CN104630568B - A kind of ferromagnetic Martensitic Transformation Materials of MnCoGe bases and its production and use - Google Patents
A kind of ferromagnetic Martensitic Transformation Materials of MnCoGe bases and its production and use Download PDFInfo
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Abstract
The present invention provides a kind of ferromagnetic Martensitic Transformation Materials of MnCoGe bases and its production and use, and the chemical general formula of the material is：MnCoGe1‑x, wherein, 0 ＜ x≤0.05.The material has geneva structural phase transition and is coupled with magnetic phase transition, and with the reduction of temperature, material is from paramagnetism Ni2The high temperature austenitic parent phase of In type hexagonal structures is changed into the low temperature martensitic phase of ferromagnetism TiNiSi type orthohormbic structures, and phase transition property is one-level.The magnetic of material of the present invention/structural phase transition coupling temperature can with the change of Ge vacancy concentrations a little higher than room temperature warm area scope wide（310~340K）Continuously adjustabe, the need for meeting magnetic Refrigeration Technique.The features such as material system has abundant material storage, process is simple, is suitable to industrialized production.
Description
Technical field
The present invention relates to a kind of magnetic functional material, more particularly to a kind of achievable magnetic/structural phase transition coupling has big magnetic
The MnCoGe of fuel factor1-xMagnetic refrigerating material and its production and use.
Background technology
Magnetic Refrigeration Technique is a Refrigeration Technique for environmental protection.Compared with the Refrigeration Technique of traditional gas compression-expansion,
Magnetic refrigeration is as refrigeration working medium, to ozone layer without destruction, without greenhouse effects using magnetisable material.In refrigerating efficiency side
Face, magnetic refrigeration can reach the 30%-60% of Carnot cycle, and typically can only achieve card by the kind of refrigeration cycle that gas compression expands
The 5%-10% of promise circulation, therefore, magnetic Refrigeration Technique has a good application prospect, and is described as high-new green refrigeration technology.Magnetic system
Refrigeration technique, especially room temperature magnetic refrigerating technology have great potential application market in terms of the industry such as domestic refrigerator and air-conditioning,
So being paid close attention to by domestic and international research institution and branch of industry.
Generally, people are become with adiabatic temperature change to describe the magnetic heating performance of magnetic refrigeration working substance with magnetic entropy.With adiabatic temperature
Change is compared, and magnetic entropy change is more easily measured, thus people more get used to being characterized using magnetic entropy change the magnetic heat of magnetic refrigerating material
Effect.Therefore, the magnetic refrigerating material that find has great magnetic entropy variation in room temperature warm area turns into the emphasis of research both at home and abroad.1997,
U.S. AMES laboratories find Gd5Si2Ge2Alloy has giant magnetio-caloric effects, and the source of the great magnetic entropy variation of the material is one-level magnetic phase
Become.Compared with second-order phase transistion, the magnetic entropy change that the material of first order phase change occurs often focuses on narrower warm area, can obtain higher amplitude
Magnetic entropy becomes.Then, domestic and international research institution begins look for the material for having big Entropy Changes near room temperature, for example：La(Fe,Si)13
The room temperature magnetic refrigerating materials such as based compound, MnFeP based compounds, MnAs based compounds, NiMn Ji Hasile alloys are in succession by people
Find.
Martensitic traoformation is a kind of very important non-diffusing type crystal structure phase transformation in solid-state phase changes, is first order phase change.
During phase transformation, high temperature parent phase lattice point occurs without diffusion displacement type shear in atomic scale, therefore the displacement type phase transformation that is otherwise known as.Phase
Two-phase chemical composition keeps constant before and after becoming.For the ease of description, in martensitic traoformation, usual people's high temperature parent phase is called Ovshinsky
Body, low temperature product is martensite.So, it is referred to as martensitic traoformation from austenite to the process of martensite transfor mation, conversely, referred to as horse
Family name's body reverse transformation.In numerous geneva phase-change materials, most representational is NiMn Ji Hasile sections magnetic martensitic materials, its
Physical property is enriched, and shows as Magnetic Field-Induced and strains, field drives SME, large magnetic resistance, great magnetic entropy variation, exchange biased etc.
