CN108300882A - The method that magnetic structure coupling phase transformation is realized in MnCoGe based alloys - Google Patents
The method that magnetic structure coupling phase transformation is realized in MnCoGe based alloys Download PDFInfo
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- CN108300882A CN108300882A CN201810139742.0A CN201810139742A CN108300882A CN 108300882 A CN108300882 A CN 108300882A CN 201810139742 A CN201810139742 A CN 201810139742A CN 108300882 A CN108300882 A CN 108300882A
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
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Abstract
The method that the invention discloses a kind of to obtain MnCoGe based alloy magnetic structure Coupling phase transformations by adjusting element ratio regulation and control, especially by the difference using electronegativity between different elements, adjust the ratio between transition elements and major element, design alloying component, change Mn Mn spacing and Mn atom local magnetic moments, the violent magnetic structure to obtain temperature and induced by magnetic field couples phase transformation.There is the MnCoGe based alloys provided in the present invention violent magnetic structure to couple phase transformation, and magnetic property is excellent, and alloy preparation method is simple and convenient, energy consumption is few, and manufacturing cost is low, be suitble to industrialized production.
Description
Technical field
The invention belongs to the preparation methods of MnCoGe base alloy materials, more particularly to especially by electricity between the different elements of utilization
The difference of negativity adjusts the ratio of transition elements and major element, designs alloying component, Mn-Mn spacing and local are in Mn atoms
Magnetic moment couples phase transformation to obtain violent magnetic structure.
Background technology
With sustainable development consciousness enhance, magnetic Refrigeration Technique due to its energy-efficient, environmentally protective feature by
Extensive concern is arrived, it is considered to be the New Refrigerating technology of most possible substitution vapor compression refrigeration.Magnetic Refrigeration Technique mainly according to
Rely the heat energy absorbing and releasing power in adding magnetic field and removing magnetic field process in magnetic refrigeration working substance.Magnetic refrigeration is used as a high-new green refrigeration skill
Art has non-environmental-pollution compared with traditional gas Compressing Refrigeration, energy-efficient, is easy to minimize, reliable and stable etc. competing
Strive advantage.
In addition to Heusler alloys, hexagonal MM ' X-alloys are increasingly becoming most potential magnetism in room-temperature magnetic refrigeration application
Intermetallic compound.L.Castelliz is found that MM ' X (M, M '=transiting group metal elements, X=main group members for the first time in nineteen fifty-three
Element).The magnetic structure of MM ' X-alloys is abundant, and when cooling martensitic traoformation can occur for some ingredients, by high temperature mother
Phase Ni2In type hexagonal structures generate the orthohormbic structure of TiNiSi types by distortion of lattice, simultaneous volume it is huge negative swollen
It is swollen.
MnCoGe alloys belong to the member of MM'X races.Previously to MnCoGe based alloys studies have shown that race's alloy can be with
Powerful interaction is formed between structure and magnetism, therefore has huge magnetothermal effect near room temperature.In stoichiometry
Than in MnCoGe alloy, magnetic transition is detached with martensitic traoformation, cause magnetization change (M) little.It is just at room temperature
TiNiSi type structures are handed over, in TcThe two level magnetic transition from ferromagnetism (FM) to paramagnetism (PM) is shown when~345K.And
More than room temperature (structural transition temperatures TM~650K) occur without the inverse martinsite structure reverts of diffusion) (the Ni under PM states2In types six
Corner structure Curie temperature) from orthorhombic phase to high temperature hexagonal Ni2In type phases.At present in adjustment structure phase transition temperature TM
It arrivesWithBetween have serial of methods, such as change and apply external pressure, element substitution, element is vacant, gap digit atom is mixed
It is miscellaneous etc..In such ways, magnetic phase transition and crystalline transformation can be made to couple.MnCoGe alloys are changed caused by changing to ingredient
It is very sensitive to learn pressure, people mostly use greatly substitutes transition elements Mn and Co or major element Ge, such as V by other elements,
The doping of Cr, Fe, Cu, Sn, Ga, Al etc. couple phase transformation to regulate and control to obtain magnetic structure.Although the magnetic structure coupling of MnCoGe based alloys
It is very violent to close phase transformation, but the weakness such as that there is also operation temperature areas simultaneously is narrow, and Ge element costs are higher, becomes and restrict the main of its development
Obstacle.Therefore in order to cost-effective, and the features such as make full use of the electronegativity of Co-Ge hydridization and Ge higher, main group member is adjusted
The content of plain Ge becomes the important goal of regulation and control MnCoGe base ferromagnetic shape memory alloys magnetothermal effects, has one for industrialized production
Fixed directive function.
