CN105400998A - Ni-Mn-Ga alloy ribbon and preparation method thereof - Google Patents
Ni-Mn-Ga alloy ribbon and preparation method thereof Download PDFInfo
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- CN105400998A CN105400998A CN201510753357.1A CN201510753357A CN105400998A CN 105400998 A CN105400998 A CN 105400998A CN 201510753357 A CN201510753357 A CN 201510753357A CN 105400998 A CN105400998 A CN 105400998A
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- 229910000807 Ga alloy Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 57
- 239000000956 alloy Substances 0.000 claims abstract description 57
- 230000005291 magnetic effect Effects 0.000 claims abstract description 50
- 230000009466 transformation Effects 0.000 claims abstract description 43
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 38
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 7
- 238000002074 melt spinning Methods 0.000 claims abstract description 5
- 230000005294 ferromagnetic effect Effects 0.000 claims abstract description 4
- 230000005298 paramagnetic effect Effects 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010791 quenching Methods 0.000 claims description 18
- 230000000171 quenching effect Effects 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010453 quartz Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 230000008859 change Effects 0.000 claims description 15
- 229910052733 gallium Inorganic materials 0.000 claims description 13
- 230000006698 induction Effects 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000013467 fragmentation Methods 0.000 claims description 4
- 238000006062 fragmentation reaction Methods 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000000137 annealing Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000010891 electric arc Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007499 fusion processing Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000005347 demagnetization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0611—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars formed by a single casting wheel, e.g. for casting amorphous metal strips or wires
-
- 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
- C22C1/023—Alloys based on nickel
-
- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- Mechanical Engineering (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Hard Magnetic Materials (AREA)
Abstract
The invention discloses a Ni-Mn-Ga alloy ribbon and a preparation method thereof and belongs to the technical field of new materials. The sum of the molar percents of elements in the alloy ribbon is 100, and the molar ratio of the elements meets the formula that Ni:Mn:Ga=(51.5-52.5):(25.5-26.5):(21.5-22.5). The preparation method of the Ni-Mn-Ga alloy ribbon comprises the steps that (1) vacuum electric arc melting is conducted repeatedly; (2) a melt-spun alloy ribbon with the thickness being 90-120 micrometers is prepared through a melt-spinning method; and (3) annealing treatment is conducted. In the cooling process, the alloy ribbon has the characteristic that three kinds of transformation occur at the same time, namely (1) magnetic transformation occurs, and a paramagnetic austenite is directly transformed into a ferromagnetic martensite; (2) martensite transformation occurs, and the austenite is transformed into a 7M martensite; and (3) intermediate martensite transformation occurs, and the 7M martensite is transformed into an NM martensite. Under a 2T magnetic field, the magnetic entropy of the alloy ribbon changes from -12.5 to -16.4 Jkg to 1K-1; under a 5T magnetic field, the magnetic entropy of the alloy ribbon changes from -25.5 to -30.0 Jkg-1K-1.
Description
Technical field
The invention belongs to new material technology field, particularly a kind of Ni-Mn-Ga alloy thin band and preparation method thereof.
Background technology
Ni-Mn-Ga alloy is the new function material that a class has martensitic transformation and paramagnetic-ferromagnetic transformation characteristic concurrently.Recent study finds, externally-applied magnetic field can bring out Ni-Mn-Ga alloy and produce significant magnetothermal effect.Due to the magnetic transformation of Ni-Mn-Ga alloy and martensite transformation temperature comparatively large by composition influence, if suitably adjust alloying constituent, realize magnetic transformation and martensitic transformation occurs (magnetic-structural transformation) simultaneously, then can significantly improve magnetic entropy change.At present, in Ni-Mn-Ga alloy monocrystalline, maximum magnetic entropy change (-86JKg is obtained
-1k
-1, 5T magnetic field).But, single crystal preparation complex process, consuming time and cost of manufacture is high, large-scale production is difficult, be difficult to be dropped into industrial production and enter practical stage.By comparison, the relatively simple and manufacturing cost of the preparation of polycrystalline alloy and energy consumption much lower, but the intrinsic fragility of polycrystalline Ni-Mn-Ga block alloy causes it to be difficult to carry out following process, and a large amount of introducings of crystal boundary can cause the remarkable reduction of its magnetic heating performance, seriously limit practical application.
