CN103334043B - Magnetic alloy serving as magnetic refrigeration material - Google Patents
Magnetic alloy serving as magnetic refrigeration material Download PDFInfo
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- CN103334043B CN103334043B CN201310251161.3A CN201310251161A CN103334043B CN 103334043 B CN103334043 B CN 103334043B CN 201310251161 A CN201310251161 A CN 201310251161A CN 103334043 B CN103334043 B CN 103334043B
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Abstract
The invention discloses a magnetic alloy. The chemical general formula of the magnetic alloy is (Mn100-deltaCodelta) alphaNibetaGegamma, wherein alpha is more than or equal to 25 and less than or equal to 40, beta is more than or equal to 25 and less than or equal to 40, gamma is more than or equal to 25 and less than or equal to 40, alpha+beta+gamma is equal to 100, delta is more than 0 and less than 50, and alpha, beta, gamma and delta refer to the atomic percent content. The magnetic alloy has a huge magnetocaloric effect and high magnetic refrigeration efficiency and can stably operate in a wide temperature range temperature area by serving as a magnetic refrigeration working medium. The required raw materials Mn, Co, Ni and Ge are the conventional metal elements which are low in price, rich in reserves and easy to store. The material is simple and reliable in preparation process, high in process stability and easy to industrially produce. The provided magnetic material (Mn100-deltaCodelta) alphaNibetaGegamma with the huge magnetocaloric effect has excellent comprehensive performance and is an ideal Mn-based non-rare earth magnetic refrigeration candidate material.
Description
Technical field
The present invention relates to magnetic refrigerating material, particularly relate to a kind of magneticalloy that can be used as magnetic refrigerating material.
Background technology
Common magnetic refrigerating material has a kind of crystalline structure (hereinafter referred to as high-temperature-phase) at relatively high temperature, and spontaneously at relatively low temperatures becomes another crystalline structure (hereinafter referred to as low-temperature phase).When from higher greenhouse cooling to lower temperature, material is low-temperature phase from high-temperature phase-transitional.Conversely, from relatively low heating temperatures material, material can change high-temperature-phase into from low-temperature phase, and this contrary phase in version is called the reverse transformation of crystalline structure.
Usually, the material with this phase transformation is at extraneous physical condition, and under the effect as temperature, pressure or magnetic field, while causing crystalline structure phase transformation, also along with the change of magnetism of material, this is called magnetic-structure Coupling phenomenon.The change of structure can cause structure entropy to change.Meanwhile, the generation of structural phase transition also can bring the transformation of material magnetic states, thus produces the change of magnetic entropy.Because the entropy state of material changes, material can absorb or release of heat to external world, forms heat effect.When applying foreign field, material can issue magnetisation bullet at Magnetic Field-Induced to be changed or magnetic-structural transformation and the entropy state that produces magnetic order degree changes, and form the large magnetothermal effect of Magnetic control, environment generation heat exchange to external world, can be applied to solid-state magnetic Refrigeration Technique.
Magnetic Refrigeration Technique has the advantages such as environmental protection, noise are low, high-level efficiency, is the new technology of refrigerating industry and new development trend.1881, people found magnetothermal effect at the magnetic order of iron-unordered Curie temperature transition point first.After this, people start to attempt adopting the change of the magnetic entropy state before and after ferromagnetic substance magnetic phase transition to freeze to environment.1933, the people such as Giauque adopted paramagnetic ion salt working medium to carry out adiabatic demagnetization, obtain the extremely low temperature of 0.53K.In the development of more than 100 years, people have successively found a series of magnetic refrigerating material working medium.Wherein, be operated in the magnetic refrigerating material of near room temperature, Gd, Gd-Si-Ge, La-Fe-Si, Mn-Fe-P-As, Ni-Co-Mn-Sn etc. become the magnetic refrigerating material candidate working medium of better performances.
