CN107164681A - A kind of method that induced by magnetic field metamagnetism martensitic traoformation is realized in MnCoGe based alloys - Google Patents
A kind of method that induced by magnetic field metamagnetism martensitic traoformation is realized in MnCoGe based alloys Download PDFInfo
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Abstract
The invention discloses a kind of method for the metamagnetism martensitic traoformation that induced by magnetic field is realized in MnCoGe based alloys, especially by regulation Co/Mn ratio, design alloying component, increase valence electron Konzentration/a of alloy, increase the unstability of Mn atomic magnetic moments, so as to improve sensitivity of the magnetic structure phase transformation to magnetic field, the metamagnetism martensitic traoformation of induced by magnetic field is obtained.The method that is there is provided in the present invention is simple and convenient, energy resource consumption is few, and it is low to prepare cost, is adapted to industrialized production, the MnCoGe based alloys prepared have the metamagnetism martensitic traoformation of induced by magnetic field, and magnetic property is excellent.
Description
Technical field
The invention belongs to the preparation method of MnCoGe base alloy materials, more particularly to by way of adjusting Co/Mn ratios
Composition is designed, to increase valence electron Konzentration/a of alloy, increases the unstability of Mn atomic magnetic moments, improves alloy martensite phase
Become the method to the sensitivity in magnetic field, so as to obtain induced by magnetic field metamagnetism martensitic traoformation in MnCoGe based alloys.
Background technology
Magnetic Refrigeration Technique based on magnetothermal effect be described as most possibly substituting current gas compression instruction a class it is new
Type Refrigeration Technique, has the advantages that energy-efficient, environment-friendly, small volume.Gone from bad to worse in human environment ecology, energy crisis
Increasingly serious development today and application magnetic refrigeration, especially near room temperature magnetic Refrigeration Technique is particularly important.
First order phase change alloy is due to big intensity of magnetization mutation near transformation temperature, along with very big magnetothermal effect, simultaneously
Primary magnetic phase change was once turning into the focus and emphasis that people study with the potential application of its phase transformation easy-regulating and near room temperature.Except this
Outside, also there are other abundant physical effects, such as magneto-resistor, magneto-strain, shape memory etc. near primary magnetic phase change point,
Very big potential application is suffered from terms of current magnetic pumping, artificial intelligence.
It is, in general, that primary magnetic phase change can be by temperature and induced by magnetic field.For one-level magnetic structure phase transformation, temperature and magnetic field
Can simultaneously occur with induction magnetic and crystal structure phase transformation, intercouple, so as to obtain violent one-level magnetic structure phase transformation, phase transformation is attached
Near is even more to have big magnetic functional character, therefore the magnetic structure phase transformation for regulating and controlling to obtain coupling by phase transformation just causes people to be closed extensively
Note.Relative to temperature-induced, induced by magnetic field one-level magnetic structure phase transformation shows following spy in isothermal magnetization curve M (H) measurements
Point：
(1) violent intensity of magnetization mutation occurs near phase transformation, with very big magnetization change, shows very bright
Aobvious metamagnetism behavior；
(2) it is accompanied by obvious magnetic hysteresis；
(3) there is small metamagnetism critical field (Hreq) and phase transformation completion field (Hcomp)；
(4) as the change of temperature causes material to be developed toward weak magnetic phase (antiferromagnetic or paramagnetic), phase transformation critical field HreqHave bright
The rule of aobvious increase, shows very strong temperature dependence.Induced by magnetic field one-level magnetic structure phase transformation is waiting field thermomagnetization curve M (T)
Measurement in also show, as magnetic field increases, phase transition temperature substantially toward high temperature or toward low temperature move the characteristics of, i.e. phase alternating temperature
Degree shows very strong magnetic sensitivity.
