CN110453132A - A kind of Ni-Mn-Sn-Co-Si magnetic refrigerating material - Google Patents

A kind of Ni-Mn-Sn-Co-Si magnetic refrigerating material Download PDF

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Publication number
CN110453132A
CN110453132A CN201910746476.2A CN201910746476A CN110453132A CN 110453132 A CN110453132 A CN 110453132A CN 201910746476 A CN201910746476 A CN 201910746476A CN 110453132 A CN110453132 A CN 110453132A
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magnetic
alloy
temperature
magnetic refrigerating
refrigerating material
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CN201910746476.2A
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CN110453132B (en
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李宗宾
杨嘉晶
杨波
赵骧
左良
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Northeastern University China
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Northeastern University China
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
    • H01F1/015—Metals or alloys

Abstract

A kind of Ni-Mn-Sn-Co-Si magnetic refrigerating material, belongs to technical field of magnetic materials.The chemical molecular formula of the Ni-Mn-Sn-Co-Si magnetic refrigeration alloy material is Ni38Mn42SnxCo10Siy, and the sum of molal quantity of element is 100 in alloy, wherein 8≤x≤9,1≤y≤2.The present invention prepares polycrystalline cast ingot by raw material proportioning, the multiple melt back of vacuum arc, anneals under high purity inert gas protection, then rapid water cooling, to prepare Ni-Mn-Sn-Co-Si magnetic refrigeration alloy block blank.Alloy block of the invention is insulated temperature and becomes variation range as 0.66-2.70K under the magnetic field 1.5T.Magnetic alloy of the invention can obtain excellent insulation temperature near room temperature and become, and be accompanied by huge magnetothermal effect, can be used as magnetic refrigeration working substance magnetic refrigerating efficiency with higher and wide temperature range working range.