Single roller based on rapid solidification gets rid of band method and is widely used in recent years in the preparation work of magnetic refrigerating material.This method can not only improve the fragility of alloy by crystal grain thinning, and can prepare the thin band material (the demagnetization impact of thin band material is minimum) of applicable practical application.But grain refining can reduce the atomic ordered degree of thin band material further, causes the magnetic entropy change of thin band material even lower than the magnetic entropy change of polycrystalline bulk material.Therefore, design and develop the polycrystalline Ni-Mn-Ga alloy thin band with great magnetic entropy variation and promotion Ni-Mn-Ga alloy is moved towards practical significant as New Magnetic Field Controlled material of cooling.The present invention's employing is got rid of band technology and is prepared polycrystalline fast quenching Ni-Mn-Ga strip, magnetic transformation and the simultaneous strip of structural transformation is developed based on Composition Design, and in conjunction with the high temperature anneal, middle martensitic transformation is incorporated into magnetic structure transition process, increases substantially the magnetic heating performance of fast quenching thin strap.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of Ni-Mn-Ga alloy thin band and preparation method thereof.This alloy thin band is a kind of great magnetic entropy variation polycrystalline Ni-Mn-Ga alloy thin band with magnetic-many structural transformations coupling feature.
Ni-Mn-Ga alloy thin band of the present invention, in alloy thin band, the mole number sum of element is 100, and the mol ratio of element is Ni: Mn: Ga=(51.5 ~ 52.5): (25.5 ~ 26.5): (21.5 ~ 22.5).
In the temperature-fall period of Ni-Mn-Ga alloy thin band within the scope of 87 ~ 57 DEG C, present 3 kinds and change simultaneous feature: (1) magnetic transformation: directly change ferromagnetic martensite into by paramagnetic austenite; (2) martensitic transformation: austenitic transformation is 7M martensite; (3) martensitic transformation in the middle of: 7M martensitic transformation is NM martensite.
Ni-Mn-Ga alloy thin band is under 2T magnetic field, and magnetic entropy change is-12.5 ~-16.4Jkg
-1k
-1, under 5T magnetic field, magnetic entropy change is-25.5 ~-30.0Jkg
-1k
-1.
The thickness of Ni-Mn-Ga alloy thin band is 90 ~ 120 μm.
The preparation method of Ni-Mn-Ga alloy thin band of the present invention, comprises the following steps:
Step 1, the preparation of polycrystalline parent state alloy:
(1) according to the composition of Ni-Mn-Ga alloy thin band, take Ni, Mn and Ga respectively, be placed in vacuum arc melting furnace water jacketed copper crucible, arc melting furnace cavity is evacuated to 3 × 10
-3~ 5 × 10
-3after Pa, pass into inert protective gas to 0.05MPa, under induction stirring, carry out arc melting, obtain button shape ingot casting;
(2) by the method for ingot casting according to above-mentioned (1), then melt back 4 ~ 5 times, obtain the polycrystalline parent state alloy of uniform composition;
Step 2, melt spinning prepares alloy thin band:
(1) high purity quartz pipe is loaded the polycrystalline parent state alloy after fragmentation, and be fixed on and get rid of in the Medium frequency induction coil of band machine; Band machine cavity will be got rid of and be evacuated to 3 × 10
-3~ 5 × 10
-3after Pa, filling with inert gas to 0.04 ~ 0.05MPa does shielding gas; The rare gas element of 0.04 ~ 0.08MPa is filled with in gas-holder;
(2) start Medium frequency induction coil, the polycrystalline parent state alloy in high purity quartz pipe is heated to melt completely;
(3) utilize the spraying pressure of rare gas element in gas-holder that the polycrystalline parent state alloy of melting is sprayed from the ozzle of high purity quartz pipe, molten state polycrystalline parent state alloy is formed alloy thin band by the towing of the running roller of high speed rotating, roller surface linear velocity is 15 ~ 20m/s, high purity quartz pipe nozzle is of a size of (4 ~ 5) mm × 0.5mm, the spacing of nozzle and roll surface is 0.3 ~ 0.6mm, obtains the fast quenching Ni-Mn-Ga alloy thin band that thickness is 90 ~ 120 μm.