Deng.
Geneva phase transformation with Haas Le type alloy is similar, and MnCoGe alloys are also presented the martensitic traoformation characteristic without diffusion.
In alloy during the High-temperature cooling, lattice structure is transformed into the positive knot of low temperature from the hexagonal structure austenite parent phase of high temperature
The martensite low-temperature phase of structure.For the sample for just dividing, martensitic structure phase transition temperature is 650K, and the temperature is with the difference of component
And change.High temperature hexagonal Ovshinsky phase and the orthogonal geneva of low temperature are mutually all presented intrinsic ferromagnetic characteristic, its molecule saturation magnetic moment and Curie
Temperature is respectively 2.76 μ B and 275K, 4.13 μ B and 345K, and the magnetic phase transition of the two is presented the characteristic of second-order phase transistion.Just divide
The martensitic structure phase transition temperature of MnCoGe compounds（650K）Do not coupled far above room temperature, and magnetic phase transition, therefore occurred in magnetic
Magnetothermal effect near phase transformation is smaller.
To obtain big magnetothermal effect, for just dividing MnCoGe systems people by introducing pressure or Mn, Co, Ge atom
Replacement attempts to couple geneva structural phase transition and magnetic phase transition, but the introducing up to the present still without Ge rooms is to geneva structure
Phase transformation influence and the report of magnetothermal effect.
The content of the invention
It is therefore an object of the present invention to provide a kind of MnCoGe bases MnCoGe with big Entropy Changes1-xFerromagnetic martensitic traoformation
Material and its preparation method and application.
The present inventor has found that introducing Ge rooms, can make geneva in MnCoGe systems are just divided by numerous studies
Structural transition temperatures are moved to low temperature, and are coupled with magnetic phase transition, so as to great magnetic entropy variation occur.Can be real by adjusting Ge vacancy concentrations
Existing phase transition temperature is adjustable near room temperature warm area wide（Especially 310~340K of high temperature section warm area）And big magnetothermal effect is obtained, with
Meet the refrigeration needs of near room temperature warm area wide.Using adjust Ge rooms method realize structural phase transition and the coupling of magnetic phase transition and its
Its means is compared（Pressure, atom is such as introduced to substitute）With spies such as element species are few, easy control of components, preparation process is simples
Point.MnCoGe systems magnetic derives from Mn and Co atoms, by adjusting nonmagnetic Ge rooms（Rather than Mn or Co rooms）It is real
Existing magnetic/structural phase transition coupling has that physical mechanism is simple, the manageable feature of phase transition temperature, and the material prepared can obtain magnetic system
Cold application.
The present invention realizes foregoing invention purpose by the following technical solutions.
On the one hand, the invention provides a kind of ferromagnetic Martensitic Transformation Materials of MnCoGe bases, its chemical general formula is：
MnCoGe1-x, wherein, 0 ＜ x≤0.05.
According to the present invention provide the ferromagnetic Martensitic Transformation Materials of MnCoGe bases, the material have geneva structural phase transition and with
Magnetic phase transition is coupled.With the reduction of temperature, the material is from paramagnetism Ni2The high temperature austenitic parent phase of In type hexagonal structures is changed into iron
The low temperature martensitic phase of magnetic TiNiSi type orthohormbic structures, phase transition property is one-level.
On the other hand, the invention provides the preparation method of the above-mentioned ferromagnetic Martensitic Transformation Materials of MnCoGe bases, the system
Preparation Method includes：
（1）According to MnCoGe1-xChemical formula dispensing, wherein, 0 ＜ x≤0.05, the raw material that will be prepared is put into electric arc furnaces,
It is evacuated to≤1 × 10-2Handkerchief, with argon purge after, argon gas protection under, Arc, each alloy pig is 1500~2500
Melting 3~5 times at DEG C, obtain alloy pig；
（2）By step（1）Melted alloy pig is less than 1 × 10 in 800~900 DEG C, vacuum-3Annealing 2~10 under handkerchief
My god, then it is less than 1 × 10 in vacuum-3Room temperature is naturally cooled under handkerchief, MnCoGe is obtained1-xMagnetic material.
