CN109763050A - Rare earth-silicon materials for magnetic refrigeration apparatus and preparation method thereof, magnetic refrigeration apparatus - Google Patents
Rare earth-silicon materials for magnetic refrigeration apparatus and preparation method thereof, magnetic refrigeration apparatus Download PDFInfo
- Publication number
- CN109763050A CN109763050A CN201910219974.1A CN201910219974A CN109763050A CN 109763050 A CN109763050 A CN 109763050A CN 201910219974 A CN201910219974 A CN 201910219974A CN 109763050 A CN109763050 A CN 109763050A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- magnetic
- magnetic refrigeration
- refrigeration apparatus
- silicon materials
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Hard Magnetic Materials (AREA)
Abstract
This application involves compound magnetic refrigeration rare earth-silicon materials and preparation method thereof, magnetic refrigeration apparatus.According to an embodiment, the rare earth-silicon materials for magnetic refrigeration are the compound for including group as ReSi, and wherein Re is mixed rare-earth elements.The preparation cost of material is reduced using composite rare earth material, while the compound magnetic refrigerating material shows platform magnetothermal effect, there is excellent refrigeration performance, can be used in various magnetic refrigeration apparatus.
Description
Technical field
Present invention relates generally to magnetic refrigerating fields, relate more specifically to a kind of magnetic functional material, specially a kind of magnetic
Refrigeration mischmetal composite material and preparation method.The invention further relates to the magnetic refrigeration for including the compound magnetic refrigerating material to set
It is standby.
Background technique
Magnetic refrigerating material is a kind of a kind of free of contamination refrigeration working medium of magnetic entropy effect realization refrigeration using magnetic material
Material, compared with traditional gas Compressing Refrigeration, with high cooling efficiency (up to 30~60%), low noise, service life it is long,
The remarkable advantages such as good reliability are known as high-tech green refrigeration technology, in cryogenic engineering, petrochemical industry, high-energy physics, electric power
The various fields such as industry, precision instrument, superconducting technology, aerospace, medical instrument have huge application potential.
In general, magnetic material, which will become excellent magnetic refrigeration working substance, must have the biggish magnetic heat near operating temperature
The performances such as effect, high refrigerating efficiency, low heat capacity, cheap, chemical property stabilization.By operating temperature interval division, magnetic system
Cold material can be divided into extremely low temperature warm area (20K or less), low temperature warm area (20-77K) and high temperature warm area (77K or more).Wherein low
Warm field, magnetic Refrigeration Technique have preferable application prospect in terms of producing liquid nitrogen, liquid helium, especially green energy resource liquid hydrogen.
Existing magnetic refrigerating material master to be applied is chemical combination between simple substance and rare earth metal containing rare earth elements such as Gd, Er
Object, but the metals such as Gd are oxidizable and expensive, constrain it in the practicability of refrigeration equipment.As a result, as magnetic refrigeration skill
The core of art, exploitation high-performance, inexpensive magnetic refrigerating material are the key points of magnetic refrigerating material research field.
Summary of the invention
The purpose of the present invention is to provide one kind, cost is relatively low and has the rare earth for magnetic refrigeration of high refrigerating capacity multiple
Condensation material, another object of the present invention is to provide the preparation method of the rare earth composite material for magnetic refrigeration, the present invention
A further object be to provide the rare earth composite material in the purposes of refrigeration equipment.
According to an embodiment, a kind of rare earth-silicon materials for magnetic refrigeration are provided, the material includes that group becomes ReSi
Compound, wherein Re be mixed rare-earth elements.
In some instances, the Re is selected from light rare earth elements.
In some instances, wherein Re is the two or more combinations in La, Ce, Pr, Nd, Sm.In a preferred embodiment
In, Re can be the combination of tri- kinds of rare earth elements of Ce, Pr, Nd.
In some instances, wherein the ratio of La, Ce, Pr, Nd, Sm are 25-40:20-60:4-30:2-30:0-1, with weight
Measure percentages.
In a preferred embodiment, wherein in the material containing Fe≤0.02%, Cr≤0.03%, Cu≤0.01%,
Ni≤0.01%, Co≤0.01%, by weight percentage.
According to another embodiment, a kind of method preparing magnetic refrigerating material is provided, comprising the following steps:
1) it weighs the raw material Re and Si of predetermined ratio and mixes, wherein Re is mixed rare-earth elements；
2) raw material in step 1) is put into smelting equipment and carries out melting；
3) material obtained in step 2) is subjected to vacuum annealing process.
In some instances, in step 1), the mixed proportion of Re and Si are 1.01-1.05: 1, with atomic percentage.