Step 3, thermal treatment:
By fast quenching Ni-Mn-Ga alloy thin band, at 850 ~ 950 DEG C, water-cooled after insulation 12 ~ 24h, obtains finished product Ni-Mn-Ga alloy thin band.
Wherein, Ni is 99.97wt.% high-purity N i, Mn in step 1 (1) be 99.9wt.% high-purity Mn, Ga is the high-purity Ga of 99.99wt.%; In step 1 (1), Ni, Mn and Ga laying method in water jacketed copper crucible is that Mn is placed in the bottommost of water jacketed copper crucible, more than Mn places Ni and Ga, to reduce the volatilization of Mn in fusion process; By ingot casting melt back 4 times again in step 1 (2); Rare gas element in step 1 and step 2 is high-purity argon gas; Running roller in step 2 (3) is copper running roller.
Ni-Mn-Ga alloy thin band of the present invention and preparation method thereof, beneficial effect is compared with prior art:
(1) Ni-Mn-Ga alloy thin band of the present invention overcomes Ni-Mn-Ga block alloy because of fragility and is difficult to greatly be processed into the deficiency of thin slice;
(2) Ni-Mn-Ga alloy thin band of the present invention is in temperature-fall period, magnetic-structural transformation process is introduced in middle martensite, achieve the coupling of magnetic transformation, martensitic transformation and middle martensitic transformation, and significantly improve the magnetic heating performance of polycrystalline Ni-Mn-Ga alloy thin band;
(3) preparation method of Ni-Mn-Ga alloy thin band of the present invention, choose highly purified Ni (99.97wt.%), Mn (99.9wt.%), Ga (99.99wt.%) is raw material, utilize the method for vacuum arc melting to prepare Ni-Mn-Ga polycrystalline parent state alloy, by alloy again melt back repeatedly to ensure uniform composition.
Accompanying drawing explanation
Fig. 1 embodiment of the present invention Ni
52mn
26ga
22heat-magnetic curve under the DSC curve of alloy thin band and 5mT and 5T magnetic field, wherein, (a) fast quenching thin strap; (b) annealing strip;
Fig. 2 embodiment of the present invention Ni
52mn
26ga
22the room temperature XRD figure spectrum of alloy thin band;
Fig. 3 embodiment of the present invention fast quenching Ni
52mn
26ga
22alloy thin band under magnetic field-Δ S
mvary with temperature curve;
Fig. 4 embodiment of the present invention annealing Ni
52mn
26ga
22alloy thin band under magnetic field-Δ S
mvary with temperature curve.
Specific embodiment
In following examples, Ni is 99.97wt.% high-purity N i, Mn be 99.9wt.% high-purity Mn, Ga is the high-purity Ga of 99.99wt.%.
In following examples, vacuum arc melting furnace and get rid of band machine and purchase in Shenyang Scientific Instrument Research & Mfg. Center Co., Ltd., C.A.S, vacuum arc melting furnace model is DHL-400, and getting rid of band type number is XC-500.
The detection technique means of following examples are:
Adopt martensitic transformation and the Reverse Martensitic Transformation Temperatures of differential scanning calorimetric analysis (DSC) instrument measure sample.During measurement, the intensification of sample and rate of temperature fall are 10K/min, and transformation temperature is determined on DSC curve by tangent method.
Utilize PANalyticalX ' PertProMPD diffractometer (Cu target) to measure X-ray diffraction (XRD) collection of illustrative plates of alloy, scanning step is 0.0334 °.
Comprehensive physical property measuring system (PPMS-9T, QuantumDesign) is adopted to measure the heat-magnetic curve of strip sample, isothermal magnetization curve and magnetic hysteresis loop.In test process, magnetic field applies along strip length direction to reduce demagnetization effects.The magnetothermal effect of alloy can adopt magnetic entropy change Δ S
mcharacterize, calculated according to Maxwell equation by isothermal magnetization (M-H) curved measurement, namely
Embodiment 1
Ni-Mn-Ga alloy thin band, in alloy thin band, the mole number sum of element is 100, and the mol ratio of element is Ni: Mn: Ga=52: 26: 22.
