CN108486449B - Low-thermal-hysteresis MnNiGe-based magnetic phase change alloy - Google Patents
Low-thermal-hysteresis MnNiGe-based magnetic phase change alloy Download PDFInfo
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- CN108486449B CN108486449B CN201810245317.XA CN201810245317A CN108486449B CN 108486449 B CN108486449 B CN 108486449B CN 201810245317 A CN201810245317 A CN 201810245317A CN 108486449 B CN108486449 B CN 108486449B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 48
- 239000000956 alloy Substances 0.000 title claims abstract description 48
- 230000008859 change Effects 0.000 title claims abstract description 32
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 24
- 108010053481 Antifreeze Proteins Proteins 0.000 claims abstract description 9
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 238000010791 quenching Methods 0.000 claims abstract description 3
- 230000000171 quenching effect Effects 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003723 Smelting Methods 0.000 abstract 2
- 238000000034 method Methods 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 12
- 230000005415 magnetization Effects 0.000 description 8
- 229910000927 Ge alloy Inorganic materials 0.000 description 4
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 230000005298 paramagnetic effect Effects 0.000 description 4
- 229910006137 NiGe Inorganic materials 0.000 description 3
- 230000005290 antiferromagnetic effect Effects 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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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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- 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
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2202/00—Physical properties
- C22C2202/02—Magnetic
Abstract
The invention discloses a low-thermal-hysteresis MnNiGe-based magnetic phase change alloy, wherein the atomic expression of the magnetic phase change alloy is Mn0.9Ni0.9Fe0.2Ge, wherein the thermal hysteresis of alloy hexagonal-orthogonal structure phase change is 5.3K; the magnetic phase change alloy is prepared by taking high-purity metal simple substances Ni, Mn, Fe and Ge as raw materials, accurately proportioning the simple substances according to an alloy expression, and carrying out smelting under the protection of a high-purity argon atmosphere by an arc smelting method; the alloy after melting was annealed at 800 ℃ for 120 hours, followed by quenching in cold water. The thermal hysteresis of the alloy hexagonal-orthogonal structure phase change is the lowest of the alloys of the same type, namely the phase change temperature of the system structure is reduced to the lowest level.
Description
Technical Field
The invention relates to a low-thermal-hysteresis magnetic phase change alloy MnNiGe, belonging to the field of phase change alloy preparation.
Background
MnMX (M = Co, Ni; X = Ge, Si) alloys commonly exhibit temperature induced structural phase transformations that occur between a hexagonal parent phase and an orthogonal martensite phase. The thermal lag associated with this phase change is generally large, typically above 20K. The larger thermal hysteresis is not favorable for the reversible occurrence of the alloy phase transformation accompanying effect. Currently, the lowest reported thermal lag for this system is 7K. This value is determined by the physical location of Mn in the Chinese academy of sciences1-xFexNiGe (x =0.11 and 0.18) alloys. In Mn1-xFexIn the NiGe alloy, Fe replaces the Mn atom.
Disclosure of Invention
The invention aims to provide a low-thermal-hysteresis magnetic phase change alloy MnNiGe.
The technical solution for realizing the purpose of the invention is as follows:
a low thermal hysteresis magnetic phase change alloy MnNiGe with Mn as its alloy expression0.9Ni0.9Fe0.2Ge, and the thermal hysteresis of the alloy hexagonal-orthogonal structure phase change is 5.3K.
Compared with the prior art, the invention has the advantages that: the thermal hysteresis of the alloy hexagonal-orthogonal structure phase change is 5.3K, which is the lowest of the similar alloys, namely the phase change temperature of the system structure is reduced to the lowest level at present.
Drawings
FIG. 1 is (MnNiGe) x1-(Fe2Ge) x Alloy (0.02 ≤ andxless than or equal to 0.16) of the sample.
FIG. 2 shows the magnetic field (MnNiGe) in the 5T external field x1-(Fe2Ge) x Alloy (0.02 ≤ andx≦ 0.16) magnetization as a function of temperature.
FIG. 3 is (MnNiGe) x1-(Fe2Ge) x Magnetic and structural phase diagrams of alloy systems.
FIG. 4 is a preferred Mn0.9Ni0.9Fe0.2Isothermal magnetization curves of the Ge alloy at the up-field and down-field in the vicinity of the phase transition.
FIG. 5 is a preferred Mn0.9Ni0.9Fe0.2And (3) a graph of the relationship between the magnetic entropy change of the Ge alloy and the temperature change under different external magnetic fields.
Detailed Description
The invention is based on the existing alloy Mn1-xFexOn the basis of NiGe (x =0.11 and 0.18), the thermal hysteresis is further reduced by simultaneously replacing Mn and Ni atoms with Fe atoms.
The preparation process of the alloy comprises the following steps: high-purity (99.99%) metal simple substances Ni, Mn, Fe and Ge are used as raw materials, and Mn is adopted according to a molecular formula0.9Ni0.9Fe0.2Ge is accurately proportioned to each alloy simple substance. The alloy is prepared by arc melting, and the melting is carried out under the protection of a high-purity argon atmosphere. The alloy after melting was annealed at 800 ℃ for 120 hours, followed by quenching in cold water.
