CN104357727A - Mn-Fe-P-Si magnetic refrigeration material and preparation method thereof - Google Patents
Mn-Fe-P-Si magnetic refrigeration material and preparation method thereof Download PDFInfo
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- CN104357727A CN104357727A CN201410597188.2A CN201410597188A CN104357727A CN 104357727 A CN104357727 A CN 104357727A CN 201410597188 A CN201410597188 A CN 201410597188A CN 104357727 A CN104357727 A CN 104357727A
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Abstract
The invention belongs to the field of magnetic refrigeration materials, and discloses an Mn-Fe-P-Si magnetic refrigeration material and a preparation method thereof. The material composition is selectively Mn1.15Fe0.85P0.52Si0.45B0.03. The preparation method comprises the following steps: (1) mixing Mn sheets, Fe blocks, FeP blocks, Si blocks and B blocks after weighing according to the mass percentages of elements in a chemical formula, wherein 5% of balance is added to the Mn; (2) putting raw materials prepared in the step (1) into a vacuum electric arc furnace, and utilizing high-purity argon gas shield for smelting to obtain an alloy pig; (3) breaking up the alloy pig, putting into a vacuum rapid quenching furnace for smelting alloy, and carrying out copper mold casting; (4) sealing the copper mold casting alloy into a quartz tube, vacuumizing to below 10<-4> Pa, carrying out annealing treatment, and then rapidly quenching into cold water to obtain the magnetic refrigeration material. The mn-Fe-P-Si magnetic refrigeration material is simple in technology, low in cost, and the magnetic refrigeration material with high density and excellent magnetocaloric effect can be obtained.
Description
Technical field
The invention belongs to the preparation field of magnetic refrigerating material, be specifically related to a kind of Mn-Fe-P-Si magnetic refrigerating material and preparation method thereof.
Background technology
Magnetic Refrigeration Technique is is working medium with magneticsubstance, utilize the change of spin system magnetic entropy to realize a kind of brand-new Refrigeration Technique of refrigeration.Compared with Compressing Refrigeration, magnetic Refrigeration Technique has the many merits such as compact construction, energy-efficient, non-environmental-pollution, is just becoming the focus of researcher research instantly.Magnetic Refrigeration Technique has wide practical use in fields such as refrigerator, air-conditioning and large-scale food product refrigerations.But magnetic Refrigeration Technique will be achieved, also have problems to have to be solved, comprise the design in magnetic field, the selection of refrigeration cycle, the selection, heat transfer technology etc. of magnetic refrigeration working substance.Be the important stage of room temperature magnetic refrigerating working material research and development at present, only have and select and develop the development process that suitable magnetic refrigeration working substance could accelerate to advance magnetic Refrigeration Technique.
Common room temperature magnetic refrigerating material mainly contains heavy rare earths class magnetic refrigerating material, LaFe
13-xsi
xseries alloy, perovskite-like type Mn oxide, Heusler type ferromagnetic material and MnFePSi series alloy.MnFePSi series alloy is by MnFePAs alloy development the earliest, and within 2002, Tegus has found the giant magnetio-caloric effects of MnFePAs alloy, thus opens the gate of research MnFePSi series alloy.MnFePSi series alloy due to not containing rare earth element, the prices of raw and semifnished materials are cheap and wide material sources, magnetic heating performance excellent, Curie temperature at many merits such as near room temperature are adjustable, be one of optimal candidate material of room temperature magnetic refrigerating.
The preparation of existing MnFePSi series alloy adopts ball milling-sintering process or flash set technology mostly, these two kinds of preparation technologies need to utilize highly purified elemental powders as starting material, this not only greatly improves raw-material cost, and powder exists active, the oxidizable problem of chemical property.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is to provide a kind of Mn-Fe-P-Si simply efficient, with low cost series magnetic refrigerating material.