In some instances, in step 2), the melting carries out under protection of argon gas, specifically includes:
(2-1) puts into weighed Re and Si in smelting equipment, is warming up to 1700-1750 DEG C, keeps the temperature 1-2 minutes；
(2-2) is cooled to 1660-1670 DEG C, keeps the temperature 1-2 minutes；
(2-3) is cooled to 1600-1630 DEG C, and heat preservation naturally cools to room temperature after 1-2 minutes, forms block objects；
(2-4) is heated to 1700-1750 DEG C after overturning block objects to it again, and (the 2- that repeats the above steps
2)-(2-3)。
In some instances, in step 3), the temperature of the annealing is 950-1050 DEG C, and annealing time is 5-20 days.
Preferably, it after step 3), is rapidly cooled, such as is put into liquid nitrogen or dry ice after material is taken out.
According to another embodiment, a kind of magnetic refrigeration apparatus is provided, including the magnetic system formed by above-mentioned magnetic refrigeration composite material
Cold element.
Compared with prior art, it is had at least the following advantages provided by the present invention for rare earth-silicon materials of magnetic refrigeration:
1. the present invention uses light rare earth elements, together compared to the existing intermetallic compound comprising heavy rare earth such as Gd, Er
When material without containing the precious metals such as Cr, Ni, Co, it is low in cost；
2. the step of using composite rare earth material, eliminating purification rare earth simple substance, further reduced magnetic refrigerating material
Cost；
3. mischmetal-silicon refrigerating material has multiple phase transition temperatures, corresponding magnetic entropy, which becomes peak value, also has two or more,
Platform magnetothermal effect is showed, superposition improves the refrigerating capacity of composite material, has very big industrial efficiency.
The above and other feature and advantage of the application will become aobvious and easy from the following description to exemplary embodiment
See.
Detailed description of the invention
The exemplary embodiment of the application is described in more detail in conjunction with the accompanying drawings, the application above-mentioned and its
His purpose, feature and advantage will be apparent.Attached drawing is used to provide to further understand the embodiment of the present application, and structure
At part of specification, it is used to explain the application together with the embodiment of the present application, does not constitute the limitation to the application.Attached
In figure, identical reference label typically represents same parts or step.
Fig. 1 illustrates the flow charts according to the method for preparing magnetic refrigeration composite material of one exemplary embodiment of the application；
Fig. 2 shows the magnetic entropies of the magnetic refrigeration composite material of an exemplary embodiment according to the present invention to become bent with temperature relation
Line.
Specific embodiment
In the following, the exemplary embodiment that the application will be described in detail by referring to the drawings.Obviously, described embodiment is only
It is a part of the embodiment of the application, but should not be understood as the whole embodiments of the application, it should be appreciated that the application is not retouched here
The limitation for the example embodiment stated, but by these embodiments make those skilled in the art comprehensively, be fully understood by and can be real
Apply the present invention.
As shown in Figure 1, including the following steps: it illustrates the preparation method for magnetic refrigerating material of the invention
Step 12: rare earth, silicon raw material are mixed.
For example, rare earths material (RE) and silicon raw material (Si) can be weighed according to predetermined ratio, and the two is mixed.This hair
Bright middle rare earth Re uses mixed rare-earth elements rather than rare earth simple substance, and which reduce the dependences to simple substance rare earths material, therefore drops
The low preparation cost of material.Commercial product then can be used in silicon raw material, and purity is preferably higher than 99.9%.
In one embodiment, weighing can be carried out by the atomic ratio in RESi chemical formula, since rare earth element is in melting
In be inevitably present volatilization and scaling loss, can preferably be mixed by the atomic ratio that Re:Si is 1.01-1.05: 1.
In a preferred embodiment, light rare earth elements can be used in rare earths material of the invention, compared to existing using packet
Intermetallic compound containing heavy rare earth prepares magnetic refrigerating material with the advantage in cost using light rare earth.Specifically, rare earth
Raw material Re can be the two or more combinations in La, Ce, Pr, Nd, Sm, the preferably combination of Ce, Pr, Nd, more preferably Ce, Pr
Combination.In a specific embodiment, the ratio of La, Ce, Pr, Nd, Sm are 25-40: 20-60: 4-30: 2-30: 0-1, with
Weight percent meter, preferably 27-30: 40-55: 15-20: 0.04-0.06 can obtain higher magnetic entropy within this range
Become peak value.
Other than mischmetal raw material, Ga can be also added in the feed, the curie point of magnetic refrigerating material can be improved, together
When keep preferable magnetothermal effect, the additional amount of Ga is 0.005-0.03wt.%, in order to save cost, it is also contemplated that being not added
Enter Ga.
