CN105568108B - Keep method and the application of the co-structured phase transformation of strong magnetic of MnNiGe sills - Google Patents
Keep method and the application of the co-structured phase transformation of strong magnetic of MnNiGe sills Download PDFInfo
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Abstract
The present invention provides method and the application of a kind of co-structured phase transformation of strong magnetic of holding MnNiGe sills, and methods described includes removing the particle that particle diameter is less than 100 μm, and the MnNiGe sills are Mn1‑ xFexNiGe or MnNi1‑yFeyGe, wherein, 0.08<X≤0.26,0.10≤y≤0.27.Advantage of the invention is that：With Ni2The Mn of In type hexagonal structures1‑xFexNiGe and MnNi1‑yFeyGe materials have the characteristics of magnetic co-structured phase transformation, and phase transformation is front and rear to have a big volume differences, material brittle, it is freshly prepared go out sample be often broken into powder.In order to keep magnetic property outstanding as bulk, need to screen out the particle that particle diameter is less than 100 μm in material actual application.The present invention is for MnNiGe:Application of the Fe materials in fields such as Magnetic driving, magnetic transducing, magnetic refrigeration has important practical significance.
Description
Technical field
It is Ni the present invention relates to a kind of high-temperature-phase2In types hexagonal structure, low-temperature phase are total to for the magnetic of TiNiSi type orthohormbic structures
Structural phase-change material Mn1-xFexNiGe and MnNi1-yFeyGe, the method for keeping its strong co-structured phase transformation of magnetic and in Magnetic driving, magnetic
The application in the fields such as transducing, magnetic refrigeration.
Background technology
The co-structured phase transformation of magnetic refers to while magnetic phase transition occurs with unit cell volume or/and structural symmetry (space group)
Change, the former is referred to as magnetoelasticity phase transformation, the latter is referred to as magnetic structure phase transformation.It is co-structured that material with this phase change characteristics is referred to as magnetic
Phase-change material.The co-structured phase-change material of magnetic has extensive use in fields such as Magnetic driving, magnetic transducing, magnetic refrigeration.Such as：With change
With geneva structural phase transition while the high Mn content Heusler alloys magnetic phase transition of magnetic characteristic occurs, big Zeeman before and after phase transformation
Can poor μ0Δ MH can make field drives structural phase transition, the stress for the Ni-Co-Mn-In systems material under 7T magnetic fields reported
More than 50 times of output higher than traditional ferromagnetic shape-memory materials.In addition, the co-structured phase-change material of magnetic with high saturation magnetic moment
Because first order phase change property often shows big magnetothermal effect, such as：The Gd- that the U.S., China, Holland, Japan find in succession
Si-Ge、LaCaMnO3、Ni-Mn-Ga、La(Fe,Si)13, a few class materials with the giant magnetocaloric effect such as MnAs based compounds be the co-structured phase of magnetic
Become material.
In recent years, there is Ni2Ternary MM ' the X-alloy systems of In type hexagonal structures attract attention, as MM ' X
A member of series alloy family, the MnNiGe alloys that are just dividing are presented anti-ferromagnetism, and with without diffusion geneva structural phase transition, but horse
Family name's structural phase transition and magnetic phase transition do not couple, and decline with temperature and occur geneva structural phase transition in paramagnetic region, and crystal structure is from height
The Ni of temperature2In type hexagonal structure (space groups：P63/ mmc) austenite parent phase is transformed into the TiNiSi type (space groups of low temperature：Pnma)
The martensitic phase of orthohormbic structure, its martensitic structure phase transition temperature are located at Tstru~483K, temperature is further reduced in TN~356K
There is paramagnetic-antiferromagnetic phase transformation (Ne＆1＆el temperature) of geneva phase, the MnNiGe alloy geneva structural phase transitions just divided and magnetic phase transition are not
Overlap.Research is found, can also be realized in the ternary system MM ' X with hexagonal structure by introducing chemical pressure, physical pressure
The co-structured phase transformation of magnetic, the method for constructional alloy such as utilize to replace Mn or Ni by introducing Fe, can be in Mn1-xFexNiGe and MnNi1- yFeyThe co-structured phase transformation of magnetic is realized in Ge materials, geneva structural phase transition is occurred in paramagnetic austenite parent phase and ferromagnetic or antiferromagnetic
Between geneva phase, and it was found that the adjoint huge lattice negative expansion (2~4%) of such system magnetic phase transition has exceeded all reported
Other systems with different spaces group lattice knots modification, so as to bring superior Magnetic driving, Magnetic Memory, magnetothermal effect,
It imply that material has bigger application potential.