The preparation method of Ni-Mn-Ga alloy thin band, comprises the following steps:
Step 1, the preparation of polycrystalline parent state alloy:
(1) according to the composition of Ni-Mn-Ga alloy thin band, take Ni, Mn and Ga respectively, be placed in vacuum arc melting furnace water jacketed copper crucible, Mn is placed in the bottommost of water jacketed copper crucible, more than Mn places Ni and Ga, to reduce the volatilization of Mn in fusion process, arc melting furnace cavity is evacuated to 3 × 10
-3after Pa, pass into high-purity argon gas to 0.05MPa, under induction stirring, carry out arc melting, obtain button shape ingot casting;
(2) by the method for ingot casting according to above-mentioned (1), then melt back 3 times, obtain the polycrystalline parent state alloy of uniform composition;
Step 2, melt spinning prepares alloy thin band:
(1) high purity quartz pipe is loaded the polycrystalline parent state alloy after fragmentation, and be fixed on and get rid of in the Medium frequency induction coil of band machine; Band machine cavity will be got rid of and be evacuated to 3 × 10
-3after Pa, fill high-purity argon gas and do shielding gas to 0.05MPa; The high-purity argon gas of 0.08MPa is filled with in gas-holder;
(2) start Frequency Induction Heating, the polycrystalline parent state alloy in high purity quartz pipe is heated to melt completely;
(3) utilize the spraying pressure of high-purity argon gas in gas-holder that the polycrystalline parent state alloy of melting is sprayed from the ozzle of high purity quartz pipe, molten state polycrystalline parent state alloy is formed alloy thin band by the towing of the copper running roller of high speed rotating, copper roller surface linear velocity is 15m/s, high purity quartz pipe nozzle is of a size of 5mm × 0.5mm, the spacing of nozzle and roll surface is 0.5mm, obtains the fast quenching Ni-Mn-Ga alloy thin band that thickness is 100 μm.
Step 3, thermal treatment:
By fast quenching Ni-Mn-Ga alloy thin band, water-cooled be incubated 18h at 900 DEG C after, obtains annealing Ni-Mn-Ga alloy thin band, i.e. finished product Ni-Mn-Ga alloy thin band.
Adopt differential scanning calorimetric analysis (DSC) instrument and heat-magnetic (M-T) to measure, analyze the transformation behavior of the Ni-Mn-Ga alloy thin band of this enforcement preparation.As shown in Figure 1, fast quenching Ni
52mn
26ga
22strip and annealing Ni
52mn
26ga
22strip, drops in the process of 330K in temperature by 360K, directly changes ferromagnetic martensite into by paramagnetic austenite, and magnetic transformation and structural transformation occur simultaneously (i.e. magnetic-structural transformation).
The crystalline structure of the Ni-Mn-Ga alloy thin band utilizing this enforcement of X-ray diffraction analysis to prepare, as shown in Figure 2.Fast quenching Ni
52mn
26ga
22strip is at room temperature single-phase 7M martensite, and strip of annealing at room temperature comprises 7M martensite and NM martensite simultaneously, shows that part 7M martensite changes NM martensite further into, namely there occurs middle martensitic transformation.
Comprehensive analysis heat-magnetic measurement and XRD result show, fast quenching Ni
52mn
26ga
22strip only experienced by a kind of structural transformation of austenite to 7M martensitic transformation, and strip of annealing experienced by austenite to 7M martensitic transformation and then two kinds of structural transformations to NM martensitic transformation, that is introduce middle martensitic transformation in magnetic structure transition process.
The magnetothermal effect of the Ni-Mn-Ga alloy thin band of this enforcement preparation adopts magnetic entropy change Δ S
mcharacterize, calculated according to Maxwell equation by isothermal magnetization (M-H) curved measurement, namely
as shown in Figure 3, fast quenching Ni under 2T and 5T magnetic field
52mn
26ga
22the maximum magnetic entropy variable of strip turns to-5.3Jkg
-1k
-1with-11.4Jkg
-1k
-1, after annealed, annealing Ni
52mn
26ga
22-16.4Jkg is respectively under 2T and 5T magnetic field
-1k
-1with-30.0Jkg
-1k
-1.Under same magnetic field, the maximum magnetic entropy variable in annealing strip, apparently higher than the maximum magnetic entropy variable of fast quenching thin strap, is about three times of fast quenching thin strap.