In numerous primary magnetic phase change alloys, new MnCoGe bases ferromagnetic shape memory alloys can with its magnetic structure phase transformation
Regulation and control and excellent room-temperature zone magnetic heating performance are by people's extensive concern.There are some researches show the MnCoGe alloys just divided are not sent out
Magnetisation structure Coupling phase transformation.People by changing that alloy composition, gap digit are atom doped, apply the method such as external pressure can be with
Regulation and control obtain magnetic structure coupling magnetothermal effect big mutually and near phase transformation in MnCoGe based alloys.But make a general survey of the conjunction of MnCoGe bases
The so many research of gold finds that in addition to temperature can be induced, MnCoGe based alloys are rarely reported induced by magnetic field magnetic knot so far
Structure phase transformation, though individual components have associated magnetic field induced martensite phase transformation report, but it is all very weak, show as magnetization before and after phase transformation
Strength Changes amount is very small, and metamagnetism critical field is also very high, and thus caused magnetothermal effect does not reach practical application much
It is required that.Such as, K.Koyama et al. is to Mn1.07Co0.92Propose there is induced by magnetic field phase transformation in the alloy in Ge alloy research,
But magnetization change is also very small before and after metamagnetism critical field is up to 7.3T, phase transformation at a temperature of 220K, has even more arrived 13T magnetic fields
Also their so-called induced by magnetic field phase transformations of completion are not observed；The CoMn of Y ü z ü ak et al. reports0.9Fe0.1Ge alloy phase changes
Magnetization change only has~12Am before and after induced by magnetic field phase transformation under (300K) 7T magnetic fields near temperature2/ kg, critical field is also up to
~4.2T.Therefore people, which obtain one, almost turns into the conclusion of general character：I.e. to MnCoGe based alloys, magnetic field is not an induction change
One effective ways of magnetic martensitic traoformation, the i.e. martensitic traoformation of MnCoGe based alloys are very low to the sensitiveness in magnetic field.
But, it is known that for almost all of magnetic structure phase change alloy material, than Ni-Mn bases as everyone knows
Ferromagnetic shape memory alloys, temperature and magnetic field can induce violent magnetic structure phase transformation, that is, martensitic traoformation, obtain
Big abundant magnetic functional character.The mutation of the big intensity of magnetization and low change near relative temperature, induced by magnetic field martensitic traoformation
Magnetic critical field is to magnetic material magnetic functional character and its more direct decisive action of practical application.Therefore, for new
MnCoGe base ferromagnetic shape memory alloys, obtain the induced by magnetic field with big intensity of magnetization mutation and low metamagnetism critical field
Magnetic structure phase transformation undoubtedly has critically important scientific meaning and potential using value.
The content of the invention
Effectively MnCoGe based alloy induced by magnetic field metamagnetism martensites are realized object of the present invention is to provide one kind
The method of phase transformation, it has the advantages that simple and convenient, high-efficiency environment friendly and low energy consumption.
The method that induced by magnetic field metamagnetism martensitic traoformation is realized in MnCoGe based alloys that the present invention is provided, specifically
It is：By adjusting the ratio of Co/Mn in MnCoGe based alloys, alloying component is designed, increases valence electron Konzentration/a of alloy, is increased
Plus the unstability of Mn atomic magnetic moments, so as to improve sensitivity of the magnetic structure phase transformation to magnetic field, obtain the change magnetic of induced by magnetic field
Property martensitic traoformation.
Preferably, the alloy formula of the metamagnetism martensitic traoformation of the induced by magnetic field obtained by the above method is
Mn1-xCo1+xGe, wherein, the moiety content of Mn metals can also be by other metallic elements in 0.01≤x≤0.11, and the formula
Substitution.
The chemical general formula of the alloy is Mn1-xCo1+xGe (1), wherein, 0.01≤x≤0.11；Or
The chemical general formula of the alloy is Mn1-yAyCoGe (2), wherein, 0.02≤y≤0.12, and A be selected from Fe, Ni, Cu,
The metallic element of any one in Cr, V, Sn, Al, Ga, B, In；Or
The chemical general formula of the alloy is MnaDbCo1+yGe (3), wherein a+b=1-y, 0.02≤y≤0.12, and D are selected from
The metallic element of any one in Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical general formula of the alloy is Mn1-yCocEdGe (4), wherein c+d=1+y, 0.02≤y≤0.12, and E are selected from
The metallic element of any one in Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical general formula of the alloy is Mn1-yCo1+yGeeFf(5), wherein e+f=1,0.02≤y≤0.12, and F are selected from
Any one metallic element in Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；
In above-mentioned formula (3)-(5), b, d, f are less than or equal to 0.1.
