CN101923933B - Hydrogenated NiMn-based alloy magnetic refrigeration material and preparation method and use thereof - Google Patents

Hydrogenated NiMn-based alloy magnetic refrigeration material and preparation method and use thereof Download PDF

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CN101923933B
CN101923933B CN2009100866484A CN200910086648A CN101923933B CN 101923933 B CN101923933 B CN 101923933B CN 2009100866484 A CN2009100866484 A CN 2009100866484A CN 200910086648 A CN200910086648 A CN 200910086648A CN 101923933 B CN101923933 B CN 101923933B
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alloy
magnetic
annealing
purity
hydrogen
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CN101923933A (en
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胡凤霞
王晶
赵金良
孙继荣
沈保根
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Institute of Physics of CAS
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Abstract

The invention provides a hydrogenated NiMn-based alloy magnetic refrigeration material with big magnetic entropy change. The magnetic refrigeration material has a chemical general formula of NixMnyMzHalpha, and a NixMnyMz alloy before hydrogen absorption has L21 Heusler (Heusler) type structure, wherein M is the combination of one or more of the following elements in any ratio: In, Sb, Sn and Ga. The invention also provides a method for preparing the material, which comprises the following steps of: firstly, smelting and annealing to prepare a NixMnyMz single-phase alloy; then annealing to prepare a NixMnyMzHalpha hydride under hydrogen pressure; and regulating the hydrogen content in the alloy by controlling the hydrogen pressure, the annealing temperature and time. The introduction of a hydrogen atom makes the martensite phase transformation temperature move to low temperature. Therefore, huge magnetic entropy change occurs in a controllable temperature region, the magnetic entropy amplitude is higher than Gd, and the material is an ideal magnetic refrigeration material in a high-temperature region even in a room temperature region.

Description

Hydrogenation NiMn based alloy magnetic refrigeration material, Preparation Method And The Use
Technical field
The present invention relates to a kind of magnetic refrigerating material, particularly relate to a kind of hydrogenation NiMn base Heusler alloy magnetic refrigeration material and preparation method thereof with great magnetic entropy variation.
Background technology
The modern society human lives more and more be unable to do without Refrigeration Technique, and is little of daily life, arrives industrial and agricultural production, science and techniques of defence greatly and all be unable to do without Refrigeration Technique.The magnetic Refrigeration Technique, particularly the room temperature magnetic refrigerating technology has the huge market demand, will play a great role to global energy saving and environmental protection in case realize using.The research of magnetic refrigeration mainly is divided into two aspects, the one, the exploration of efficient magnetic cooling material; The one, the development of magnetic refrigeration model machine.Aspect the research of room temperature magnetic refrigerating model machine, representational work is: 1998, the room temperature magnetic refrigerating model machine of Astronics Corp research and development, the temperature with 38K is striden, the refrigerating capacity of 600W, failure-free operation 18 months; Calendar year 2001, Astronics Corp has released first permanent magnetism, rotary type room-temperature magnetic refrigerator that success is turned round in the world again, has quickened the commercialization process of room-temperature magnetic refrigerator.Domestic in the achievement in research that has also obtained some world levels aspect the refrigeration prototyping: Sichuan University, Nanjing University and Chinese Academy of Sciences's room temperature magnetic refrigerating principle prototype that physics and chemistry has been developed respectively, the refrigeration temperature that adopts the NdFeB permanent magnet can obtain about 20K is striden.
Above-mentioned all magnetic refrigeration model machines all adopt Gd or Gd alloy as refrigeration working medium.Yet since the unicity of simple substance rare-earth Gd Curie temperature with characteristics such as cost an arm and a leg, be that the refrigeration machine of working medium in fact is difficult to realize general cold warm area magnetic refrigeration application widely with Gd.Therefore during the nearly last ten years, the substitute that a large amount of manpower and materials are sought Gd is dropped in countries in the world, has found several types of huge magneto-caloric effect materials in succession, for example: Gd 5Si 2Ge 2, LaCaMnO 3, LaFe 13-xSi x, NiMnGa, MnFeP 0.45As 0.55Etc. system.Wherein the magneto-caloric effect of Heusler alloy NiMnGa research receives extensive concern.Discover, though this quasi-tradition Heusler alloy show huge magnetic entropy change effect (for example :-86J/kgK), its magnetic entropy variate (for example: 1-2K) often appears at very narrow warm area.People know that the magnetic refrigerator device in the practical application not only needs magnetic refrigerating material to have big magneto-caloric effect, and have wide warm area.The novel Heusler alloy with high Mn content of up-to-date report is because its superior SME has caused people's very big interest.With traditional X that has 2The Mn base Heusler alloy phase ratio of YZ proportioning; High Mn alloy is under the appropriate proportioning condition; Ma Shi presents weak magnetic mutually; Cause externally-applied magnetic field to bring out generation change magnetic transition behavior with the huge difference of the Ovshinsky parent phase magnetization, magnetic field can promote the Ma Shi phase transformation and move to low temperature, thereby magnetic entropy becomes the warm area that can appear at a broad.
