CN101055777A - Magnetic material with the magnetic field driving martensite phase change effect and its making method - Google Patents
Magnetic material with the magnetic field driving martensite phase change effect and its making method Download PDFInfo
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- CN101055777A CN101055777A CN 200710064282 CN200710064282A CN101055777A CN 101055777 A CN101055777 A CN 101055777A CN 200710064282 CN200710064282 CN 200710064282 CN 200710064282 A CN200710064282 A CN 200710064282A CN 101055777 A CN101055777 A CN 101055777A
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Abstract
The invention discloses a magnetic material having a magnetic field martensite phase-change effect and a chemical formula: NimConMnoSbp; wherein 35<m<55, 2<n<17, 28<0<42, 10<p<18, m+n+o+p=100, m, n, o, p represent atom content in percent. The invention also discloses a preparing method of the magnetic material having the magnetic field martensite phase-change effect, the method comprises steps: (1) weighting the material based on the chemical formula NimConMnoSbp, (2) storing the weighted material in a crucible, growing NimConMnoSbp magnetic monocrystal or multicrystal by using a general pulling method, (3) holding the material in the crucible under a melting temperature condition of 1000-1330 DEG C in 10-30 minutes, and then preparing the monocrystal or multicrystal. Compared with a current alloy, the magnetic material NimConMnoSbp of the invention has a higher controllability, thereby having a wider application, such as drivers, temperature and/or magnetism sensing members, magnetic refrigerating devices and apparatus, magnetic memories, micro-electromechanical devices and systems, etc.
Description
Technical field
The present invention relates to a kind of shape-memory material, particularly relate to and have ferromagnetism and bidirectional shape memory effect, magneto-resistor and magneto-caloric effect, and have NiCoMnSb magnetic material of the character that magnetic field can drive martensitic phase transformation and preparation method thereof.
Background technology
The general shape memorial alloy has a kind of crystal structure (hereinafter referred to as parent phase) under high relatively temperature, and under low relatively temperature spontaneous another crystal 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 phase 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 martensite transfor mation
sPoint 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 phase 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 austenite, 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.
Marmem has been widely used in various " intelligence " type purposes, as various drivers, and temperature-sensing element (device), medicine equipment etc.
Just because of the special function that marmem represented, attracted more people doing further further investigation, can control the method for its phase transformation in the hope of obtaining except that temperature other, or obtain to control the new marmem of its phase transformation by other modes, so that accessing more fully, uses the shape memory function of this material.
Summary of the invention
For these reasons, the inventor has found a kind of marmem that can be driven martensitic phase transformation by magnetic field through research, therefore, primary and foremost purpose of the present invention is to provide a kind of magnetic material with magnetic field driven martensitic transformation effect, this magnetic material not only has the character of common shape-memory material phase transformation: drive martensitic phase transformation by variations in temperature (heat energy) or external carbuncle (mechanical energy), and its martensitic phase transformation can be driven by magnetic field.Thereby the controllability of material is improved greatly, range of application is more extensive.And this material has also had the more applications prospect, as large magnetic resistance and magneto-caloric effect etc.Further aim of the present invention is to provide a kind of method for preparing the monocrystalline of this magnetic material with magnetic field driven martensitic transformation effect.
For achieving the above object, the inventor invents a kind of magnetic material with magnetic field driven martensitic transformation effect, and its chemical formula is: Ni
mCo
nMn
oSb
pWherein, 35＜m＜55,2＜n＜17,28＜o＜42,10＜p＜18, m+n+o+p=100, m, n, o, p represent atom percentage content.
Further, described Ni
mCo
nMn
oSb
pThe form of magnetic material comprises mono-crystalline structures and polycrystalline structure.
The preparation method of the magnetic material with magnetic field driven martensitic transformation effect that the present invention proposes comprises the steps:
(1) presses chemical formula Ni
mCo
nMn
oSb
pRaw materials weighing, wherein, 35＜m＜55,2＜n＜17,28＜o＜42,10＜p＜18, m+n+o+p=100, m, n, o, p represent atom percentage content;
(2) raw material that weighs up is contained in the crucible, adopts conventional Czochralski grown Ni
mCo
nMn
oSb
pMagnetic mono crystal or polycrystalline, its growth conditions is: the heating mentioned component former expect make it fusion; Its fusion environment is 1 * 10
-2To 5 * 10
-5The argon shield state of the vacuum state of Pa or 0.01～1MPa normal pressure; Fix a seed crystal in the seed rod lower end that rotates with 0.5～50 rev/min speed; Described seed crystal is a composition monocrystalline identical or approaching, that have needed orientation;
(3) raw material in making crucible kept under the temperature conditions of 1000～1330 ℃ fusion 10～30 minutes, liquid level with end in contact melt under the seed crystal, promote seed rod with 3～80mm/ hour uniform rate then, the monocrystalline or the polycrystalline of solidification and crystallization are upwards lifted, and make the monocrystalline of growth or polycrystalline diameter become big or keep certain;
(4) when the monocrystalline of growth or polycrystalline when reaching required size, monocrystalline or polycrystalline are lifted the raw material surface that breaks away from fusion, be cooled to room temperature, take out at last with 0.5～20 ℃/minute rate of temperature fall.
