CN1584082A - Compounds with large magnetic entropy changes and their preparation - Google Patents
Compounds with large magnetic entropy changes and their preparation Download PDFInfo
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- CN1584082A CN1584082A CN 200410009188 CN200410009188A CN1584082A CN 1584082 A CN1584082 A CN 1584082A CN 200410009188 CN200410009188 CN 200410009188 CN 200410009188 A CN200410009188 A CN 200410009188A CN 1584082 A CN1584082 A CN 1584082A
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Abstract
A big magnetic entropy variation compound and its preparing method are disclosed. It consists of NixMnyGaz (50 is less than or equal to x is less than or equal to 56, 22 is less than or equal to y is less than or equal to 30, 22 is less than or equal to z is less than or equal to 30), with martensite and magnetic conversion under -80deg.C- 80deg.C. When 53 is less than or equal to x is less than or equal to 56, 19 is less than or equal to y is less than or equal to 22, 23 is less than or equal to z is less than or equal to 26, it make austenite phase-transition temperature range and magnetic transition temperature between -20deg.C-80 deg.C by component regulation. It is prepared by proportioning nickel, mangan and gallium etc. raw materials by chemical component, laying vacuum arc furnace or inducing furnace, vacuum pumping up to 10 to the power -1 , passing argon, smelting and cooling to obtain uniform compound, homogeneous treating the compound for 24-120 hrs under 900-1100deg.C, and annealing for 12-72 hrs under 600-800deg.C. Its advantages include simple process, big magnetic entropy and regulating temperature.
Description
Technical field
The invention belongs to technical field of magnetic, a kind of great magnetic entropy variation compound and preparation method thereof particularly is provided.
Background technology
Magnetic refrigeration is exactly to utilize magnetic field, the degree of order of the spin orientation spatial distribution of refrigeration work material atom is changed, and causes that magnetic entropy becomes to realize.When the cooling substance adiabatic demagnetization, temperature reduces; When the cooling substance adiabatic magnetization, temperature raises.Also we can say, when the degaussing of cooling substance isothermal, absorb heat; During isothermal magnetization, emit heat, magnetothermal effect that Here it is also claims magnetic calorie effect to be called for short magneto-caloric effect
Magnetic entropy is the sign of magnetic order degree, and magnetic substance will cause magnetic entropy to change as long as its ordered magnetic state changes, and causes magnetothermal effect.For ferromagnetic material, the maximum value that magnetic entropy becomes occurs in the Curie temperature place.Utilizing the magnetothermal effect of magnetic substance to reach the refrigeration purpose, is the target that people pursue for a long time.The magnetic refrigeration is compared with conventional gas compression refrigeration technology, has the refrigerating efficiency height, and energy consumption is little, and volume is little, and noise is little, with advantages of environment protection.For a long time, simple substance rare earth metal gadolinium is considered to be near the classic magnetic refrigeration working substance of room temperature, but because magnetic entropy becomes high not enough, thereby restricted room temperature and the practical application of above warm area magnetic refrigerating.1997, the Pecharsky of U.S.'s Ames Lab, people such as Gschneidner have reported the GdSiGe compound, its the highest magnetic entropy becomes much larger than gadolinium (Phys.Rev.Lett, 78 (1997) 4494), but compound requires height and indissoluble to material purity, and preparation technology is complicated.The Hu Fengxia of physics institute of China Chinese Academy of Sciences, LaFeSi compound (Phys.Rev.B, 64 of people such as Shen Baogen report, (2001) 012409), its the highest magnetic entropy becomes also much larger than gadolinium, and suitable with GdSiGe, and existing problems are that preparation technology's more complicated is difficult to scale operation.
