CN102115914A - Mn50CoxNiySnz high temperature ferromagnetic shape memory alloy material and preparation method thereof - Google Patents
Mn50CoxNiySnz high temperature ferromagnetic shape memory alloy material and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 33
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 32
- 230000008018 melting Effects 0.000 claims abstract description 32
- 230000005291 magnetic effect Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 82
- 239000011572 manganese Substances 0.000 claims description 72
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- 239000000463 material Substances 0.000 claims description 22
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- 229910052786 argon Inorganic materials 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 12
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 5
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- 238000007670 refining Methods 0.000 claims description 5
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- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
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Abstract
本发明公开了一种Mn50CoxNiySnz高温铁磁形状记忆合金材料，式中，0≤x≤12，32≤y≤39，6≤z≤11，x+y+z＝50，x、y、z表示原子百分比含量。其制备方法一：按化学式称量原料，将原料盛放在水冷铜坩埚中，采用常规的电弧熔炼法制得Mn50CoxNiySnz多晶锭材。或方法二：将方法一得到的多晶锭料采用快淬甩带的方法制得Mn50CoxNiySnz多晶薄带。或方法三：将制得的多晶锭材采用常规的提拉法生长制得Mn50CoxNiySnz磁性单晶。本发明的磁性材料可用于制作驱动器、温度和/或磁性敏感元件、磁制冷器件和设备、磁存储器、微型机电器件和系统等。
The invention discloses a Mn 50 Co x Ni y Sn z high temperature ferromagnetic shape memory alloy material, where 0≤x≤12, 32≤y≤39, 6≤z≤11, x+y+z=50 , x, y, z represent atomic percentage content. The first preparation method: Weigh the raw materials according to the chemical formula, place the raw materials in a water-cooled copper crucible, and use the conventional arc melting method to prepare the Mn 50 Co x Ni y Snz polycrystalline ingot. Or method two: using the polycrystalline ingot obtained in method one to prepare Mn 50 Co x Ni y Snz polycrystalline thin ribbons by the method of rapid quenching and stripping. Or method three: growing the obtained polycrystalline ingot by conventional pulling method to obtain Mn 50 Co x Ni y Snz magnetic single crystal. The magnetic material of the present invention can be used to make drivers, temperature and/or magnetic sensitive components, magnetic refrigeration devices and equipment, magnetic memories, micro-electromechanical devices and systems, and the like.
Description
Technical field
The present invention relates to a kind of high temperature ferromagnetic shape memory alloys, particularly a kind of have ferromegnetism and a high-temperature shape-memory effect, as chemical formula Mn
50Co
xNi
ySn
zFerromagnetic shape memory alloy material of high temperature and preparation method thereof.
Background technology
The general shape memorial alloy has a kind of crystalline structure (hereinafter referred to as parent phase) under high relatively temperature, and under low relatively temperature spontaneous another crystalline structure that becomes, generally be referred to as martensitic phase.When from higher greenhouse cooling to lower temperature, material changes martensitic phase into from parent phase, and this changes mutually and is called martensitic transformation.Conversely, from low relatively temperature heating material, alloy can change parent phase into from martensitic phase, and this opposite transformation mutually is called the martensite reverse transformation.Generally, be called M with the starting point and the terminal point of martensitic transformation
1Point and M
fPoint, beginning and terminal point with the martensite reverse transformation are called A
sPoint and A
fThe point.If M
sAnd A
