CN101477864A - Rear earth refrigeration material having large magnetic heating effect and preparation thereof - Google Patents
Rear earth refrigeration material having large magnetic heating effect and preparation thereof Download PDFInfo
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Abstract
The invention relates to a rare earth magnetic refrigeration material provided with a large magnetocaloric effect and a preparation technology thereof. The general chemical formula of the magnetic refrigeration material is (La(1minus x)R(x))(Fe(1minus z)M(z))(13minus Alpha), and the preparation technology is an melting-mechanical grinding technology or an ball mill milling-sintering technology. The magnetic refrigeration material has the advantages that through adding other elements, the magnetic refrigeration material prepared by using a novel material preparation technology forms interstitial atoms containing C, H, N and B and exists in a NaZn13 crystal structure phase, thereby stabilizing the phase structure and improving the magnetocaloric effect of the material; the working temperature of the magnetic refrigeration material is above room temperature and is in a magnetic field range which can be provided by a permanent magnet; and the magnetic refrigeration material has the advantages of big magnetic entropy change and adiabatic temperature change, high oxidation resistance and corrosion resistance, continuous and adjustable Curie temperature and simple process, is suitable for mass production, and can be widely applied to an magnetic refrigeration technology.
Description
Technical field:
The present invention relates to a kind of Rare-Earth Magnetic refrigerating material and preparation technology thereof with big magneto-caloric effect.
Background technology:
In the world today, Refrigeration Technique plays important effect, as in industries such as food storage, air-conditioning, medical treatment.Modern Refrigeration Technique is based on the kind of refrigeration cycle process of gas compression/expansion basically, and not only efficient is low, energy consumption is high for this process, but also can destroy atmospheric ozone layer or cause greenhouse effect.Therefore, seek a kind of Refrigeration Technique novel, efficient, energy-saving and environmental protection and become the urgent problem that solves of current society need.
The magnetic refrigeration is to be a kind of brand-new Refrigeration Technique of working medium with the magnetic material.At present, the magnetic Refrigeration Technique is in low temperature field extensive use, explores and conceptual phase but also be in the room temperature field.Therefore, it is significant that exploitation has the room temperature magnetic refrigerating material of huge magneto-caloric effect (GMCE).
In the magnetic Refrigeration Technique, key is the performance of magnetic refrigerating material, and the size of its MCE directly influences the refrigerating efficiency of refrigeration machine.Obtain bigger magnetic entropy and become, two approach are arranged: one needs very high externally-applied magnetic field; Its two, magnetic refrigerating material itself has stronger MCE.Wherein, article one approach can adopt superconducting magnet to solve, but superconducting magnet makes magnetic refrigerating system complex structure, cost costliness, becomes the restraining factors of room temperature magnetic refrigerating technical development.Therefore, comparatively feasible way is developed Curie temperature T exactly
CNear room temperature and have the magnetic refrigerating material of strong MCE, so that under the magnetizing field that permanent magnet provides, just can obtain higher magnetic entropy change, to satisfy the demand.
Along with the further investigation of people, except that Metal Gd, found to have the Gd5 (Si of huge magneto-caloric effect in succession to room temperature magnetic refrigerating material
xGe
1-x)
4Alloy, Mn (As
1-xSb
x) alloy, Mn
1-xFe
xAs alloy, MnFe (P
1-xAs
x) alloy and La (Fe
xSi
1-x)
13It is alloy.The discovery of above-mentioned material makes the room temperature magnetic refrigerating technology present bright prospect.
For magnetic refrigerating material with superperformance, though material itself can obtain big magneto-caloric effect, but be limited by preparation technology, can't the stable product of obtained performance, therefore adopting advanced preparation technology to prepare magnetic refrigerating material also is the approach that obtains big magneto-caloric effect.
The preparation technology of magnetic refrigerating material, what generally adopt both at home and abroad at present is electric arc fusion method, high-frequency melting method molten alloy, at high temperature carries out long heat treatment then.But adopt the general composition of alloy of this method preparation inhomogeneous, contain a large amount of α-Fe phase, do not generate NaZn substantially
13Type crystalline texture phase must could obtain NaZn by long homogenization heat treatment after the melting
13Type crystalline texture phase is unfavorable for the practicability of magnetic Refrigeration Technique.
