample is answered
Power-strain curve shows a wider approximate stage area after linear approximate relationship, and breaking strength reaches 159MPa.
Embodiment 5La1.7Fe11.6Si1.4H2.9/ Al magnetic refrigeration composite material
(1) La is pressed1.7Fe11.6Si1.4La, Fe, Si raw material prepared is packed into vacuum induction melting furnace earthenware by chemical formula ingredient
In crucible, it is evacuated to 5 × 10-2Pa, after be filled with high-purity argon gas to 0.05MPa.High frequency electric source is opened, heating a period of time, is started
Smelting metal is completely melt to raw material and keeps the temperature 5 minutes, aluminium alloy is poured onto copper mold and prepares La1.7Fe11.6Si1.4Block
Alloy；
(2) alloy pig in step (1) is cut into fritter, is put into corundum crucible, places into quartz ampoule, is evacuated to
1×10-4Pa is filled with the argon gas of 0.05MPa, by the quartzy seal of tube；
(3) quartz ampoule sealed in step (2) is put into Muffle furnace and is warming up to 1050 DEG C, after taking out after heat preservation 24 hours
It is quickly put into ice water and is cooled to room temperature；
(4) by La after annealing in step (3)1.7Fe11.6Si1.4The further crushing grinding of block, filters out partial size 74~150
μm powder, it is uniformly mixed with 54~74 μm of partial size of Al powder, embodiment La1.7Fe11.6Si1.4Powder and Al powder weight ratio
For 8:2；
(5) step (4) mixed powder is poured into mold, mold is placed in the load coil center of vacuum hotpressing machine,
It is evacuated to 6 × 10-2For Pa hereinafter, in 500 DEG C of progress hot pressing, pressing pressure 200MPa, the heat-insulation pressure keeping time is 2min, is obtained
Block La1.7Fe11.6Si1.4/ Al magnetic refrigeration composite material.
(6) by the La after hot pressing in step (5)1.7Fe11.6Si1.4/ Al block sample, is put into hydrogenation treatment furnace cavity,
It is evacuated to 5Pa or less and is filled with argon gas, gas washing three times, is then charged with 0.2MPa hydrogen repeatedly, and is heated to 300 DEG C, heat preservation 5
Hour, obtain La1.7Fe11.6Si1.4H2.9/ Al magnetic refrigeration composite material.
Performance test:
One, using superconducting quantum interference device (SQUID) vibrating specimen magnetometer (Quantum Design, SQUID-VSM) determination step
(6) the block La obtained1.7Fe11.6Si1.4H2.9The isothermal magnetization curve of/Al magnetic refrigeration composite material.Figure 15 is given at 500 DEG C
The La of hot pressing1.7Fe11.6Si1.4/ Al (Al content 20wt.%) block composite material hydride La1.7Fe11.6Si1.4H2.9/ Al is different
At a temperature of rise field and drop field process isothermal magnetization (M-H) curve.Within the temperature range of becoming magnetic transition from paramagnetic to ferrimagnetic state,
There is inflection point near Curie temperature in the sample magnetization curve, and magnetic hysteresis occurs, has more obvious first order phase change feature.Root
According to the relational expression based on Maxwell equation:
Entropy Changes is calculated from the isothermal magnetization curve tested.As can be seen from Figure 16, relative to 500 DEG C of heat in embodiment 2
The LaFe of pressure11Co0.8Si1.2/ Al composite material, composite material work temperature range narrows, but Entropy Changes is remarkably reinforced, additional magnetic
From 0 increase to 2T when, Entropy Changes be 8.7J/kg K.
Two, obtained using laser analysis of thermal conductivity instrument (NETZSCH, LFA457) testing procedure (6)
La1.7Fe11.6Si1.4H2.9The thermal diffusion coefficient α and specific heat C of/Al composite materialp, according to relational expression λ=α ρ CpCalculate material heat
Conductance.Test result shows that thermal conductivity reaches 41W/m K under sample 300K.
Three, the La made from electronic universal tester testing procedure (6)1.7Fe11.6Si1.4H2.9/ Al composite material room temperature pressure
Contracting intensity.Figure 17 provides 500 DEG C of typical stress-strain curves of hot pressed samples.As can be seen that the sample stress-strain is bent
LaFe in line and embodiment 311.6Si1.4H1.7/ Al sample is significantly different, after linear approximate relationship, show one it is relatively narrow
Approximate stage area.Because of the La that hot pressing uses1.7Fe11.6Si1.4There are La in particle5Si3It is compound after equal miscellaneous phases, hot pressing and hydrogenation
Sample is more in void ratio embodiment 3 in material, therefore the embodiment sample breaking strength is reduced to 127MPa.
It will be apparent that rare earth-iron provided by the invention-silicon substrate magnetic refrigeration composite material compression strength can reach 186MPa,
And it can be plastically deformed.Therefore, machine-shaping and use process mechanical property can be better than resin-bonded magnetic refrigerating material.More
For importantly, the room temperature thermal conductivity of magnetic refrigeration composite material provided by the invention can reach 55W/m K, far more than resin-bonded
Magnetic refrigerating material, while there is biggish magnetothermal effect within the scope of operation temperature area.
It should be understood that for those of ordinary skill in the art, can do in accordance with the technical idea of the present invention
Other various changes and modifications out, and all these changes and deformation all should belong to the protection model of the claims in the present invention
It encloses.
Claims (10)
1. a kind of rare earth-iron-silicon substrate magnetic refrigeration composite material, it is characterised in that: the composite material include functive constituent element and
Matrix constituent element, the functive constituent element include rare earth-iron-silicon-base alloy particle, and described matrix constituent element includes aluminum metal simple substance
Or aluminium alloy, the rare earth-iron-silicon-base alloy particle by described matrix constituent element be bonded to block materials or functive constituent element with
Matrix constituent element reactant is bonded to block materials.