Invention content
In order to solve the deficiencies in the prior art, the present invention provides one kind to regulate and control to obtain by adjusting element ratio
The method of MnCoGe based alloy magnetic structure Coupling phase transformations, it has the advantages that cost-effective, high-efficiency environment friendly and prepares simple.
The method provided by the invention that magnetic structure coupling phase transformation is realized in MnCoGe based alloys specifically utilizes difference
The difference of electronegativity between element, by adjust Mn/Ge or Co/Ge ratio, design MnCoGe alloying components, change Mn-Mn between
Away from Mn atom local magnetic moments, the violent magnetic structure to obtain temperature and induced by magnetic field couples phase transformation.
Preferably, it is by the alloy general formula of the metamagnetism martensitic traoformation of the induced by magnetic field of above method acquisition
Mn1-xCoGe1+x、Mn1+xCoGe1-x、MnCo1-xGe1+xAnd MnCo1-xGe1+x, and in the general formula Mn or Co metals moiety content also
It can be replaced by other metallic elements.
The chemical formula of the MnCoGe alloys is Mn1-xCoGe1+x(1), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is Mn1+xCoGe1-x(2), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is MnCo1-xGe1+x(3), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is MnCo1+xGe1-x(4), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is (Mn1-yAy)1-xCoGe1+x(5), wherein 0.01≤x≤0.21,0.01≤
Y≤0.12, and A any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical formula of the MnCoGe alloys is (Mn1-yDy)1+xCoGe1-x(6), wherein 0.01≤x≤0.21,0.01≤
Y≤0.12, and D any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical formula of the MnCoGe alloys is Mn (Co1-yEy)1-xGe1+x(7), wherein 0.01≤x≤0.21,0.01≤
Y≤0.12, and E any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical formula of the MnCoGe alloys is Mn (Co1-yFy)1+xGe1-x(8), wherein 0.01≤x≤0.21,0.01≤
Y≤0.12, and F any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In.
It is highly preferred that the preparation process of the MnCoGe alloys is specially：
S1：Dispensing is carried out according to the stoichiometric ratio of chemical formula, the raw material prepared is put into water-cooled copper crucible electric arc furnaces
In, vacuum degree is evacuated to 10-3Pa carries out electric arc melting hereinafter, the argon gas that the purity for being filled with 0.8~1 atmospheric pressure is 99.999%,
Melting 3~5 times is repeated, MnCoGe based alloy ingot castings are obtained；
S2：Part MnCoGe based alloy ingot castings are fitted into the quartz ampoule of 10~11mm of internal diameter, are then put into quartz ampoule
In fast quenching furnace chamber, 10 are evacuated in furnace chamber-4Pa is passed through argon gas, by high-frequency induction heating by ingot melting at liquid, then
It is sprayed onto on high-speed rotating copper roller by the aperture of quartzy bottom of the tube, the rotating speed of copper roller is 10~40m/s, obtains quick quenching band sample
Product；
S3：The alloy cast ingot of remainder and the quick quenching band sample are put into the closed internal diameter 10mm quartz ampoules in one end
In, vacuum degree is evacuated to 4Pa hereinafter, the argon gas for being filled with 0.3~0.5 atmospheric pressure is used for gas washing, and repetition 3~5 times is washed for the last time
Vacuum degree is evacuated to 3Pa hereinafter, then rapidly being blown the quartz ampoule of elongation with acetylene flame after gas, sample is enclosed after vacuumizing
Quartz ampoule in；Then the sample sealed is put into high temperature furnace and carries out annealing heat-treats, annealing temperature is 600 DEG C~1000
DEG C, time 0h~120h then takes out and is put into cold quenching-in water rapidly, obtains the MnCoGe that magnetic structure coupling phase transformation can occur
Based alloy.
It is highly preferred that the simple substance purity of metal representated by Mn, Co, Ge and A, D, E and F is more than 99.99%.
It is highly preferred that in S1, the step of electric arc melting, is specific as follows：
First since Co so that Co envelopes volatile Mn after melting and is easy the Ge splashed, first time melting
When, with 20~30A electric currents by metal molten, it is seen that crucible inner metal liquid flows, and the sample turn-over of first time melting adds
High current is to 35~40A melting 4~5 times again, you can obtains uniform MnCoGe based alloys ingot casting sample.