Another object of the present invention is to the preparation method that above-mentioned Mn-Fe-P-Si series magnetic refrigerating material is provided, controlled the microstructure of alloy by annealing process, thus control the magnetic heating performance of alloy.
Object of the present invention is achieved through the following technical solutions:
A kind of Mn-Fe-P-Si magnetic refrigerating material, chemical formula is Mn
1.15fe
0.85p
0.52si
0.45b
0.03.
The preparation method of described Mn-Fe-P-Si magnetic refrigerating material, comprises the steps:
(1) mix after Mn sheet, Fe block, FeP block, Si block and B block being weighed by the mass percent of element each in chemical formula, wherein Mn adds the surplus (amount of losing with Mn in subsequent technique is suitable) of 5%;
(2) starting material step (1) prepared load in vacuum arc fumace, utilize high-purity argon gas to protect melting to obtain alloy pig;
(3) alloy pig described in step (2) is broken, get alloy pig and load melted alloy in vacuum quick quenching furnace, utilize copper mold to cast obtained Mn
1.15fe
0.85p
0.52si
0.45b
0.03alloy bar material;
(4) by the copper mold casting alloy described in step (3), be sealed in silica tube, be evacuated to 10
-4below Pa, the sample after sealing is annealed 48 ~ 96h under 1123 ~ 1423K, quenches fast afterwards in cold water, obtained Mn
1.15fe
0.85p
0.52si
0.45b
0.03magnetic refrigerating material.
Step (2) described vacuum arc fumace is evacuated to 5 × 10
-3below Pa, is filled with the high-purity argon gas of 0.03 ~ 0.05MPa, and melting number of times is 5 times.
Vacuum quick quenching furnace described in step (3) is evacuated to 8 × 10
-4below Pa, is filled with the high-purity argon gas of 0.03 ~ 0.05MPa, carries out induction heating.
Described vacuum quick quenching furnace type of heating is high-frequency induction heating, and utilize argon gas pressure reduction by the aluminium alloy spray of melting in copper mold, argon gas pressure reduction is 0.08 ~ 0.1MPa.
The internal diameter of described copper mold is 2mm, is highly 120mm.
Annealing temperature described in step (4) is 1123K, 1223K, 1323K or 1423K, and annealing time is 48h.
Material purity is Fe>99.8wt.%, Mn>99.9wt.%, FeP>98wt.%, Si>99.9wt.%, B>99.9wt.%.
The material of described FeP consists of Fe=71.5wt.%, P=26.5wt.%, Si=1.3wt.%, C=0.36wt.%, Mn=0.31wt.%, S=0.03wt.%.
The present invention adopts melting-copper mold foundry engieering then to adopt block materials as starting material, and raw-material purity requirement is well below ball milling-sintering or flash set technology.In melt back process, not only by each component uniform alloy, and can have certain refining effect, after melting, some oxide inclusions are mainly gathered in the surface of ingot casting, are easy to remove.More tiny tissue can be obtained after the casting of melted ingot copper mold, by suitable annealing process namely by the size that control group is knitted, control the magnetic heating performance of material.
In practical application, block materials prepared by MnFePSi series alloy bar and the ball milling-sintering process prepared by melting-copper mold foundry engieering is compared with band prepared by flash set technology has obvious advantage.First, alloy density prepared by melting-copper mold foundry engieering is higher, and the defects such as less hole make the corrosion resistance nature of alloy also greatly improve; Secondly, the alloy bar material that melting-prepared by copper mold foundry engieering is beneficial to clamping, more conveniently can load in magnetic refrigerator and use.