It is to obtain outstanding magnetic property (Magnetic driving, Magnetic Memory, magnetothermal effect) to keep the strong co-structured phase transformation coupling intensity of magnetic
Key.Due to huge lattice negative expansion, the ternary system MM ' X with hexagonal structure show frangible feature, freshly prepared
The sample gone out is often broken into powder.But do not know grain size whether to the co-structured phase transformation coupling intensity of magnetic, Yi Jicai at present
Material stability has an impact.Due to different materials system chemical potential, with reference to energy difference, its mechanical stability, anti-oxidation characteristics etc.
It is dramatically different, it is also different so as to the particle diameter limit of material modification.
The content of the invention
The present inventor has found by in-depth study, for the co-structured phase transformation material of magnetic with first order phase change property
Expect Mn1-xFexNiGe and MnNi1-yFeyGe, when particle diameter is reduced to<100 μm, there is unstability, the co-structured phase transformation portion of magnetic in material
Divide uncoupling (i.e. magnetic phase transition and structural phase transition separates), occur unnecessary magnetic phase transition in low-temperature space, tied altogether so as to influence magnetic
Structure phase transformation coupling intensity, magnetic heating performance decline.Therefore, in order to ensure the excellent in performance of material, needed in actual application by
Particle of the particle diameter less than 100 μm screens out.This is significant for the practical application of material.
Therefore, it is an object of the invention to provide the strong magnetic of a kind of material with the co-structured phase transformation of magnetic, holding is co-structured
The application of the method for phase transformation coupling intensity and the material in fields such as Magnetic driving, magnetic transducing, magnetic refrigeration.
To help to understand the present invention, some terms are defined below.Term defined herein has the present invention is related to lead
The implication that the those of ordinary skill in domain is generally understood that.
Unless otherwise indicated, term Mn used herein1-xFexNiGe and MnNi1-yFey" Ni corresponding to Ge2In types structure "
It is P6 to refer to space group3/ mmc structure, " TiNiSi types structure " refer to the structure that space group is pnma.
The purpose of the present invention is realized by the following technical solutions.
The invention provides a kind of method of the co-structured phase transformation of strong magnetic of holding MnNiGe sills, methods described includes going
Except particle diameter is less than 100 μm of particle, the MnNiGe sills are Mn1-xFexNiGe or MnNi1-yFeyGe, wherein, 0.08<x≤
0.26,0.10≤y≤0.27.
According to method provided by the invention, wherein, the MnNiGe sills have the co-structured phase change characteristics of magnetic, interconvertibility
Matter is one-level, and 100 μm of irregular shape is not less than for particle diameter.The material at high temperature mutually has Ni2In type hexagonal structures, low temperature
Mutually there is TiNiSi type orthohormbic structures.
According to the co-structured phase-change material Mn of magnetic provided by the invention1-xFexNiGe and MnNi1-yFeyGe, when the particle diameter of particle
When being reduced to less than 100 μm, the material loss of stability, magnetic co-structured phase change portion uncoupling (i.e. magnetic phase transition and structure phase
Change separates), there is unnecessary magnetic phase transition in low-temperature space, so as to influence the co-structured phase transformation coupling intensity of magnetic, under magnetic heating performance
Drop.Therefore, in order to keep the outstanding magnetic property as bulk, need to screen out particle diameter in material actual application and be less than 100 μ
M particle.
Present invention also offers the preparation method of the above-mentioned co-structured phase-change material of MnNiGe bases magnetic, this method includes following step
Suddenly：
1) chemical formula preparation raw material is pressed；
2) raw material prepared in step 1) is put into electric arc furnaces, vacuumized, with argon purge, and under argon gas protection
Melting, obtain alloy pig；
3) the melted alloy pig of step 2) is annealed for 800~900 DEG C under vacuum conditions, then natural cooling, so as to
Prepare Mn1-xFexNiGe and MnNi1-yFeyThe co-structured phase-change material of Ge magnetic；
4) the co-structured phase-change material of magnetic made from step 3) is crushed, ground and sieved, obtain particle size range 1~
200 μm of random particle, then screen out the particle that particle diameter is less than 100 μm.