It is highly preferred that the preparation process of the alloy of the metamagnetism martensitic traoformation with induced by magnetic field is specially：
S1：Dispensing is carried out according to chemical general formula, the raw material prepared is put into water-cooled copper crucible electric arc furnaces, vacuum is taken out
To 10-3Below Pa, be filled with 0.8~1 atmospheric pressure purity be 99.999% argon gas, carry out electric arc melting, repeat melting 4~
5 times, obtain MnCoGe based alloy ingot castings；
S2：Part MnCoGe based alloy ingot castings are fitted into internal diameter 10-11mm quartz ampoule, are then put into quartz ampoule soon
Quench in furnace chamber, 10 are evacuated in furnace chamber-4Pa, is passed through argon gas, by high-frequency induction heating by ingot melting into liquid, Ran Houtong
The aperture for crossing quartzy bottom of the tube is sprayed onto on the copper roller of rotation at a high speed, and 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 fast quenching rule carry sample are put into the internal diameter 10mm quartz of one end closing
Guan Zhong, vacuum is evacuated to below 4Pa, and the argon gas for being filled with 0.3~0.5 atmospheric pressure is used for gas washing, repeats 3-5 times, last time
Vacuum is evacuated to below 3Pa after gas washing, then rapidly the quartz ampoule of elongation is blown with acetylene flame, sample is enclosed and vacuumized
In quartz ampoule afterwards；Then the sample sealed is put into high temperature furnace and carries out annealing heat-treats, annealing temperature is 600~1000
DEG C, 0~120h of time then takes out and is put into cold quenching-in water rapidly, obtains the metamagnetism martensitic traoformation with induced by magnetic field
MnCoGe based alloys.
It is highly preferred that the simple substance purity of each metal is more than 99.99%.
It is specific as follows the step of electric arc melting it is highly preferred that in S1：
First since Co so that Co envelopes the volatile Mn and Ge easily splashed, first time melting after melting
When, with 20~30A electric currents by metal molten, it is seen that crucible inner metal liquid flows, by the sample turn-over of first time melting, plus
High current is to 35~40A melting 4~5 times again, you can obtain uniform MnCoGe based alloys ingot casting sample.
It is highly preferred that in S3, annealing temperature is set in 600-1000 DEG C, time 10min-120h.
The present invention, which changes simple transition elements Mn or Co omission, reduces e/a, makes the reduction of alloy structure phase transition temperature
General idea, by adjusting Co/Mn ratio, increase valence electron Konzentration/a of alloy, increase Mn atomic magnetic moments it is unstable
Property, cause the reduction of alloy structure phase transition temperature so that alloy magnetic and structural phase transition occur simultaneously, intercouple, so as to improve magnetic
Structural phase transition obtains the induced by magnetic field with big intensity of magnetization mutation and low metamagnetism critical field to the sensitivity in magnetic field
Magnetic structure phase transformation.Alloy preparation method that the present invention is provided is simple and convenient, energy resource consumption is few, and it is low to prepare cost, is adapted to industrialization
Production.
Brief description of the drawings
Fig. 1 be 1- of embodiment of the present invention embodiments 6 provide alloy etc. field thermomagnetization curve；
Fig. 2 is the DSC curve for the alloy that 1- of embodiment of the present invention embodiments 6 are provided；
Fig. 3 is the isothermal magnetization curve for the alloy that the embodiment of the present invention 1 is provided；
Fig. 4 is the isothermal magnetic entropy varied curve that the embodiment of the present invention 1 is provided；
Fig. 5 is the isothermal magnetization curve for the alloy that the embodiment of the present invention 4 is provided；
Fig. 6 is the isothermal magnetic entropy varied curve that the embodiment of the present invention 4 is provided.
Embodiment
In order that those skilled in the art more fully understand that technical scheme can be practiced, with reference to specific
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
For MnCoGe based alloys, the present invention one is anti-general to make valency electricity by simple transition elements Mn or Co omission
Sub- Konzentration/a reduces, the idea for reducing alloy structure phase transition temperature, substitutes part Mn by increasing Co content, increase is closed
Valence electron Konzentration/a of gold, designs alloying component, increases Mn atomic magnetic moment unstability, improves alloy martensite phase transformation to magnetic
The sensitivity of field, so as to realize induced by magnetic field metamagnetism martensitic traoformation in MnCoGe based alloys.While the structure of alloy
Phase transition temperature is substantially reduced so that magnetic phase transition and structural phase transition occur simultaneously, intercouple, and obtains magnetic structure coupling phase transformation.