The present invention has following advantage and effect relative to prior art:
(1) raw material sources that the present invention is used is extensive, cheap, and not containing rare earth element and toxic element, commercial application prospect is considerable;
(2) starting material that the present invention is used are block materials, and for powdered material, the cost of block materials is lower, chemical stability is also better;
(3) the present invention controls the microstructure of alloy by changing thermal treatment process, thus prepares the magnetic refrigerating material that magnetic entropy becomes greatly, Curie temperature levels off to room temperature;
(4) the present invention can regulate Curie temperature, magnetic entropy to become and heat stagnation by the composition proportion changing alloy;
(5) the Mn-Fe-P-Si magnetic refrigerating material prepared by the present invention, by changing composition and thermal treatment process, Curie temperature, heat stagnation and magnetic entropy can be regulated to become, and composition is Mn
1.15fe
0.85p
0.52si
0.45b
0.03alloy is annealed after 48h through 1423K, and Curie temperature is that the magnetic entropy under 251K, 2T foreign field uprises and reaches 19.8J/ (kgK);
(6) the Mn-Fe-P-Si magnetic refrigerating material density prepared by the present invention is higher, erosion resistance better, is beneficial to commercial applications;
(7) preparation method's technique of the present invention is simple, with low cost, favorable repeatability, is applicable to producing in enormous quantities.
Accompanying drawing explanation
Fig. 1 is Mn prepared by embodiment 1
1.15fe
0.85p
0.52si
0.45b
0.03the XRD figure of alloy after differing temps annealing.
Fig. 2 is Mn prepared by embodiment 1
1.15fe
0.85p
0.52si
0.45b
0.03alloy is metallographic structure photo after differing temps annealing, and the annealing temperature of Fig. 2 (a), (b), (c), (d) correspondence is respectively 1123K, 1223K, 1323K, 1423K.
Fig. 3 is Mn prepared by embodiment 1
1.15fe
0.85p
0.52si
0.45b
0.03alloy through differing temps annealing after intensification and cooling M-T curve (applying foreign field is 0.05T).
Fig. 4 is Mn prepared by embodiment 1
1.15fe
0.85p
0.52si
0.45b
0.03the isothermal magnetization curve of alloy near Curie temperature after differing temps annealing, the annealing temperature of Fig. 4 (a), (b), (c), (d) correspondence is respectively 1123K, 1223K, 1323K, 1423K.
Fig. 5 is Mn prepared by embodiment 1
1.15fe
0.85p
0.52si
0.45b
0.03the magnetic entropy of the near Curie temperature of alloy after differing temps annealing becomes variation with temperature relation curve.
Fig. 6 is Mn prepared by embodiment 1
1.15fe
0.85p
0.52si
0.45b
0.03the polarization curve (corrosive fluid be the NaCl solution of 3.5%) of alloy after 1223K and 1423K annealing.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of Mn-Fe-P-Si magnetic refrigerating material, its preparation method is as follows:
(1) Mn sheet, Fe block, FeP block, Si block and B block are pressed Mn
1.15fe
0.85p
0.52si
0.45b
0.03the atomic ratio batching of alloy.Wherein the quality of Mn sheet, Fe block, FeP block, Si block and B block is respectively 4.758g, 0.287g, 4.439g, 0.906g, 0.023g, weighs four parts;
(2) starting material prepared are loaded in vacuum arc fumace, be evacuated to 5 × 10
-3below Pa, is filled with the high-purity argon gas of 0.03 ~ 0.05MPa, utilizes arc melting to obtain alloy pig.In order to ensure that each component mixes, often melting and once having overturn sample afterwards, melt back 5 times;
(3) broken after the alloy pig described in step (2) being removed surface scale, get 5g alloy pig loading lower end and open in foraminate silica tube.Silica tube is installed in vacuum quick quenching furnace, is evacuated to 8 × 10
-4below Pa, utilizes high-frequency induction heating melted alloy, and being 2mm by the alloy of melting quick spray to cast under the effect of argon gas pressure reduction (0.08 ~ 0.1MPa) to diameter, is highly in the copper mold of 120mm, obtained Mn
1.15fe
0.85p
0.52si
0.45b
0.03alloy bar material;
(4) by the copper mold casting alloy described in step (3), be sealed in silica tube, be evacuated to 10
-4below Pa, the sample (four parts) after sealing is annealed 48h under 1123K, 1223K, 1323K and 1423K, quenches fast afterwards in cold water, obtained Mn
1.15fe
0.85p
0.52si
0.45b
0.03magnetic refrigerating material (four parts).