When obtaining the big magneto-caloric effect of material, can regulated at will refrigeration warm area be that people thirst for always.We find by current research that the introducing of hydrogen atom influences the Mn-Mn spacing in the NiMn base Heusler alloy, thereby influences the magnetic of system, and the introducing of hydrogen atom can make phase transition temperature move to low temperature.Through regulating hydrogen content, can make the Ma Shi phase transition temperature of NiMn base Heusler alloy occur in the different temperature scope, keep material to have big magnetic entropy luffing degree and wide refrigeration warm area simultaneously.
Summary of the invention
For helping to understand the present invention, some terms have been defined below.The term of this paper definition has the implication of those of ordinary skill in the related art's common sense of the present invention.
Unless otherwise indicated, term " L2 used herein 1Structure " be meant that inferior lattice A, B, C, D by four face-centred cubic structures move the structure that 1/4th mutual intussusceptions form successively along diagonal.
Unless otherwise indicated, term used herein " Haas is reined in (Heusler) type alloy " or " Heusler type alloy " are meant a kind of orderly intermetallic compound, have L2 1Structure, space group are Fm3m (O 5 h), here be meant multiple atom in order according to certain lattice dot matrix, occupy the chemical ordered structure of the formed height in peculiar position of oneself separately.Germany scientist F.Heusler reported the chemical ordered alloy of this height first in 1903, afterwards people to be referred to as this type alloy be Heusler type alloy.
The present invention is through having L2 1Introduce the H atom in the NiMn of the structure base Heusler alloy, regulate the warm area that great magnetic entropy variation takes place, become the hydrogenation NiMn base Heusler alloy magnetic refrigeration material that is superior to Gd thereby obtain near a kind of adjustable high temperature and even room temperature, magnetic entropy on a large scale.
One object of the present invention is, a kind of hydrogenation NiMn based alloy magnetic property material is provided.
Another object of the present invention is, a kind of method that is used to prepare described hydrogenation NiMn based alloy magnetic property material is provided.
A further object of the present invention is, a kind of magnetic refrigeration machine is provided, and said refrigeration machine comprises foregoing hydrogenation NiMn based alloy magnetic property material.
Another purpose of the present invention is, the application of described hydrogenation NiMn based alloy magnetic property material in making refrigerating material is provided.
To the foregoing invention purpose, the present invention provides following technical scheme:
On the one hand, the present invention provides a kind of hydrogenation NiMn based alloy magnetic property material, and the chemical general formula of said material is Ni xMn yM zH α, inhale the preceding Ni of hydrogen xMn yM zAlloy has L2 1Haas is reined in (Heusler) type ordered structure, wherein:
M is selected from one or more in the following element: In, Sb, Sn and Ga;
The scope of x is: 0＜x≤60;
The scope of y is: 0＜y≤80, and satisfy y>=x/2;
The scope of z is: 0＜z≤50, and satisfy 90≤x+y+z≤110; And
The scope of α is: 0＜α≤50.0.
Preferably, hydrogenation NiMn based alloy magnetic property material of the present invention, its magnetic entropy variate is under the 0-5T changes of magnetic field: 5.0J/kgK-50.0J/kgK, transition temperature area is positioned at 150K-350K.
On the other hand, the present invention provides a kind of method that is used to prepare described hydrogenation NiMn based alloy magnetic property material, said method comprising the steps of:
1) presses Ni xMn yM zChemical formula batching, wherein M, x, y and z in the claim 1 definition;
2) raw material for preparing in the step 1) is put into arc furnace, vacuumize, clean furnace chamber and charge into argon gas to the 0.5-1.5 atmospheric pressure, the electric arc starting the arc, each alloy pig melt back 1-6 time with argon gas;
3) through step 2) melted alloy pig is under 600-1000 degree centigrade, and vacuum annealing with cooling off in stove cooling or quench liquid nitrogen or the water, has L2 thereby prepare afterwards 1The Haas of structure is reined in (Heusler) type Ni xMn yM zSingle-phase sample; With
4) the single-phase sample of preparing in the step 3) is divided into piece or processes powder, put into hydrogen annealing, thereby prepare Ni xMn yM zH αHydride; Control the hydrogen content α in the alloy through regulating Hydrogen Vapor Pressure, annealing temperature and time therebetween, the scope of α in the claim 1 definition.