Preferably, in S3, annealing temperature is set in 700 DEG C~800 DEG C, when 5min~12h.
Compared with prior art, the beneficial effects of the present invention are：
The present invention changes simple regulation and control transition elements Mn, Co or the content of major element Ge, makes alloy structure phase alternating temperature
The general idea reduced is spent, using the difference of electronegativity between different elements, by adjusting transition elements Ge and major element simultaneously
The method of (Mn, Co) ratio changes Mn-Mn spacing and Mn atom local magnetic moments, changes simultaneously the content of different elements in alloy,
Temperature-induced magnetic and structure Coupling phase transformation are realized in the alloy, while may also improve sensitivity of the magnetic structure phase transformation to magnetic field
Degree, obtaining has big intensity of magnetization mutation and the induced by magnetic field magnetic structure phase transformation of low metamagnetism critical field.The present invention provides
Alloy preparation method is simple and convenient, energy consumption is few, manufacturing cost is low, is suitble to industrialized production.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the equal fields thermomagnetization curve of the alloys that provide of 1-3 of the embodiment of the present invention；
Fig. 2 is the isothermal magnetization curve for the alloy that the embodiment of the present invention 4 provides.
Specific implementation mode
In order to enable those skilled in the art to more fully understand, technical scheme of the present invention is practiced, with reference to specific
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
Unless otherwise defined, the hereinafter used all technical terms for being and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.Unless otherwise specified, it the various raw materials used in the following embodiment of the present invention, reagent, instrument and sets
It is standby to be commercially available by market or be prepared by existing method.
An anti-general content by simple adjusting transition elements Mn, Co or major element Ge of the invention keeps valence electric
Sub- Konzentration/a reduces, the idea for making alloy structure phase transition temperature reduce, by the ratio for adjusting transition element and major element
Example, using the difference of electronegativity between different elements, while adjusting the content of transition elements and major element in alloy, regulates and controls alloy
Valence electron Konzentration/a, design alloying component, change Mn-Mn spacing and local Mn atomic magnetic moments, realize that temperature lures in the alloy
Magnetic conduction phase transformation and structure change the magnetic structure phase transformation to intercouple, while may also improve sensitivity of the magnetic structure phase transformation to magnetic field
Degree, obtaining has big intensity of magnetization mutation and the induced by magnetic field magnetic structure phase transformation of low metamagnetism critical field.
Actually include the alloy expression formula of at least four meanings based on above-mentioned principle：
The expression formula of the first meaning of alloy is Mn1-xCoGe1+x(1) or Mn1+xCoGe1-x(2), wherein 0.01≤x≤
0.21；The ratio between Mn and Ge is adjusted particular by x values.
The expression formula of second of meaning of alloy is MnCo1-xGe1+x(3) or MnCo1+xGe1-x(4), wherein 0.01≤x≤
0.21；The ratio between Co and Ge is adjusted particular by x values.
The expression formula of the third meaning of alloy is (Mn1-yAy)1-xCoGe1+x(5) or (Mn1-yDy)1+xCoGe1-x(6),
In, 0.01≤x≤0.21,0.01≤y≤0.12, and A is arbitrary in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In
A kind of element；D any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In.Mainly by by portion
Other metallic elements for dividing Mn elements to replace with y contents, such as general formula can be extended to (Mn1-yFey)1±xCoGe1±x(0.01≤x
≤ 0.21,0.01≤y≤0.12), (Mn1-yNiy)1±xCoGe1±x(0.01≤x≤0.21,0.01≤y≤0.12) etc..
The expression formula of 4th kind of meaning of alloy is Mn (Co1-yEy)1-xGe1+x(7) or Mn (Co1-yFy)1+xGe1-x(8),
In, 0.01≤x≤0.21,0.02≤y≤0.12, and E is arbitrary in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In
A kind of element；F any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In.Mainly by by portion
Other metallic elements for dividing Co elements to replace with y contents, such as general formula can be extended to Mn (Co1-yFey)1±xGe1±x(0.01≤x
≤ 0.21,0.01≤y≤0.12), Mn (Co1-yNiy)1±xGe1±x(0.01≤x≤0.21,0.01≤y≤0.12) etc..