Performance test
For Mn prepared by above-described embodiment
1.15fe
0.85p
0.52si
0.45b
0.03the stuctures and properties of alloy, is undertaken characterizing and analyzing by X-ray diffractometer, metaloscope, comprehensive physical property measuring system etc., is described further below in conjunction with accompanying drawing.
Fig. 1 is Mn
1.15fe
0.85p
0.52si
0.45b
0.03the XRD figure spectrum of alloy after 1123K, 1223K, 1323K and 1423K anneal 48h.Because the size of sample is less, so all adopt powder X-ray diffraction during test.As seen from the figure, the alloy after annealing all defines two-phase, and principal phase has hexagonal Mn
1.9p type phase structure, spacer is
dephasign is hexagonal Mn
3fe
2si
3phase, spacer is P63/mcm.Along with the rising of annealing temperature, Mn
1.9the diffraction peak intensity of P type principal phase obviously increases, it is worthy of note that the sample diffraction peak intensity that 1123K anneals is much more weak than the sample of other annealing temperatures, and diffraction peak exists weak broadening phenomenon, illustrate that the sample that lesser temps is annealed exists a small amount of micron crystalline substance or nanocrystalline.Mn
3fe
2si
3the relative content of phase does not significantly change with the change of annealing temperature.
Fig. 2 is the Mn after differing temps annealing
1.15fe
0.85p
0.52si
0.45b
0.03the microstructure of alloy after wang aqueous solution corrosion, mainly there is two-phase in visible alloy, the sample of 1123K and 1223K annealing exists obvious dentrite, and along with the rising of annealing temperature, dendritic structure fades away, and organizes more even.
Fig. 3 is Mn
1.15fe
0.85p
0.52si
0.45b
0.03the intensification of alloy under 0.05T foreign field and cooling M-T curve, in order to ensure that alloy starts test under more stable state, first stablizing 300s and applying magnetic field again and carry out heating-cooling test after being cooled to 100K.Slowly, when being warming up to 350K, the specific magnetising moment does not also reach 0, illustrates that alloy is not also transformed into paramagnetic state completely in the change of the sample magnetization intensity temperature of visible 1123K annealing.In addition, the ferromagnetic-paramagnetic transition temperature of this alloy is also slower.But along with the rising of annealing temperature, intensification and temperature lowering curve all become more and more steep, illustrate that ferromagnetic-paramagnetic transition is more and more obvious.Calculating shows, the Curie temperature of alloy linearly increases with the rising of annealing temperature, and 205K when annealing from 1123K has been elevated to 251K during 1423K annealing.Intensification and cooling M-T curve do not overlap, and illustrate that alloy exists certain heat stagnation, the heat stagnation of alloy reduces with the rising of annealing temperature, and along with annealing temperature is increased to 1423K by 1223K, heat stagnation has been reduced to 10.5K from 17K.This be due to comparatively high temps annealing after sample composition more evenly, less, the internal stress of defect also decreases, so heat stagnation is lower.Mn
1.15fe
0.85p
0.52si
0.45b
0.03the Curie temperature of alloy and the detailed data of heat stagnation are in table 1.
Fig. 4 is Mn
1.15fe
0.85p
0.52si
0.45b
0.03the isothermal magnetization curve of alloy, the annealing temperature of Fig. 4 (a), (b), (c), (d) correspondence is respectively 1123K, 1223K, 1323K, 1423K.During test, T
c2K is got, away from T in neighbouring temperature interval
c5K, 10K get in temperature interval in place.As seen from the figure, alloy is at low temperatures in obvious ferromegnetism, and the specific magnetising moment is substantially tending towards saturated under 2T, along with the rising generation ferromegnetism of temperature changes to paramagnetism.But the sample ferromagnetic-paramagnetic transition of 1123K annealing slowly, does not still become complete paramagnetic state when 270K.The sample of 1323K annealing and 1423K annealing, there occurs obvious field near Curie temperature and causes change magnetic transition.