Embodiment 2
Ni-Mn-Ga alloy thin band, in alloy thin band, the mole number sum of element is 100, and the mol ratio of element is Ni: Mn: Ga=51.8: 26.5: 21.7.
The preparation method of Ni-Mn-Ga alloy thin band, comprises the following steps:
Step 1, the preparation of polycrystalline parent state alloy:
(1) according to the composition of Ni-Mn-Ga alloy thin band, take Ni, Mn and Ga respectively, be placed in vacuum arc melting furnace water jacketed copper crucible, Mn is placed in the bottommost of water jacketed copper crucible, more than Mn places Ni and Ga, to reduce the volatilization of Mn in fusion process, arc melting furnace cavity is evacuated to 3 × 10
-3after Pa, pass into high-purity argon gas to 0.05MPa, under induction stirring, carry out arc melting, obtain button shape ingot casting;
(2) by the method for ingot casting according to above-mentioned (1), then melt back 4 times, obtain the polycrystalline parent state alloy of uniform composition;
Step 2, melt spinning prepares alloy thin band:
(1) high purity quartz pipe is loaded the polycrystalline parent state alloy after fragmentation, and be fixed on and get rid of in the Medium frequency induction coil of band machine; Band machine cavity will be got rid of and be evacuated to 3 × 10
-3after Pa, fill high-purity argon gas and do shielding gas to 0.05MPa; The high-purity argon gas of 0.04MPa is filled with in gas-holder;
(2) start Frequency Induction Heating, the polycrystalline parent state alloy in high purity quartz pipe is heated to melt completely;
(3) utilize the spraying pressure of high-purity argon gas in gas-holder that the polycrystalline parent state alloy of melting is sprayed from the ozzle of high purity quartz pipe, molten state polycrystalline parent state alloy is formed alloy thin band by the towing of the copper running roller of high speed rotating, copper roller surface linear velocity is 15m/s, high purity quartz pipe nozzle is of a size of 4mm × 0.5mm, the spacing of nozzle and roll surface is 0.6mm, obtains the fast quenching Ni-Mn-Ga alloy thin band that thickness is 120 μm.
Step 3, thermal treatment:
By fast quenching Ni-Mn-Ga alloy thin band, water-cooled be incubated 12h at 950 DEG C after, obtains annealing Ni-Mn-Ga alloy thin band, i.e. finished product Ni-Mn-Ga alloy thin band.
The magnetothermal effect of the Ni-Mn-Ga alloy thin band of this enforcement preparation adopts magnetic entropy change Δ S
mcharacterize, calculated according to Maxwell equation by isothermal magnetization (M-H) curved measurement, namely
annealing Ni
52mn
26ga
22-12.5Jkg is respectively under 2T and 5T magnetic field
-1k
-1with-25.5Jkg
-1k
-1.
Claims (10)
1. a Ni-Mn-Ga alloy thin band, it is characterized in that, in described alloy thin band, the mole number sum of element is 100, and the mol ratio of element is Ni: Mn: Ga=(51.5 ~ 52.5): (25.5 ~ 26.5): (21.5 ~ 22.5).
2. Ni-Mn-Ga alloy thin band according to claim 1, it is characterized in that, in the temperature-fall period of described alloy thin band within the scope of 87 ~ 57 DEG C, present 3 kinds and change simultaneous feature: (1) magnetic transformation: directly change ferromagnetic martensite into by paramagnetic austenite; (2) martensitic transformation: austenitic transformation is 7M martensite; (3) martensitic transformation in the middle of: 7M martensitic transformation is NM martensite.
3. Ni-Mn-Ga alloy thin band according to claim 1, is characterized in that, described alloy thin band is under 2T magnetic field, and magnetic entropy change is-12.5 ~-16.4Jkg
-1k
-1; Under 5T magnetic field, magnetic entropy change is-25.5 ~-30.0Jkg
-1k
-1.