According to the preparation method that the present invention is provided, wherein, step（1）Used in raw material be Mn, Co and Ge simple substance, it is excellent
Selection of land, the raw material is the simple substance of purity >=99.9wt%.
According to the preparation method that the present invention is provided, wherein, the step（1）The middle argon gas for using is high-purity argon gas, preferably
Argon gas for purity more than 99wt%.
Another aspect, present invention also offers the ferromagnetic Martensitic Transformation Materials of MnCoGe bases in refrigerating material is prepared
Application.
Another further aspect, present invention also offers a kind of magnetic refrigeration machine, the magnetic refrigeration machine includes what the present invention was provided
The ferromagnetic Martensitic Transformation Materials of MnCoGe bases, or according to the ferromagnetic martensite of MnCoGe bases obtained in the preparation method for providing of the invention
Phase-change material.
Compared with existing magnetic refrigerating material and technology, the advantage of the invention is that：
1st, the present invention in the ferromagnetic Martensitic Transformation Materials of MnCoGe bases by introducing Ge atom vacancies so that martensite knot
The regulation of structure phase transition temperature couples magnetic phase transition and structural phase transition near room temperature, so as to bring big Entropy Changes；
2nd, the present invention using adjust MnCoGe system Ge rooms method realize structural phase transition and the coupling of magnetic phase transition and other
Means are compared（Pressure, atom is such as introduced to substitute）With element species are few, easy control of components, without rare earth element, prepare work
The features such as skill is simple.MnCoGe systems magnetic derives from Mn and Co atoms, by adjusting nonmagnetic Ge rooms（Rather than Mn or
Co rooms）Realizing the coupling of magnetic/structural phase transition has that physical mechanism is simple, the manageable feature of phase transition temperature, the material prepared
Magnetic refrigeration application can be obtained；
3、MnCoGe1-xThe great magnetic entropy variation of system occurs near room temperature high temperature section, i.e. 310K~340K warm areas, and shows
Go out than traditional magnetic refrigerating material and other new magnetic refrigerating materials（Such as traditional material Gd, new Gd5Si2Ge2Base materials with the giant magnetocaloric effect
Deng）Entropy Changes value higher.
Brief description of the drawings
Hereinafter, embodiment of the present invention is described in detail with reference to accompanying drawing, wherein：
Fig. 1 is MnCoGe prepared by the embodiment of the present invention 10.99The room temperature X-ray diffraction spectral line of phase-change material, wherein, it is horizontal
Coordinate is the angle of diffraction, and ordinate is diffracted intensity, wherein, the Miller index of hexagonal phase and orthorhombic phase is marked with Arabic numerals.
Fig. 2 is MnCoGe prepared by the embodiment of the present invention 10.99The intensity of magnetization-temperature of the phase-change material under 500Oe magnetic fields
（M-T）Curve, wherein abscissa are temperature, and ordinate is the intensity of magnetization.
Fig. 3 is MnCoGe prepared by the embodiment of the present invention 10.99The magnetization curve of phase-change material, wherein abscissa are magnetic field
Intensity, ordinate is the intensity of magnetization.
Fig. 4 is MnCoGe prepared by the embodiment of the present invention 10.99Phase-change material is in 1T, 2T, 3T, 4T, 5T, 6T and 7T magnetic field
Under magnetic entropy become Δ S variation with temperature curves, wherein abscissa be temperature, ordinate be magnetic entropy become.
Fig. 5 is MnCoGe prepared by the embodiment of the present invention 20.97The room temperature X-ray diffraction spectral line of phase-change material, wherein, it is horizontal
Coordinate is the angle of diffraction, and ordinate is diffracted intensity, wherein, the Miller index of hexagonal phase and orthorhombic phase is marked with Arabic numerals.
