CN104630568A - MnCoGe based ferromagnetic martensite phase-change material, preparation method and applications thereof - Google Patents
MnCoGe based ferromagnetic martensite phase-change material, preparation method and applications thereof Download PDFInfo
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Abstract
The invention provides a MnCoGe based ferromagnetic martensite phase-change material, a preparation method and applications thereof. The chemical formula of the phase-change material is MnCoGe<1-x>, 0<x<=0.05. The phase-change material has a martensite structure phase change, which is coupled with a magnetic phase change. As the temperature decreases, the phase change material changes from paramagnetic high-temperature austenite parent phase with a Ni2In hexagonal structure to ferromagnetic low-temperature martensite phase with a TiNiSi type orthorhombic structure, and the phase change property is one grade. The magnetic/structural phase-change coupling temperature of the provided phase-change material is continuously adjustable in a wide temperature range (310-340K), which is slightly higher than the room temperature, along with the change of the Ge vacancy concentration. The material system has the characteristics of abundant raw material reserves, simple technology, and suitability for industrial production.
Description
Technical field
The present invention relates to a kind of magnetic functional material, particularly a kind ofly realize the MnCoGe that the coupling of magnetic/structural phase transition has large magnetothermal effect
1-xmagnetic refrigerating material and its production and use.
Background technology
Magnetic Refrigeration Technique is the Refrigeration Technique of an environmental protection.Compared with the Refrigeration Technique of traditional gas compression-expansion, magnetic refrigeration adopts magnetic substance as refrigeration working medium, to ozonosphere without destruction, without Greenhouse effect.In refrigerating efficiency, magnetic refrigeration can reach the 30%-60% of carnot's working cycle, and the refrigeration cycle relying on gas compression to expand generally can only reach the 5%-10% of carnot's working cycle, therefore, magnetic Refrigeration Technique has a good application prospect, and is described as high-new green refrigeration technology.Magnetic Refrigeration Technique, especially room temperature magnetic refrigerating technology have great potential application market in the industry such as home freezer and air-conditioning, so receive the concern of domestic and international research institution and branch of industry.
Usually, people describe the magnetic heating performance of magnetic refrigeration working substance with magnetic entropy change and adiabatic temperature change.Compared with changing with adiabatic temperature, magnetic entropy changes to add and is easy to measure, and thus people more get used to adopting magnetic entropy to become the magnetothermal effect characterizing magnetic refrigerating material.Therefore, the emphasis that the magnetic refrigerating material having a great magnetic entropy variation at room temperature warm area becomes research is both at home and abroad found.1997, U.S. AMES laboratory found Gd
5si
2ge
2alloy has giant magnetio-caloric effects, and the source of the great magnetic entropy variation of this material is primary magnetic phase change.Compared with second-order phase transition, the magnetic entropy change that the material of first-order phase transition occurs often concentrates on narrower warm area, can obtain higher amplitude magnetic entropy and become.Subsequently, domestic and international research institution starts to find the material near room temperature with large Entropy Changes, such as: La (Fe, Si)
13the room temperature magnetic refrigerating materials such as based compound, MnFeP based compound, MnAs based compound, NiMn Ji Hasile alloy be it is found that in succession.
Martensitic transformation is a kind of very important non-diffusing type crystal structure phase transformation in solid-state phase changes, is first-order phase transition.During phase transformation, high temperature parent phase lattice point occurs without the shear of diffusion displacement type in atomic scale, and be therefore otherwise known as displacement type phase transformation.Before and after phase transformation, two-phase chemical composition remains unchanged.For convenience of description, in martensitic transformation, usual people claim high temperature parent phase to be austenite, and low temperature product is martensite.Like this, be called martensitic transformation by austenite to the process of martensitic transformation, otherwise, be called martensite reverse transformation.In numerous geneva phase change material, most is representational is NiMn Ji Hasile sections magnetic martensitic material, and its physical property is enriched, and shows as Magnetic Field-Induced strain, field drives shape memory effect, large magnetic resistance, great magnetic entropy variation, exchange biased etc.