Preferably, the vacuum degree according to method of the present invention, said step 2) is less than 1 * 10 -2Pa, said purity of argon is greater than 99%; And/or
Vacuum degree described in the said step 3) vacuum annealing operation is less than 1 * 10 -3Pa; And/or
The powder that the said single-phase sample of said step 4) is processed is a particle diameter less than 2 millimeters irregular powder, and the purity of hydrogen described in the said hydrogen annealing is greater than 99%.
Preferably, according to method of the present invention, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn and Ga is preferably greater than 98% weight greater than 95% weight, more preferably greater than 99% weight.
Preferably, the temperature of melting is 1000-2500 degree centigrade according to method of the present invention, said step 2).
Preferably, according to method of the present invention, the annealing time in the said step 3) is 30 minutes to 30 days.
Preferably, according to method of the present invention, the Hydrogen Vapor Pressure in the said step 4) is the 0-100 atmospheric pressure, and annealing temperature is 0-600 degree centigrade, and annealing time is 1 minute to 30 days.
On the one hand, the present invention provides a kind of magnetic refrigeration machine again, and said refrigeration machine comprises foregoing hydrogenation NiMn based alloy magnetic property material.
Another aspect, the present invention provides the application of described hydrogenation NiMn based alloy magnetic property material in making refrigerating material.
The object of the invention also can be realized through following technical method:
On the one hand, the invention provides a kind of hydrogenation NiMn base Heusler alloy magnetic refrigeration material, the chemical general formula of said material is Ni xMn yM zH α, inhale the preceding Ni of hydrogen xMn yM zAlloy has L2 1Haas is reined in (Heusler) type ordered structure, wherein:
M is selected from one or more in the following element: In, Sb, Sn and Ga;
The scope of x is: 0＜x≤60;
The scope of y is: 0＜y≤80, and satisfy y>=x/2;
The scope of z is: 0＜z≤50, and satisfy 90≤x+y+z≤110; With
The scope of α is: 0＜α≤50.0.
On the other hand, the invention provides a kind of method for preparing hydrogenation NiMn base Heusler alloy magnetic refrigeration material of the present invention, said method comprising the steps of:
1) presses Ni xMn yM zChemical formula batching, wherein:
M is selected from one or more in the following element: In, Sb, Sn and Ga;
The scope of x is: 0＜x≤60;
The scope of y is: 0＜y≤80, and satisfy y>=x/2; With
The scope of z is: 0＜z≤50, and satisfy 90≤x+y+z≤110;
2) raw material for preparing in the step 1) is put into arc furnace, be evacuated to less than 1 * 10 - 2Pa cleans furnace chamber 1-2 time with purity greater than 99% argon gas, charges into purity afterwards in the furnace chamber greater than argon gas to 0.5～1.5 atmospheric pressure of 99%, the electric arc starting the arc, each alloy spindle melt back 1-6 time;
3) through step 2) melted alloy pig under 600-1000 degree centigrade, in vacuum degree less than 1 * 10 -3Anneal in the vacuum of Pa, with in stove cooling or quench liquid nitrogen or the water, have L2 afterwards thereby prepare 1The Haas of structure is reined in the single-phase sample of (Heusler) type NixMnyMz; With
4) the single-phase sample of preparing in the step 3) is divided into piece or processes the irregular powder less than 2 millimeters, put into purity greater than 99% hydrogen annealing, thereby prepare Ni xMn yM zH αHydride; Control the hydrogen content α in the alloy through control Hydrogen Vapor Pressure, annealing temperature and time therebetween.
Preferably, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn, Ga is greater than 95wt%.
More preferably, the temperature of melting is 1000-2500 degree centigrade said step 2).
More preferably, the annealing time in the said step 3) is 30 minutes-30 days.
Further preferably, the Hydrogen Vapor Pressure in the said step 4) is the 0-100 atmospheric pressure, and annealing temperature is 0-600 degree centigrade, and annealing time is 1 minute-30 days.
Another aspect the invention provides the application of hydrogenation NiMn base Heusler alloy magnetic refrigeration material of the present invention in making the magnetic refrigerator device.