sBetween difference less, such as be the several years or tens the degree, this martensitic transformation of material is called as thermoelastic martensitic transformation.Usually, certain alloy material is cooled off with the shape of determining at parent phase, behind martensitic phase, change original shape more artificially, then, alloy material is heated up, when being transformed into parent phase, if the shape of alloy material completely or partially changes original shape into, this phenomenon is called shape memory effect.In addition, if in the circulation of same said temperature, the shape of parent phase is out of shape constantly in the phase transformation that cooling causes, the reverse transformation redeformation constantly that causes in subsequently intensification again, and partly or entirely be transformed into the shape of original parent phase, be referred to as bidirectional shape memory effect.Type purposes that shape memory alloy is widely used in various " intelligence ", as various driving mechanisms, temperature-sensing element, medicine equipment etc.The Ni that in the past had similarity
2The parent phase fragility of MnGa alloy is bigger, and the Ga element is relatively more expensive simultaneously, thereby has influenced the element manufacturing of material.And, Ni
2MnGa material phase transformation and reverse transformation temperature are lower, have influenced material at higher temperature environmental applications, for example document: P.J.Webster, K.R.A.Ziebeck, S.L.Town, and M.S.Peak, PhilosophicalMagazine B, 49,295 (1984).Afterwards, people attempted replacing Ga so that material has better character, Ni with other element
2MnSn and Ni
2The appearance of MnAl has reduced the production cost of material, but the transformation temperature of NiMn-base shape memory material is not very high, and material is more crisp, be difficult for preparation, such as, H.C.Xuan in 2008, the article Effect of annealing on the martensitic transformation and magnetocaloriceffect in Ni that people such as K.X.Xie and D.H.Wang deliver on Applied Physics Letters
44.1Mn
44.2Sn
11.7Having studied chemical formula among the ribbons is Ni
44.1Mn
44.2Sn
11.7The transformation temperature of alloy only be 270K.And research major part afterwards concentrates on other character of material, as exchange biased, magnetic refrigeration effect and huge Hall effect etc., corresponding document has Chao Jing, Jiping Chen, Zhe Li, Yanfei Qiao, Baojuan Kang, Shixun Cao and Jincang Zhang, Journal of Alloys andCompounds 475 (2009) 1-4 and I.Dubenko, A.K.Pathak, S.Stadler and N.Ali, Physical Review B 80,092408 (2009), and few to the research that improves its transformation temperature, this has just limited the application of these alloys in the high temperature field.
Summary of the invention
The purpose of this invention is to provide a kind of as chemical formula Mn
50Co
xNi
ySn
zThe ferromagnetic shape memory alloy material of high temperature, 0≤x in the formula≤12,32≤y≤39,6≤z≤11, x+y+z=50, x, y, z represent atom percentage content, this alloy material can be widely used in the high temperature field.
The present invention also aims to provide a kind of as chemical formula Mn
50Co
xNi
ySn
zThe preparation method of the ferromagnetic shape memory alloy material of high temperature.
Mn of the present invention
50Co
xNi
ySn
zThe atomic percent of the ferromagnetic shape memory alloy material of high temperature is formed and is based on that following principle determines:
The martensitic transformation temperature of NiMn alloy is 1000K, but its Curie temperature is very low, the character that does not have magnetic field driven martensitic transformation, mix after the Co, exchange interaction between the Co-Mn is stronger than the exchange interaction between the Ni-Mn, can improve the Curie temperature of material, and excessive Co can produce dephasign, phase transformation is disappeared, so after mixing a certain amount of Co, replace Ni with Sn again the valence electron of material is reduced, and then the martensitic transformation temperature of reduction material, in experimentation, the preparation of monocrystalline strip can be removed and be mixed a small amount of dephasign that produces behind the Co, finally realizes Mn
50Co
xNi
ySn
zThe high temperature ferromagnetic shape memory alloys.Consisting of of final definite alloy material: Mn
50Co
xNi
ySn
z, 0≤x in the formula≤12,32≤y≤39,6≤z≤11, x+y+z=50, x, y, z represent atom percentage content.
The said Mn of the present invention
50Co
xNi
ySn
zThe form of the ferromagnetic shape memory alloy material of high temperature comprises monocrystalline and polycrystalline.