The geneva phase transformation of strangling type alloy with Haas is similar, and MnCoGe alloy also presents the martensitic transformation characteristic without diffusion.The process of alloy from high temperature cooling, crystalline network is transformed into the martensite low-temperature phase of the orthohormbic structure of low temperature from the hexagonal structure austenite parent phase of high temperature.For the sample just divided, martensitic structure transformation temperature is 650K, and this temperature changes along with the difference of component.High temperature hexagonal Ovshinsky phase and the orthogonal geneva of low temperature all present intrinsic ferromagnetic characteristic mutually, and its molecule saturation magnetic moment and Curie temperature are 2.76 μ B and 275K, 4.13 μ B and 345K respectively, and the magnetic phase transition of the two all presents the characteristic of second-order phase transition.Just dividing the martensitic structure transformation temperature (650K) of MnCoGe compound far above room temperature, and magnetic phase transition is not coupled, the magnetothermal effect therefore occurred near magnetic phase transition is less.
For obtaining large magnetothermal effect, for just dividing MnCoGe system people to substitute attempt to make geneva structural phase transition and magnetic phase transition coupling by introducing pressure or Mn, Co, Ge atom, but up to the present still there is no the introducing in Ge room to the report of geneva structural phase transition impact and magnetothermal effect.
Summary of the invention
Therefore, the object of this invention is to provide a kind of MnCoGe base MnCoGe with large Entropy Changes
1-xferromagnetic Martensitic Transformation Materials and its preparation method and application.
The present inventor finds through large quantity research, introduces Ge room just dividing in MnCoGe system, geneva structural transition temperatures can be made to move to low temperature, and be coupled with magnetic phase transition, thus occur great magnetic entropy variation.Transformation temperature can be realized at the wide warm area of near room temperature adjustable (especially high temperature section warm area 310 ~ 340K) by regulating Ge vacancy concentration and obtain large magnetothermal effect, to meet the refrigeration needs of the wide warm area of near room temperature.Utilize adjustment Ge room method implementation structure phase transformation to compare (as introduced pressure, atom substitutes) with other means with the coupling of magnetic phase transition and there is the features such as element kind is few, easy control of components, preparation technology are simple.MnCoGe system magnetic derives from Mn and Co atom, realize the coupling of magnetic/structural phase transition by regulating nonmagnetic Ge room (but not Mn or Co room) and have that physical mechanism is simple, the manageable feature of transformation temperature, the material prepared can obtain magnetic refrigeration application.
The present invention achieves foregoing invention object by the following technical solutions.
On the one hand, the invention provides the ferromagnetic Martensitic Transformation Materials of a kind of MnCoGe base, its chemical general formula is: MnCoGe
1-x, wherein, 0 < x≤0.05.
According to the ferromagnetic Martensitic Transformation Materials of MnCoGe base provided by the invention, this material has geneva structural phase transition and is coupled with magnetic phase transition.Along with the reduction of temperature, this material is from paramagnetism Ni
2the high temperature austenitic parent phase of In type hexagonal structure changes the low temperature martensitic phase of ferromegnetism TiNiSi type orthohormbic structure into, and phase transition property is one-level.
On the other hand, the invention provides the preparation method of the ferromagnetic Martensitic Transformation Materials of above-mentioned MnCoGe base, described preparation method comprises:
(1) according to MnCoGe
1-xchemical formula batching, wherein, 0 < x≤0.05, puts into electric arc furnace by the raw material prepared, and is evacuated to≤1 × 10
-2handkerchief, after argon purge, under argon shield, Arc, the melting 3 ~ 5 times at 1500 ~ 2500 DEG C of each alloy pig, obtains alloy pig;
(2) by alloy pig melted for step (1) 800 ~ 900 DEG C, vacuum tightness is less than 1 × 10
-3anneal 2 ~ 10 days under handkerchief, be then less than 1 × 10 in vacuum tightness
-3naturally cool to room temperature under handkerchief, obtain MnCoGe
1-xmagneticsubstance.