According to of the present invention one preferred embodiment, the preparation method of the hydrogenation NiMn base Heusler alloy magnetic refrigeration material with great magnetic entropy variation provided by the invention comprises the steps:
1) presses Ni xMn yM zThe chemical formula batching, the purity of material N i, Mn, In, Sb, Sn, Ga is greater than 95wt%;
2) raw material for preparing in the step 1) is put into arc furnace, be evacuated to less than 1 * 10 -2Pa; Clean furnace chamber 1-2 time with high-purity argon gas (purity is greater than 99%), charge into about high-purity argon gas (purity is greater than 99%) a to atmospheric pressure (0.5～1.5 atmospheric pressure) the electric arc starting the arc afterwards in the furnace chamber; Each alloy spindle melt back 1-6 time, smelting temperature is 1000-2500 degree centigrade;
3) through step 2) (vacuum degree is less than 1 * 10 in 600-1000 degree centigrade of following vacuum for melted alloy pig -3Pa) annealing is 30 minutes-30 days in, with in stove cooling or quench liquid nitrogen or the water, has L2 thereby prepare afterwards 1The Haas of structure is reined in (Heusler) type Ni xMn yM zSingle-phase sample;
4) the single-phase sample of preparing in the step 3) is divided into piece or does into irregular powder (less than 2 millimeters), put into high-purity hydrogen (purity is greater than 99%) annealing, thereby prepare Ni xMn yM zH αHydride is controlled the hydrogen content α in the alloy through control Hydrogen Vapor Pressure, annealing temperature and time therebetween, and wherein, the Hydrogen Vapor Pressure scope is the 0-100 atmospheric pressure, and annealing temperature is 0-600 degree centigrade, and annealing time is 1 minute-30 days.
Compared with prior art, advantage of the present invention is:
1) the present invention has prepared a kind of hydrogenation NiMn base Heusler alloy magnetic refrigeration material with great magnetic entropy variation, i.e. NixMnyMzH α compound.Through regulating hydrogen content, the Ma Shi phase transition temperature is adjustable on a large scale in the 150K-350K interval, and magnetic entropy luffing degree is higher than Gd, is a kind of desirable magnetic refrigerating material that is suitable for high temperature and even room temperature district.
2) method for preparing hydrogenation NiMn base Heusler alloy magnetic refrigeration material provided by the invention, employed raw material are transition group metallic element, do not contain rare earth, the preparation process is friendly, nontoxic and have heat conduction good, cheap, be prone to advantage such as preparation.
Description of drawings
Below, specify embodiments of the invention in conjunction with accompanying drawing, wherein:
Fig. 1 is Ni in the preparation process in the embodiment of the invention 1 51Mn 32.4In 16.6X x ray diffraction (XRD) spectral line of gathering under the alloy room temperature can find that sample presents L2 1Structure is Ovshinsky cube phase under the room temperature, and wherein the early process of the splitting at (220) peak and martensitic phase is relevant.The Ma Shi phase transition temperature (255K) of this system is very near from room temperature;
Fig. 2 is the Ni of preparation in the embodiment of the invention 1 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2At different magnetic field (0.05T, pyromagnetic (M-T) curve under 5T).Can find Ni 51Mn 32.4In 16.6Alloy and Ni 51Mn 32.4In 16.6H 5.2The Ma Shi phase transition temperature of hydride lays respectively at 255K and 226K, and the introducing of H atom makes the Ma Shi phase transition temperature move nearly 30K to low temperature.We find simultaneously, and magnetic field can promote the Ma Shi phase transition temperature and move Ni to low temperature in the alloy 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2The Ma Shi phase transition temperature move to low temperature with the speed of 4.8K/T with 4.2 respectively;
Fig. 3 is Ni 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2Magnetization curve under the different temperatures.The temperature step-length is 2K, and magnetization curve is all rising measurement after the match.Two samples all show the change magnetic transition behavior of field drives;