It should be noted that the raw material of preparation magnetic refrigerating material of the present invention does not use the precious metals such as Fe, Cr, Cu, Ni, can drop
Low cost of material.But due to, there are inevitable impurity element, may cause in the magnetic refrigerating material of preparation in mischmetal
It is mixed with above-mentioned impurity element, in the magnetic refrigerating material that the present invention obtains, can control the content of above-mentioned element is Fe≤0.02%, Cr
≤ 0.03%, Cu≤0.01%, Ni≤0.01%, Co≤0.01%, by weight percentage.
Step 14: mixed raw material being put into smelting equipment and carries out heating melting.
Since rare earth element is easily oxidized, the preparation of magnetic refrigerating material be should ensure that under vacuum environment or inert gas shielding
It carries out, such as first smelting equipment can be carried out being evacuated to vacuum degree being 10-2Pa or more.Being then charged with argon gas makes pressure in equipment
Power reaches 0.98 standard atmospheric pressure or so.
The smelting equipment can be water cooling copper crucible or electric arc furnaces, be heated to melting completely by arc discharge.For
The material with intended tissue structure is formed, the present invention can preferably use following melting mode:
141 put into weighed Re and Si in smelting equipment, are warming up to 1700-1750 DEG C, keep the temperature 1-2 minutes；
142 are cooled to 1660-1670 DEG C, keep the temperature 1-2 minutes；
143 are cooled to 1600-1630 DEG C, and heat preservation naturally cools to room temperature after 1-2 minutes, form block objects；
144 block objects are overturn after 1700-1750 DEG C is heated to it again, and the 142- that repeats the above steps
143, it thus can get the uniform alloy of ingredient.By above-mentioned melting mode, it can obtain and change between desired rare earth-silicon metal
Object is closed, to improve the magnetic refrigeration effect of magnetic refrigerating material.
Step 16: vacuum annealing process.
Alloy cast ingot prepared by melting is wrapped with aluminium foil, is placed in quartz container, wherein quartz container is using high-purity
Argon gas-sealed, the high temperature anneal 5-20 days at 950-1050 DEG C are spent, such as can be made annealing treatment 10 days at 900 DEG C, through true
The stress of ingot casting is released after sky annealing, and facilitates the uniform at phase constitution of intermetallic compound.It, can after vacuum annealing
It is put into liquid nitrogen or dry ice and is rapidly cooled after material is taken out, magnetic refrigerating material product is made.
Another embodiment of the present invention provides a kind of magnetic refrigerating material, and there is group to become the compound of ReSi, wherein
Re is mixed rare-earth elements.Fig. 2 shows the magnetic entropy of the magnetic refrigeration composite material of an exemplary embodiment according to the present invention become with
Temperature curve, the group in mischmetal that the present embodiment uses become La 28.27%, Ce 50.46%, Pr 5.22%,
Nd 15.66%, remaining be inevitable impurity, wherein Fe be 0.017%, Cr 0.015%, Cu 0.005%, Ni≤
0.003%, Co≤0.003%.Melting is carried out using La, Ce, Pr, Nd and Si in proportion, 2% (atom is excessively added in rare earth
Percentage).
It can be seen in fig. 2 that magnetic refrigerating material shows multiple phase transformations, correspondingly there are multiple magnetic entropies to become peak value (this implementation
Example is two), show platform magnetothermal effect.Compared to the single phase transformation of existing magnetic refrigerating material, the material that the present invention obtains
With superposition refrigerating capacity, therefore there is good industrial feasibility.As shown in Fig. 2, under 0-2T changes of magnetic field, compound
Magnetic entropy becomes peak value in 5.1J/kgK, and under 0-5T changes of magnetic field, it is about 10J/kgK that maximum magnetic entropy, which becomes peak value, display
Excellent magnetic refrigeration performance out.
The application another embodiment also provides a kind of magnetic refrigeration apparatus comprising made of above-mentioned rare earth-silicon materials
Magnetic cooling module.Magnetic refrigeration apparatus can be the equipment for preparing liquid hydrogen, liquid nitrogen, can be used for preparing clean energy resource and aerospace fuel storage
Energy.
The basic principle of the application is described in conjunction with specific embodiments above, however, it is desirable to, it is noted that in this application
The advantages of referring to, advantage, effect etc. are only exemplary rather than limitation, must not believe that these advantages, advantage, effect etc. are the application
Each embodiment is prerequisite.In addition, detail disclosed above is merely to exemplary effect and the work being easy to understand
With, rather than limit, it is that must be realized using above-mentioned concrete details that above-mentioned details, which is not intended to limit the application,.