According to preparation method provided by the invention, wherein, the raw material used in step (1) is Mn, Co and Ge simple substance, and preferably, described raw material is the simple substance of purity >=99.9wt%.
According to preparation method provided by the invention, wherein, the argon gas used in described step (1) is high-purity argon gas, is preferably the argon gas that purity is greater than 99wt%.
Another aspect, present invention also offers the ferromagnetic Martensitic Transformation Materials of described MnCoGe base and is preparing the application in refrigerating material.
Again on the one hand, present invention also offers a kind of magnetic refrigerator, described magnetic refrigerator comprises the ferromagnetic Martensitic Transformation Materials of MnCoGe base provided by the invention, or according to the ferromagnetic Martensitic Transformation Materials of MnCoGe base that preparation method provided by the invention obtains.
Compare with technology with existing magnetic refrigerating material, the invention has the advantages that:
1, the present invention by introducing Ge atom vacancy in the ferromagnetic Martensitic Transformation Materials of MnCoGe base, makes martensitic structure transformation temperature be adjusted near room temperature, and make magnetic phase transition and structural phase transition coupling, thus bring large Entropy Changes;
2, the present invention utilize regulate the coupling of the method implementation structure phase transformation of MnCoGe system Ge room and magnetic phase transition (as introduced pressure, atom substitutes) compared with other means to have element kind is few, easy control of components, do not contain the features such as rare earth element, preparation technology are simple.MnCoGe system magnetic derives from Mn and Co atom, realize the coupling of magnetic/structural phase transition by regulating nonmagnetic Ge room (but not Mn or Co room) and have that physical mechanism is simple, the manageable feature of transformation temperature, the material prepared can obtain magnetic refrigeration application;
3, MnCoGe
1-xthe great magnetic entropy variation of system occurs near room temperature high temperature section, i.e. 310K ~ 340K warm area, and shows than traditional magnetic refrigerating material and other New Magnetic Field Controlled refrigerating material (as traditional material Gd, novel Gd
5si
2ge
2base materials with the giant magnetocaloric effect etc.) higher Entropy Changes value.
Accompanying drawing explanation
Below, describe embodiment of the present invention in detail by reference to the accompanying drawings, wherein:
Fig. 1 is MnCoGe prepared by the embodiment of the present invention 1
0.99the room temperature X-ray diffraction spectral line of phase change material, wherein, X-coordinate is diffraction angle, and ordinate zou is diffracted intensity, and wherein, the Miller's indices Arabic numerals of hexagonal phase and orthorhombic phase mark.
Fig. 2 is MnCoGe prepared by the embodiment of the present invention 1
0.99the specific magnetising moment-temperature (M-T) curve of phase change material under 500Oe magnetic field, wherein X-coordinate is temperature, and ordinate zou is the specific magnetising moment.
Fig. 3 is MnCoGe prepared by the embodiment of the present invention 1
0.99the magnetzation curve of phase change material, wherein X-coordinate is magneticstrength, and ordinate zou is the specific magnetising moment.
Fig. 4 is MnCoGe prepared by the embodiment of the present invention 1
0.99the magnetic entropy of phase change material under 1T, 2T, 3T, 4T, 5T, 6T and 7T magnetic field becomes Δ S variation with temperature curve, and wherein X-coordinate is temperature, and ordinate zou is that magnetic entropy becomes.
Fig. 5 is MnCoGe prepared by the embodiment of the present invention 2
0.97the room temperature X-ray diffraction spectral line of phase change material, wherein, X-coordinate is diffraction angle, and ordinate zou is diffracted intensity, and wherein, the Miller's indices Arabic numerals of hexagonal phase and orthorhombic phase mark.