In recent years, because the material of magnetic-structure Coupling generation has the large change of structure entropy and magnetic entropy simultaneously, this kind of material becomes the emerging magnetic refrigerating material of a class, shows large magnetic refrigerant capacity.But, in the magnetic refrigerating material that these have developed, remain in many weak points.For these materials, magnetothermal effect is generally near 20J/kgK, and refrigeration capacity is limited; For rare earth compound refrigerating material, contained a high proportion of valuable rare earth metal makes application cost too high; In a lot of system, the heat effect direction that the heat effect of structure Entropy Changes and magnetic entropy become is contrary, counteracts effective heat effect; Further, the refrigeration work warm area of most of material is narrower, can only be operated in the warm area of any one Finite Width in low temperature, middle temperature or room temperature.For working temperature, there is Gradient distribution or the occasion changed greatly (when as larger in the temperature difference), can only combinationally use by adopting the magnetic refrigerating material belonging to differing materials system.And due to different material systems, required work system is different as externally-applied magnetic field, heat-transfer medium etc., for multiple differing materials system, just needs multiple work system, whole refrigeration system bulky complex can be caused like this, not easy to operate.These existing problems, hinder the practical working medium of ideal that existing magnetic refrigerating material becomes magnetic Refrigeration Technique.
Along with the development of novel material and refrigeration techniques, solid-state magnetic refrigeration more and more becomes New Refrigerating technology likely.Desirable magnetic refrigeration working substance still needs to be developed further, and the design of New Magnetic Field Controlled refrigerating material and discovery are the directions that people make great efforts.
Summary of the invention
One object of the present invention is, for one of above-mentioned defect existed in prior art, to provide a kind of new magneticalloy.Another object of the present invention is to provide a kind of magneticsubstance with large magnetothermal effect.Another object of the present invention is to provide a kind of magneticalloy that can regulate and control in larger composition and temperature range, the heat effect of the structure Entropy Changes of this magneticalloy is consistent with the heat effect that magnetic entropy becomes on suction heat release direction, its effective magnetic refrigerating efficiency is improved greatly, there is range of application more widely.
In order to realize object of the present invention, the invention provides a kind of magneticalloy, its chemical general formula is (Mn
100-δco
δ)
αni
βge
γ, wherein, 25≤α≤40,25≤β≤40,25≤γ≤40, alpha+beta+γ=100,0< δ <50, α, β, γ, δ represent atom percentage content.Here, in chemical general formula, the subscript of component represents corresponding element atom number degree in the alloy respectively.
Preferably, 30≤α≤37,30≤β≤37,30≤γ≤37.Described magneticalloy can more preferably Mn
30co
4ni
33ge
33.
Present invention also offers a kind of magnetic refrigerating material, formed by above-mentioned magneticalloy.
The present invention also additionally provides the application of a kind of above-mentioned magneticalloy as magnetic refrigerating material.
The beneficial effect that technical solution of the present invention is brought is:
1) magneticsubstance provided by the invention, demonstrates paramagnetic high-temperature-phase and changes to ferromagnetic low-temperature phase, show large magnetic contrast.Under outside magnetic field effect, the magnetic-structural transformation under this magneticsubstance generation field drives, shows huge magnetothermal effect.Because the heat effect of the structure Entropy Changes of this kind of magneticsubstance remains consistent with the heat effect direction that magnetic entropy becomes, therefore its effective heat effect is enhanced, and magnetic refrigerating efficiency improves greatly.
2) magneticalloy of the present invention is along with the change of composition, and phase in version can continue efficient generation from 90K to 260K, magnetic refrigeration working substance can in wide temperature range warm area steady operation.As required, single composite material or multicomponent gradient material can also be provided to freeze.For the occasion that working temperature is single warm area, the magneticalloy that phase transition temperature is identical or close with working temperature can be chosen; And for working temperature, there is thermograde or the occasion changed greatly (situation as larger in the temperature difference), then the multiple magneticalloys by phase transition temperature is corresponding respectively with multiple working temperature can be adopted to combine.Because these magneticalloys all belong to same material system, therefore, can adopt identical work system, structure is simple, is easy to control.