Example (b):
the phase structure of the alloy is characterized by an X-ray diffractometer (X-ray Diffraction: XRD). FIG. 1 is (MnNiGe) x1-(Fe2Ge) x Alloy (0.02 ≤ andx0.16) at room temperature withxThe room temperature structure of the system gradually becomes high-temperature hexagonal Ni2The In-type structure was transformed into a low temperature orthorhombic TiNiSi type structure, which indicates Fe2The introduction of Ge lowers the structural phase transition temperature of the alloy.
Measurement (MnNiGe) with comprehensive Property Measurement System (PPMS) x1-(Fe2Ge) x Alloy (0.02 ≤ andx≦ 0.16) isothermal magnetization curve and temperature dependent magnetization. FIG. 2 shows a 5T external field (MnNiGe) x1-(Fe2Ge) x Alloy (0.02 ≤ andx≦ 0.16) magnetization as a function of temperature.xAnd the magnetization of the component sample is jumped at 380K, and the corresponding temperature rise and temperature drop curves are not coincident, which indicates that the system undergoes structural phase change, the structural phase change occurs between paramagnetic states, and when the structural phase change temperature is lower, the component sample undergoes paramagnetic to antiferromagnetic transition, corresponding to Neel transition of MnNiGe alloy. With followingxThe phase transition temperature of the alloy is gradually reduced, the low-temperature spiral antiferromagnetic structure induces the formation of a ferromagnetic state, and the paramagnetic Ni is realized in the system under the combined action of the low-temperature spiral antiferromagnetic structure and the ferromagnetic state2Magnetic structure transition of In-type to ferromagnetic TiNiSi-type structure, wherein Mn is preferred0.9Ni0.9Fe0.2The thermal hysteresis of Ge alloys is only 5.3K, the lowest of all such phase change alloys. When in usexFurther increase, the phase transition temperature of the alloy structure is lowered to high temperature Ni2Below the curie temperature of the In structure, the magnetic and structural transitions decouple. For thexFor the 0.16 sample, the structural phase transition is suppressed and disappears, and only the paramagnetic to ferromagnetic curie transition is observed in the figure.
FIG. 3 is (MnNiGe) x1-(Fe2Ge) x Magnetic and structural phase diagrams of alloy systems. As can be seen from the phase diagram, Fe2The Ge introduction can construct a Curie temperature window from 175K to 345K wide by about 170K in the system, and the alloy system in the window realizes the coupling of structural phase change and magnetic transition. Wherein Mn0.9Ni0.9Fe0.2The thermal lag of Ge alloy is the lowest, only 5.3K.
FIG. 4 is a preferred Mn0.9Ni0.9Fe0.2Isothermal magnetization curve of Ge. The magnetic field induced metamagnetic behavior can be obviously observed near the phase transition, and the magnetic hysteresis accompanied by the rising field and the falling field indicates the metamagnetic toolThere is a first order phase change characteristic, corresponding to a magnetic field induced structural phase change.
FIG. 5 is a preferred Mn0.9Ni0.9Fe0.2And (3) a graph of the magnetic entropy change of Ge as a function of temperature. Isothermal magnetization curve based on rising field, and Maxwell equation
The relationship change is obtained. It can be seen from the figure that the alloy exhibits a pronounced magnetocaloric effect with a maximum magnetic entropy variation of up to-40J/(kg ∙ K).
Claims (2)
1. The low-thermal-hysteresis MnNiGe-based magnetic phase change alloy is characterized in that Fe atoms are used for replacing Mn atoms and Ni atoms at the same time, and the atomic expression of the magnetic phase change alloy is Mn0.9Ni0.9Fe0.2And the thermal hysteresis of the alloy hexagonal-orthorhombic structure phase change of the Ge is 5.3K.
2. The magnetic phase change alloy according to claim 1, wherein the magnetic phase change alloy is prepared by taking high-purity metal simple substances of Ni, Mn, Fe and Ge as raw materials, accurately proportioning the simple substances according to an alloy expression and carrying out arc melting under the protection of a high-purity argon atmosphere; the alloy after melting was annealed at 800 ℃ for 120 hours, followed by quenching in cold water.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3844775A (en) * | 1972-11-24 | 1974-10-29 | Du Pont | Polynary germanides and silicides |
| CN105154694A (en) * | 2015-09-29 | 2015-12-16 | 南昌航空大学 | Method for preparing magnetic heat material Mn-Ni-Ge:Fe-based series alloy bar through electric arc melting and copper mold spray casting |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3844775A (en) * | 1972-11-24 | 1974-10-29 | Du Pont | Polynary germanides and silicides |
| CN105154694A (en) * | 2015-09-29 | 2015-12-16 | 南昌航空大学 | Method for preparing magnetic heat material Mn-Ni-Ge:Fe-based series alloy bar through electric arc melting and copper mold spray casting |
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