Fig. 5 is the Mn of differing temps annealing
1.15fe
0.85p
0.52si
0.45b
0.03(-Δ the S of alloy under the change of 0-1T and 0-2T foreign field
m)-T curve.The calculation formula of isothermal magnetic entropy change can be derived according to Maxwell relational expression:
again continuous integration is changed into discrete sum formula, the magnetic entropy of isothermal M-H curve calculation alloy can be utilized to become.As shown in Figure 5, the isothermal magnetic entropy of alloy becomes and increases with the rising of annealing temperature, and detailed data lists in table 1.Under 2T foreign field, sample is after 1123K, 1223K, 1323K and 1423K annealing, and maximum isothermal magnetic entropy change is respectively 0.6,5.0,19.1 and 19.8Jkg
-1k
-1.The magnetic sample Entropy Changes that 1123K anneals is very little, but the magnetic entropy of alloy becomes increase rapidly after comparatively high temps annealing, and after annealing temperature is more than 1323K, magnetic entropy change remains unchanged substantially.XRD analysis above shows, the alloy of differing temps annealing all has Mn
1.9p type hexagonal structure, although phase structure does not change, magnetic entropy becomes and but there is very big-difference, and the change that may have occurred phase composite is described in annealing process, and the atom in principal phase and dephasign there occurs diffusion in annealing process.
Fig. 6 is the Mn of 1223K and 1423K annealing
1.15fe
0.85p
0.52si
0.45b
0.03alloy and the polarization curve of pure Gd in 3.5%NaCl solution.Visible Mn
1.15fe
0.85p
0.52si
0.45b
0.03the corrosion current density of alloy is well below pure Gd, and corrosion potential is also high than pure Gd.Gd is E in 3.5%NaCl solution
corrfor-1.493V, J
corrbe 322.6 μ A/cm
2, (E more very different than the erosion resistance of pure Gd in distilled water
corr=-1.269V, J
corr=1.072 μ A/cm
2).The alloy E of 1223K, 1423K annealing
corrand J
corrbe respectively-0.372V, 0.904 μ A/cm
2with-0.294V, 0.866 μ A/cm
2.Corrosion-resistant the increasing of the alloy of 1423K annealing is because after comparatively high temps annealing, and organizing in alloy is more even, defect reduces.Mn
1.15fe
0.85p
0.52si
0.45b
0.03the erosion resistance of alloy substantially can be comparable with general stainless steel, is very promising room temperature magnetic refrigerating material.
The magnetic property data summarization of table 1 Mn-Fe-P-Si alloy
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a Mn-Fe-P-Si magnetic refrigerating material, is characterized in that, chemical formula is Mn
1.15fe
0.85p
0.52si
0.45b
0.03.
2. the preparation method of Mn-Fe-P-Si magnetic refrigerating material described in claim 1, is characterized in that, comprise the steps:
(1) mix after Mn sheet, Fe block, FeP block, Si block and B block being weighed by the mass percent of element each in chemical formula, wherein Mn adds the surplus of 5%;
(2) starting material step (1) prepared load in vacuum arc fumace, utilize high-purity argon gas to protect melting to obtain alloy pig;
(3) alloy pig described in step (2) is broken, get alloy pig and load melted alloy in vacuum quick quenching furnace, utilize copper mold to cast obtained Mn
1.15fe
0.85p
0.52si
0.45b
0.03alloy bar material;
(4) by the copper mold casting alloy described in step (3), be sealed in silica tube, be evacuated to 10
-4below Pa, the sample after sealing is annealed 48 ~ 96h under 1123 ~ 1423K, quenches fast afterwards in cold water, obtained Mn
1.15fe
0.85p
0.52si
0.45b
0.03magnetic refrigerating material.