Nickel manganese gallium (NiMnGa) compound as a kind of shape-memory material be studied more.This kind compound has the austenite phase under comparatively high temps, have martensitic phase under the lesser temps.That is to say, when NiMnGa when comparatively high temps cools to lesser temps, compound changes martensitic phase into mutually from austenite, this phase transition process is called martensitic transformation; On the other hand, along with the rising of temperature, compound can take place again to change the austenite phase into from martensitic phase, and this phase transition process is called austenite phase transformation, i.e. the inverse process of martensitic transformation.In this compound phase-variable process, martensitic transformation exists initial and the finishing temperature point, is called as M respectively
sPoint and M
fThe point.Equally, the initial and point of ending of austenitic transformation is called as A respectively
sAnd A
fThe point.
Summary of the invention
The object of the present invention is to provide a kind of great magnetic entropy variation compound and preparation method thereof, simplified preparation technology, be suitable for industrial application.
The chemical constitution of The compounds of this invention is Ni
xMn
yGa
z, 50≤x≤56,18≤y≤25,22≤z≤30 wherein), electron density (e/a) in 7.38～8.22 scopes (electron density is calculated referring to Scripta Materialia, 40 (5), (1999), 523),, have martensitic transformation and magnetic transformation-80 ℃～80 ℃ temperature ranges.Have following characteristics:
This compound has big magnetic entropy and becomes in certain temperature range, and the magnetic entropy variate provides the size in magnetic field to change with the external world, and when 0～2T magnetic field, magnetic entropy becomes 0～16J/kgK.And can regulate martensite transformation temperature scope and Curie-point temperature by regulating chemical composition.When 53≤x≤56,19≤y≤22,23≤z≤26 o'clock, and electron density is in 7.59～7.8 scopes, can make martensite in austenite phase transformation temperature range and magnetic transition temperature are controlled at-20 ℃～80 ℃ scopes by regulating composition, and can make the magnetic transition temperature point in this transformation temperature scope.Simultaneously, the magnetic entropy variate provides the size in magnetic field to change with the external world, and when 0～2T magnetic field, magnetic entropy becomes 0～16J/kgK.Particularly, when regulating Curie temperature when martensite is in austenite begins the transition temperature interval, the phase transition process of compound arrives the austenitic transformation of paramagnetism for ferromegnetism martensite, and this kind composition easily obtains bigger magnetic moisture in the soil and becomes.
The present invention can adopt single or more than one following element: Fe, Co Ni is substituted, the amount that substitutes is calculated with atomic percent, in＜3% scope; Can adopt single or more than one following element: Fe, Co Mn is substituted, the amount that substitutes is calculated with atomic percent, in＜3% scope; Can adopt single or more than one following element: Al, Si, Ge Ga is substituted, the amount that substitutes is calculated with atomic percent, in＜3% scope.
Involved in the present inventionly be to compounds process for production thereof:
With nickel, manganese, starting material such as gallium carry out proportioning by chemical composition, put into vacuum arc fumace, in induction furnace or other smelting furnace, are evacuated to more than the 10-1, feed argon gas, obtain the compound of uniform ingredients after the melt back cooling.The compound that melting obtains was handled 24～120 hours 900～1100 ℃ of following homogenizing, annealed 12～72 hours down at 600～800 ℃ then.For preventing the sample oxidation, homogenizing is handled and annealing process can be carried out under vacuum or argon shield.Through the compound that above-mentioned steps makes, its magnetic entropy variate is apparently higher than the rare earth metal gadolinium.
Method of the present invention also can be handled and obtain amorphous, and is nanocrystalline, and monocrystalline has big magnetic entropy and becomes, and when 0～2T magnetic field, magnetic entropy becomes 0～16J/kgK.Of the present inventionly can be processed into spherical, powdery, sheet, have big magnetic entropy and become, when 0～2T magnetic field, magnetic entropy becomes 0～16J/kgK.
The invention has the advantages that manufacturing process is simple, it is big that magnetic entropy becomes, and Curie temperature is adjustable, can be widely used in magnetic refrigerator.