3) starting material Mn, Co, Ni, Ge required for the present invention are cheap, rich reserves, are easy to the transition element that stores.Consisting of magnetic alloy material there is low specific heat, high thermal conductivity, magnetic working medium has obvious temperature variation can carry out heat exchange fast.Because magnetic alloy material of the present invention can freeze in wide temperature range, therefore insensitive to chemical composition, stability is good.
4) the present invention also has good moulding processability, can be processed into different shape and use, as band or bulk.The equipment adopted for conventional melting and can get rid of carrying equipment, without the need to other optional equipment.The preparation technology of material is simple, reliable, and technology stability is good, is easy to suitability for industrialized production.
5) magneticsubstance (Mn with large magnetothermal effect provided by the invention
100-δco
δ)
αni
βge
γhaving excellent over-all properties, is desirable Mn base non-Rare-Earth Magnetic refrigeration candidate material.
Accompanying drawing explanation
Fig. 1 is the Mn that the embodiment of the present invention 1 obtains
30co
3ni
30ge
37the X ray diffracting spectrum of alloy.
Fig. 2 is the Mn that the embodiment of the present invention 4 obtains
22co
15ni
33ge
30the specific magnetising moment-the Magnetic field strength curve of alloy in phase transition process during differing temps.
Fig. 3 is the Mn that the embodiment of the present invention 5 obtains
30co
4ni
33ge
33the specific magnetising moment-temperature curve under alloy upfield.
Fig. 4 is the Mn that the embodiment of the present invention 5 obtains
30co
4ni
33ge
33magnetic entropy change-temperature curve in alloy phase change process.
Fig. 5 is the Mn that the embodiment of the present invention 6 obtains
26co
7ni
33ge
34the specific magnetising moment-temperature curve under alloy downfield.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Embodiment 1
The preparation of this embodiment consists of Mn
30co
3ni
30ge
37magneticalloy bulk, each element subscript represents corresponding element atom number degree in the alloy respectively.Such as, Mn
30co
3ni
30ge
37what alloy represented is containing the Mn element that atomic percent is 30% in this alloy, and atomic percent is the Co element of 3%, atomic percent be 30% Ni element and atomic percent be 37% Ge element.In other examples, also same interpretation is done.
Step 1.1: by the molar ratio of Mn:Co:Ni:Ge=30:3:30:37, weighs Mn, Co, Ni, Ge raw metal that purity is 99.9% respectively;
Step 1.2: the raw material weighed up is put into crucible, with mechanical pump, vacuum tightness is evacuated to 2 × 10
-3below Pa, passes into argon gas as shielding gas, and adopt arc melting method melting Polycrystalline ingot, melting electric current 100A, each sample overturns 3 times, and congruent melting refines 4 times to ensure uniform composition;
Step 1.3: the button spindle material seal obtained, in vitreosil pipe, carries out homogenizing annealing process in 120 hours 850 DEG C of annealing, and then is cooled to room temperature with the rate of temperature fall of 2 DEG C/sec, obtains the block ingot of the diameter 1cm of uniform composition;
Step 1.4: the sample above-mentioned polycrystalline bulk ingot WEDM processing being prepared into 4 × 4 × 8mm; Get sample segment to grind simultaneously, be prepared into powder.Measure various physical property, sample is high-temperature-phase in room temperature, and its X ray diffracting spectrum is shown in Fig. 1.The transformation temperature of sample and magnetic entropy variate are in table 1.
Embodiment 2
Preparation consists of Mn
23co
10ni
32ge
35magneticalloy band:
Step 2.1: by the molar ratio of Mn:Co:Ni:Ge=23:10:32:35, weighs Mn, Co, Ni, Ge raw metal that purity is 99.9% respectively;
Step 2.2: the raw material weighed up is put into crucible, with mechanical pump, vacuum tightness is evacuated to 2 × 10
-3below Pa, passes into argon gas as shielding gas, and adopt arc melting method melting Polycrystalline ingot, melting electric current 100A, each sample overturns 3 times, and congruent melting refines 4 times to ensure uniform composition;
Step 2.3: the button spindle material seal obtained, in vitreosil pipe, carries out homogenizing annealing process in 120 hours 850 DEG C of annealing, and then is cooled to room temperature with the rate of temperature fall of 2 DEG C/sec;
Step 2.4: the button spindle after annealing is put into the foraminate silica tube of a bottom belt, is placed to and gets rid of in band machine furnace chamber, be evacuated down to 10
-3below Pa, high-purity argon gas is passed in furnace chamber, pressure is-0.05MPa, adopt induction heating, alloy is made to be in molten state, then open gas control valve, be blown into from silica tube top on molten alloy liquid is ejected into from the aperture copper wheel that linear velocity is the high speed rotating of 25m/s of the high-purity argon gas with 0.05MPa and throw away fast, the band that acquisition width is 3-4mm, thickness is 30-40 μm.The transformation temperature of sample and magnetic entropy variate are in table 1.