Fig. 6 is MnCoGe prepared by the embodiment of the present invention 2
0.97the specific magnetising moment-temperature (M-T) curve of phase change material under 500Oe magnetic field, wherein X-coordinate is temperature, and ordinate zou is the specific magnetising moment.
Fig. 7 is MnCoGe prepared by the embodiment of the present invention 2
0.97the magnetzation curve of phase change material, wherein X-coordinate is magneticstrength, and ordinate zou is the specific magnetising moment.
Fig. 8 is MnCoGe prepared by the embodiment of the present invention 2
0.97the magnetic entropy of phase change material under 1T, 2T, 3T, 4T, 5T, 6T and 7T magnetic field becomes Δ S variation with temperature curve, and wherein X-coordinate is temperature, and ordinate zou is that magnetic entropy becomes.
Fig. 9 is MnCoGe prepared by the embodiment of the present invention 3
0.96the room temperature X-ray diffraction spectral line of phase change material, wherein, X-coordinate is diffraction angle, and ordinate zou is diffracted intensity, and wherein, the Miller's indices Arabic numerals of hexagonal phase and orthorhombic phase mark.
Figure 10 is MnCoGe prepared by the embodiment of the present invention 3
0.96the specific magnetising moment-temperature (M-T) curve of phase change material under 500Oe magnetic field, wherein X-coordinate is temperature, and ordinate zou is the specific magnetising moment.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment provided only in order to illustrate the present invention, instead of in order to limit the scope of the invention.
Raw material used in the embodiment of the present invention is: simple substance Mn, purity 99.9wt%, is purchased from Beijing dicyclo chemical reagent factory; Simple substance Co, purity 99.9wt%, be purchased from Beijing Non-Ferrous Metal Research General Academy; Simple substance Ge, purity is 99.999wt%, is purchased from Beijing Non-Ferrous Metal Research General Academy.
Electric arc furnace used is that Beijing WuKe opto-electrical Technology Co., Ltd produces, model: WK-II type non-consumable arc furnace; Cu target X-ray diffractometer is that Rigaku company produces, and model is RINT2400; Superconductive quantum interference vibrating sample magnetometer (MPMS(SQUID) VSM) be Quantum Design(USA) company's production, model is MPMS(SQUID) VSM.
embodiment 1
The present embodiment is according to chemical formula MnCoGe
0.99prepare phase change material of the present invention, concrete preparation method is as follows:
(1) by chemical formula MnCoGe
0.99preparation raw material, puts into electric arc furnace by the raw material prepared, is evacuated to 3 × 10
-3more than handkerchief, after cleaning 1 time with high-purity argon gas (purity 99.996wt%), under 1 atmospheric high-purity argon gas (purity 99.996wt%) protection, Arc, melt back 5 times, smelting temperature is 2000 DEG C.After melting terminates, in copper crucible, be cooled to room temperature, obtain cast alloy ingot.
(2) wrapped with metal molybdenum sheet respectively by alloy pig obtained for step (1), being sealed in vitreosil pipe, interior (vacuum tightness is 1 × 10
-4pa), after annealing 6 days at 875 DEG C, take out silica tube, after naturally cooling to room temperature, break silica tube, obtain MnCoGe
0.99phase change material sample.
performance test:
(1) Cu target X-ray diffractometer is utilized to measure the obtained MnCoGe of the present embodiment
0.99room temperature (300K) the X-ray diffraction spectral line of phase change material, as shown in Figure 1.Result shows, MnCoGe
0.99sample presents orthogonal geneva structure (spacer: Pnma) and occurs (spacer: P6 mutually with a small amount of hexagonal Ovshinsky
3/ mmc).For the MnCoGe alloy just divided, geneva structural transition temperatures is 650K.Under room temperature, the appearance of a small amount of hexagonal phase shows that the introducing in (1%) Ge room on a small quantity can make geneva structural transition temperatures move from high temperature (650K) to low temperature.