Fig. 6 is MnCoGe prepared by the embodiment of the present invention 20.97The intensity of magnetization-temperature of the phase-change material under 500Oe magnetic fields
（M-T）Curve, wherein abscissa are temperature, and ordinate is the intensity of magnetization.
Fig. 7 is MnCoGe prepared by the embodiment of the present invention 20.97The magnetization curve of phase-change material, wherein abscissa are magnetic field
Intensity, ordinate is the intensity of magnetization.
Fig. 8 is MnCoGe prepared by the embodiment of the present invention 20.97Phase-change material is in 1T, 2T, 3T, 4T, 5T, 6T and 7T magnetic field
Under magnetic entropy become Δ S variation with temperature curves, wherein abscissa be temperature, ordinate be magnetic entropy become.
Fig. 9 is MnCoGe prepared by the embodiment of the present invention 30.96The room temperature X-ray diffraction spectral line of phase-change material, wherein, it is horizontal
Coordinate is the angle of diffraction, and ordinate is diffracted intensity, wherein, the Miller index of hexagonal phase and orthorhombic phase is marked with Arabic numerals.
Figure 10 is MnCoGe prepared by the embodiment of the present invention 30.96The intensity of magnetization-temperature of the phase-change material under 500Oe magnetic fields
Degree（M-T）Curve, wherein abscissa are temperature, and ordinate is the intensity of magnetization.
Specific embodiment
The present invention is further described in detail with reference to specific embodiment, the embodiment for being given is only for explaining
The bright present invention, rather than in order to limit the scope of the present invention.
Raw material used is in the embodiment of the present invention：Simple substance Mn, purity 99.9wt%, are purchased from the bicyclic chemical reagent factory in Beijing；
Simple substance Co, purity 99.9wt%, is purchased from Beijing Non-Ferrous Metal Research General Academy；Simple substance Ge, purity is 99.999wt%, and being purchased from Beijing has
The total institute of non-ferrous metal research.
Electric arc furnaces used is produced for Beijing WuKe opto-electrical Technology Co., Ltd, model：WK-II type non-consumable vacuum arcs
Stove；Cu targets X-ray diffractometer is produced for Rigaku companies, model RINT2400；Superconductive quantum interference vibrating specimen magnetometer
（MPMS（SQUID）VSM）It is Quantum Design（USA）Company produces, model MPMS（SQUID）VSM.
Embodiment 1
The present embodiment is according to chemical formula MnCoGe0.99Phase-change material of the invention is prepared, specific preparation method is as follows：
（1）By chemical formula MnCoGe0.99Preparation raw material, the raw material that will be prepared is put into electric arc furnaces, is evacuated to 3 × 10-3More than handkerchief, use high-purity argon gas（Purity 99.996wt%）After cleaning 1 time, in 1 high-purity argon gas of atmospheric pressure（Purity
99.996wt%）Under protection, Arc, melt back 5 times, smelting temperature is 2000 DEG C.After melting terminates, in copper crucible
In be cooled to room temperature, obtain cast alloy ingot.
（2）By step（1）Obtained alloy pig is wrapped with metal molybdenum sheet respectively, is sealed in vitreosil pipe（Vacuum
It is 1 × 10-4Pa）, after being annealed 6 days at 875 DEG C, quartz ampoule is taken out, after naturally cooling to room temperature, break quartz ampoule, obtain
MnCoGe0.99Phase-change material sample.
Performance test：
（1）MnCoGe obtained in the present embodiment is determined using Cu target X-ray diffractometers0.99The room temperature of phase-change material（300K）
X-ray diffraction spectral line, as shown in Figure 1.Result shows, MnCoGe0.99Sample is presented orthogonal geneva structure（Space group：Pnma）And
Mutually occur with a small amount of hexagonal Ovshinsky（Space group：P63/mmc）.For the MnCoGe alloys for just dividing, geneva structural transition temperatures
It is 650K.The appearance of a small amount of hexagonal phase at room temperature shows on a small quantity（1%）The introducing in Ge rooms can make geneva structural transition temperatures from height
Temperature（650K）Moved to low temperature.