Embodiment 3
Preparation consists of Mn
24co
6ni
37ge
33magneticalloy: the molar ratio except component is Mn:Co:Ni:Ge=24:6:37:33, and sample annealing temperature is 900 DEG C, and annealing time is outside 96 hours, and all the other steps are with embodiment 1.The transformation temperature of sample and magnetic entropy variate are in table 1.
Embodiment 4
Preparation consists of Mn
22co
15ni
33ge
30magneticalloy: except the molar ratio of component is Mn:Co:Ni:Ge=22:15:33:30, and the argon pressure got rid of in band machine furnace chamber is 0.08MPa, and copper wheel rotating speed is outside 20m/s, and all the other steps are with embodiment 2.The transformation temperature of sample and magnetic entropy variate are in table 1.The specific magnetising moment-the Magnetic field strength curve of this alloy in phase transition process during differing temps as shown in Figure 2.
Embodiment 5
Preparation consists of Mn
30co
4ni
33ge
33magneticalloy: the molar ratio except component is Mn:Co:Ni:Ge=30:4:33:33, and sample annealing temperature is 1000 DEG C, and annealing time is outside 72 hours, and all the other steps are with embodiment 1.The transformation temperature of sample and magnetic entropy variate are in table 1.The specific magnetising moment-the temperature curve of this alloy under upfield is shown in Fig. 3, can see the generation of magnetic-structure Coupling phase transformation; Magnetic entropy change-temperature curve in this alloy phase change process is shown in Fig. 4, can obtain the huge great magnetic entropy variation of-42J/kgK, show significant magnetothermal effect under the changes of magnetic field amount of 50ke.In addition, for Mn
30co
4ni
33ge
33material, its room temperature is high-temperature-phase, and along with the reduction of temperature, crystalline structure is low-temperature phase by high-temperature phase-transitional, and the structure entropy of material reduces.And as can be seen from Figure 4, this material is by high temperature in the process of low temperature, its specific magnetising moment is changed from small to big, and material magnetic order degree strengthens gradually, and magnetic entropy reduces.As can be seen here, the structure Entropy Changes of this material is identical with the heat effect direction that magnetic entropy becomes, and therefore has very strong refrigeration capacity.
Embodiment 6
Preparation consists of Mn
26co
7ni
33ge
34magneticalloy: except the molar ratio of component is Mn:Co:Ni:Ge=26:7:33:34, and the argon pressure got rid of in band machine furnace chamber is 0.06MPa, and copper wheel rotating speed is outside 30m/s, and all the other steps are with embodiment 2.The transformation temperature of sample and magnetic entropy variate are in table 1.The specific magnetising moment-the temperature curve of this alloy under downfield as shown in Figure 5, can see the generation of magnetic-structure Coupling phase transformation.
(the Mn of table 1 heterogeneity
100-δco
δ)
αni
βge
γthe transformation temperature of material and in 50kOe magnetic field
Magnetic entropy variate during variable quantity.