According to preparation method provided by the invention, wherein, raw material Mn, Fe, Ni, Ge are commercialization simple substance rare earth members
Element.Commercialization purity is usually not less than 98.5wt%.
According to preparation method provided by the invention, specifically, the step 2) can include：By what is prepared in step 1)
Raw material is put into electric arc furnaces, is evacuated to vacuum less than 1 × 10-2Pa, furnace chamber 1 is cleaned with high-purity argon gas of the purity more than 99%
~2 times, the argon gas to 0.5~1.5 atmospheric pressure, Arc is filled with furnace chamber afterwards and obtains alloy pig, each alloy pig exists
Melt back 1~3 time at 1500~2500 DEG C.
According to preparation method provided by the invention, specifically, the step 3) can include：By the conjunction that step 2) is melted
Ingot is less than 1 × 10 in 870~880 DEG C, vacuum-3Annealed 1~7 day under conditions of Pa, then stove is cold or ice water quenching.
According to preparation method provided by the invention, specifically, the step 4) can include：By material made from step 3)
Coarse granule is ground to particle diameter≤200 μm with agate mortar in protection gas or protection liquid, afterwards with standard screen to metal dust
Sieved, the particle that 1~200 μm of collection cut size scope, and screen out the particle that particle diameter is less than 100 μm.
Present invention also offers the co-structured phase-change material of the magnetic or according to the co-structured phase of magnetic made from the inventive method
Become application of the material in fields such as Magnetic driving, magnetic transducing, magnetic refrigeration.
Present invention also offers the method for the co-structured phase transformation of strong magnetic of the holding MnNiGe sills to prepare magnetic refrigeration
Application in material, Magnetic driving material and magnetic transductive material.
Compared with prior art, advantage of the invention is that：With Ni2The Mn of In type hexagonal structures1-xFexNiGe and
MnNi1-yFeyGe materials have the characteristics of magnetic co-structured phase transformation, and phase transformation is front and rear to have a big volume differences, and material brittle is freshly prepared
The sample gone out has often been broken into powder, thus studies grain dispersion and seem particularly important.And so far, people do not know grain
Whether footpath size has an impact to the co-structured phase transformation coupling intensity of magnetic.The present invention is in the case where keeping component constant by protecting
Block materials are divided into the irregular powder that particle size range is 1~200 μm in shield atmosphere or liquid, found when particle diameter is less than
When 100 μm, the co-structured phase transformation coupling intensity of magnetic reduces with particle diameter to decline to a great extent, and performance weakens therewith.Therefore, in order to keep
With the particle for needing to screen out particle diameter in outstanding magnetic property as bulk, material actual application and being less than 100 μm.The present invention is right
In MnNiGe:Application of the Fe materials in fields such as Magnetic driving, magnetic transducing, magnetic refrigeration has important practical significance.
Brief description of the drawings
Hereinafter, embodiment of the present invention is described in detail with reference to accompanying drawing, wherein：
Fig. 1 is Mn made from embodiment 11-xFexThe room temperature X of NiGe (x=0.08,0.10,0.15,0.18) bulk sample
X ray diffraction (XRD) collection of illustrative plates；
Fig. 2 is MnNi made from embodiment 21-yFeyThe room temperature X-ray diffraction of Ge (y=0.20,0.23) bulk sample
(XRD) collection of illustrative plates；
Fig. 3 is Mn made from embodiment 11-xFexNiGe (x=0.08,0.10,0.15,0.18) bulk sample is in 0.01T
Pyromagnetic (M-T) curve of heating under magnetic field；
Fig. 4 is MnNi made from embodiment 21-yFeyHeat of Ge (y=0.20,0.23) the bulk samples under 0.01T magnetic fields
Magnetic (M-T) curve；
Fig. 5 is Mn made from embodiment 10.82Fe0.18NiGe bulks and the sample of 6 particle size ranges (60~100 μm, 20
~40 μm, 10~20 μm, 5~10 μm, 2~5 μm, 1~2 μm) pyromagnetic (M-T) curve of heating under 0.01T magnetic fields；
Fig. 6 is Mn made from embodiment 10.82Fe0.18NiGe bulks and 60~100 μm of the sample of 5 particle size ranges, 20
~40 μm, 10~20 μm, 5~10 μm, 2~5 μm) Maxwell relation is utilized, obtained from the calculating of isothermal magnetization curve not
With dependence graphs of the Δ S to temperature that field process is risen under magnetic field.