Present cube of NaZn
13La (the Fe of type
xSi
1-x)
13Be alloy because Curie temperature is higher, and can obtain under downfield that higher magnetic entropy becomes and the concern that is subjected to the researcher.But in material preparation, in order to obtain single NaZn
13Phase need be annealed 30-50 days about 1000 ℃, therefore had complex process, was not easy mass-produced problem.
The preparation technology of alloy adopts smelting process in the patent 200610066146.1 " magnetic refrigerating material and manufacture method thereof ", and the type of cooling adopts forces refrigerating work procedure, by cooling rate greater than 1*10
4℃/pressure of s cooling, its fused solution chilling is solidified obtain to have NaZn
13The quick cooling alloy of type crystalline texture phase.
The preparation technology of magnetic refrigerating material adopts smelting process in the patent 03121051.1 " having rare earth-iron base compound magnetic refrigerating material of great magnetic entropy variation and preparation method thereof ", at 900-1100 ℃ of vacuum treatment 7-30 days, take out in quench fast liquid nitrogen or the water afterwards then.
What these two kinds of methods adopted all is that smelting process and chilling are handled, and the technology relative complex is unfavorable for the production in enormous quantities of material.
Summary of the invention:
The purpose of this invention is to provide a kind of working temperature more than room temperature, in the magnetic field range that permanent magnet can provide, magnetic entropy becomes and adiabatic Wen Bianda, the non-oxidizability and the corrosion resistance of material are strong, Curie temperature is adjustable continuously, technology is simple, is fit to produce in enormous quantities, can be widely used in Rare-Earth Magnetic refrigerating material and preparation technology thereof with big magneto-caloric effect in the magnetic Refrigeration Technique.
The chemical general formula of magnetic refrigerating material involved in the present invention is: (La
(1-x)R
(x)) (Fe
(1-z)M
(z))
(13-α)A
(α)D
β, the scope of X is 0～0.5; The scope 0～1.0 of Z; The scope of α is 0～2.0; The scope of β is 0～0.5 wherein: R satisfies the combination in any of the following rare earth element of X scope: Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc for one or more; M satisfies the combination in any of the following element of Z scope: Ti, Zr, V, Cr, Mn, Co, Ni, Cu, Zn, Sn, Be, Ga, Zr, Nb, Mo, Hf, Ta or W for one or more; A satisfies the combination in any Si or the Al of the following element of α scope for one or more; D satisfies combination in any C, H, N or the B of the following element of β scope for one or more.
The preparation technology of magnetic refrigerating material of the present invention is a kind of in following two kinds of technologies:
First kind: adopt melting-mechanical lapping technology preparation; it is good that raw material La, Fe, R, M, A and D press the weighing of atom proportioning; in the vacuum shower furnace of argon shield, be smelted into foundry alloy; foundry alloy is by broken under nitrogen protection; and machinery is ground to 200～400 order powder, in the mould of packing into, at the 5-30Pa forming under the pressure; at 900～1180 ℃ of sintering, can prepare (La at 500-920 ℃ of annealing in process 2-70 hour then
(1-x)R
(x)) (Fe
(1-z)M
(z))
(13-α)A
(α)D
β
Second kind: raw material La, Fe, R, M, A and D are pressed the good and mixing of atom proportioning weighing; putting into ball grinder with abrading-ball by ratio of grinding media to material 35～10:1 seals; ball grinder is evacuated and feeds argon gas; under greater than 200 rev/mins rotational speed of ball-mill; with the mixture in the continuous ball milling method mechanical lapping jar; ball milling obtained greater than 300 purpose material powders in 10～40 hours; powder is packed under nitrogen protection in the grinding tool; at the 5-30Pa forming under the pressure, then at 900～1180 ℃ of sintering, can prepare (La 500-920 ℃ of annealing in process
(1-x)R
(x)) (Fe
(1-z)M
(z))
(13-α)A
(α)D
β
Advantage of the present invention is: adopt the magnetic refrigerating material of new material preparation technology preparation, by adding other element, form contain C, H, N, the B interstitial atom is present in NaZn
13Crystalline texture mutually in, stablized phase structure, improved the magneto-caloric effect of material, its working temperature is more than room temperature, in the magnetic field range that permanent magnet can provide, magnetic entropy becomes and adiabatic Wen Bianda, the non-oxidizability and the corrosion resistance of material are strong, and Curie temperature is adjustable continuously, and technology is simple, be fit to produce in enormous quantities, can be widely used in the magnetic Refrigeration Technique.