Based on above-mentioned principle, actually include the alloy expression formula of at least five kinds implications：
The first chemical general formula of alloy is made up of tri- kinds of metallic elements of Mn, Co, Ge, specifically Mn1-xCo1+xGe (1), its
In, 0.01≤x≤0.11 adjusts the ratio between Mn and Co particular by x values.
Second of chemical general formula of alloy is Mn1-yAyCoGe (2), wherein, 0.02≤y≤0.12, and A be selected from Fe, Ni,
The metallic element of any one in Cu, Cr, V, Sn, Al, Ga, B, In, mainly by by part Mn elements replace with y contents its
His metal element A, such as formula can expand to Mn1-yFeyCoGe (0.02≤y≤0.12), Mn1-yNiyCoGe(0.02≤y≤
0.12) etc..
The third chemical general formula of alloy is MnaDbCo1+yGe (3), wherein a+b=1-y, 0.02≤y≤0.12, and D are selected
Any one metallic element from Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Further, above-mentioned b is less than or equal to 0.1.
For example the third chemical general formula can be expanded to：Mn0.92-yCu0.08Co1+yGe(0.02≤y≤0.12)、Mn0.98-yCo1+yGeB0.02
(0.02≤y≤0.12)、Mn0.96-yCr0.04Co1+yGe(0.02≤y≤0.12)、Mn0.98-yV0.02Co1+yGe(0.02≤y≤
0.12) etc..
4th kind of chemical general formula of alloy is Mn1-yCocEdGe (4), wherein c+d=1+y, 0.02≤y≤0.12, and E are selected
Any one metallic element from Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Further, above-mentioned d is less than or equal to 0.1.
Such as the 4th kind chemical general formula can be expanded to：Mn1-yCo0.985+yGeIn0.015(0.02≤y≤0.12) etc..
5th kind of chemical general formula of alloy is Mn1-yCo1+yGeeFf(5), wherein e+f=1,0.02≤y≤0.12, and F are selected
From any one metallic element in Fe, Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Further, above-mentioned f is less than or equal to
0.1.Such as the 5th kind chemical general formula can be expanded to：Mn1-yCo1+yGe0.945Ga0.055(0.02≤y≤0.12)、Mn1-yCo1+ yGe0.98Al0.02(0.02≤y≤0.12)、Mn1-yCo1+yGe0.95Sn0.05(0.02≤y≤0.12) etc..
Below just in the form of specific example, technical scheme is further illustrated.
Embodiment 1
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.98Co1.02Ge
According to principle design alloy, specific chemical general formula is Mn0.98Co1.02Ge, needed for being calculated according to stoichiometric proportion
The quality of the simple substance of Mn, Co, Ge element carries out dispensing, it is necessary to be accurate to 0.1mg, the purity of metal simple-substance 99.99% with
On.The raw material prepared is put into water-cooled copper crucible electric arc furnaces, vacuum is evacuated to 10-3Below Pa, is filled with the pure of 1 atmospheric pressure
The argon gas for 99.999% is spent, electric arc melting is carried out.During first pass melting, with 25A electric currents by metal molten, it is seen that golden in crucible
Belong to liquid flowing, by the bulk sample turn-over of first pass melting, somewhat high current is to 35A melting 4 times again, you can obtain
MnCoGe based alloy ingot castings；Part MnCoGe based alloy ingot castings are fitted into internal diameter 10mm quartz ampoule, then quartz ampoule are put
Enter 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 into liquid, so
It is sprayed onto afterwards by the aperture of quartzy bottom of the tube on the copper roller of rotation at a high speed, the rotating speed of copper roller is 25m/s, obtains quick quenching band sample
Product；In the internal diameter 10mm quartz ampoules that the alloy cast ingot of remainder and the fast quenching rule carry sample are put into one end closing, very
Reciprocal of duty cycle is evacuated to below 4Pa, and the argon gas for being filled with 0.5 atmospheric pressure is used for gas washing, is repeated 4 times, by vacuum after last time gas washing
Below 3Pa is evacuated to, then rapidly the quartz ampoule of elongation is blown with acetylene flame, sample is enclosed in the quartz ampoule after vacuumizing；
Then the sample sealed is put into high temperature furnace and carries out annealing heat-treats, annealing temperature is 850 DEG C, and time 10min then takes out
Cold quenching-in water is put into rapidly, obtains texture and the good Tape samples of micro-structural.In Mn0.98Co1.02Observed in Ge samples
The metamagnetism martensitic traoformation of induced by magnetic field, and obtain the phase transformation of one-level magnetic structure and the big magnetic thermal effect of magnetic and structure Coupling
Should.