Embodiment
The present invention is further described in detail with reference to embodiment, the embodiment provided is only for explaining
The bright present invention, the scope being not intended to be limiting of the invention.
The raw material that is used in embodiment and equipment are described as follows：
1) raw materials used Mn, Fe, Ni, Ge are commercialization simple substance elements in the embodiment of the present invention.Mn purity is
99.9wt%, purchased from the bicyclic chemical reagent factory in Beijing；Ge (purity 99.999wt%), Fe (purity 99wt%), Ni (purity
99.999wt%) it is purchased from Beijing Non-Ferrous Metal Research General Academy.
2) electric arc furnaces used in produces for Beijing WuKe opto-electrical Technology Co., Ltd, model：WK-II type non-consumable vacuum arcs
Stove；Cu targets X-ray diffractometer produces for Rigaku companies, model RINT2400；Superconductive quantum interference vibrating specimen magnetometer
(MPMS (SQUID) VSM), produced for Quantum Design (USA) company, model MPMS (SQUID) VSM.
Embodiment 1
Mn1-xFexNiGe (x is respectively 0.08,0.10,0.15,0.18,0.22,0.26)
1) chemical formula Mn is pressed1-xFexNiGe (x is respectively 0.08,0.10,0.15,0.18,0.22 and 0.26) weigh sample,
Dispensing.
2) raw material for preparing step 1) is respectively put into electric arc furnaces, is evacuated to 3 × 10-3More than pa, use is common
After high-purity argon gas (purity 99.996wt%) cleaning method cleans 2 times, in the high-purity argon gas (purity of 1 atmospheric pressure
Under 99.996wt%) protecting, Arc, melt back 3 times, smelting temperature is 2000 DEG C.After melting terminates, in copper crucible
Middle cooling obtains cast alloy ingot.
3) alloy pig for preparing step 2) is wrapped with metal molybdenum sheet respectively, is sealed in (vacuum in vitreosil pipe
For 1 × 10-4Pa), after 875 DEG C are annealed 6 days, stove breaks quartz ampoule after being as cold as room temperature, and acquisition low-temperature phase is TiNiSi (space groups
For Pnma), high-temperature-phase Ni2In (space group P63/ mmc) Mn1-xFexNiGe series of magnetic material samples.
4) that is prepared in step 2) has the characteristics of frangible into phase sample, powder has been broken into, for system research particle diameter
The influence of size coupling phase transformation co-structured to sample stability and magnetic, material made from step 3) is used into agate under acetone protection
Coarse granule is further ground into the irregular powder of particle diameter≤200 μm by mortar, afterwards with the standard screen of different meshes to metal
Powder is sieved, so as to prepare the powder with different-grain diameter scope.For anti-oxidation, screening process is in acetone liquid
Carry out.
Embodiment 2
MnNi1-yFeyGe (y is respectively 0.10,0.20,0.23,0.27)
Sample of magnetic material is prepared according to method similarly to Example 1, unlike, the chemical formula of material is MnNi1- yFeyGe (y is respectively 0.10,0.20,0.23,0.27).
The sample detection of Examples 1 and 2 and interpretation of result
First, the sign of crystal structure
Mn is determined using Cu target X-ray diffractometers1-xFexNiGe (x is respectively 0.08,0.10,0.15,0.18,0.22,
And MnNi 0.26)1-yFeyThe room temperature X-ray diffraction of Ge (y is respectively 0.10,0.20,0.23,0.27) series of samples bulk
(XRD) collection of illustrative plates, increasing with doping is found, orthogonal Phase Proportion reduces, and this illustrates increasing of the martensitic transformation temperature with doping
Add and reduce.Fig. 1 and Fig. 2 provides the XRD spectrum of typical sample.As can be seen from Figure 1 during room temperature, x=0.08 samples are almost complete
For orthorhombic phase, x=0.10 samples are mainly orthorhombic phase, it can be seen that martensitic transformation temperature x=0.08 is higher than x=
0.10, and it is above room temperature.X=0.15, x=0.18 sample are almost pure hexagonal phase, show that geneva phase transition temperature is less than room
Temperature；As shown in Figure 2, two-phase coexistent during y=0.20 samples room temperature, it is almost pure hexagonal structure during y=0.23 sample room temperatures.