The Mn that the present invention provides
50Co
xNi
ySn
zThe preparation method of the ferromagnetic shape memory alloy material of high temperature comprises:
Method one: preparation polycrystalline ingot
(1) weighing proportioning
Press chemical formula Mn
50Co
xNi
ySn
zAtomic percent to take by weighing purity be that 99.9% manganese (Mn), purity are that 99.9% cobalt (Co), purity are that 99.9% nickel (Ni) and purity are 99.99% tin (Sn) bulk;
(2) melting (preparation) polycrystalline ingot
The material that weighs up is placed in the smelting pot, adopts conventional arc melting method to obtain Mn
50Co
xNi
ySn
zPolycrystalline, melting condition is: extracting vacuum makes vacuum tightness reach 1 * 10
-4Pa, feed argon gas, make melting chamber internal pressure reach 0.1MPa, produce electric arc, melting electric current 100A, the electric arc head remains on 2-5cm place, sample top and swings about 1min repeatedly among a small circle, each sample upset 3 times, congruent melting refining 4 times is even to guarantee composition, and the button spindle sample that is obtained is packed into after with the tantalum piece parcel and is carried out high-temperature homogenization in the vitreosil pipe of sealing under 800 ℃ and handle 72h, quench then to realize the arrangement of atom high-sequential, finally obtain Mn
50Co
xNi
ySn
zFerromagnetic shape memory alloys polycrystalline ingot.
Method two: fast quenching gets rid of band, preparation polycrystalline strip
To put into the silica tube that a upper end open, bottom sealing and bottom have aperture according to the polycrystalline ingot that method one makes, and the silica tube opening end will be placed to up get rid of in the band machine furnace chamber again, vacuumize, treat that vacuum tightness reaches 6.6 * 10
-3During Pa, feed high-purity argon gas to getting rid of band machine furnace chamber, wait to get rid of in the band machine furnace chamber pressure and reach 350 mmhg (0.05Mpa) time, adopt induction heating, and constantly regulate the power of induction heating, make alloy be in molten state, be blown into high-purity argon gas from the silica tube opening end then and molten alloy liquid be ejected on the copper wheel of high speed rotating that linear velocity is 17m/s throw away fast, finally obtain Mn from aperture with certain pressure
50Co
xNi
ySn
zFerromagnetic shape memory alloys polycrystalline strip.
Method three: the long monocrystalline of crystal pulling method, preparation shape memory alloy monocrystalline
To be contained in the crucible according to the polycrystalline ingot that method one makes, adopt conventional Czochralski grown Mn
50Co
xNi
ySn
zMonocrystalline, its growth conditions is: the heating ingot makes it fusion, and its fusion environment is 1 * 10
-2～5 * 10
-5The argon shield gas of the vacuum of Pa or 0.01～1MPa positive pressure is fixed a seed crystal with the seed rod lower end that the speed of 0.5～50 commentaries on classics/min is rotated; Described seed crystal is a composition monocrystalline identical or approaching, that have needed orientation, under 1000～1330 ℃ melt temperature condition, keep 10～30min, liquid level with end in contact melt under the seed crystal, uniform rate with 3～80mm/h promotes seed rod then, lift on the single crystal direction with solidification and crystallization, and make the single crystal diameter of growth become big or keep certain; When the monocrystalline of growth when reaching desired size, single crystal pulling is broken away from fused raw material surface, slowly reduce temperature with the rate of temperature fall of 0.5～20 ℃/min and be cooled to room temperature, take out at last.Further, with the above-mentioned sample that the prepares 0.01～100h that in 500～1200 ℃ temperature range, anneals again, and then, finally obtain Mn with the rate of temperature fall cooling of 0.01～1000 ℃/s
50Co
xNi
ySn
zThe ferromagnetic shape memory alloys monocrystalline.
In preparation method three of the present invention, the growth type of heating can heat or the resistive heating mode with the radio frequency of 50～245 kilohertzs.Described crucible can be a kind of in magnetic levitation cold crucible, plumbago crucible, the quartz crucible.