（2）MnCoGe obtained in the present embodiment under the 0.05T magnetic fields determined on superconducting quantum magnetometer0.99Phase-change material
Thermomagnetization curve（M-T）, it is shown in Fig. 2.Geneva structural transition temperatures can be determined from M-T curves（Tstru）And magnetic phase transition temperature
（TC）.It can be seen that there is temperature lag near phase transformation（8K）, show first order phase change feature, it is possible to determine that and paramagnetic-
Ferromagnetic phase transition overlaps with geneva structural phase transition, Tstru=TC=330K；The introducing in 1%Ge rooms can be such that geneva phase transition temperature is moved from 650K
330K is moved, is shown：Structural transition temperatures TstruIntroducing to Ge atom vacancies is extremely sensitive, therefore by controlling Ge atoms empty
The content of position, can be with control structure phase transition temperature.
（3）MnCoGe obtained in the present embodiment is measured on SQUID0.99Isothermal magnetic of the phase-change material near phase transition temperature
Change curve（As shown in Figure 3）.According to Maxwell relation：
Magnetic entropy can be calculated from isothermal magnetization curve to become（Such as Fig. 4）.From fig. 4, it can be seen that under 0-5T changes of magnetic field, this reality
Apply MnCoGe obtained in example0.99The magnetic entropy change of phase-change material reaches 21.5J/kgK（328.5K）, more than traditional magnetic refrigerating material Gd
（The Curie temperature of Gd is 293K, and magnetic entropy is changed into 9.8J/kgK under 0-5T changes of magnetic field）.
Embodiment 2
The present embodiment is according to chemical formula MnCoGe0.97Phase-change material of the invention is prepared, specific preparation method is as follows：
（1）By chemical formula MnCoGe0.97Preparation raw material, the raw material that will be prepared is put into electric arc furnaces, is evacuated to 3 × 10-3More than handkerchief, use high-purity argon gas（Purity 99.996wt%）After cleaning 2 times, in 1 high-purity argon gas of atmospheric pressure（Purity
99.996wt%）Under protection, Arc, melt back 5 times, smelting temperature is 2000 DEG C.After melting terminates, in copper crucible
In be cooled to room temperature, obtain cast alloy ingot.
（2）By step（1）Obtained alloy pig is wrapped with metal molybdenum sheet respectively, is sealed in vitreosil pipe（Vacuum
It is 1 × 10-4Pa）, after being annealed 6 days at 875 DEG C, quartz ampoule is taken out, after naturally cooling to room temperature, break quartz ampoule, obtain
MnCoGe0.97Phase-change material sample.
Performance test：
（1）MnCoGe obtained in the present embodiment is determined using Cu target X-ray diffractometers0.97The room temperature of phase-change material（300K）
X-ray diffraction spectral line, as shown in Figure 5.Result shows, MnCoGe0.97Sample is presented orthogonal geneva structure（Space group：Pnma）And
Mutually occur with a small amount of hexagonal Ovshinsky（Space group：P63/mmc）.For the MnCoGe alloys for just dividing, geneva structural transition temperatures
It is 650K.The appearance of a small amount of hexagonal phase at room temperature shows that the introducing in Ge rooms can make geneva structural transition temperatures from high temperature（650K）
Moved to low temperature.