Device involved in the application, device, equipment, system block diagram only as illustrative example and be not intended to
It is required that or hint must be attached in such a way that box illustrates, arrange, configure.As those skilled in the art will appreciate that
, it can be connected by any way, arrange, configure these devices, device, equipment, system.Such as "include", "comprise", " tool
" etc. word be open vocabulary, refer to " including but not limited to ", and can be used interchangeably with it.Vocabulary used herein above
"or" and "and" refer to vocabulary "and/or", and can be used interchangeably with it, unless it is not such that context, which is explicitly indicated,.Here made
Vocabulary " such as " refers to phrase " such as, but not limited to ", and can be used interchangeably with it.
It may also be noted that each component or each step are can to decompose in the device of the application, device and method
And/or reconfigure.These decompose and/or reconfigure the equivalent scheme that should be regarded as the application.
The above description of disclosed aspect is provided so that any person skilled in the art can make or use this
Application.Various modifications in terms of these are readily apparent to those skilled in the art, and are defined herein
General Principle can be applied to other aspect without departing from scope of the present application.Therefore, the application is not intended to be limited to
Aspect shown in this, but according to principle disclosed herein and the consistent widest range of novel feature.
In order to which purpose of illustration and description has been presented for above description.In addition, this description is not intended to the reality of the application
It applies example and is restricted to form disclosed herein.Although already discussed above multiple exemplary aspects and embodiment, this field skill
Its certain modifications, modification, change, addition and sub-portfolio will be recognized in art personnel.
Claims (10)
1. a kind of rare earth-silicon materials for magnetic refrigeration, which is characterized in that the material includes the compound that group becomes ReSi,
Wherein Re is mixed rare-earth elements.
2. material as described in claim 1, wherein the Re is selected from light rare earth elements.
3. material as claimed in claim 1 or 2, wherein Re is the two or more combinations in La, Ce, Pr, Nd, Sm.
4. material as claimed in claim 3, wherein the ratio of La, Ce, Pr, Nd, Sm are 25-40: 20-60: 4-30: 2-30:
0-1, by weight percentage.
5. material as claimed in claim 4, wherein in the material containing Fe≤0.02%, Cr≤0.03%, Cu≤
0.01%, Ni≤0.01%, Co≤0.01%, by weight percentage.
6. a kind of method for preparing any one of claim 1-5 material, it is characterised in that: the method includes walking as follows
It is rapid:
1) it weighs the raw material Re and Si of predetermined ratio and mixes, wherein Re is mixed rare-earth elements；
2) raw material in step 1) is put into smelting equipment and carries out melting；
3) material obtained in step 2) is subjected to vacuum annealing process.
7. method as claimed in claim 6, wherein in step 1), the mixed proportion of Re and Si are 1.01-1.05: 1, with atom
Percentages.
8. method as claimed in claim 6, wherein in step 2), the melting carries out under protection of argon gas, specifically include:
(2-1) puts into weighed Re and Si in smelting equipment, is warming up to 1700-1750 DEG C, keeps the temperature 1-2 minutes；
(2-2) is cooled to 1660-1670 DEG C, keeps the temperature 1-2 minutes；
(2-3) is cooled to 1600-1630 DEG C, and heat preservation naturally cools to room temperature after 1-2 minutes, forms block objects；
(2-4) is heated to 1700-1750 DEG C after overturning block objects to it again, and repeats the above steps (2-2)-
(2-3)。
9. method as claimed in claim 6, wherein in step 3), the temperature of the annealing is 950-1050 DEG C, annealing time
It is 5-20 days.