Description of drawings:
Fig. 1 is the LaFe of the embodiment of the invention 4 preparations
11.1Co
0.8Si
1.1B
0.2The X-ray diffraction spectrum;
Fig. 2 is the LaFe of the embodiment of the invention 10 preparations
11.2Co
0.7Si
1.1B
0.2The X-ray diffraction spectrum.
Embodiment:
The raw material that embodiment 1-12 is adopted are: metal La (98.4wt%), metal Fe (99wt%), metal Si (99.99wt%), metal Co (99wt%), metal B (99.99wt%), metal Ce (98.5wt%), metal A l (99.0wt%).
Molten alloy ingot casting 100g, its molecular formula is as follows:
Embodiment 1 alloy molecular formula is: (La
0.9Ce
0.1)
1Fe
12.05Co
0.65Si
0.3B
0.05
Embodiment 2 alloy molecular formula are: (La
0.9Ce
0.1)
1Fe
10.8Co
0.4Si
1.8B
0.1
Embodiment 3 alloy molecular formula are: LaFe
10.7Co
0.7Si
1.6B
0.1
Embodiment 4 alloy molecular formula are: LaFe
11.1Co
0.8Si
1.1B
0.2
Embodiment 5 alloy molecular formula are: LaFe
12.1Co
0.1Si
0.8B
0.3
Embodiment 6 alloy molecular formula are: LaFe
11.6Co
0.2Si
1.2B
0.4
Embodiment 7 alloy molecular formula are: LaFe
10.8Co
0.9(Si
1.0Al
0.3) B
0.4
Embodiment 8 alloy molecular formula are: LaFe
10.45Co
0.75Si
1.8B
0.45
Embodiment 9 alloy molecular formula are: LaFe
12.0Co
0.5Si
0.5B
0.05
Embodiment 10 alloy molecular formula are: LaFe
11.2Co
0.7Si
1.1B
0.2
Embodiment 11 alloy molecular formula are: LaFe
11.1Co
1.1Si
0.8B
0.3
Embodiment 12 alloy molecular formula are: LaFe
11.95Co
0.95Si
0.1B
0.45
The proportioning of alloy is as follows:
| Embodiment | La | Fe | Co | Si | B | Ce | Al |
| 1 | 14.55 | 78.32 | 4.46 | 0.98 | 0.06 | 1.63 | |
| 2 | 15.30 | 73.79 | 2.88 | 6.19 | 0.13 | 1.71 | |
| 3 | 16.86 | 72.54 | 5.01 | 5.46 | 0.13 | ||
| 4 | 16.73 | 74.67 | 5.68 | 2.66 | 0.26 | ||
| 5 | 16.42 | 79.85 | 0.70 | 2.65 | 0.38 | ||
| 6 | 16.60 | 77.44 | 1.41 | 4.03 | 0.52 | ||
| 7 | 16.62 | 72.18 | 6.35 | 3.36 | 0.52 | 0.97 | |
| 8 | 16.90 | 70.98 | 5.38 | 6.15 | 0.59 | ||
| 9 | 16.28 | 78.55 | 3.46 | 1.65 | 0.06 | ||
| 10 | 16.56 | 74.58 | 4.92 | 3.68 | 0.26 | ||
| 11 | 16.36 | 72.98 | 7.63 | 2.65 | 0.38 | ||
| 12 | 15.97 | 76.71 | 6.44 | 0.32 | 0.56 |
Wherein, embodiment 1-8 adopts melting-mechanical lapping technology preparation
With joining metal clean up; adopt GP100-0.1-R type vacuum high frequency shower furnace to be smelted into alloy pig, under nitrogen protection, be broken into granule then, and adopt agate mortar that alloy is ground to the 200-300 order; pack in the mould shaped by fluid pressure under 15-20Pa pressure into.Adopt vacuum sintering furnace at 1030-1070 ℃ of heat treatment 2-6h, at 600-900 ℃ of insulation 2-16h.