Description of drawings
Fig. 1 is Ni of the present invention
54.9Mn
20.5Ga
24.6X ray diffracting spectrum at room temperature.Wherein, X-coordinate is a diffraction angle, and ordinate zou is an intensity.
Fig. 2 is Ni of the present invention
54.9Mn
20.5Ga
24.6Rise isothermal magnetzation curve under the magnetic field.Wherein, X-coordinate is a magneticstrength, and ordinate zou is the specific magnetising moment.
Fig. 3 is Ni of the present invention
54.9Mn
20.5Ga
24.61 and 2T magnetic field under magnetic entropy become with the variation of temperature curve.Wherein, X-coordinate is a temperature, and ordinate zou is that magnetic entropy becomes.
Fig. 4 is Ni of the present invention
55.5Mn
19.8Ga
24.7X ray diffracting spectrum at room temperature.Wherein, X-coordinate is a diffraction angle, and ordinate zou is an intensity.
Fig. 5 is Ni of the present invention
55.5Mn
19.8Ga
24.7Rise isothermal magnetzation curve under the magnetic field.Wherein, X-coordinate is a magneticstrength, and ordinate zou is the specific magnetising moment.
Fig. 6 is Ni of the present invention
55.5Mn
19.8Ga
24.71 and 2T magnetic field under magnetic entropy become with the variation of temperature curve.Wherein, X-coordinate is a temperature, and ordinate zou is that magnetic entropy becomes.
Embodiment
Embodiment 1:
With nickel, manganese, starting material such as gallium are by chemical composition Ni
51.5Mn
22.7Ga
25.8Proportioning (electron density is 7.513) is put into vacuum arc fumace, in induction furnace or other smelting furnace, is evacuated to 10
-1Or more than, feed argon gas, obtain the compound of uniform ingredients after the melt back cooling.The compound that melting obtains was handled 72 hours 900 ℃ of following homogenizing, annealed 60 hours down at 700 ℃ then.For preventing the sample oxidation, homogenizing is handled and annealing process can be carried out under vacuum or argon shield.Sample proves non-modulation square structure through X-ray diffraction, belongs to martensitic phase.Adopting SQUID to measure magnetzation curve varies with temperature.Through the compound that above-mentioned steps makes, Curie temperature is-77 ℃.Calculation result shows that under 1T magnetic field, magnetic entropy becomes 4.6J/kgK.
Embodiment 2:
With nickel, manganese, starting material such as gallium are by chemical composition Ni
54.9Mn
20.5Ga
24.6Proportioning (electron density is 7.663) is put into vacuum arc fumace, in induction furnace or other smelting furnace, is evacuated to 10
-1Or more than, feed argon gas, obtain the compound of uniform ingredients after the melt back cooling.The compound that melting obtains was handled 48 hours 1050 ℃ of following homogenizing, annealed 72 hours down at 650 ℃ then.For preventing the sample oxidation, homogenizing is handled and annealing process can be carried out under vacuum or argon shield.Zhi Bei sample proves non-modulation square structure through X-ray diffraction like this, belongs to the martensitic phase (see figure 1).Adopt vibrating sample magnetometer LakeShore-7410 to measure near the isothermal magnetization curve (see figure 2) of transformation temperature.Through the compound that above-mentioned steps makes, Curie temperature is 68 ℃, austenitic transformation starting temperature A
sBe 61 ℃, final temperature A
fBe 74 ℃, that is to say that Curie temperature has dropped on martensite in the austenite transformation temperature scope.Calculation result shows that under 1T magnetic field, magnetic entropy becomes 7J/kgK, 2T after the match its magnetic entropy variate be 13.1J/kgK, apparently higher than rare earth metal gadolinium (see figure 3).