(2) MnCoGe that under the 0.05T magnetic field measured on superconducting quantum magnetometer, the present embodiment is obtained
0.99the thermomagnetization curve (M-T) of phase change material, is shown in Fig. 2.Geneva structural transition temperatures (T can be determined from M-T curve
stru) and magnetic phase transition temperature (T
c).As can be seen from the figure, there is temperature hysteresis (8K) near phase transformation, show first-order phase transition feature, can judge that paramagnetic-ferromagnetic phase transformation overlaps with geneva structural phase transition, T
stru=T
c=330K; The introducing in 1%Ge room can make geneva transformation temperature move to 330K from 650K, shows: structural transition temperatures T
struextremely responsive to the introducing of Ge atom vacancy, therefore by the content of control Ge atom vacancy, can control texture transformation temperature.
(3) on SQUID, measure the MnCoGe that the present embodiment is obtained
0.99the isothermal magnetization curve (as shown in Figure 3) of phase change material near transformation temperature.According to Maxwell relations:
(as Fig. 4) can be become from isothermal magnetization curve calculation magnetic entropy.As can be seen from Figure 4, under 0-5T changes of magnetic field, the MnCoGe that the present embodiment is obtained
0.99the magnetic entropy change of phase change material reaches 21.5J/kgK(328.5K), the Curie temperature exceeding traditional magnetic refrigerating material Gd(Gd is 293K, and under 0-5T changes of magnetic field, magnetic entropy becomes 9.8J/kgK).
embodiment 2
The present embodiment is according to chemical formula MnCoGe
0.97prepare phase change material of the present invention, concrete preparation method is as follows:
(1) by chemical formula MnCoGe
0.97preparation raw material, puts into electric arc furnace by the raw material prepared, is evacuated to 3 × 10
-3more than handkerchief, after cleaning 2 times with high-purity argon gas (purity 99.996wt%), under 1 atmospheric high-purity argon gas (purity 99.996wt%) protection, Arc, melt back 5 times, smelting temperature is 2000 DEG C.After melting terminates, in copper crucible, be cooled to room temperature, obtain cast alloy ingot.
(2) wrapped with metal molybdenum sheet respectively by alloy pig obtained for step (1), being sealed in vitreosil pipe, interior (vacuum tightness is 1 × 10
-4pa), after annealing 6 days at 875 DEG C, take out silica tube, after naturally cooling to room temperature, break silica tube, obtain MnCoGe
0.97phase change material sample.
performance test:
(1) Cu target X-ray diffractometer is utilized to measure the obtained MnCoGe of the present embodiment
0.97room temperature (300K) the X-ray diffraction spectral line of phase change material, as shown in Figure 5.Result shows, MnCoGe
0.97sample presents orthogonal geneva structure (spacer: Pnma) and occurs (spacer: P6 mutually with a small amount of hexagonal Ovshinsky
3/ mmc).For the MnCoGe alloy just divided, geneva structural transition temperatures is 650K.Under room temperature, the appearance of a small amount of hexagonal phase shows that the introducing in Ge room can make geneva structural transition temperatures move from high temperature (650K) to low temperature.
(2) MnCoGe that under the 0.05T magnetic field measured on superconducting quantum magnetometer, the present embodiment is obtained
0.97the thermomagnetization curve (M-T) of phase change material, is shown in Fig. 6.Geneva structural transition temperatures (T can be determined from M-T curve
stru) and magnetic phase transition temperature (T
c).As can be seen from the figure, there is temperature hysteresis (8K) near phase transformation, show first-order phase transition feature, can judge that paramagnetic-ferromagnetic phase transformation overlaps with geneva structural phase transition, T
stru=T
c=324K; The MnCoGe in the Ge room 1% obtained with embodiment 1
0.99sample (T
stru=T
c=330K) compare and can find, magnetic/structural phase transition coupling temperature (T
stru=T
c) move to low temperature with the increase of Ge vacancy concentration.