According to different purposes, each characteristic temperature point of its martensitic transformation of magneticsubstance with high-temperature shape-memory effect provided by the invention and molecular magnetic moment value and Curie temperature value can be by changing Mn, Co, and Ni, the Sn ratio of components is adjusted.Say Mn of the present invention exactly
50Co
xNi
ySn
zThe alloy material martensitic transformation temperature can 50K～600K on a large scale in adjustable arbitrarily, the molecular magnetic moment value is at 3 μ
B～6 μ
BAdjustable, the Curie temperature value reaches as high as 560K, and these parameters can satisfy various application requiring.This Mn simultaneously
50Co
xNi
ySn
zMaterial can be prepared into forms such as ingot, strip and monocrystalline and conveniently be applied to different field.
The beneficial effect that the present invention obtains is: the Mn with high-temperature shape-memory effect provided by the invention
50Co
xNi
ySn
zAlloy material has purposes widely, driving mechanism for example, temperature and/or magnetic sensor, magnetic refrigeration device and equipment, magneticstorage, micro-electro-mechanical device and system etc.Conventional melting equipment, fast quenching gets rid of carrying equipment or pulling single crystal equipment all can successfully prepare, and does not need additional miscellaneous equipment, and therefore, preparation method's cost of the present invention is low, be easy to industrialized mass production.
Description of drawings
Fig. 1 is Mn
50Co
xNi
ySn
zAlloy DSC figure.
Fig. 2 is Mn
50Co
xNi
ySn
zAlloy ac magnetic susceptibility figure.
Fig. 3 is Mn
50Co
4Ni
37Sn
9Alloy M-H curve.
Embodiment
Following examples are used to illustrate the present invention.
Embodiment 1 preparation Mn
50Ni
39Sn
11Ferromagnetic shape memory alloys polycrystalline ingot
(1) weighing proportioning
Press chemical formula Mn
50Ni
39Sn
11Atomic percent to take by weighing purity be that 99.9% manganese (Mn), purity are that 99.9% nickel (Ni) and purity are 99.9% tin (Sn);
(2) melting (preparation) polycrystalline ingot
The above-mentioned Mn that weighs up, Ni bulk are placed in the smelting pot, and extracting vacuum makes vacuum tightness reach 1 * 10
-4Pa, feed argon gas, make melting chamber internal pressure reach 0.1MPa, produce electric arc, melting electric current 100A, the electric arc head remains on 2-5cm place, sample top and swings about 1min repeatedly among a small circle, each sample upset 3 times, congruent melting refining 4 times is even to guarantee composition, and the button spindle sample that is obtained is packed into after with the tantalum piece parcel and is carried out high-temperature homogenization in the vitreosil pipe of sealing under 800 ℃ and handle 72h, quench then to realize the arrangement of atom high-sequential, finally obtain Mn
50Ni
39Sn
11Shape memory alloy polycrystalline ingot.
Adopt wire cutting method, at the above-mentioned Mn that makes
50Ni
39Sn
11Cut in the polycrystalline ingot and be of a size of 1 * 1 * 3mm
3Rectangular parallelepiped as the phase transformation specimen, adopting differential scanning calorimetry instrument (DSC) to measure martensitic transformation temperature is 98K (as shown in Figure 1), be applicable to the application of extremely low temperature, ac magnetization rate curve (as shown in Figure 2) with ac magnetic susceptibility test macro measure sample, spike has appearred in ac magnetic susceptibility when 50K, illustrate that the magnetic material has the existence of spin glass attitude below 50K, frustrate system for fundamental research provides a new resistance; Sample has been carried out phase transformation and magnetometric analysis, and respective value sees Table 1.