10. a kind of magnetic refrigeration apparatus, including magnetic system made of rare earth-silicon materials described in any one of claim 1-5
Cold element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910219974.1A CN109763050A (en) | 2019-03-21 | 2019-03-21 | Rare earth-silicon materials for magnetic refrigeration apparatus and preparation method thereof, magnetic refrigeration apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910219974.1A CN109763050A (en) | 2019-03-21 | 2019-03-21 | Rare earth-silicon materials for magnetic refrigeration apparatus and preparation method thereof, magnetic refrigeration apparatus |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109763050A true CN109763050A (en) | 2019-05-17 |
Family
ID=66459564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910219974.1A Pending CN109763050A (en) | 2019-03-21 | 2019-03-21 | Rare earth-silicon materials for magnetic refrigeration apparatus and preparation method thereof, magnetic refrigeration apparatus |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109763050A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703037A (en) * | 2011-03-28 | 2012-10-03 | 中国科学院物理研究所 | Rare earth-iron-silicon material for magnetic refrigeration, and preparation method and application thereof |
| CN103045177A (en) * | 2011-10-12 | 2013-04-17 | 中国科学院物理研究所 | La (Fe, si)13-based magnetic refrigeration material prepared from high Ce industrial pure mischmetal as raw material, its preparation method and application |
| WO2018129476A1 (en) * | 2017-01-09 | 2018-07-12 | General Engineering & Research, L.L.C. | Magnetocaloric alloys useful for magnetic refrigeration applications |
-
2019
- 2019-03-21 CN CN201910219974.1A patent/CN109763050A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102703037A (en) * | 2011-03-28 | 2012-10-03 | 中国科学院物理研究所 | Rare earth-iron-silicon material for magnetic refrigeration, and preparation method and application thereof |
| CN103045177A (en) * | 2011-10-12 | 2013-04-17 | 中国科学院物理研究所 | La (Fe, si)13-based magnetic refrigeration material prepared from high Ce industrial pure mischmetal as raw material, its preparation method and application |
| WO2018129476A1 (en) * | 2017-01-09 | 2018-07-12 | General Engineering & Research, L.L.C. | Magnetocaloric alloys useful for magnetic refrigeration applications |
Non-Patent Citations (1)
| Title |
|---|
| JUNGHWAN KIM ETC.: "Critical evaluation and thermodynamic optimization of the Si-RE", 《J. CHEM. THERMODYNAMICS》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Phejar et al. | Structural and magnetic properties of magnetocaloric LaFe13–xSix compounds synthesized by high energy ball-milling | |
| US8109100B2 (en) | Magnetocaloric refrigerant | |
| US20130200293A1 (en) | La(fe,si)13-based multi-interstitial atom hydride magnetic refrigeration material with high temperature stability and large magnetic entropy change and preparation method thereof | |
| CN103502497B (en) | Magnetic refrigerating material | |
| TW201113911A (en) | Polycrystalline magnetocaloric materials | |
| JP4399771B2 (en) | Magnetic particle and method for producing the same, and magnetic particle unit | |
| US20220238262A1 (en) | Modified La-Fe-Si magnetocaloric alloys | |
| Hu et al. | Effect of excess lanthanum on corrosion and magnetocaloric property of LaFe11. 5Si1. 5 compounds | |
| CN114231794A (en) | A2B7 type hydrogen storage alloy for nickel-metal hydride battery and preparation method thereof | |
| CN109763050A (en) | Rare earth-silicon materials for magnetic refrigeration apparatus and preparation method thereof, magnetic refrigeration apparatus | |
| CN105834407B (en) | With NaZn13The preparation method of the rare-earth iron-based alloy cpd of type structure | |
| CN104357727A (en) | Mn-Fe-P-Si magnetic refrigeration material and preparation method thereof | |
| CN103649352B (en) | Magnetic refrigerating material and magnetic refrigeration apparatus | |
| CN100489137C (en) | Rare earth-iron-silicon base compound having primary magnetic phase change characteristics and its preparation method | |
| CN105986177B (en) | Room temperature magnetic refrigerating situ composite material, its preparation method and the application of high heat conduction | |
| CN114561580A (en) | RE4TCd magnetic refrigeration material and preparation method thereof | |
| CN109266951B (en) | LaFeSiCu magnetic refrigeration alloy and preparation method thereof | |
| Liu et al. | Microstructure and magnetocaloric properties in melt-spun and high-pressure hydrogenated La0. 5Pr0. 5Fe11. 4Si1. 6 ribbons | |
| Gjoka et al. | Temperature-compensated Sm1− xGdx (Co0. 74Fe0. 10Cu0. 12Zr0. 04) 7.50 permanent magnets (x= 0, 0.2, 0.4, 0.6, 0.8) | |
| CN102162056A (en) | Rare earth tin-based low-temperature magnetic refrigeration material and preparation method thereof | |
| Lin et al. | The magnetic entropy change in La0. 8Ce0. 2Fe11. 4Si1. 6Bx compounds prepared by copper-mold casting | |
| CN110364324A (en) | The stagnant Mn-Fe-P-Si base magnetic refrigerating material and preparation method thereof of low-heat | |
| Gębara et al. | The evolution of microstructure in annealed LaFeSi-type alloys | |
| Bouzidi et al. | Effect of carbonation on the structural, magnetic and magnetocaloric properties of uniaxial nanocrystalline Pr5Co19Cx compound | |
| CN117637274B (en) | Rare earth-iron-silicon magnetic refrigeration material with low magnetic field, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190517 |