3. preparation method according to claim 2, is characterized in that, step (2) described vacuum arc fumace is evacuated to 5 × 10
-3below Pa, is filled with the high-purity argon gas of 0.03 ~ 0.05MPa, and melting number of times is 5 times.
4. preparation method according to claim 2, is characterized in that, the vacuum quick quenching furnace described in step (3) is evacuated to 8 × 10
-4below Pa, is filled with the high-purity argon gas of 0.03 ~ 0.05MPa, carries out induction heating.
5. preparation method according to claim 4, is characterized in that, described vacuum quick quenching furnace type of heating is high-frequency induction heating, and utilize argon gas pressure reduction by the aluminium alloy spray of melting in copper mold, argon gas pressure reduction is 0.08 ~ 0.1MPa.
6. preparation method according to claim 2, is characterized in that, the internal diameter of described copper mold is 2mm, is highly 120mm.
7. the preparation method according to Claims 2 or 3 or 4 or 5 or 6, is characterized in that, the annealing temperature described in step (4) is 1123K, 1223K, 1323K or 1423K, and annealing time is 48h.
8. the preparation method according to Claims 2 or 3 or 4 or 5 or 6, it is characterized in that, material purity is Fe>99.8wt.%, Mn>99.9wt.%, FeP>98wt.%, Si>99.9wt.%, B>99.9wt.%.
9. preparation method according to claim 8, is characterized in that, the material of described FeP consists of Fe=71.5wt.%, P=26.5wt.%, Si=1.3wt.%, C=0.36wt.%, Mn=0.31wt.%, S=0.03wt.%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018041958A1 (en) * | 2016-08-31 | 2018-03-08 | Basf Se | Controlled variation of parameters of magnetocaloric materials |
| CN108642355A (en) * | 2018-05-17 | 2018-10-12 | 内蒙古科技大学 | A kind of ferromanganese basal cell temperature magnetic refrigerating material and preparation method thereof |
| CN110364324A (en) * | 2019-06-19 | 2019-10-22 | 南京理工大学 | The stagnant Mn-Fe-P-Si base magnetic refrigerating material and preparation method thereof of low-heat |
| CN110449585A (en) * | 2019-08-29 | 2019-11-15 | 华南理工大学 | A kind of Mn base magnetic refrigeration composite material and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881393A (en) * | 2012-09-11 | 2013-01-16 | 华南理工大学 | MnFePSi-based room-temperature magnetic refrigeration material and preparation method thereof |
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2014
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881393A (en) * | 2012-09-11 | 2013-01-16 | 华南理工大学 | MnFePSi-based room-temperature magnetic refrigeration material and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018041958A1 (en) * | 2016-08-31 | 2018-03-08 | Basf Se | Controlled variation of parameters of magnetocaloric materials |
| CN108642355A (en) * | 2018-05-17 | 2018-10-12 | 内蒙古科技大学 | A kind of ferromanganese basal cell temperature magnetic refrigerating material and preparation method thereof |
| CN108642355B (en) * | 2018-05-17 | 2019-11-22 | 内蒙古科技大学 | A kind of iron-based room temperature magnetic refrigerating material of manganese and preparation method thereof |
| CN110364324A (en) * | 2019-06-19 | 2019-10-22 | 南京理工大学 | The stagnant Mn-Fe-P-Si base magnetic refrigerating material and preparation method thereof of low-heat |
| CN110364324B (en) * | 2019-06-19 | 2021-07-06 | 南京理工大学 | Mn-Fe-P-Si based magnetic refrigeration material with low thermal hysteresis and preparation method thereof |
| CN110449585A (en) * | 2019-08-29 | 2019-11-15 | 华南理工大学 | A kind of Mn base magnetic refrigeration composite material and preparation method |
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