(1) weighing proportioning
Press chemical formula Mn
50Co
4Ni
37Sn
9Atomic percent to take by weighing purity be that 99.9% manganese (Mn), purity are that 99.9% cobalt (Co), purity are that 99.9% nickel (Ni) and purity are 99.9% tin (Sn);
(2) melting (preparation) polycrystalline ingot
The above-mentioned Mn that weighs up, Co, Ni, Sn bulk are placed in the smelting pot, and extracting vacuum makes vacuum tightness reach 1 * 10
-4Pa feeds argon gas, makes melting chamber internal pressure reach 0.1MPa; Produce electric arc, melting electric current 100A, the electric arc head remains on 2-5cm place, sample top and swings about 1min repeatedly among a small circle, each sample upset 3 times, congruent melting refining 4 times is even to guarantee composition, under 800 ℃, carry out high-temperature homogenization in the vitreosil pipe of the button spindle sample that is obtained with the sealing of packing into behind the tantalum piece parcel and handle 72h, quench then, finally obtain Mn to realize that the atom high-sequential arranges
50Co
4Ni
37Sn
9Shape memory alloy polycrystalline ingot.
(3) fast quenching gets rid of band, preparation polycrystalline strip
The arc melting polycrystalline ingot that obtains is put into the silica tube that a upper end open, bottom sealing and bottom have aperture, the silica tube opening end is placed to up gets rid of in the band machine furnace chamber again, vacuumize, treat that vacuum tightness reaches 6.6 * 10
-3During Pa, feed high-purity argon gas to getting rid of band machine furnace chamber furnace chamber, wait to get rid of in the band machine furnace chamber pressure and arrive 350 mmhg (0.05Mpa) time, adopt induction heating, and constantly regulate the power of induction heating, make alloy be in white molten state of processing, being blown into the high-purity argon gas with certain pressure from the silica tube opening end is ejected on the copper wheel of high speed rotating that linear velocity is 17m/s molten alloy liquid to throw away fast from aperture, obtain the polycrystalline strip, width is 3-4mm, and thickness is 40-50 μ m.
With the above-mentioned Mn that makes
50Co
4Ni
37Sn
9Polycrystalline gets rid of carry sample, measures martensitic transformation temperature (as shown in Figure 1) with differential scanning calorimetry instrument (DSC), and martensitic transformation temperature is 219K; With the ac magnetization rate curve (as shown in Figure 2) of ac magnetic susceptibility test macro measure sample, find that its transformation temperature is consistent with the DSC test, is higher than Mn
50Ni
39Sn
11Material; Utilize PPMS near transformation temperature, to measure the M-H curve (as shown in Figure 3) of sample, observe tangible round trip and become magnetic transition, therefore this material has the double-pass memory effect of magnetic field driven martensitic transformation, promptly only changes magnetic field and just can realize shape memory effect under specified temp; Sample has been carried out phase transformation and magnetometric analysis, and respective value sees Table 1.
Embodiment 3 preparations consist of: Mn
50Co
8Ni
34Sn
8Ferromagnetic shape memory alloys polycrystalline ingot
The preparation method measures its DSC curve (as shown in Figure 1) with embodiment 1, and the martensitic transformation temperature of sample is 317K; Measure ac magnetization rate curve (as shown in Figure 2), martensitic transformation temperature is consistent with DSC, and Curie temperature is 520K; Sample has been carried out phase transformation and magnetometric analysis, and respective value sees Table 1.
(1) weighing proportioning
Press chemical formula Mn
50Co
12Ni
32Sn
9Atomic percent to take by weighing purity be that 99.9% manganese (Mn), purity are that 99.9% cobalt (Co), purity are that 99.9% nickel (Ni) and purity are 99.9% tin (Sn);
(2) melting (preparation) polycrystalline ingot
The above-mentioned Mn that weighs up, Co, Ni, Sn bulk are placed in the smelting pot, and extracting vacuum makes vacuum tightness reach 1 * 10
-4Pa feeds argon gas, makes melting chamber internal pressure reach 0.1MPa; Produce electric arc, melting electric current 100A, the electric arc head remains on 2-5cm place, sample top and swings about 1min repeatedly among a small circle, each sample upset 3 times, congruent melting refining 4 times is even to guarantee composition, under 800 ℃, carry out high-temperature homogenization in the vitreosil pipe of the button spindle sample that is obtained with the sealing of packing into behind the tantalum piece parcel and handle 72h, quench then, finally obtain Mn to realize that the atom high-sequential arranges
50Co
12Ni
32Sn
9Ferromagnetic shape memory alloys polycrystalline ingot.