4. Ni-Mn-Ga alloy thin band according to claim 1, is characterized in that, described alloy thin band thickness is 90 ~ 120 μm.
5. the preparation method of Ni-Mn-Ga alloy thin band according to claim 1, is characterized in that, comprise the following steps:
Step 1, the preparation of polycrystalline parent state alloy:
(1) according to the composition of Ni-Mn-Ga alloy thin band, take Ni, Mn and Ga respectively, be placed in vacuum arc melting furnace water jacketed copper crucible, arc melting furnace cavity is evacuated to 3 × 10
-3~ 5 × 10
-3after Pa, pass into inert protective gas to 0.05MPa, under induction stirring, carry out arc melting, obtain button shape ingot casting;
(2) by the method for ingot casting according to above-mentioned (1), then melt back 4 ~ 5 times, obtain the polycrystalline parent state alloy of uniform composition;
Step 2, melt spinning prepares alloy thin band:
(1) high purity quartz pipe is loaded the polycrystalline parent state alloy after fragmentation, and be fixed on and get rid of in the Medium frequency induction coil of band machine; Band machine cavity will be got rid of and be evacuated to 3 × 10
-3~ 5 × 10
-3after Pa, filling with inert gas to 0.04 ~ 0.05MPa does shielding gas; The rare gas element of 0.04 ~ 0.08MPa is filled with in gas-holder;
(2) start Medium frequency induction coil, the polycrystalline parent state alloy in high purity quartz pipe is heated to melt completely;
(3) utilize the spraying pressure of rare gas element in gas-holder that the polycrystalline parent state alloy of melting is sprayed from the ozzle of high purity quartz pipe, molten state polycrystalline parent state alloy is formed alloy thin band by the towing of the running roller of high speed rotating, roller surface linear velocity is 15 ~ 20m/s, high purity quartz pipe nozzle is of a size of (4 ~ 5) mm × 0.5mm, the spacing of nozzle and roll surface is 0.3 ~ 0.6mm, obtains the fast quenching Ni-Mn-Ga alloy thin band that thickness is 90 ~ 120 μm.
Step 3, thermal treatment:
By fast quenching Ni-Mn-Ga alloy thin band, at 850 ~ 950 DEG C, water-cooled after insulation 12 ~ 24h, obtains finished product Ni-Mn-Ga alloy thin band.
6. the preparation method of Ni-Mn-Ga alloy thin band according to claim 5, is characterized in that, Ni is 99.97wt.% high-purity N i, Mn in described step 1 (1) be 99.9wt.% high-purity Mn, Ga is the high-purity Ga of 99.99wt.%.
7. the preparation method of Ni-Mn-Ga alloy thin band according to claim 5, it is characterized in that, in described step 1 (1), Ni, Mn and Ga laying method in water jacketed copper crucible is that Mn is placed in the bottommost of water jacketed copper crucible, more than Mn places Ni and Ga.
8. the preparation method of Ni-Mn-Ga alloy thin band according to claim 5, is characterized in that, by ingot casting melt back 3 times again in described step 1 (2).
9. the preparation method of Ni-Mn-Ga alloy thin band according to claim 5, is characterized in that, the rare gas element in described step 1 and step 2 is high-purity argon gas.
10. the preparation method of Ni-Mn-Ga alloy thin band according to claim 5, is characterized in that, the running roller in described step 2 (3) is copper running roller.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510753357.1A CN105400998B (en) | 2015-11-05 | 2015-11-05 | A kind of Ni Mn Ga alloy thin bands and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510753357.1A CN105400998B (en) | 2015-11-05 | 2015-11-05 | A kind of Ni Mn Ga alloy thin bands and preparation method thereof |
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| CN108559873A (en) * | 2018-04-17 | 2018-09-21 | 西北工业大学 | A kind of nickel-zirconium alloys thin-band material and preparation method |
| 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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| CN110846551B (en) * | 2019-11-26 | 2020-12-08 | 贵州师范大学 | Preparation method of NiMnGaCoCu memory alloy thin strip |
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