Below just in the form of specific example, technical scheme of the present invention is further illustrated.
Embodiment 1
The present embodiment has the alloy Mn of magnetic structure coupling phase transformation1.01CoGe0.99
Alloy is designed according to principle, specific chemical formula is Mn1.01CoGe0.99, according to stoichiometric ratio calculate required Mn,
The quality of the simple substance of Co, Ge element carries out dispensing, needs to be accurate to 0.1mg-0.01mg, the purity of metal simple-substance exists
99.99% or more.The raw material prepared is put into water-cooled copper crucible electric arc furnaces, vacuum degree is evacuated to 10-3Pa is hereinafter, be filled with 1
The argon gas that the purity of atmospheric pressure is 99.999% carries out electric arc melting.When first pass melting, with 25A electric currents by metal molten, see
It is flowed to crucible inner metal liquid, by the bulk sample turn-over of first pass melting, slightly high current to 35A melting 4 times again,
It can be obtained MnCoGe based alloy ingot castings；Part MnCoGe based alloy ingot castings are fitted into the quartz ampoule of internal diameter 10mm, then will
Quartz ampoule is put into fast quenching furnace chamber, and 10 are evacuated in furnace chamber-4Pa is passed through argon gas, will be ingot melting by high-frequency induction heating
It at liquid, is then sprayed onto on high-speed rotating copper roller by the aperture of quartzy bottom of the tube, the rotating speed of copper roller is 25m/s, is obtained fast
It quenches Tape samples；The alloy cast ingot of remainder and the fast quenching rule carry sample are put into the closed internal diameter 10mm quartz in one end
Guan Zhong, vacuum degree are evacuated to 4Pa hereinafter, being filled with the argon gas of 0.5 atmospheric pressure for gas washing, are repeated 4 times, will after last time gas washing
Vacuum degree is evacuated to 3Pa hereinafter, then rapidly being blown the quartz ampoule of elongation with acetylene flame, and sample is enclosed the quartz after vacuumizing
Guan Zhong；Then the sample sealed is put into high temperature furnace and carries out annealing heat-treats, annealing temperature is 800 DEG C, time 5min, then
Taking-up is put into rapidly cold quenching-in water, obtains texture and the good Tape samples of micro-structure.In Mn1.01CoGe0.99It is seen in sample
The magnetic structure coupling phase transformation of induced by magnetic field is observed, and obtains the level-one magnetic structure phase transformation of magnetic and structure Coupling and big magnetic thermal effect
It answers.
Embodiment 2
The present embodiment has the alloy Mn of magnetic structure coupling phase transformation1.02CoGe0.98, the system of specific preparation method and embodiment 1
Standby process is identical, the difference is that only, according to Mn1.02CoGe0.98Stoichiometric ratio calculate required Mn, Co, Ge element
The quality of simple substance carries out dispensing.
Embodiment 3
The present embodiment has the alloy MnCo of magnetic structure coupling phase transformation1.02Ge0.98, the system of specific preparation method and embodiment 1
Standby process is identical, the difference is that only, according to MnCo1.02Ge0.98Stoichiometric ratio calculate required Mn, Co, Ge element
The quality of simple substance carries out dispensing.
We to the alloy that above-described embodiment 1- embodiments 3 provide carry out that fields thermomagnetization curve is waited to measure respectively, acquired results
Specifically as shown in Figure 1, as seen from Figure 1, temperature-induced magnetic knot is obtained in the alloy that our embodiment 1- embodiments 3 provide
Structure couples phase transformation.
Embodiment 4
The present embodiment has the alloy Mn of magnetic structure coupling phase transformation1.03CoGe0.97, the system of specific preparation method and embodiment 1
Standby process is identical, the difference is that only, according to Mn1.03CoGe0.97Stoichiometric ratio calculate required Mn, Co, Ge element
The quality of simple substance carries out dispensing.
The Mn that we provide embodiment 41.03CoGe0.97The isothermal magnetization curve and isothermal magnetic entropy varied curve of alloy carry out
It measures, it is specific as shown in Fig. 2, this curve uses so-called round-robin method, before each temperature measurement, it is necessary to which first null field increases temperature
Degree makes sample enter weak magnetic state, and then null field is reduced to measuring temperature and carries out magnetization curve measurement again, as seen from Figure 2, I
The temperature-induced magnetic structure coupling phase transformation of relatively low magnetic hystersis loss is obtained in the special component.