Fig. 4 is Ni 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2Magnetic entropy becomes the dependence of Δ S to temperature under different magnetic field.According to Maxwell relation, the magnetic entropy that can be calculated under different magnetic field, the different temperatures by the magnetization curve data among Fig. 3 becomes Δ S.Can find Ni 51Mn 32.4In 16.6H 5.2Hydride and Ni 51Mn 32.4In 16.6Compare, magnetic entropy becomes the position at peak and has moved 27K to low temperature, though magnetic entropy change Δ S amplitude drops to 13.0J/kgK from 17.0J/kgK under the 5T magnetic field, the halfwidth that magnetic entropy becomes the peak has been increased to 23K from 17K, is more conducive to the needs of Ericsson type magnetic refrigerator device;
Fig. 5 is Ni in the preparation process in the embodiment of the invention 2 51Mn 32.8In 16.2X x ray diffraction (XRD) spectral line of gathering under the alloy room temperature can find that sample presents L2 1Structure is Ovshinsky cube phase under the room temperature, and wherein the early process of the splitting at (220) peak and martensitic phase is relevant.The Ma Shi phase transition temperature (259K) of this system is very near from room temperature;
Fig. 6 is the Ni of preparation in the embodiment of the invention 2 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4At different magnetic field (0.05T, pyromagnetic (M-T) curve under 5T).Can find Ni 51Mn 32.8In 16.2Alloy and Ni 51Mn 32.8In 16.2H 1.4The Ma Shi phase transition temperature of hydride lays respectively at 259K and 250K, and the introducing of H atom makes the Ma Shi phase transition temperature move 9K to low temperature.We find simultaneously, and magnetic field can promote the Ma Shi phase transition temperature and move Ni to low temperature in the alloy 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4The Ma Shi phase transition temperature move to low temperature with the speed of 4.2K/T with 3.4 respectively;
Fig. 7 is Ni 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4Magnetization curve under the different temperatures.The temperature step-length is 2K, and magnetization curve is all rising measurement after the match.Two samples all show the change magnetic transition behavior of field drives; With
Fig. 8 is Ni 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4Magnetic entropy becomes the dependence of AS to temperature under different magnetic field.According to Maxwell relation, the magnetic entropy that can be calculated under different magnetic field, the different temperatures by the magnetization curve data among Fig. 7 becomes AS.Can find Ni 51Mn 32.8In 16.2H 1.4Hydride and Ni 51Mn 32.8In 16.2Compare, magnetic entropy becomes the position at peak and has moved 8K to low temperature, though magnetic entropy change AS amplitude drops to 17.4J/kgK from 19.2J/kgK under the 5T magnetic field, the halfwidth that magnetic entropy becomes the peak has been increased to 21K from 17K, is more conducive to the needs of Ericsson type magnetic refrigerator device.
Embodiment
The concrete embodiment of following reference explains the present invention.It will be appreciated by those skilled in the art that these embodiment only are used to explain the object of the invention, the scope that it does not limit the present invention in any way.
Embodiment 1 preparation Ni 51 Mn 32.4 In 16.6 H 3 Hydride
Present embodiment provides by chemical formula and prepares Ni 51Mn 32.4In 16.6H 5.2The instantiation of hydride, concrete technology is:
1) at first presses chemical formula Ni 51Mn 32.4In 16.6Batching, the purity of material N i, Mn, In is respectively 99.99wt%, 99.9wt%, 99.99wt%.
2) Ni that step 1) is prepared, Mn, In raw material are put into arc furnace, are evacuated to 2 * 10 -3Pa; Using purity is that 99.996% high-purity argon gas cleans furnace chamber 2 times, and charging into purity afterwards in the furnace chamber is 99.996% high-purity argon gas to an atmospheric pressure, the electric arc starting the arc; Each alloy spindle melt back 4 times; Smelting temperature is 2000 degrees centigrade, and after melting finished, cooling obtained cast alloy in the copper crucible.
3) with step 2) in the cast alloy ingot for preparing wrap with molybdenum foil respectively, be sealed in high vacuum (1 * 10 -4Pa) in the quartz ampoule, annealed 24 hours down, break the quartz ampoule ice water quenching, obtain to have L2 at 900 degrees centigrade 1The Haas of structure is reined in (Heusler) type Ni 51Mn 32.4In 16.6Single-phase sample.
(Rigaku company produces, model: RINT2400) measured room temperature X-ray diffraction (XRD) collection of illustrative plates of sample, the result shows Ni to utilize Cu target X-ray diffractometer 51Mn 32.4In 16.6Sample is L2 1Structure is a cube Ovshinsky phase under the room temperature.Fig. 1 illustrates Ni 51Mn 32.4In 16.6XRD spectral line under the alloy room temperature.