Description

A kind of Ni-Mn-Sn-Co-Si magnetic refrigerating material
Technical field
The present invention relates to magnetic alloy material, which may be used as Ni-Mn-Sn-Co-Si magnetic refrigeration material The preparation of material.
Background technique
Compared with traditional gas compression-type refrigeration technology, magnetic refrigeration uses magnetisable material as refrigeration working medium, to ozone layer Without destruction, no greenhouse effects, and the magnetic entropy density ratio gas of Magnetic material is big, therefore refrigerating plant can be more compact； Due to not needing compressor, moving component is few and movement velocity is slow, mechanical oscillation and noise are small, high reliablity, service life are long；In Thermal efficiency, gas compression formula Refrigeration Technique are generally only capable of reaching the 5~10% of Carnot cycle, and magnetic Refrigeration Technique can be with Reach 30~60%, shows high refrigerating efficiency.Based on the above advantage, room temperature magnetic refrigerating magnetic refrigerator, air-conditioning and The huge application prospect such as space technology and nuclear technology and become current various countries' keen competition high-technology field.
In the development process of magnetic Refrigeration Technique, ideal magnetic cooling material includes at least 80% and has big magnetic moment Transiting group metal elements, as Fe or Mn etc.；It also include some elements of IIIA, IVA and VA isofamily, such as Al, Si, P etc., this A little elements are primarily used to adjust the performance of material.Therefore, design is substituted Sn member by the doping using Si element and usually adjusted Its martensitic transformation temperature is saved, to increase substantially the magnetothermal effect of Ni-Mn-Sn-Co-Si alloy, makes it near room temperature With good magnetothermal effect, excellent properties of the Ni-Mn-Sn-Co-Si as magnetic refrigeration working substance are then greatly promoted.
Summary of the invention
The present invention provides a kind of Ni-Mn-Sn-Co-Si magnetic alloys with big magnetothermal effect, can be biggish The magnetic alloy regulated and controled in ingredient and temperature range, greatly improves its effective magnetic refrigerating efficiency, has and is more widely applied Range.
Technical scheme is as follows:
The present invention provides a kind of magnetic alloy material, the chemical general formula of element is in the magnetic alloy material Ni38Mn42SnxCo10Siy, the sum of molal quantity of element is 100 in alloy, wherein 8≤x≤9,1≤y≤2.
Above-mentioned magnetic alloy material can be used as Ni-Mn-Sn-Co-Si magnetic refrigerating material.Preparation method includes as follows Step:
(1) raw material proportioning: according to chemical formula Ni38Mn42SnxCo10SiyMolar ratio ingredient, 8≤x≤9 in formula, 1≤y≤ 2；
(2) it prepares polycrystalline cast ingot: step (1) weighed raw material is contained up in vacuum arc melting furnace water jacketed copper crucible, Electric arc melting furnace cavity is evacuated to 3 × 10-3~5 × 10-3After Pa, it is passed through inert protective gas 0.05MPa, melt back 4 ~5 times, electric arc melting is carried out under electromagnetic agitation, obtains the uniform polycrystalline parent state alloy of ingredient；
(3) it is heat-treated: Ni-Mn-Sn-Co-Si alloy cast ingot is directly quenched in ice water after keeping the temperature for 24 hours at 900 DEG C Fire prepares the Ni38Mn42SnxCo10SiyMagnetic alloy.
Further, the Ni-Mn-Sn-Co-Si magnetic refrigerating material is insulated temperature change variation model under 1.5 T externally-applied magnetic fields It encloses for 0.66-2.70K, transition temperature area 240-327K.
Ni-Mn-Sn-Co-Si magnetic refrigerating material of the invention, having the beneficial effect that compared with prior art
(1) by adjusting the proportion of alloying component, enable Ni-Mn-Sn-Co-Si alloy before and after martensitic traoformation The magnetic performance of material goes out biggish difference, under extracorporeal magnetic driving, magnetic field driven martensitic transformation occurs, shows big Magnetothermal effect.
(2) with the variation of ingredient, the phase transformation of magnetic alloy of the invention comprising room temperature wide temperature (240~ It 327K) is all continuously adjusted in range and continues efficiently to occur.This makes for different application demands, which both may be used To realize single temperature zone refrigeration by choosing the phase transition temperature magnetic alloy same or similar with operating temperature, can also use Corresponding multiple magnetic alloys, which are distinguished, with multiple operating temperatures by phase transition temperature combines the larger operation temperature area of realization or ladder Spend the demand of refrigeration.
(3) material N i, Mn, Sn, Co, Si needed for magnetic alloy provided by the invention be cheap, rich reserves.Together When such alloy is nontoxic and good heat conductivity, refrigerating capacity is preferable, and stability is good.
(4) the magnetic alloy Ni provided by the invention with huge magnetothermal effect38Mn42SnxCo10SiyWith excellent Comprehensive performance is the non-Rare-Earth Magnetic refrigeration candidate material of ideal Mn base.
Detailed description of the invention
Fig. 1 is the alloy Ni of the embodiment of the present invention 138Mn42Sn9Co10Si1DSC curve.
Fig. 2 is the alloy Ni of the embodiment of the present invention 238Mn42Sn8.5Co10Si1.5DSC curve.
Fig. 3 is the alloy Ni of the embodiment of the present invention 338Mn42Sn8Co10Si2DSC curve.
Fig. 4 is the alloy Ni of the embodiment of the present invention 138Mn42Sn9Co10Si1△ TadT curve.
Fig. 5 is the alloy Ni of the embodiment of the present invention 238Mn42Sn8.5Co10Si1.5△ TadT curve.
Fig. 6 is the alloy Ni of the embodiment of the present invention 338Mn42Sn8Co10Si2△ TadT curve.
Specific embodiment
In following embodiment, Ni is 99.97wt.% high-purity N i, and Mn is the high-purity Mn of 99.9wt.%, and Sn is 99.99 wt.% High-purity In, Co are the high-purity Co of 99.9wt.%, and Cu is 99.9wt.% high-purity Si.
In following embodiment, vacuum arc melting furnace buying is limited in Shenyang Scientific Instrument Development Centre, Chinese Academy of Sciences Company, vacuum arc melting furnace model DHL-400.
The detection technique means of following embodiment are as follows:
Using differential scanning calorimetric analysis instrument (DSC), the martensitic traoformation and Reverse Martensitic Transformation Temperatures of sample are measured.When measurement The heating of sample and rate of temperature fall are 10 K/min, and phase transition temperature is determined on DSC curve by tangential method.
Insulation temperature using permanent magnetism mce direct measurement automatic device measurement sample becomes.The instrument is used using poly- magnetic technology NdFeB permanent magnet assembles the permanent magnetic field (1.5 T) of closure.The magnetothermal effect of alloy passes through △ Tad- T is characterized.In martensite Phase transformation is nearby in temperature range, and 1 DEG C/min of its heating rate in measurement process, magnetic field is fixed, passes in and out magnetic field by sample Measure temperature change of the sample inside and outside magnetic field.
Embodiment 1
Ni-Mn-Sn-Co-Si magnetic alloy, the sum of molal quantity of element is 100 in alloy material, the molar ratio of element For Ni:Mn:Sn:Co:Si=38:42:9:10:1.
Ni38Mn42Sn9Co10Si1The preparation method of magnetic alloy, comprising the following steps:
(1) raw material proportioning: according to the molar ratio ingredient of Ni:Mn:Sn:Co:Si=38:42:9:10:1；
(2) it prepares polycrystalline cast ingot: step (1) weighed raw material is contained up in vacuum arc melting furnace water jacketed copper crucible, Electric arc melting furnace cavity is evacuated to 3 × 10-3~5 × 10-3After Pa, it is passed through inert protective gas 0.05MPa, melt back 4 ~5 times, smelting time is 2~2.5 hours, and electric arc melting is carried out under electromagnetic agitation, obtains the uniform polycrystalline parent state of ingredient and closes Gold；
(3) it is heat-treated: by Ni38Mn42Sn9Co10Si1Alloy cast ingot, at 900~950 DEG C keep the temperature 20~for 24 hours after directly In ice quenching-in water, the Ni is obtained38Mn42Sn9Co10Si1Magnetic alloy.
Using differential scanning calorimetric analysis instrument (DSC), the Ni of this implementation preparation is analyzed39Mn42Sn9Co9Si1The phase of alloy Change behavior.As shown in Figure 1, Ni38Mn42Sn9Co10Si1Magnetic alloy, during temperature is raised to 267K by 252K, by weak magnetic Martensite is directly translated into ferromagnetic austenite, and (i.e. magnetic-structure changes) occurs simultaneously for magnetic transformation and structure transformation.
Insulation temperature using permanent magnetism mce direct measurement automatic device measurement sample becomes.Forever by the fixed NdFeB of measurement 1.5T Under magnetic field, alloy sample is in 238-283K temperature-rise period, 1 DEG C/min of heating rate, and disengaging magnetic field measures it in magnetic field Outer temperature change measures Δ T at 252Kad=0.66K.
Embodiment 2
Ni-Mn-Sn-Co-Si magnetic freezes alloy material, and the sum of molal quantity of element is 100 in alloy material, element Molar ratio is Ni:Mn:Sn:Co:Si=38:42:8.5:10:1.5.
Ni38Mn42Sn8.5Co10Si1.5The preparation method of magnetic refrigeration alloy material, comprising the following steps:
(1) raw material proportioning: according to the molar ratio ingredient of Ni:Mn:Sn:Co:Si=38:42:8.5:10:1.5；
(2) it prepares polycrystalline cast ingot: step (1) weighed raw material is contained up in vacuum arc melting furnace water jacketed copper crucible, Electric arc melting furnace cavity is evacuated to 3 × 10-3~5 × 10-3After Pa, it is passed through inert protective gas 0.05MPa, melt back 4 ~5 times, smelting time is 2~2.5 hours, and electric arc melting is carried out under electromagnetic agitation, obtains the uniform polycrystalline parent state of ingredient and closes Gold；
(3) it is heat-treated: by Ni38Mn42Sn8.5Co10Si1.5Alloy cast ingot, at 900~950 DEG C heat preservation 20~for 24 hours after Directly in ice quenching-in water, the Ni is obtained38Mn42Sn8.5Co10Si1.5Magnetic alloy.
Using differential scanning calorimetric analysis instrument (DSC), the Ni of this implementation preparation is analyzed39Mn42Sn8.5Co9Si1.5The phase of alloy Change behavior.As shown in Fig. 2, Ni38Mn42Sn8.5Co10Si1.5Magnetic refrigerating material, during temperature is raised to 303K by 292K, Ferromagnetic austenite is directly translated by weak magnetic martensite, (i.e. magnetic-structure changes) occurs simultaneously for magnetic transformation and structure transformation.
Insulation temperature using permanent magnetism mce direct measurement automatic device measurement sample becomes.Forever by the fixed NdFeB of measurement 1.5T Under magnetic field, alloy sample is in 263-303K temperature-rise period, 1 DEG C/min of heating rate, and disengaging magnetic field measures it in magnetic field Outer temperature change measures △ T at 295Kad=2.70K.
Embodiment 3
Ni-Mn-Sn-Co-Si magnetic freezes alloy material, and the sum of molal quantity of element is 100 in alloy material, element Molar ratio is Ni:Mn:Sn:Co:Si=38:42:8:10:2.
Ni38Mn42Sn8Co10Si2The preparation method of magnetic alloy, comprising the following steps:
(1) raw material proportioning: according to chemical formula Ni38Mn42Sn8Co10Si2Molar ratio ingredient；
(2) it prepares polycrystalline cast ingot: step (1) weighed raw material is contained up in vacuum arc melting furnace water jacketed copper crucible, Electric arc melting furnace cavity is evacuated to 3 × 10-3~5 × 10-3After Pa, it is passed through inert protective gas 0.05MPa, melt back 4 ~5 times, smelting time is 2~2.5 hours, and electric arc melting is carried out under electromagnetic agitation, obtains the uniform polycrystalline parent state of ingredient and closes Gold；
(3) it is heat-treated: by Ni38Mn42Sn8Co10Si2Alloy cast ingot, at 900~950 DEG C keep the temperature 20~for 24 hours after directly In ice quenching-in water, the Ni is obtained38Mn42Sn8Co10Si2Magnetic alloy.
Using differential scanning calorimetric analysis instrument (DSC), the Ni of this implementation preparation is analyzed38Mn42Sn8Co10Si2The phase of alloy Change behavior.As shown in figure 3, Ni38Mn42Sn8Co10Si2Magnetic alloy, during temperature is raised to 332K by 318K, by weak magnetic Martensite is directly translated into ferromagnetic austenite, and (i.e. magnetic-structure changes) occurs simultaneously for magnetic transformation and structure transformation.
Insulation temperature using permanent magnetism mce direct measurement automatic device measurement sample becomes.Forever by the fixed NdFeB of measurement 1.5T Under magnetic field, alloy sample is in 303-338K temperature-rise period, 1 DEG C/min of heating rate, and disengaging magnetic field measures it in magnetic field Outer temperature change measures △ T at 323Kad=2.50K.