(3) the long monocrystalline of crystal pulling method
Adopting growth parameter(s) is the radio frequency heating of 245 kilohertzs, with 0.01 to the argon gas of 1MPa positive pressure as shielding gas, in magnetic levitation cold crucible, 20 kilowatts of heating powers.The polycrystalline ingot of 30g left and right sides arc melting is contained in the crucible, is heated to 1230 ℃ of fusions, keep 10～30min; NiMnSn[001 with 2 * 2 * 7mm size] oriented single crystal is the seeded growth monocrystalline; The seed rod speed of rotation is 30 commentaries on classics/min in its process of growth, and pulling growth speed is 30mm/h; When obtaining diameter is 10mm, when length is the high quality single crystal of 100mm, single crystal pulling is broken away from fused raw material surface, slowly reduces temperature with the rate of temperature fall of 0.5～20 ℃/min and is cooled to room temperature, takes out at last; With the sample that the prepares 0.01～100h that in 500-1200 ℃ temperature range, anneals again, and then, obtain Mn with the rate of temperature fall cooling of 0.01～1000 ℃/s
50Co
12Ni
32Sn
9Single crystal samples.
With Mn
50Co
12Ni
32Sn
9Single crystal samples cuts into small sample along [001] direction, measures its DSC and ac magnetic susceptibility, and the character of this monocrystalline is identical with the character of its polycrystalline strip.
Embodiment 5 preparations consist of: Mn
50Co
12Ni
32Sn
8The ferromagnetic shape memory alloys monocrystalline
(1) weighing proportioning
Method is with embodiment 4.
(2) melting (preparation) polycrystalline ingot
Method is with embodiment 4.
(3) the long monocrystalline of crystal pulling method
Adopting growth parameter(s) is the radio frequency heating of 150 kilohertzs, with 0.01 to the argon gas of 1MPa positive pressure as shielding gas, in plumbago crucible, 20 kilowatts of heating powers.The polycrystalline ingot of 30g left and right sides arc melting is contained in the crucible, is heated to 1230 ℃ of fusions, keep 10～30min; NiMnSn[001 with 2 * 2 * 7mm size] oriented single crystal is the seeded growth monocrystalline; The seed rod speed of rotation is 30 commentaries on classics/min in its process of growth, and pulling growth speed is 30mm/h; When obtaining diameter is 10mm, when length is the high quality single crystal of 100mm, single crystal pulling is broken away from fused raw material surface, slowly reduce temperature with the rate of temperature fall of 0.5～20 ℃/min and be cooled to room temperature, take out at last, with the sample that the prepares 0.01～100h that in 500-1200 ℃ temperature range, anneals again, and then, obtain Mn with the rate of temperature fall cooling of 0.01～1000 ℃/s
50Co
12Ni
32Sn
8Single crystal samples.
With Mn
50Co
12Ni
32Sn
8Single crystal samples cuts into small sample along [001] direction, measures its DSC and ac magnetic susceptibility, and the character of this monocrystalline is identical with the character of its polycrystalline ingot.
(1) weighing proportioning
Method is with embodiment 4.
(2) melting (preparation) polycrystalline ingot
Method is with embodiment 4.