With the irregular powder of preparing in the step 3) of single-phase sample knock (less than 1 millimeter), to put into purity and be 99.99% high-purity hydrogen and anneal, annealing temperature is 250 degrees centigrade, and Hydrogen Vapor Pressure is 50 atmospheric pressure, and the annealing time in hydrogen is 60 minutes.After annealing finished, sample was quenched into 20 degrees centigrade from 250 degrees centigrade in hydrogen atmosphere.Use PCT ability meter (this equipment is available from Iron and Steel Research Geueral Inst) therebetween, the hydrogen of working sample.Analyze through PCT, sample component is Ni 51Mn 32.4In 16.6H 5.2
In superconductive quantum interference magnetometer (SQUID, trade name: superconductive quantum interference magnetometer, manufacturer's name: Quantum Design, USA, marque: MPMS-7) go up mensuration Ni 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2Different magnetic field (0.05T, pyromagnetic (M-T) curve under 5T), as shown in Figure 2, can find Ni 51Mn 32.4In 16.6Alloy and Ni 51Mn 32.4In 16.6H 5.2The Ma Shi phase transition temperature of hydride lays respectively at 255K and 226K, and the introducing of H atom makes the Ma Shi phase transition temperature move nearly 30K to low temperature.We find simultaneously, and magnetic field can promote the Ma Shi phase transition temperature and move Ni to low temperature in the alloy 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2The Ma Shi phase transition temperature move to low temperature with the speed of 4.8K/T with 4.2 respectively.
On SQUID, measured Ni 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2Magnetization curve under the different temperatures is shown in Fig. 3.
According to Maxwell relation: Δ S ( T , H ) = S ( T , H ) - S ( T , 0 ) = ∫ 0 H ( ∂ M ∂ T ) H DH , Can become Δ S from isothermal magnetization curve calculation magnetic entropy.Fig. 4 illustrates Ni 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2Δ S is to the dependence of temperature under different magnetic field.Can find Ni 51Mn 32.4In 16.6H 5.2Hydride and Ni 51Mn 32.4In 16.6Compare, magnetic entropy becomes the position at peak and has moved 27K to low temperature, though magnetic entropy change Δ S amplitude drops to 13.0J/kgK from 17.0J/kgK under the 5T magnetic field, the halfwidth that magnetic entropy becomes the peak has been increased to 23K from 17K, is more conducive to the needs of Ericsson type magnetic refrigerator device.Ni 51Mn 32.4In 16.6Alloy and hydride Ni thereof 51Mn 32.4In 16.6H 5.2Magnetic entropy luffing degree all be higher than Gd.Ni 51Mn 32.4In 16.6H 5.2It is 13.0J/kgK that the magnetic entropy of hydride under the 0-5T changes of magnetic field becomes peak value, and halfwidth is 23K and the Ni that does not inhale hydrogen 51Mn 32.4In 16.6Compare to low temperature and moved 27K.So considerable magnetic entropy luffing degree and temperature are striden for practical application very attractively in the intermetallic compound that does not contain rare earth, are suitable for the needs of Ericsson type magnetic refrigerator device.
Comparative example: rare metal Gd
Select typical room temperature magnetic refrigerating material for use---99.9% rare metal Gd is as comparative example.On SQUID, recording its Curie temperature is 293K, and under the 0-5T changes of magnetic field, the magnetic entropy at the Curie temperature place becomes 9.8J/kgK.
Embodiment 2 preparation Ni 51 Mn 32.8 In 16.2 H 1.4 Hydride
Present embodiment provides by chemical formula and prepares Ni 51Mn 32.8In 16.2H 1.4The instantiation of hydride, concrete technology is:
1) at first presses chemical formula Ni 51Mn 32.8In 16.2Batching, the purity of material N i, Mn, In is respectively 99.99wt%, 99.9wt%, 99.99wt%.
2) Ni that step 1) is prepared, Mn, In raw material are put into arc furnace, are evacuated to 2 * 10 -3Pa, using purity is that 99.996% high-purity argon gas cleans furnace chamber 2 times, charges into purity afterwards in the furnace chamber and be high-purity argon gas to an atmospheric pressure of 99.996%.The electric arc starting the arc, each alloy spindle melt back 4 times, smelting temperature is 2000 degrees centigrade.After melting finished, cooling obtained cast alloy in the copper crucible.
3) with step 2) in the cast alloy ingot for preparing wrap with molybdenum foil respectively, be sealed in high vacuum and (in 1 * 10-4Pa) quartz ampoule,, break the quartz ampoule ice water quenching, obtain to have L2 900 degrees centigrade of annealing 24 hours down 1The Haas of structure is reined in (Heusler) type Ni 51Mn 32.4In 16.6Single-phase sample.
(Rigaku company produces, model: RINT2400) measured room temperature X-ray diffraction (XRD) collection of illustrative plates of sample, the result shows Ni to utilize Cu target X-ray diffractometer 51Mn 32.8In 16.2Sample is L2 1Structure is a cube Ovshinsky phase under the room temperature.Fig. 5 illustrates Ni 51Mn 32.8In 16.2XRD spectral line under the alloy room temperature.