（2）MnCoGe obtained in the present embodiment under the 0.05T magnetic fields determined on superconducting quantum magnetometer0.97Phase-change material
Thermomagnetization curve（M-T）, it is shown in Fig. 6.Geneva structural transition temperatures can be determined from M-T curves（Tstru）And magnetic phase transition temperature
（TC）.It can be seen that there is temperature lag near phase transformation（8K）, show first order phase change feature, it is possible to determine that and paramagnetic-
Ferromagnetic phase transition overlaps with geneva structural phase transition, Tstru=TC=324K；With the MnCoGe in Ge rooms 1% obtained in embodiment 10.99Sample
（Tstru=TC=330K）Comparing to find, magnetic/structural phase transition coupling temperature（Tstru=TC）With the increase of Ge vacancy concentrations to low
Temperature is mobile.
（3）MnCoGe obtained in the present embodiment is measured on SQUID0.97Isothermal magnetic of the phase-change material near phase transition temperature
Change curve（As shown in Figure 7）.According to Maxwell relation：
Magnetic entropy can be calculated from isothermal magnetization curve to become（Such as Fig. 8）.From figure 8, it is seen that under 0-7T changes of magnetic field, this reality
Apply MnCoGe obtained in example0.97The magnetic entropy change of phase-change material reaches 47.4J/kgK（327K）, magnetic entropy variate under 0-5T changes of magnetic field
It is 35.1J/kgK（327K）, more than the sample MnCoGe of Ge vacancy concentrations obtained in embodiment 1 1%0.99Entropy Changes amplitude, while super
Cross conventional refrigeration material Gd（The Curie temperature of Gd is 293K, and magnetic entropy is changed into 9.8J/kgK under 0-5T changes of magnetic field）.
Embodiment 3
The present embodiment is according to chemical formula MnCoGe0.96Phase-change material of the invention is prepared, specific preparation method is as follows：
（1）By chemical formula MnCoGe0.96Preparation raw material, the raw material that will be prepared is put into electric arc furnaces, is evacuated to 3 × 10-3More than handkerchief, use high-purity argon gas（Purity 99.996wt%）After cleaning 2 times, in 1 high-purity argon gas of atmospheric pressure（Purity
99.996wt%）Under protection, Arc, melt back 5 times, smelting temperature is 2000 DEG C.After melting terminates, in copper crucible
In be cooled to room temperature, obtain cast alloy ingot.
（2）By step（1）Obtained alloy pig is wrapped with metal molybdenum sheet respectively, is sealed in vitreosil pipe（Vacuum
It is 1 × 10-4Pa）, after being annealed 6 days at 875 DEG C, quartz ampoule is taken out, after naturally cooling to room temperature, break quartz ampoule, obtain
MnCoGe0.96Phase-change material sample.
Performance test：
（1）MnCoGe obtained in the present embodiment is determined using Cu target X-ray diffractometers0.96The room temperature of phase-change material（300K）
X-ray diffraction spectral line, as shown in Figure 9.Result shows, MnCoGe0.96MnCoGe in sample and embodiment 1 and 20.99、
MnCoGe0.97Material is compared, and high temperature hexagonal Ovshinsky phase also occurs（Space group：P63/mmc）, show geneva structural transition temperatures with
The increase in Ge rooms is moved to low temperature.
（2）MnCoGe obtained in the present embodiment under the 0.05T magnetic fields determined on superconducting quantum magnetometer0.96Phase-change material
Thermomagnetization curve（M-T）, it is shown in Figure 10.Geneva structural transition temperatures can be determined from M-T curves（Tstru）With magnetic phase transition temperature
Degree（TC）.It was found that there is temperature lag near phase transformation（6K）, show first order phase change feature, it is possible to determine that paramagnetic-ferromagnetic phase transformation
Overlapped with geneva structural phase transition, Tstru=TC=316K；Compared with embodiment 1 and embodiment 2 it can be found that magnetic/structural phase transition coupling
Close temperature（Tstru=TC）Further moved to low temperature with the increase of Ge vacancy concentrations, it is consistent with X-ray diffraction result.