2nd, the sign of phase transition temperature
Utilize superconductive quantum interference vibrating specimen magnetometer【MPMS(SQUID)VSM】Determine Mn1-xFex(x distinguishes NiGe
For 0.08,0.10,0.15,0.18,0.22,0.26) and MnNi1-yFeyGe (y is respectively 0.10,0.20,0.23,0.27) bulk
Pyromagnetic (M-T) curve under downfield (in 0.01T).It was found that for Mn1-xFexNiGe, magnetic structure coupling temperature Tmstru(refer to horse
Family name's structural phase transition TstruWith magnetic phase transition TCThe temperature T of couplingstru=TC, i.e. Tmstru, it is defined as temperature-rise period dM/dT on M-T curves
Corresponding peak temperature) as the change of Fe dopings is in wide warm area (74K-335K) continuously adjustabe, TmstruFrom x=0.08 when
Tmstru=335K changes to T during x=0.26mstru=74K；And for MnNi1-yFeyGe, TmstruThen at (230K-400K)
Wide warm area continuously adjustabe, from y=0.10 when Tmstru=400K changes to T during y=0.27mstru=230K.Fig. 3 and Fig. 4 give
The result of typical sample is gone out.
3rd, the research of grain dispersion
It is to study granularity size to Mn1-xFexNiGe (x is respectively 0.08,0.10,0.15,0.18,0.22,0.26) and
MnNi1-yFeyGe (y is respectively 0.10,0.20,0.23,0.27) magnetic structure coupling phase transformation and the influence of magnetic thermal property, invention
It is bent that people measures pyromagnetic (M-T) curve and isothermal magnetization of the sample of corresponding bulk and different-grain diameter scope under 0.01T magnetic fields
Line.It was found that for all samples, consistent with bulk M-T curves when granularity is not less than 200 μm, low-temperature space does not have abnormality
There is unnecessary magnetic phase transition in ground, and phenomenon (the i.e. magnetic of the co-structured phase change portion uncoupling of magnetic occurs when particle diameter is less than 100 μm
Phase transformation and structural phase transition separate), show as unnecessary magnetic phase transition occur in low-temperature space and increasingly show with the reduction of particle
Write, so as to have impact on the co-structured phase transformation coupling intensity of magnetic.Fig. 5 contrasts provide the typical component determined on (SQUID) VSM
Mn0.82Fe0.18NiGe bulks (individual particle, weight：1.31mg) and less than 100 μm 6 different-grain diameter scopes sample (60~
100 μm of (weight：7.36mg), 20~40 μm of (weight：4.38mg), 10~20 μm of (weight：3.51mg), 5~10 μm of (weight：
4.63mg), 2~5 μm of (weight：5.50mg), 1~2 μm of (weight：The 6.96mg)) heat of the heating, cooling under 0.01T magnetic fields
Magnetic (M-T) curve, warming and cooling rate is 10K/min.As seen from Figure 5, when particle size range is reduced to below 100 μm,
Except the co-structured coupling phase transformation (T of magnetic corresponding to generation and bulkmstruPlace) outside, low-temperature space TaAlso there is phase transformation in place, and with
The reduction of granularity, the co-structured coupling phase transformation of magnetic weaken and T rapidlyaLocate phase transformation to strengthen；When particle diameter is further reduced to 1~2 μm,
The co-structured phase transformation of magnetic disappears substantially, i.e., complete uncoupling.