(3) the long monocrystalline of crystal pulling method
Adopting growth parameter(s) is the radio frequency heating of 100 kilohertzs, with 0.01 to the argon gas of 1MPa positive pressure as shielding gas, in quartz crucible, 20 kilowatts of heating powers.The polycrystalline ingot of 30g left and right sides arc melting is contained in the crucible, is heated to 1230 ℃ of fusions, keep 10～30min; NiMnSn[001 with 2 * 2 * 7mm size] oriented single crystal is the seeded growth monocrystalline, and the seed rod speed of rotation is 30 commentaries on classics/min in its process of growth, and pulling growth speed is 30mm/h; When obtaining diameter is 10mm, when length is the high quality single crystal of 100mm, single crystal pulling is broken away from fused raw material surface, slowly reduces temperature with the rate of temperature fall of 0.5～20 ℃/min and is cooled to room temperature, takes out at last; With the sample that the prepares 0.01～100h that in 500-1200 ℃ temperature range, anneals again, and then, obtain Mn with the rate of temperature fall cooling of 0.01～1000 ℃/s
50Co
12Ni
32Sn
6Single crystal samples.
With Mn
50Co
12Ni
32Sn
6Single crystal samples cuts into small sample along [001] direction, measure its DSC and ac magnetic susceptibility, obtain the various characteristics curve, its martensitic transformation temperature is 528K, Curie temperature is 552K, be the highest material of Curie temperature in the ferromagnetic shape memory alloys of being found at present, the molecular magnetic moment value of sample is up to 6.04 μ
B, also be the strongest material of magnetic in the present ferromagnetic shape memory alloys.
That table 1 provides is the Mn of heterogeneity
50Co
xNi
ySn
zMartensitic transformation temperature (the T of material
M), the reverse alternating temperature degree of martensite (T
A), Curie temperature (T
C) and molecular magnetic moment (M) value.
Table 1
| T M(K) | T A(K) | T C(K) | M(μ B/f.u.) | |
| Mn 50Ni 39Sn 11 | 98 | 114 | 284 | 4.36 |
| Mn 50Co 4Ni 37Sn 9 | 219 | 249 | 370 | 5 |
| Mn 50Co 8Ni 34Sn 8 | 317 | 353 | 520 | 5.4 |
| Mn 50Co 12Ni 32Sn 6 | 528 | 562 | 552 | 6.04 |
Claims (6)
1. Mn
50Co
xNi
ySn
zThe ferromagnetic shape memory alloy material of high temperature is characterized in that in the formula: 0≤x≤12,32≤y≤39,6≤z≤11, and x+y+z=50, x, y, z represent atom percentage content.
2. Mn as claimed in claim 1
50Co
xNi
ySn
zHigh-temperature shape memory alloy material is characterized in that: the form of material is divided into monocrystalline and polycrystalline.
3. one kind prepares Mn as claimed in claim 1 or 2
50Co
xNi
ySn
zThe method of the ferromagnetic shape memory alloy material of high temperature is characterized in that comprising the steps:
(1) weighing proportioning
Press chemical formula Mn
50Co
xNi
ySn
zAtomic percent to take by weighing purity be that 99.9% manganese (Mn), purity are that 99.9% cobalt (Co), purity are that 99.9% nickel (Ni) and purity are 99.99% tin (Sn) bulk;
(2) melting (preparation) polycrystalline ingot
The material that weighs up is placed in the smelting pot, adopts conventional arc melting method to obtain Mn
50Co
xNi
ySn
zPolycrystalline, melting condition is: extracting vacuum makes vacuum tightness reach 1 * 10
-4Pa, feed argon gas, make melting chamber internal pressure reach 0.1MPa, produce electric arc, melting electric current 100A, the electric arc head remains on 2-5cm place, sample top and swings about 1min repeatedly among a small circle, each sample upset 3 times, congruent melting refining 4 times is even to guarantee composition, and the button spindle sample that is obtained is packed into after with the tantalum piece parcel and is carried out high-temperature homogenization in the vitreosil pipe of sealing under 800 ℃ and handle 72h, quench then to realize the arrangement of atom high-sequential, finally obtain Mn
50Co
xNi
ySn
zFerromagnetic shape memory alloys polycrystalline ingot.