On the basis of embodiment 4 embodiment 1-, based on the content by adjusting Ge, the valence electron for changing alloy is dense for we
E/a is spent, alloying component has carried out further adjustment, obtained some new alloys, just further given in exemplary fashion below
Go out.
Embodiment 5
The present embodiment has the alloy (Mn of magnetic structure coupling phase transformation0.98Fe0.02)1.02CoGe0.98, specific preparation method and
The preparation process of embodiment 1 is identical, the difference is that only, according to (Mn0.98Fe0.02)1.02CoGe0.98Stoichiometric ratio meter
The quality of the simple substance of Mn, Co, Fe, Ge element needed for calculating carries out dispensing.
Embodiment 6
The present embodiment has the alloy (Mn of magnetic structure coupling phase transformation0.9Ni0.1)1.03CoGe0.97, specific preparation method and reality
The preparation process for applying example 1 is identical, the difference is that only, according to (Mn0.9Ni0.1)1.03CoGe0.97Stoichiometric ratio calculate
The quality of the simple substance of required Mn, Co, Ni, Ge element carries out dispensing.
Embodiment 7
The present embodiment has the alloy (Mn of magnetic structure coupling phase transformation0.89Sn0.11)0.98CoGe1.02, specific preparation method and
The preparation process of embodiment 1 is identical, the difference is that only, according to (Mn0.89Sn0.11)0.98CoGe1.02Stoichiometric ratio meter
The quality of the simple substance of Mn, Co, Sn, Ge element needed for calculating carries out dispensing.
Embodiment 8
The present embodiment has the alloy (Mn of magnetic structure coupling phase transformation0.95Cu0.05)0.88CoGe1.12, specific preparation method and
The preparation process of embodiment 1 is identical, the difference is that only, according to (Mn0.95Cu0.05)0.88CoGe1.12Stoichiometric ratio meter
The quality of the simple substance of Mn, Co, Cu, Ge element needed for calculating carries out dispensing.
Embodiment 9
The present embodiment has the alloy Mn (Co of magnetic structure coupling phase transformation0.89V0.11)0.99Ge1.01, specific preparation method and reality
The preparation process for applying example 1 is identical, the difference is that only, according to Mn (Co0.88V0.12)0.99Ge1.01Stoichiometric ratio calculate
The quality of the simple substance of required Mn, Co, V, Ge element carries out dispensing.
Embodiment 10
The present embodiment has the alloy Mn (Co of magnetic structure coupling phase transformation0.98Ti0.02)0.79Ge1.21, specific preparation method and
The preparation process of embodiment 1 is identical, the difference is that only, according to Mn (Co0.98Ti0.02)0.79Ge1.21Stoichiometric ratio meter
The quality of the simple substance of Mn, Co, Ti, Ge element needed for calculating carries out dispensing.
Embodiment 11
The present embodiment has the alloy (Mn of magnetic structure coupling phase transformation0.98Fe0.02)0.98CoGe1.02, specific preparation method and
The preparation process of embodiment 1 is identical, the difference is that only, annealing temperature is 700 DEG C, time 1h.
We test the alloy that phase transformation is coupled with magnetic structure that embodiment 5- embodiments 7 provide, and similarly obtain
Obtained obtained in annealing specimen temperature and induced by magnetic field magnetic structure coupling phase transformation, and obtain level-one magnetic structure coupling phase transformation and
Big magnetothermal effect.
It should be noted that involved in claims of the present invention when numberical range, it is thus understood that each numberical range
Any one numerical value can be selected between two endpoints and two endpoints, due to step method and the Examples 1 to 7 phase of use
Together, it repeats in order to prevent, description of the invention preferred embodiment, but the present invention is not limited thereto, but can also be with
Other modes in the range of the technical solution defined in appended claims implement, according to ingredient MnCo1- xGe1+x、MnCo1+xGe1-x、Mn1-xCoGe1+xEtc. equal strip sample and nano powder is made, ideal level-one magnetic structure is obtained
Phase transformation and its corresponding magnetothermal effect.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.Embodiment described above is only to absolutely prove the present invention
And the preferred embodiment lifted, protection domain are without being limited thereto.Those skilled in the art institute on the basis of the present invention
The equivalent substitute of work or transformation, within protection scope of the present invention, protection scope of the present invention is subject to claims.