Result above shows：For MnCoGe systems, geneva structural transition temperatures can be made to low by introducing Ge rooms
Temperature is mobile, so as to be coupled with magnetic phase transition, realizes that big magnetic entropy becomes, MnCoGe1-xMaterial is shown than tradition and other New Magnetic Field Controlled systems
Cold material（Such as traditional material Gd, new Gd5Si2Ge2Base materials with the giant magnetocaloric effect（Entropy Changes value under 0-5T changes of magnetic field：18J/kgK, position
In 276K）, etc.）Entropy Changes value high, and magnetic/structural phase transition coupling temperature（Tstru=TC）Can be with the change of Ge vacancy concentrations slightly
Higher than the warm area scope wide of room temperature（310~340K）Continuously adjustabe, the need for meeting magnetic Refrigeration Technique.
Comparative example 1
Will typical tradition room temperature magnetic refrigerating material --- rare metal Gd（Purity 99.9wt%）With phase transformation material of the invention
Material is contrasted.
In MPMS（SQUID）The Curie temperature that the rare metal Gd that purity is 99.9wt% is measured on VSM is 293K, in 0-
Magnetic entropy under 5T changes of magnetic field at Curie temperature is changed into 9.8J/kgK.As can be seen here, obtained MnCoGe in embodiment 1-31-xMaterial
The magnetic entropy of material becomes significantly more than Gd, and illustrating the material of present invention offer has bigger magnetothermal effect.
Below the present invention is describe in detail with reference to specific embodiment, to those skilled in the art, should
It should be appreciated that, above-mentioned specific embodiment shall not be construed as to limit the scope of the present invention.Therefore, this hair is not being departed from
In the case of bright spirit and scope, embodiment of the present invention can be made various changes and modifications.
Claims (9)
1. a kind of ferromagnetic Martensitic Transformation Materials of MnCoGe bases, its chemical general formula is：MnCoGe1-x, wherein 0 ＜ x≤0.05；Its
In, with the reduction of temperature, the material is from paramagnetism Ni2The high temperature austenitic parent phase of In type hexagonal structures is changed into ferromagnetism
The low temperature martensitic phase of TiNiSi type orthohormbic structures, phase transition property is one-level.
2. ferromagnetic Martensitic Transformation Materials of MnCoGe bases according to claim 1, wherein, the material has geneva structure phase
Become and coupled with magnetic phase transition.
3. the preparation method of material described in claim 1 or 2, the preparation method includes：
(1) according to MnCoGe1-xChemical formula dispensing, wherein, 0 ＜ x≤0.05, the raw material that will be prepared is put into electric arc furnaces, takes out true
Empty extremely≤1 × 10-2Handkerchief, with argon purge after, argon gas protection under, Arc, each alloy pig is at 1500~2500 DEG C
Melting 3~5 times, obtains alloy pig；
(2) the melted alloy pig of step (1) is less than 1 × 10 in 800~900 DEG C, vacuum-3Annealed 2~10 days under handkerchief, so
Afterwards 1 × 10 is less than in vacuum-3Room temperature is naturally cooled under handkerchief, MnCoGe is obtained1-xMagnetic material.
4. preparation method according to claim 3, wherein, the raw material used in step (1) is Mn, Co and Ge simple substance.
5. preparation method according to claim 4, wherein, the purity of Mn, Co and Ge simple substance >=99.9wt%.
6. the preparation method according to any one of claim 3 to 5, wherein, the argon gas used in the step (1) is height
Pure argon.
7. the preparation method according to any one of claim 3 to 5, wherein, the argon gas used in the step (1) is pure
Argon gas of the degree more than 99wt%.
8. ferromagnetic Martensitic Transformation Materials of MnCoGe bases described in claim 1 or 2 or by any one of claim 3 to 7
Application of the ferromagnetic Martensitic Transformation Materials of MnCoGe bases in refrigerating material is prepared obtained in the preparation method.
9. a kind of magnetic refrigeration machine, the magnetic refrigeration machine includes the ferromagnetic martensitic phase of MnCoGe bases described in claim 1 or 2
Become material, or the ferromagnetic Martensitic Transformation Materials of MnCoGe bases obtained in preparation method any one of claim 3 to 7.
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