(3) on SQUID, measure the MnCoGe that the present embodiment is obtained
0.97the isothermal magnetization curve (as shown in Figure 7) of phase change material near transformation temperature.According to Maxwell relations:
(as Fig. 8) can be become from isothermal magnetization curve calculation magnetic entropy.As can be seen from Figure 8, under 0-7T changes of magnetic field, the MnCoGe that the present embodiment is obtained
0.97the magnetic entropy change of phase change material reaches 47.4J/kgK(327K), under 0-5T changes of magnetic field, magnetic entropy variate is 35.1J/kgK(327K), exceed the Ge vacancy concentration 1% sample MnCoGe that embodiment 1 is obtained
0.99entropy Changes amplitude, the Curie temperature simultaneously exceeding conventional refrigeration material Gd(Gd is 293K, and under 0-5T changes of magnetic field, magnetic entropy becomes 9.8J/kgK).
embodiment 3
The present embodiment is according to chemical formula MnCoGe
0.96prepare phase change material of the present invention, concrete preparation method is as follows:
(1) by chemical formula MnCoGe
0.96preparation raw material, puts into electric arc furnace by the raw material prepared, is evacuated to 3 × 10
-3more than handkerchief, after cleaning 2 times with high-purity argon gas (purity 99.996wt%), under 1 atmospheric high-purity argon gas (purity 99.996wt%) protection, Arc, melt back 5 times, smelting temperature is 2000 DEG C.After melting terminates, in copper crucible, be cooled to room temperature, obtain cast alloy ingot.
(2) wrapped with metal molybdenum sheet respectively by alloy pig obtained for step (1), being sealed in vitreosil pipe, interior (vacuum tightness is 1 × 10
-4pa), after annealing 6 days at 875 DEG C, take out silica tube, after naturally cooling to room temperature, break silica tube, obtain MnCoGe
0.96phase change material sample.
performance test:
(1) Cu target X-ray diffractometer is utilized to measure the obtained MnCoGe of the present embodiment
0.96room temperature (300K) the X-ray diffraction spectral line of phase change material, as shown in Figure 9.Result shows, MnCoGe
0.96mnCoGe in sample and embodiment 1 and 2
0.99, MnCoGe
0.97material is compared, and also occurs high temperature hexagonal Ovshinsky phase (spacer: P6
3/ mmc), show that geneva structural transition temperatures moves to low temperature with the increase in Ge room.
(2) MnCoGe that under the 0.05T magnetic field measured on superconducting quantum magnetometer, the present embodiment is obtained
0.96the thermomagnetization curve (M-T) of phase change material, is shown in Figure 10.Geneva structural transition temperatures (T can be determined from M-T curve
stru) and magnetic phase transition temperature (T
c).Find to there is temperature hysteresis (6K) near phase transformation, show first-order phase transition feature, can judge that paramagnetic-ferromagnetic phase transformation overlaps with geneva structural phase transition, T
stru=T
c=316K; Compare can find with embodiment 1 and embodiment 2, magnetic/structural phase transition coupling temperature (T
stru=T
c) move to low temperature further with the increase of Ge vacancy concentration, consistent with X-ray diffraction result.
Above result shows: for MnCoGe system, geneva structural transition temperatures can be moved to low temperature by introducing Ge room, thus be coupled with magnetic phase transition, realize large magnetic entropy and become, MnCoGe
1-xbill of material reveal than tradition and other New Magnetic Field Controlled refrigerating material (as traditional material Gd, novel Gd
5si
2ge
2base materials with the giant magnetocaloric effect (under 0-5T changes of magnetic field, Entropy Changes value: 18J/kgK, is positioned at 276K), etc.) high Entropy Changes value, and magnetic/structural phase transition coupling temperature (T
stru=T
c) with wide warm area scope (310 ~ 340K) continuously adjustabe of the change of Ge vacancy concentration in a little higher than room temperature, the needs of magnetic Refrigeration Technique can be met.
comparative example 1
By typical conventional chamber temperature magnetic refrigerating material---rare metal Gd (purity 99.9wt%) and phase change material of the present invention contrast.