Embodiment 3:
With nickel, manganese, starting material such as gallium are by chemical composition Ni
55.5Mn
19.8Ga
24.7Proportioning (electron density is 7.677) is put into vacuum arc fumace, in induction furnace or other smelting furnace, be evacuated to 10-1 or more than, feed argon gas, obtain the compound of uniform ingredients after the melt back cooling.The compound that melting obtains was handled 72 hours 950 ℃ of following homogenizing, annealed 48 hours down at 750 ℃ then.For preventing the sample oxidation, homogenizing is handled and annealing process can be carried out under vacuum or argon shield.Zhi Bei sample proves non-modulation square structure through X-ray diffraction like this, belongs to the martensitic phase (see figure 4).Adopt vibrating sample magnetometer LakeShore-7410 to measure near the isothermal magnetization curve (see figure 5) of transformation temperature.Through the compound that above-mentioned steps makes, Curie temperature is 51 ℃.Calculation result shows that under 1T magnetic field, magnetic entropy becomes 7.6J/kgK, 2T after the match its magnetic entropy variate be 15.3J/kgK, apparently higher than rare earth metal gadolinium (see figure 6).
Claims (6)
1, a kind of great magnetic entropy variation compound is characterized in that: chemical constitution is Ni
xMn
yGa
z, wherein 50≤x≤56,22≤y≤30,22≤z≤30 in-80 ℃～80 ℃ temperature ranges, have martensitic transformation and magnetic transformation.
2, according to the described compound of claim 1, it is characterized in that: electron density (e/a) is in 7.38～8.22 scopes.
3, according to the described compound of claim 1, it is characterized in that: the magnetic entropy variate provides the size in magnetic field to change with the external world, and when 0～2T magnetic field, magnetic entropy becomes 0～16J/kgK.
4, according to the described compound of claim 1, it is characterized in that: when 53≤x≤56,19≤y≤22,23≤z≤26 o'clock, and electron density is in 7.59～7.8 scopes, can make martensite in austenite transformation temperature and magnetic transition temperature are controlled at-20 ℃～80 ℃ scopes by regulating composition, and can make the magnetic transition temperature point at martensite in the austenite transformation temperature scope.
5, according to the described compound of claim 1, it is characterized in that: can adopt single or more than one following element: Fe, Co Ni is substituted, the amount that substitutes is calculated with atomic percent, in＜3% scope; Can adopt single or more than one following element: Fe, Co Mn is substituted, the amount that substitutes is calculated with atomic percent, in＜3% scope; Can adopt single or more than one following element: Al, Si, Ge Ga is substituted, the amount that substitutes is calculated with atomic percent, in＜3% scope.
6, a kind of method for preparing the described compound of claim 1 is characterized in that: with nickel, and manganese, the gallium starting material carry out proportioning by chemical composition, put into vacuum arc fumace, in induction furnace or other smelting furnace, are evacuated to 10
-1More than, feed argon gas, obtain the compound of uniform ingredients after the melt back cooling; The compound that melting obtains was handled 24～120 hours 900～1100 ℃ of following homogenizing, annealed 12～72 hours down at 600～800 ℃ then, for preventing the sample oxidation, homogenizing is handled and annealing process is carried out under vacuum or argon shield.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228964A (en) * | 2011-06-21 | 2011-11-02 | 哈尔滨工业大学 | Method for preparing Ni-Mn-Ga ferromagnetic shape memory alloy continuous fibers by adopting spinning method |
| CN102764887A (en) * | 2012-08-02 | 2012-11-07 | 西安市嘉闻材料技术有限公司 | Method for preparing polymer-bonded magnetic refrigerating composite material |