4), put into purity and be ultra-pure hydrogen annealing of 99.99% with the irregular powder of preparing in the step 3) of single-phase sample knock (less than 1 millimeter).Annealing temperature is 250 degrees centigrade, and Hydrogen Vapor Pressure is 50 atmospheric pressure, and the annealing time in hydrogen is 20 minutes.After annealing finished, sample was quenched into 20 degrees centigrade from 250 degrees centigrade in hydrogen atmosphere.Use PCT ability meter (this equipment is available from Iron and Steel Research Geueral Inst) therebetween, the hydrogen of working sample.Analyze through PCT, sample component is Ni 51Mn 32.8Inl 6.2H 1.4
In superconductive quantum interference magnetometer (SQUID, trade name: superconductive quantum interference magnetometer, manufacturer's name: Quantum Design, USA, marque: MPMS-7) go up mensuration Ni 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4Different magnetic field (0.05T, pyromagnetic (M-T) curve under 5T), as shown in Figure 6, can find Ni 51Mn 32.8In 16.2Alloy and Ni 51Mn 32.8In 16.2H 1.4The Ma Shi phase transition temperature of hydride lays respectively at 259K and 250K, and the introducing of H atom makes the Ma Shi phase transition temperature move 9K to low temperature.We find simultaneously, and magnetic field can promote the Ma Shi phase transition temperature and move Ni to low temperature in the alloy 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4The Ma Shi phase transition temperature move to low temperature with the speed of 4.2K/T with 3.4 respectively.
On SQUID, measured Ni 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4Magnetization curve under the different temperatures is shown in Fig. 7.
According to Maxwell relation: Δ S ( T , H ) = S ( T , H ) - S ( T , 0 ) = ∫ 0 H ( ∂ M ∂ T ) H DH , Can become Δ S from isothermal magnetization curve calculation magnetic entropy.Fig. 8 illustrates Ni 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4Δ S is to the dependence of temperature under different magnetic field.Can find Ni 51Mn 32.8In 16.2H 1.4Hydride and Ni 51Mn 32.8In 16.2Compare, magnetic entropy becomes the position at peak and has moved 8K to low temperature, though magnetic entropy change Δ S amplitude drops to 17.4J/kgK from 19.2J/kgK under the 5T magnetic field, the halfwidth that magnetic entropy becomes the peak has been increased to 21K from 17K, is more conducive to the needs of Ericsson type magnetic refrigerator device.Ni 51Mn 32.8In 16.2Alloy and hydride Ni thereof 51Mn 32.8In 16.2H 1.4Magnetic entropy luffing degree all be higher than Gd.Ni 51Mn 32.8In 16.2H 1.4It is 17.4J/kgK that the magnetic entropy of hydride under the 0-5T changes of magnetic field becomes peak value, and halfwidth is 21K and the Ni that does not inhale hydrogen 51Mn 32.8In 16.2Compare to low temperature and moved 8K.So considerable magnetic entropy luffing degree and temperature are striden for practical application very attractively in the intermetallic compound that does not contain rare earth, are suitable for the needs of Ericsson type magnetic refrigerator device.
Below described the present invention in detail with reference to embodiment, to those skilled in the art, should be understood that, above-mentioned embodiment should not be understood that to limit scope of the present invention.Therefore, can make various changes and improvement to embodiment of the present invention without departing from the spirit and scope of the present invention.

Claims (15)

1. a hydrogenation NiMn based alloy magnetic property material is characterized in that the chemical general formula of said material is Ni xMn yM zH α, inhale the preceding Ni of hydrogen xMn yM zAlloy has L2 1Haas is reined in (Heusler) type ordered structure, wherein:
M is selected from one or more in the following element: In, Sb, Sn and Ga;
The scope of x is: 0＜x≤60;
The scope of y is: 0＜y≤80, and satisfy y>=x/2;
The scope of z is: 0＜z≤50, and satisfy 90≤x+y+z≤110; And
The scope of α is: 0＜α≤50.0.
2. hydrogenation NiMn based alloy magnetic property material as claimed in claim 1 is characterized in that the magnetic entropy variate of said magnetic material under the 0-5T changes of magnetic field is: 5.0J/kgK-50.0J/kgK, transition temperature area is positioned at 150K-350K.