At MPMS(SQUID) VSM to record purity be the Curie temperature of the rare metal Gd of 99.9wt% is 293K, under 0-5T changes of magnetic field, the magnetic entropy at Curie temperature place becomes 9.8J/kgK.As can be seen here, obtained in embodiment 1-3 MnCoGe
1-xthe magnetic entropy of material becomes all significantly more than Gd, illustrates that material provided by the invention has larger magnetothermal effect.
Below describe in detail the present invention with reference to concrete embodiment, to those skilled in the art, it should be understood that above-mentioned embodiment should not be understood as that as limiting scope of the present invention.Therefore, without departing from the spirit and scope of the present invention, various changes and improvements can be made to embodiment of the present invention.
Claims (9)
1. the ferromagnetic Martensitic Transformation Materials of MnCoGe base, its chemical general formula is: MnCoGe
1-x, wherein 0 < x≤0.05.
2. the ferromagnetic Martensitic Transformation Materials of MnCoGe base according to claim 1, wherein, this material has geneva structural phase transition and is coupled with magnetic phase transition.
3. the ferromagnetic Martensitic Transformation Materials of MnCoGe base according to claim 1 and 2, wherein, along with the reduction of temperature, this material is from paramagnetism Ni
2the high temperature austenitic parent phase of In type hexagonal structure changes the low temperature martensitic phase of ferromegnetism TiNiSi type orthohormbic structure into, and phase transition property is one-level.
4. the preparation method of material according to any one of claims 1 to 3, described preparation method comprises:
(1) according to MnCoGe
1-xchemical formula batching, wherein, 0 < x≤0.05, puts into electric arc furnace by the raw material prepared, and is evacuated to≤1 × 10
-2handkerchief, after argon purge, under argon shield, Arc, the melting 3 ~ 5 times at 1500 ~ 2500 DEG C of each alloy pig, obtains alloy pig;
(2) by alloy pig melted for step (1) 800 ~ 900 DEG C, vacuum tightness is less than 1 × 10
-3anneal 2 ~ 10 days under handkerchief, be then less than 1 × 10 in vacuum tightness
-3naturally cool to room temperature under handkerchief, obtain MnCoGe
1-xmagneticsubstance.
5. preparation method according to claim 4, wherein, the raw material used in step (1) is Mn, Co and Ge simple substance.
6. preparation method according to claim 5, wherein, the purity of described Mn, Co and Ge simple substance all >=99.9wt%.
7. the preparation method according to any one of claim 4 to 6, wherein, the argon gas used in described step (1) is high-purity argon gas, is preferably the argon gas that purity is greater than 99wt%.
8. the ferromagnetic Martensitic Transformation Materials of MnCoGe base according to any one of claims 1 to 3 or the ferromagnetic Martensitic Transformation Materials of MnCoGe base that preparation method obtains according to any one of claim 4 to 7 are preparing the application in refrigerating material.
9. a magnetic refrigerator, described magnetic refrigerator comprises the ferromagnetic Martensitic Transformation Materials of MnCoGe base according to any one of claims 1 to 3, or the ferromagnetic Martensitic Transformation Materials of MnCoGe base that the preparation method according to any one of claim 4 to 7 obtains.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342634A (en) * | 2017-01-24 | 2018-07-31 | 中国科学院物理研究所 | A kind of material and its preparation method and application of adjustable negative expansion coefficient |
| CN110004326A (en) * | 2018-01-05 | 2019-07-12 | 北京航空航天大学 | A kind of NiCuFeGa magnetic-structure Coupling phase-change alloy and preparation method thereof |
| CN108300882A (en) * | 2018-02-11 | 2018-07-20 | 江西理工大学 | The method that magnetic structure coupling phase transformation is realized in MnCoGe based alloys |
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