According to Maxwell relationCalculate isothermal magnetic entropy and become Δ
S.It was found that granularity be 150~200 μm sample it is consistent with the magnetic entropy time-varying amplitude of bulk, and particle diameter less than 100 μm sample by
In the decrease of the co-structured phase transformation coupling intensity of magnetic, magnetic entropy time-varying amplitude declines to a great extent.Fig. 6 contrasts provide typical sample
Mn0.82Fe0.18NiGe bulks and the sample of less than 100 μm 5 particle size ranges rise the Δ S of field process to temperature under different magnetic field
The dependence of (near the co-structured phase transition temperature of magnetic).As seen from Figure 6, Mn0.82Fe0.18NiGe bulks and 5 particle diameter models
Enclose effective magnetic entropy time-varying amplitude of (60~100 μm, 20~40 μm, 10~20 μm, 5~10 μm and 2~5 μm) sample under 5T magnetic fields
Respectively 67.0J/kgK, 57.0J/kgK, 40.8J/kgK, 28.0J/kgK, 10.5J/kgK and 3.5J/kg.It can be seen that
When grain size is 60~100 μm, magnetic entropy time-varying amplitude declines 15% than bulk and 150~200 μm of particle diameter samples；When particle size range drops
It is low to 20~40 μm when, the uncoupling of the co-structured phase transformation of magnetic makes magnetic entropy time-varying amplitude decline 39%；When particle size range further reduces
During to 20 μm, magnetic entropy time-varying amplitude declines 58%, and magnetic property has been greatly lowered；Particle size range is further reduced to less than 5 μm
When, magnetic entropy becomes very faint, and originally excellent magnetic property almost completely loses.
Based on the above results, for Mn1-xFexNiGe (x is respectively 0.08,0.10,0.15,0.18,0.22,0.26) and
MnNi1-yFeyGe (y is respectively 0.10,0.20,0.23,0.27) co-structured phase-change material of magnetic, find when particle diameter is less than 100 μm
When there is the phenomenon of the co-structured phase change portion uncoupling of magnetic, the co-structured phase transformation coupling intensity of magnetic declines, impaired performance.Therefore,
In order to keep the outstanding magnetic property as bulk, need to screen out the particle that particle diameter is less than 100 μm in material actual application.
The present invention is for MnNiGe:Application of the Fe materials in fields such as Magnetic driving, magnetic transducing, magnetic refrigeration has important practical significance.
Claims (6)
1. keeping the method for the co-structured phase transformation of strong magnetic of MnNiGe sills, methods described includes removal particle diameter and is less than 100 μm
Particle, the MnNiGe sills are Mn1-xFexNiGe or MnNi1-yFeyGe, wherein, 0.08<X≤0.26,0.10≤y≤
0.27。
2. according to the method for claim 1, wherein, the MnNiGe sills have the co-structured phase change characteristics of magnetic, phase transformation
Property is one-level.
3. method according to claim 1 or 2, wherein, the material at high temperature mutually has Ni2In type hexagonal structures, low-temperature phase
With TiNiSi type orthohormbic structures.
4. the preparation method of the MnNiGe sills any one of claims 1 to 3, this method comprise the following steps：
1) chemical formula preparation raw material is pressed；
2) raw material prepared in step 1) is put into electric arc furnaces, vacuumized, with argon purge, and melted under argon gas protection
Refining, obtain alloy pig；
3) the melted alloy pig of step 2) is annealed for 800~900 DEG C under vacuum conditions, then natural cooling, so as to prepare
Go out Mn1-xFexNiGe and MnNi1-yFeyThe co-structured phase-change material of Ge magnetic；
4) the co-structured phase-change material of magnetic made from step 3) is crushed, ground and sieved, obtain 1~200 μm of particle size range
Random particle, then screen out particle diameter and be less than 100 μm of particle.
5. preparation method according to claim 4, wherein, the annealing temperature of step 3) is 870~880 DEG C, annealing time
For 1~7 day, vacuum was not less than 10-4Pa, stove is cold after annealing or ice water quenching.
6. the method any one of claims 1 to 3 is in magnetic refrigerating material, Magnetic driving material and magnetic transductive material is prepared
Application.
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| CN103059815A (en) * | 2011-10-24 | 2013-04-24 | 中国科学院物理研究所 | First-order phase transition La (Fe, si)13-based magnetocaloric effect materials with small hysteresis loss, its preparation method and use |
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| CN103059815A (en) * | 2011-10-24 | 2013-04-24 | 中国科学院物理研究所 | First-order phase transition La (Fe, si)13-based magnetocaloric effect materials with small hysteresis loss, its preparation method and use |
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| Great Magnetic Entropy Change in Heusler Alloys Ni-Mn-Ga and NaZn13-type Compounds La（Fe，CO，M）13，M=Si，Al;Hu Fengxia et al;《中国科学院研究生院学报》;20020630;第19卷(第2期);192-197 * |
| stable magnetostructural coupling with tunable magnetoresponsive effects in hexagonal ferromagnets;Enke Liu et al;《nature communication》;20120529;1-10 * |
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