Embodiment 9-12 adopts ball mill ball milling-sintering technology preparation
With joining metal clean up, under nitrogen protection, be broken into granule, adopt the mechanical ball milling method that particle is ground to final size during abrasive dust.Before the ball milling ball mill barrel and the used agate ball of grinding are cleaned up with benzinum; raw material and diameter are that the agate ball of 10mm and 5mm is packed in the 1:30 ratio and sealed in the cylinder of steel; cylinder of steel covers to be equipped with and charges and discharges gas valve; be evacuated and feed argon gas to 0.2-0.3Mpa at cylinder of steel; regulate drum's speed of rotation and be respectively 350,500 and 560rpm; with feed particles mechanical lapping is powder, and ball milling method comprises continuous ball milling and ball milling at intermittence.Made powder stores in benzinum after the ball milling screening.Made powder under nitrogen protection, in the mould of packing into, shaped by fluid pressure under 12-20Pa pressure.Adopt vacuum sintering furnace at 1000-1120 ℃ of heat treatment 2-10h, at 650-850 ℃ of insulation 6-10h.
Claims (2)
1, a kind of Rare-Earth Magnetic refrigerating material with big magneto-caloric effect, it is characterized in that: the chemical general formula of magnetic refrigerating material is: (La
(1-x)R
(x)) (Fe
(1-z)M
(z))
(13-α)A
(α)D
β, the scope of X is 0～0.5; The scope 0～1.0 of Z; The scope of α is 0～2.0; The scope of β is 0～0.5 wherein: R satisfies the combination in any of the following rare earth element of X scope: Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y or Sc for one or more; M satisfies the combination in any of the following element of Z scope: Ti, Zr, V, Cr, Mn, Co, Ni, Cu, Zn, Sn, Be, Ga, Zr, Nb, Mo, Hf, Ta or W for one or more; A satisfies the combination in any Si or the Al of the following element of α scope for one or more; D satisfies combination in any C, H, N or the B of the following element of β scope for one or more.
2, a kind of preparation technology with Rare-Earth Magnetic refrigerating material of big magneto-caloric effect according to claim 1 is characterized in that: a kind of in following two kinds of technologies of preparation technology:
First kind: adopt melting-mechanical lapping technology preparation; it is good that raw material La, Fe, R, M, A and D press the weighing of atom proportioning; in the vacuum shower furnace of argon shield, be smelted into foundry alloy; foundry alloy is by broken under nitrogen protection; and machinery is ground to 200～400 order powder, in the mould of packing into, at the 5-30Pa forming under the pressure; at 900～1180 ℃ of sintering, can prepare (La at 500-920 ℃ of annealing in process 2-70 hour then
(1-x)R
(x)) (Fe
(1-z)M
(z))
(13-α)A
(α)D
β
Second kind: raw material La, Fe, R, M, A and D are pressed the good and mixing of atom proportioning weighing; putting into ball grinder with abrading-ball by ratio of grinding media to material 35～10:1 seals; ball grinder is evacuated and feeds argon gas; under greater than 200 rev/mins rotational speed of ball-mill; with the mixture in the continuous ball milling method mechanical lapping jar; ball milling obtained greater than 300 purpose material powders in 10～40 hours; powder is packed under nitrogen protection in the grinding tool; at the 5-30Pa forming under the pressure, then at 900～1180 ℃ of sintering, can prepare (La 500-920 ℃ of annealing in process
(1-x)R
(x)) (Fe
(1-z)M
(z))
(13-α)A
(α)D
β
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|---|---|---|---|
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| CN101477864B CN101477864B (en) | 2011-11-23 |
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