Embodiment 2
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.965Co1.035Ge, specific preparation side
Method is identical with the preparation process of embodiment 1, the difference is that only, according to Mn0.965Co1.035Ge stoichiometric proportion is calculated
The quality of the simple substance of required Mn, Co, Ge element carries out dispensing.
Embodiment 3
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.955Co1.045Ge, specific preparation side
Method is identical with the preparation process of embodiment 1, the difference is that only, according to Mn0.955Co1.045Ge stoichiometric proportion is calculated
The quality of the simple substance of required Mn, Co, Ge element carries out dispensing.
Embodiment 4
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.945Co1.055Ge, specific preparation side
Method is identical with the preparation process of embodiment 1, the difference is that only, according to Mn0.945Co1.055Ge stoichiometric proportion is calculated
The quality of the simple substance of required Mn, Co, Ge element carries out dispensing.
Embodiment 5
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.93Co1.07Ge, specific preparation method
It is identical with the preparation process of embodiment 1, it the difference is that only, according to Mn0.93Co1.07Needed for Ge stoichiometric proportion is calculated
The quality of the simple substance of Mn, Co, Ge element carries out dispensing.
Embodiment 6
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.91Co1.09Ge, specific preparation method
It is identical with the preparation process of embodiment 1, it the difference is that only, according to Mn0.91Co1.09Needed for Ge stoichiometric proportion is calculated
The quality of the simple substance of Mn, Co, Ge element carries out dispensing.
The alloy that we are provided above-described embodiment 1- embodiments 6 the field thermomagnetization curve such as carries out and determined respectively, acquired results
Specifically as shown in figure 1, as seen from Figure 1, magnetic structure coupling phase is obtained in the alloy that our embodiment 1- embodiments 6 are provided
Become.Further, we carry out DSC curve measure, acquired results respectively to the alloy that above-described embodiment 1- embodiments 6 are provided again
Specifically as shown in Fig. 2 as seen from Figure 2, magnetic structure coupling phase is obtained in the alloy that our embodiment 1- embodiments 6 are provided
Become, support pyromagnetic measurement result.
In addition, we also determine the Mn of the offer of embodiment 1 respectively0.965Co1.035The isothermal magnetization curve of Ge alloys and wait
Warm magnetic entropy varied curve, and the Mn that embodiment 4 is provided0.945Co1.055The isothermal magnetization curve and isothermal magnetic entropy of Ge alloys become bent
Line, specifically,
Mn0.965Co1.035Ge alloy isothermal magnetizations curve is specific as shown in figure 3, this curve uses so-called round-robin method,
Before each temperature survey, it is necessary to which first null field rise temperature makes sample enter weak magnetic state, and then null field is reduced to measurement temperature again
Magnetization curve measurement is carried out, as seen from Figure 3, we obtain more violent induced by magnetic field metamagnetism in the special component
Martensitic traoformation, more it is worthy of note that we first observe reversible induced by magnetic field metamagnetism martensitic phase in 317K temperature
Become.
Mn0.965Co1.035Ge alloy isothermal magnetic entropies varied curve it is specific as shown in figure 4, as seen from Figure 4 we obtain
Big magnetic entropy becomes, and increases great magnetic entropy variation peak value to high-temperature mobile with magnetic field, further demonstrates that we obtain induced by magnetic field
Metamagnetism martensitic traoformation.