3. a method that is used to prepare claim 1 or 2 described hydrogenation NiMn based alloy magnetic property materials is characterized in that, said method comprising the steps of:
1) presses Ni xMn yM zChemical formula batching, wherein M, x, y and z in the claim 1 definition;
2) raw material for preparing in the step 1) is put into arc furnace, vacuumize, clean furnace chamber and charge into argon gas to the 0.5-1.5 atmospheric pressure, the electric arc starting the arc, each alloy pig melt back 1-6 time with argon gas;
3) through step 2) melted alloy pig is under 600-1000 degree centigrade, and vacuum annealing with cooling off in stove cooling or quench liquid nitrogen or the water, has L2 thereby prepare afterwards 1The Haas of structure is reined in (Heusler) type Ni xMn yM zSingle-phase sample; With
4) the single-phase sample of preparing in the step 3) is divided into piece or processes powder, put into hydrogen annealing, thereby prepare Ni xMn yM zH αHydride; Control the hydrogen content α in the alloy through regulating Hydrogen Vapor Pressure, annealing temperature and time therebetween, the scope of α in the claim 1 definition.
4. method according to claim 3 is characterized in that,
Said step 2) vacuum degree described in is less than 1 * 10 -2Pa, said purity of argon is greater than 99%; And/or
Vacuum degree described in the said step 3) vacuum annealing operation is less than 1 * 10 -3Pa; And/or
The powder that the said single-phase sample of said step 4) is processed is a particle diameter less than 2 millimeters irregular powder, and the purity of hydrogen described in the said hydrogen annealing is greater than 99%.
5. method according to claim 3 is characterized in that, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn and Ga is greater than 95% weight.
6. method according to claim 5 is characterized in that, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn and Ga is greater than 98% weight.
7. method according to claim 5 is characterized in that, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn and Ga is greater than 99% weight.
8. method according to claim 4 is characterized in that, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn and Ga is greater than 95% weight.
9. method according to claim 8 is characterized in that, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn and Ga is greater than 98% weight.
10. method according to claim 8 is characterized in that, the purity of the employed material N i of said step 1), Mn, In, Sb, Sn and Ga is greater than 99% weight.
11., it is characterized in that said step 2 according to each described method among the claim 3-10) in the temperature of melting be 1000-2500 degree centigrade.
12., it is characterized in that the annealing time in the said step 3) is 30 minutes to 30 days according to each described method among the claim 3-10.
13., it is characterized in that the Hydrogen Vapor Pressure in the said step 4) is the 0-100 atmospheric pressure according to each described method among the claim 3-10, annealing temperature is 0-600 degree centigrade, annealing time is 1 minute to 30 days.
14. a magnetic refrigeration machine is characterized in that, said refrigeration machine comprises claim 1 or 2 described hydrogenation NiMn based alloy magnetic property materials.
15. claim 1 or the 2 described hydrogenation NiMn based alloy magnetic property materials application in making refrigerating material.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104630568A (en) * 2013-11-07 2015-05-20 中国科学院物理研究所 MnCoGe based ferromagnetic martensite phase-change material, preparation method and applications thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103122441B (en) * 2013-02-27 2014-12-31 上海大学 Method for expanding magnetic refrigeration temperature area of Ni-Mn-based material
CN104559943A (en) * 2013-10-09 2015-04-29 中国科学院宁波材料技术与工程研究所 Crystalline-state magnetic refrigeration metal material and preparation method thereof
CN105154802B (en) * 2015-10-16 2017-01-04 哈尔滨工业大学 A kind of method separating out the second phase in effective suppression Ni-Mn-Sn-Fe alloy
CN105755346A (en) * 2016-04-15 2016-07-13 西安交通大学 Ni-Mn-In room-temperature magnetic refrigeration material and preparation method thereof
CN112940687B (en) * 2021-01-29 2022-05-06 中国科学院合肥物质科学研究院 Pressure-driven refrigeration method based on solid-liquid phase change material

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101155938A (en) * 2005-04-05 2008-04-02 日立金属株式会社 Magnetic alloy and method for producing same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101155938A (en) * 2005-04-05 2008-04-02 日立金属株式会社 Magnetic alloy and method for producing same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
敬超 等.《哈斯勒合金Ni50Mn35In15的马氏体相变及其磁热效应》.《物理学报》.2008,第57卷(第7期),4450-4455. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104630568A (en) * 2013-11-07 2015-05-20 中国科学院物理研究所 MnCoGe based ferromagnetic martensite phase-change material, preparation method and applications thereof
CN104630568B (en) * 2013-11-07 2017-06-06 中国科学院物理研究所 A kind of ferromagnetic Martensitic Transformation Materials of MnCoGe bases and its production and use

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