2. rare earth-iron according to claim 1-silicon substrate magnetic refrigeration composite material, it is characterised in that: the rare earth-
Iron-silicon-base alloy particle, chemical general formula Rx(Fe1-a-bCoaMnb)13-ySiyAz；Wherein, A appointing in H, B and C element
One or two kinds of or more the combination of meaning, the combination of any one or two kinds or more of R in La, Ce, Pr and Nd element,
1≤x≤2,1≤y≤2,0≤z≤4,0≤a≤0.1,0≤b≤0.05；And the rare earth-iron-silicon-base alloy particle packet
Containing with NaZn13The magnetothermal effect compound of type crystal structure.
3. rare earth-iron according to claim 1-silicon substrate magnetic refrigeration composite material, it is characterised in that: the aluminium alloy
In alloying element include in Mg, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Sn, Sb, Bi, Si any one or two
Kind or more combination and inevitable impurity.
4. rare earth-iron according to claim 1-silicon substrate magnetic refrigeration composite material, it is characterised in that: the rare earth-
Iron-silicon-base alloy particle partial size is not more than 300 μm, preferably 50~150 μm；The aluminum metal simple substance or aluminium alloy
Partial size is not more than 200 μm, preferably 10~150 μm.
5. rare earth-iron according to claim 1-silicon substrate magnetic refrigeration composite material, it is characterised in that: the aluminium alloy
Density is not more than 5g/cm3, thermal conductivity is not less than 10W/m K, and purity is not less than 99%.
6. rare earth-iron according to claim 1-silicon substrate magnetic refrigeration composite material, it is characterised in that: the rare earth-
The weight percent content of aluminum metal simple substance or aluminium alloy in iron-silicon substrate magnetic refrigeration composite material is 1~30wt.%, preferably
For 10~20wt.%.
7. rare earth-iron described in claim-silicon substrate magnetic refrigeration composite material according to claim 1~any one of 6,
Be characterized in that: the rare earth-iron-silicon substrate magnetic refrigeration composite material maximum entropy variate under 2T changes of magnetic field is 4~30J/kg
K, transition temperature range are 180~350K；Room temperature uniaxial compressive strength is not less than 80MPa；Thermal conductivity is 2~100W/m under 300K
K。
8. rare earth-iron-silicon substrate magnetic refrigeration composite material preparation method according to claim 7, it is characterised in that: packet
It includes:
1) according to chemical general formula R described in rare earth-iron-silicon-base alloy particlex(Fe1-a-bCoaMnb)13-ySiyAzPreparation raw material；
Wherein, the combination of any one or two kinds or more of A in H, B and C element, R is in La, Ce, Pr and Nd element
The combination of any one or two kinds or more, 1≤x≤2,1≤y≤2,0≤z≤4,0≤a≤0.1,0≤b≤0.05.Working as
When A in formula includes H element, the raw material in addition to H element is prepared according to chemical formula；
2) raw material that step 1) is prepared is put in smelting furnace, carries out melting under high purity inert gas protection, prepares master alloy；
3) master alloy of step 2) melting is annealed in vacuum environment or inert atmosphere, then quenching rapidly, is contained
NaZn13Rare earth-iron-silicon-base alloy of type crystal structure compound；
4) rare earth-iron-silicon-base alloy prepared by step 3) is broken into the particle that partial size is not more than 300 μm, and and aluminum metal
Simple substance or aluminium alloy uniformly mix to obtain mixture；
5) mixture of step 4) is put in mold, and hot-forming in high vacuum environment or in inert gas, block is made
Body material；
6) when the A in chemical formula includes H element, by block materials made from step 5) or after molding is further processed,
The hydrogenation treatment in hydrogen atmosphere.
9. rare earth-iron according to claim 8-silicon substrate magnetic refrigeration composite material preparation method, it is characterised in that: step
It is rapid 5) in hot-forming condition include: pressing pressure no more than 1GPa, preferably 50~500MPa；Hot pressing temperature is not higher than 800
DEG C, preferably 300~600 DEG C；Dwell time is no more than 60min, preferably 0.5~30min.
10. rare earth-iron according to claim 8-silicon substrate magnetic refrigeration composite material preparation method, it is characterised in that:
Hydrogenation treating conditions include: Hydrogen Vapor Pressure no more than 5MPa, preferably 0.05~2MPa in step 6)；Hydrotreating temperatures are not high
In 600 DEG C, preferably 200~400 DEG C；Hydrogenation time is no more than 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710849594.7A CN109524190B (en) | 2017-09-20 | 2017-09-20 | Rare earth-iron-silicon-based magnetic refrigeration composite material and preparation method thereof |
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| CN110534276A (en) * | 2019-07-31 | 2019-12-03 | 华南理工大学 | A kind of La-Fe-Si base magnetic refrigeration composite material and preparation method thereof based on hot pressure reaction sintering |
| CN111403137A (en) * | 2019-12-18 | 2020-07-10 | 上海大学 | Rare earth RE 2ZnMnO6Oxide magnetic refrigeration material and preparation method thereof |
| CN111575532A (en) * | 2020-07-01 | 2020-08-25 | 江西理工大学 | Bi-substituted Mn-vacancy Mn2Sb-based alloy, and preparation method and application thereof |
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| CN117637274B (en) * | 2024-01-23 | 2024-03-29 | 北京科技大学 | Rare earth-iron-silicon magnetic refrigeration material with low magnetic field, preparation method and application |
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