Claims (6)
1. a kind of method for realizing magnetic structure coupling phase transformation in MnCoGe based alloys, which is characterized in that using between different elements
The difference of electronegativity designs MnCoGe alloying components, changes Mn-Mn spacing and Mn by adjusting the ratio of Mn/Ge or Co/Ge
Atom local magnetic moment, the violent magnetic structure to obtain temperature and induced by magnetic field couple phase transformation.
2. the method according to claim 1 for realizing magnetic structure coupling phase transformation in MnCoGe based alloys, which is characterized in that
The chemical formula of the MnCoGe alloys is Mn1-xCoGe1+x(1), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is Mn1+xCoGe1-x(2), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is MnCo1-xGe1+x(3), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is MnCo1+xGe1-x(4), wherein 0.01≤x≤0.21；Or
The chemical formula of the MnCoGe alloys is (Mn1-yAy)1-xCoGe1+x(5), wherein 0.01≤x≤0.21,0.01≤y≤
0.12, and A any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical formula of the MnCoGe alloys is (Mn1-yDy)1+xCoGe1-x(6), wherein 0.01≤x≤0.21,0.01≤y≤
0.12, and D any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical formula of the MnCoGe alloys is Mn (Co1-yEy)1-xGe1+x(7), wherein 0.01≤x≤0.21,0.01≤y≤
0.12, and E any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical formula of the MnCoGe alloys is Mn (Co1-yFy)1+xGe1-x(8), wherein 0.01≤x≤0.21,0.01≤y≤
0.12, and F any one element in Ti, Zn, Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In.
3. the method according to claim 2 for realizing magnetic structure coupling phase transformation in MnCoGe based alloys, which is characterized in that
The preparation process of the MnCoGe alloys is specially：
S1：Dispensing is carried out according to the stoichiometric ratio of chemical formula, the raw material prepared is put into water-cooled copper crucible electric arc furnaces, very
Reciprocal of duty cycle is evacuated to 10-3Pa carries out electric arc melting hereinafter, the argon gas that the purity for being filled with 0.8~1 atmospheric pressure is 99.999%, repeats
Melting 3~5 times obtains MnCoGe based alloy ingot castings；
S2：Part MnCoGe based alloy ingot castings are fitted into the quartz ampoule of 10~11mm of internal diameter, quartz ampoule is then put into fast quenching
In furnace chamber, 10 are evacuated in furnace chamber-4Pa is passed through argon gas, is then passed through ingot melting at liquid by high-frequency induction heating
The aperture of quartzy bottom of the tube is sprayed onto on high-speed rotating copper roller, and the rotating speed of copper roller is 10~40m/s, obtains quick quenching band sample；
S3：The alloy cast ingot of remainder and the quick quenching band sample are put into the closed internal diameter 10mm quartz ampoules in one end,
Vacuum degree is evacuated to 4Pa hereinafter, the argon gas for being filled with 0.3~0.5 atmospheric pressure is used for gas washing, repetition 3~5 times, last time gas washing
Vacuum degree is evacuated to 3Pa afterwards hereinafter, then rapidly being blown the quartz ampoule of elongation with acetylene flame, sample is enclosed after vacuumizing
In quartz ampoule；Then the sample sealed being put into high temperature furnace and carries out annealing heat-treats, annealing temperature is 600 DEG C~1000 DEG C,
Time 0h~120h then takes out and is put into cold quenching-in water rapidly, obtains the MnCoGe bases that magnetic structure coupling phase transformation can occur
Alloy.
4. the method according to claim 3 for realizing magnetic structure coupling phase transformation in MnCoGe based alloys, which is characterized in that
The simple substance purity of metal representated by Mn, Co, Ge and A, D, E and F is more than 99.99%.
5. the method according to claim 3 for realizing magnetic structure coupling phase transformation in MnCoGe based alloys, which is characterized in that
In S1, the step of electric arc melting, is specific as follows：
First since Co so that Co envelopes volatile Mn and be easy the Ge splashed after melting, and when first time melting, uses
20~30A electric currents are by metal molten, it is seen that crucible inner metal liquid flows, and by the sample turn-over of first time melting, increases electricity
It flow to 35~40A melting 4~5 times again, you can obtain uniform MnCoGe based alloys ingot casting sample.
6. the method according to claim 3 for realizing magnetic structure coupling phase transformation in MnCoGe based alloys, which is characterized in that
In S3, annealing temperature is set in 700 DEG C~800 DEG C, when 5min~12h.
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