Mn0.945Co1.055Ge alloy isothermal magnetizations curve is specific as shown in figure 5, this curve uses so-called standard method,
Each temperature is sequentially measured, and as seen from Figure 5, we obtain violent induced by magnetic field metamagnetism geneva in the special component
Body phase becomes, more it is worthy of note that we first observe reversible induced by magnetic field metamagnetism martensitic traoformation in 288K temperature.
Mn0.945Co1.055Ge alloy isothermal magnetic entropies varied curve it is specific as shown in fig. 6, as seen from Figure 6 we obtain
Big magnetic entropy becomes, and increases great magnetic entropy variation peak value to high-temperature mobile with magnetic field, further demonstrates that we obtain induced by magnetic field
Metamagnetism martensitic traoformation.
On the basis of embodiment 1- embodiments 6, we increase alloy based on part Mn is substituted by the content for increasing Co
Valence electron Konzentration/a principle further adjustment has been carried out to alloying component, obtained some new alloys, below just to show
The form of example is further provided.
Embodiment 7
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.98Fe0.02CoGe, specific preparation side
Method is identical with the preparation process of embodiment 1, the difference is that only, according to Mn0.98Fe0.02CoGe stoichiometric proportion is calculated
The quality of the simple substance of required Mn, Co, Fe, Ge element carries out dispensing.As a result induced by magnetic field metamagnetism is obtained in annealing specimen
Martensitic traoformation, and obtain the coupling phase transformation of one-level magnetic structure and big magnetothermal effect.
Embodiment 8
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.9Ni0.1CoGe, specific preparation method
It is identical with the preparation process of embodiment 1, it the difference is that only, according to Mn0.9Ni0.1Needed for CoGe stoichiometric proportion is calculated
The quality of the simple substance of Mn, Co, Ni, Ge element carries out dispensing.As a result induced by magnetic field metamagnetism geneva is obtained in annealing specimen
Body phase becomes, and obtains the coupling phase transformation of one-level magnetic structure and big magnetothermal effect.
Embodiment 9
The present embodiment has the alloy Mn of the metamagnetism martensitic traoformation of induced by magnetic field0.98Fe0.02CoGe, specific preparation side
Method is identical with the preparation process of embodiment 1, the difference is that only, annealing temperature is 600 DEG C, time 1h.As a result in annealing sample
Induced by magnetic field metamagnetism martensitic traoformation is obtained in product, and obtains the coupling phase transformation of one-level magnetic structure and big magnetothermal effect.
It should be noted that when being related to number range in claims of the present invention, it is thus understood that each number range
Any one numerical value can select between two end points and two end points, due to step method and the phase of embodiment 1~9 of use
Together, in order to prevent from repeating, description of the invention preferred embodiment, but the invention is not limited in this, but can also be with
Other modes in the range of the technical scheme defined in appended claims are implemented, such as can also be
In the alloy sample that can occur the coupling phase transformation of one-level magnetic structure, such as：
Mn0.92-yCu0.08Co1+yGe(0.02≤y≤0.12)、Mn0.98-yCo1+yGeB0.02(0.02≤y≤0.12)、
Mn0.96-yCr0.04Co1+yGe(0.02≤y≤0.12)、Mn0.98-yV0.02Co1+yGe(0.02≤y≤0.12)、Mn1-yCo0.985+ yGeIn0.015(0.02≤y≤0.12)、Mn1-yCo1+yGe0.945Ga0.055(0.02≤y≤0.12)、Mn1-yCo1+yGe0.98Al0.02
(0.02≤y≤0.12)、Mn1-yCo1+yGe0.95Sn0.05Preferable induced by magnetic field is obtained in alloys such as (0.02≤y≤0.12)
Metamagnetism martensitic traoformation and its corresponding larger magnetothermal effect.And other adjoint interesting things are studied in phase transition process
Manage phenomenon, such as magnetoresistance effect, magneto-strain and shape memory etc..
Claims (6)
1. a kind of method for the metamagnetism martensitic traoformation that induced by magnetic field is realized in MnCoGe based alloys, it is characterised in that logical
The ratio of Co/Mn in MnCoGe based alloys is overregulated, alloying component is designed, increases valence electron Konzentration/a of alloy, increase Mn is former
The unstability of sub- magnetic moment, so as to improve sensitivity of the magnetic structure phase transformation to magnetic field, obtains the metamagnetism geneva of induced by magnetic field
Body phase becomes.