As can be seen from Table 1, for Mn
30co
4ni
33ge
33, its magnetothermal effect up to-42J/kgK, far beyond the amplitude recorded in prior art.And for the alloy of other compositions, magnetothermal effect is also more remarkable.And along with the change of composition, (Mn
100-δco
δ)
αni
βge
γthe phase in version of alloy can occur from 95K to 255K, show such alloy system can in wide temperature range warm area steady operation.According to this character, can be made into a kind of cooling module, described cooling module comprises multiple (Mn of heterogeneity
100-δco
δ)
αni
βge
γalloy.In one embodiment, cooling module can have laminate structure, and every one deck is by (the Mn being different from other composition of layer
100-δco
δ)
αni
βge
γalloy composition.As can by Mn
30co
4ni
33ge
33, Mn
23co
10ni
32ge
35, Mn
22co
15ni
33ge
30the cooling module of composition three-decker, this cooling module can work near 235K, 160K and 95K temperature.In another embodiment, cooling module also can form array structure by multiple module, and each module is by (the Mn being different from other composition of layer
100-δco
δ)
αni
βge
γalloy composition.Cooling module of the present invention can be applied to there is multiple working temperature environment in the middle of.According to aforesaid cooling module, a kind of refrigeration system can also be provided, comprise aforesaid cooling module and externally-applied magnetic field.Externally-applied magnetic field can be provided by superconducting magnet, permanent magnet or electromagnet.
Although describe the specific embodiment of the present invention, it will be readily apparent to one skilled in the art that and can make other variations and modifications to it when without departing from the spirit and scope of the present invention.Therefore, claims are intended to cover all such changes and modifications fallen within the scope of protection of the present invention.
Claims (5)
1. a magneticalloy, its chemical general formula is (Mn
100-δco
δ)
αni
βge
γ, wherein, 25≤α≤40,25≤β≤40,25≤γ≤40, alpha+beta+γ=100,0< δ <50, α, β, γ, δ represent atom percentage content.
2. magneticalloy according to claim 1, is characterized in that, 30≤α≤37,30≤β≤37,30≤γ≤37.
3. magneticalloy according to claim 1 and 2, is characterized in that, described magneticalloy is Mn
30co
4ni
33ge
33.
4. a magnetic refrigerating material, the magneticalloy according to any one of claim 1-3 is formed.
5. the magneticalloy according to any one of claim 1-3 is as the application of magnetic refrigerating material.
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| CN106191616B (en) * | 2015-04-29 | 2018-06-26 | 中国科学院物理研究所 | A kind of magnetic phase transition alloy |
| CN106636843A (en) * | 2016-11-04 | 2017-05-10 | 北京工业大学 | MnNiSi-based magnetic alloy capable of serving as magnetic refrigeration material |
| CN107841674B (en) * | 2017-10-17 | 2020-03-13 | 上海电力学院 | Magnetic refrigeration material and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| CN1750181A (en) * | 2005-10-20 | 2006-03-22 | 中国科学院物理研究所 | Semimetal magnetic material with high spinning polarizability |
| CN101037737A (en) * | 2007-03-28 | 2007-09-19 | 中国科学院物理研究所 | Magnetic material having magnetic field driven martensitic transformation effect and preparation method thereof |
| CN101055777A (en) * | 2007-03-08 | 2007-10-17 | 中国科学院物理研究所 | Magnetic material with the magnetic field driving martensite phase change effect and its making method |
| CN101826385A (en) * | 2010-04-30 | 2010-09-08 | 中国科学院物理研究所 | Magnetic material with exchange bias effect and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230829A (en) * | 1985-08-02 | 1987-02-09 | Natl Res Inst For Metals | Working substance for magnetic refrigeration and its production |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1750181A (en) * | 2005-10-20 | 2006-03-22 | 中国科学院物理研究所 | Semimetal magnetic material with high spinning polarizability |
| CN101055777A (en) * | 2007-03-08 | 2007-10-17 | 中国科学院物理研究所 | Magnetic material with the magnetic field driving martensite phase change effect and its making method |
| CN101037737A (en) * | 2007-03-28 | 2007-09-19 | 中国科学院物理研究所 | Magnetic material having magnetic field driven martensitic transformation effect and preparation method thereof |
| CN101826385A (en) * | 2010-04-30 | 2010-09-08 | 中国科学院物理研究所 | Magnetic material with exchange bias effect and preparation method thereof |
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