4. preparation method according to claim 3, it is characterized in that: the polycrystalline ingot that obtains is put into the silica tube that a upper end open, bottom sealing and bottom have aperture, again the silica tube opening end is placed to up and gets rid of in the band machine furnace chamber, vacuumize, treat that vacuum tightness reaches 6.6 * 10
-3During Pa, in getting rid of band machine furnace chamber, feed high-purity argon gas, wait to get rid of in the band machine furnace chamber pressure and arrive 350 mmhg (0.05Mpa) time, adopt induction heating, and constantly regulate the power of induction heating, make alloy be in molten state, be blown into high-purity argon gas from the silica tube opening end then and molten alloy liquid be ejected on the copper wheel of high speed rotating that linear velocity is 17m/s throw away fast, finally obtain Mn from aperture
50Co
xNi
ySn
zFerromagnetic shape memory alloys polycrystalline strip.
5. preparation method according to claim 3 is characterized in that: the polycrystalline ingot that obtains is contained in the crucible, adopts conventional Czochralski grown Mn
50Co
xNi
ySn
zMonocrystalline, its growth conditions is: the heating ingot makes it fusion, and its fusion environment is 1 * 10
-2～5 * 10
-5The argon shield gas of the vacuum of Pa or 0.01～1MPa positive pressure; fix a seed crystal with the seed rod lower end that the speed of 0.5～50 commentaries on classics/min is rotated; described seed crystal is that composition is identical or approaching; monocrystalline with needed orientation; under 1000～1330 ℃ melt temperature condition, keep 10～30min; liquid level with end in contact melt under the seed crystal; uniform rate with 3～80mm/h promotes seed rod then; lift on the single crystal direction with solidification and crystallization; and the single crystal diameter that makes growth becomes big or keeps certain; when the monocrystalline of growth reaches desired size; single crystal pulling is broken away from fused raw material surface; slowly reduce temperature with the rate of temperature fall of 0.5～20 ℃/min and be cooled to room temperature; take out sample at last; with the above-mentioned sample that the prepares 0.01～100h that in 500～1200 ℃ temperature range, anneals; and then, finally obtain Mn with the cooling of the rate of temperature fall of 0.01～1000 ℃/s
50Co
xNi
ySn
zThe ferromagnetic shape memory alloys monocrystalline.
6. preparation method according to claim 5 is characterized in that: the growth type of heating is the radio frequency heating or the resistive heating mode of 50～245 kilohertzs, and described crucible is a kind of in magnetic levitation cold crucible, plumbago crucible, the quartz crucible.
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| CN102732762A (en) * | 2012-07-20 | 2012-10-17 | 河北师范大学 | Magnetic shape memory alloy material with great exchange bias effect and preparation method thereof |
| CN102751063A (en) * | 2012-07-20 | 2012-10-24 | 河北师范大学 | Magnetic belt material with zero field cooling exchange bias effect and method for preparing magnetic belt material |
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| CN107350439B (en) * | 2017-07-24 | 2019-06-04 | 河北工业大学 | Preparation method of highly ordered Ni2VAl alloy ultrathin ribbon with Cu2MnAl structure |
| CN109576530A (en) * | 2018-12-27 | 2019-04-05 | 江西理工大学 | Huge exchange biased Mn based alloy of one kind and its preparation method and application |
| CN113088850A (en) * | 2021-04-13 | 2021-07-09 | 哈尔滨工业大学 | Preparation method of large reversible magnetic strain NiCoMnSn alloy |
| CN113571632A (en) * | 2021-09-23 | 2021-10-29 | 南开大学 | Abnormal Hall element and preparation method thereof |
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| CN115044981A (en) * | 2022-06-15 | 2022-09-13 | 上海大学 | Preparation method and application of antiferromagnetic single crystal material with exchange bias effect |
| CN115044981B (en) * | 2022-06-15 | 2024-03-12 | 上海大学 | Preparation method and application of antiferromagnetic single crystal material with exchange bias effect |
| CN119615374A (en) * | 2024-12-10 | 2025-03-14 | 中国科学院赣江创新研究院 | NiMn-based polycrystalline alloy and preparation method and application thereof |
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