2. the side of the metamagnetism martensitic traoformation according to claim 1 that induced by magnetic field is realized in MnCoGe based alloys
Method, it is characterised in that
The chemical general formula of the alloy is Mn1-xCo1+xGe (1), wherein, 0.01≤x≤0.11；Or
The chemical general formula of the alloy is Mn1-yAyCoGe (2), wherein, 0.02≤y≤0.12, and A be selected from Fe, Ni, Cu, Cr, V,
The metallic element of any one in Sn, Al, Ga, B, In；Or
The chemical general formula of the alloy is MnaDbCo1+yGe (3), wherein a+b=1-y, 0.02≤y≤0.12, and D be selected from Fe,
The metallic element of any one in Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical general formula of the alloy is Mn1-y CocEdGe (4), wherein c+d=1+y, 0.02≤y≤0.12, and E be selected from Fe,
The metallic element of any one in Ni, Cu, Cr, V, Sn, Al, Ga, B, In；Or
The chemical general formula of the alloy is Mn1-yCo1+yGeeFf(5), wherein e+f=1,0.02≤y≤0.12, and F be selected from Fe,
Any one metallic element in Ni, Cu, Cr, V, Sn, Al, Ga, B, In；
In above-mentioned formula (3)-(5), b, d, f are less than or equal to 0.1.
3. the side of the metamagnetism martensitic traoformation according to claim 2 that induced by magnetic field is realized in MnCoGe based alloys
Method, it is characterised in that the preparation process of the alloy of the metamagnetism martensitic traoformation with induced by magnetic field is specially：
S1：Dispensing is carried out according to chemical general formula, the raw material prepared is put into water-cooled copper crucible electric arc furnaces, vacuum is evacuated to 10-3Below Pa, the purity for being filled with 0.8~1 atmospheric pressure is 99.999% argon gas, carries out electric arc melting, repeats melting 4~5 times,
Obtain MnCoGe based alloy ingot castings；
S2：Part MnCoGe based alloy ingot castings are fitted into internal diameter 10-11mm quartz ampoule, quartz ampoule is then put into quick quenching furnace
In chamber, 10 are evacuated in furnace chamber-4Pa, is passed through argon gas, and stone is then passed through into liquid by ingot melting by high-frequency induction heating
The aperture of English bottom of the tube is sprayed onto on the copper roller of rotation at a high speed, 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 fast quenching rule carry sample are put into the internal diameter 10mm quartz ampoules of one end closing
In, vacuum is evacuated to below 4Pa, and the argon gas for being filled with 0.3~0.5 atmospheric pressure is used for gas washing, repeats 3-5 times, washes for the last time
Vacuum is evacuated to below 3Pa after gas, then rapidly the quartz ampoule of elongation is blown with acetylene flame, 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 600~1000 DEG C,
0~120h of time, then takes out and is put into cold quenching-in water rapidly, obtains the metamagnetism martensitic traoformation with induced by magnetic field
MnCoGe based alloys.
4. the side of the metamagnetism martensitic traoformation according to claim 3 that induced by magnetic field is realized in MnCoGe based alloys
Method, it is characterised in that the simple substance purity of each metal is more than 99.99%.
5. the side of the metamagnetism martensitic traoformation according to claim 3 that induced by magnetic field is realized in MnCoGe based alloys
The step of method, it is characterised in that in S1, electric arc melting, is specific as follows：
First since Co so that Co envelopes the volatile Mn and Ge easily splashed after melting, during first time melting, use
20~30A electric currents are by metal molten, it is seen that crucible inner metal liquid flows, by the sample turn-over of first time melting, increase electricity
It flow to 35~40A melting 4~5 times again, you can obtain uniform MnCoGe based alloys ingot casting sample.
6. the side of the metamagnetism martensitic traoformation according to claim 3 that induced by magnetic field is realized in MnCoGe based alloys
Method, it is characterised in that in S3, annealing temperature is set in 600-850 DEG C, time 10min-120h.
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| CN108398462A (en) * | 2018-02-07 | 2018-08-14 | 三峡大学 | A kind of metamagnetism martensitic traoformation Haas strangles the survey calculation method of induced by magnetic field phase transition temperature movement in alloy |
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