| CN105390223A (en) * | 2015-10-28 | 2016-03-09 | 上海电力学院 | Room temperature magnetic refrigeration alloy material and preparation method therefor |
| CN106011713A (en) * | 2016-06-17 | 2016-10-12 | 哈尔滨工业大学 | Preparation method of nickel-manganese-gallium alloy microparticles high in refrigerating capacity |
| CN106148765A (en) * | 2015-04-07 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | Ni2feGa class stress refrigerating material and preparation method and application |
| CN106282865A (en) * | 2015-06-29 | 2017-01-04 | 中国科学院宁波材料技术与工程研究所 | The method of refrigeration temperature area when expansion primary magnetic phase change material is applied as magnetic cooling material |
| CN106917029A (en) * | 2017-04-13 | 2017-07-04 | 佛山市程显科技有限公司 | A kind of MM ' X Y metal composite functional materials and preparation method thereof |
| CN110004326A (en) * | 2018-01-05 | 2019-07-12 | 北京航空航天大学 | A kind of NiCuFeGa magnetic-structure Coupling phase-change alloy and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3881741B2 (en) * | 1997-03-19 | 2007-02-14 | Ｎｅｃトーキン株式会社 | NiMnGa alloy |
| CN1272464C (en) * | 2002-04-27 | 2006-08-30 | 艾默生电气（中国）投资有限公司 | Magnetic and heating treatment method to improve magnetically driven reversible strain property of polycrystalline Ni2 MnGa |
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2004
- 2004-06-09 CN CNB2004100091882A patent/CN1304615C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102228964B (en) * | 2011-06-21 | 2012-09-26 | 哈尔滨工业大学 | Method for preparing Ni-Mn-Ga ferromagnetic shape memory alloy continuous fibers by adopting spinning method |
| CN102228964A (en) * | 2011-06-21 | 2011-11-02 | 哈尔滨工业大学 | Method for preparing Ni-Mn-Ga ferromagnetic shape memory alloy continuous fibers by adopting spinning method |
| CN102764887A (en) * | 2012-08-02 | 2012-11-07 | 西安市嘉闻材料技术有限公司 | Method for preparing polymer-bonded magnetic refrigerating composite material |
| CN106148765A (en) * | 2015-04-07 | 2016-11-23 | 中国科学院宁波材料技术与工程研究所 | Ni2feGa class stress refrigerating material and preparation method and application |
| CN106148765B (en) * | 2015-04-07 | 2018-02-09 | 中国科学院宁波材料技术与工程研究所 | Ni2FeGa class stress refrigerating materials and preparation method and application |
| CN106282865A (en) * | 2015-06-29 | 2017-01-04 | 中国科学院宁波材料技术与工程研究所 | The method of refrigeration temperature area when expansion primary magnetic phase change material is applied as magnetic cooling material |
| CN106282865B (en) * | 2015-06-29 | 2017-11-10 | 中国科学院宁波材料技术与工程研究所 | The method for expanding refrigeration temperature area when primary magnetic phase change material is applied as magnetic cooling material |
| CN105390223A (en) * | 2015-10-28 | 2016-03-09 | 上海电力学院 | Room temperature magnetic refrigeration alloy material and preparation method therefor |
| CN105390223B (en) * | 2015-10-28 | 2018-08-28 | 上海电力学院 | A kind of room temperature magnetic refrigerating alloy material and preparation method |
| CN106011713A (en) * | 2016-06-17 | 2016-10-12 | 哈尔滨工业大学 | Preparation method of nickel-manganese-gallium alloy microparticles high in refrigerating capacity |
| CN106011713B (en) * | 2016-06-17 | 2018-02-16 | 哈尔滨工业大学 | A kind of preparation method of high refrigerating capacity nickel manganese gallium micron alloying pellet |
| CN106917029A (en) * | 2017-04-13 | 2017-07-04 | 佛山市程显科技有限公司 | A kind of MM ' X Y metal composite functional materials and preparation method thereof |
| CN106917029B (en) * | 2017-04-13 | 2018-08-21 | 佛山市程显科技有限公司 | A kind of ferromagnetic martensitic traoformation MM ' X-Y metal composite functional materials and preparation method thereof |
| CN110004326A (en) * | 2018-01-05 | 2019-07-12 | 北京航空航天大学 | A kind of NiCuFeGa magnetic-structure Coupling phase-change alloy and preparation method thereof |
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| CN1304615C (en) | 2007-03-14 |
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