Claims (3)

1. a kind of Ni-Mn-Sn-Co-Si magnetic refrigerating material, which is characterized in that the Ni-Mn-Sn-Co-Si magnetic refrigerating material The chemical general formula of middle element is Ni38Mn42SnxCo10Siy, the sum of molal quantity of element is 100 in alloy, wherein 8≤x≤9,1≤ y≤2。
2. a kind of Ni-Mn-Sn-Co-Si magnetic refrigerating material according to claim 1, which is characterized in that the Ni-Mn- Being insulated temperature in Sn-Co-Si magnetic refrigerating material under 1.5T externally-applied magnetic field becomes as 0.66-2.70K, transition temperature area 240- 327K。
3. the preparation method of Ni-Mn-Sn-Co-Si magnetic refrigerating material as claimed in claim 1 or 2, which is characterized in that including following Step:
(1) raw material proportioning: according to chemical formula Ni38Mn42SnxCo10SiyMolar ratio ingredient, the sum of the molal quantity of element in alloy It is 100,8≤x≤9 in formula, 1≤y≤2；
(2) it prepares polycrystalline cast ingot: step (1) weighed raw material being contained up in vacuum arc melting furnace water jacketed copper crucible, electric arc Melting furnace cavity is evacuated to 3 × 10-3~5 × 10-3After Pa, it is passed through inert protective gas 0.05MPa, melt back 4~5 times, Electric arc melting is carried out under electromagnetic agitation, obtains the uniform polycrystalline parent state alloy of ingredient；
(3) it is heat-treated: Ni-Mn-Sn-Co-Si alloy cast ingot is directly obtained in ice quenching-in water after keeping the temperature for 24 hours at 900 DEG C To the Ni-Mn-Sn-Co-Si magnetic refrigerating material.
CN201910746476.2A 2019-08-14 2019-08-14 Ni-Mn-Sn-Co-Si magnetic refrigeration material Expired - Fee Related CN110453132B (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851545A (en) * 2012-10-11 2013-01-02 河北工业大学 Ni-Mn-Ge magnetic shape memory alloy and preparation method thereof
CN104838033A (en) * 2012-12-07 2015-08-12 通用电气公司 Novel magnetic refrigerant materials
CN106119661A (en) * 2016-07-29 2016-11-16 东北大学 A kind of Mn Ni Sn Co alloy thin band and preparation method thereof
CN107675063A (en) * 2017-09-26 2018-02-09 东北大学 A kind of Ni Mn In Co Cu magnetic refrigeration alloy material and preparation method
CN108330372A (en) * 2018-02-28 2018-07-27 华南理工大学 A kind of Ni-Co-Mn-Sn magnetic refrigerating materials and preparation method thereof
CN108677078A (en) * 2018-05-30 2018-10-19 东北大学 A kind of Mn-Ni-In-Co-Cu magnetic refrigerating materials and preparation method thereof of richness Mn

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102851545A (en) * 2012-10-11 2013-01-02 河北工业大学 Ni-Mn-Ge magnetic shape memory alloy and preparation method thereof
CN104838033A (en) * 2012-12-07 2015-08-12 通用电气公司 Novel magnetic refrigerant materials
CN106119661A (en) * 2016-07-29 2016-11-16 东北大学 A kind of Mn Ni Sn Co alloy thin band and preparation method thereof
CN107675063A (en) * 2017-09-26 2018-02-09 东北大学 A kind of Ni Mn In Co Cu magnetic refrigeration alloy material and preparation method
CN108330372A (en) * 2018-02-28 2018-07-27 华南理工大学 A kind of Ni-Co-Mn-Sn magnetic refrigerating materials and preparation method thereof
CN108677078A (en) * 2018-05-30 2018-10-19 东北大学 A kind of Mn-Ni-In-Co-Cu magnetic refrigerating materials and preparation method thereof of richness Mn

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Title
ANNA WÓJCIK: "Structure and inverse magnetocaloric effect in Ni-Co-Mn-Sn(Si) Heusler alloys", 《INTERMETALLICS》 *

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