Further, the above-mentioned magnetic alloy for preparing was annealed in 500～1200 ℃ temperature range 0.01～100 hour again, and then be cooled to room temperature with 0.01～1000 ℃/second rate of temperature fall.
Growth mode of heating described in the above-mentioned steps (2) can adopt the radio frequency heating or the resistance heating mode of 50～245 KHz; Described crucible can be magnetic levitation cold crucible, graphite crucible or silica crucible.
Magnetic material with magnetic field driven martensitic transformation effect provided by the invention, its characteristic value dT/dH (size that unit magnetic field is moved phase transition temperature) that shows that magnetic field driven martensitic transformation is renderd a service can change by the composition proportioning that changes Mn, Co, Ni, Sb or be adjusted according to purposes.This material under martensitic state along with the increase of the magnetic field intensity that adds can produce phase transformation (contrary martensitic phase transformation) from martensite to austenitic field drives.After this reverse transformation has taken place, along with the reduction in magnetic field, material will occur from austenite to martensitic positive martensitic phase transformation.Thereby show separately by martensitic phase transformation circulation field drives, recoverable.In above-mentioned circulation, material shows the martensite transfor mation that is accompanied by field drives and reverses magnetic strain (magnetostrain) effect that becomes, and the numerical value change amplitude can reach 5.0%.In above-mentioned circulation, material also shows the character (large magnetic resistance effect) of the resistance variations with change of magnetic field strength, and the numerical value change amplitude can reach 80%.Simultaneously, material also shows the character (magneto-caloric effect) that changes the Entropy Changesization that causes with the phase transformation of field drives and magnetic order degree, and the numerical value change amplitude can reach Δ S=25J/Kkg.So, the martensitic phase transformation magnetic material Ni with field drives provided by the invention
mCo
nMn
oSb
pHas purposes widely, driver for example, temperature and/or magnetic senser, magnetic refrigeration device and equipment, magnetic memory, micro-electro-mechanical device and system etc.
Description of drawings
Accompanying drawing 1 is Ni of the present invention
mCo
nMn
oSb
pPhase transition temperature under the material field drives moves the dT/dH performance;
Accompanying drawing 3 is Ni of the present invention
mCo
nMn
oSb
pThe curve in the strain-magnetic field under the monocrystalline field drives;
Accompanying drawing 4 is Ni of the present invention
mCo
nMn
oSb
pThe curve in the resistance-magnetic field under the material field drives.
Embodiment
Below in conjunction with instantiation the present invention is described in further details.
Embodiment 1
Preparation consists of: Ni
41Co
9Mn
39Sb
11The magnetic alloy with magnetic field driven martensitic transformation effect; adopting parameter is the radio frequency heating of 245 KHz, as protective gas, uses magnetic levitation cold crucible with 0.01 argon gas that arrives the 1MPa normal pressure; heating power is 20 kilowatts, and its preparation method is specific as follows:
(1) weighing purity respectively is 99.9% Mn, Co, Ni, Sb;
(2) raw material that weighs up is put into crucible, be heated to 1230 ℃, make raw materials melt, kept 10～30 minutes;
(3) with the NiCoMnSb[001 of 2 * 2 * 7mm size] oriented single crystal is seeded growth monocrystalline or polycrystalline; The seed rod speed of rotation is 30 rev/mins in its growth course, and pulling growth speed is 30mm/ hour;
(4) be 10 millimeters, length when being 100 millimeters high quality single crystal or polycrystalline when obtaining diameter, monocrystalline or polycrystalline are lifted the raw material surface that breaks away from fusion, be cooled to room temperature, take out at last with 0.5～20 ℃/minute rate of temperature fall.
(5) monocrystalline or the polycrystalline sample that prepare were annealed in 500～1200 ℃ temperature range 0.01～100 hour again, and then cool off with 0.01～1000 ℃/second rate of temperature fall, its phase transition temperature and Curie temperature see Table 1.
The monocrystalline or the polycrystalline sample of method for preparing are cut into the small sample of 4 * 4 * 8mm and the large sample of 10 * 10 * 100mm along [001] direction, measure above-mentioned various character, obtain various characteristics curve as shown in drawings, respective value sees Table 1.
Preparation consists of: Ni
40Co
11Mn
39Sb
10The magnetic alloy with magnetic field driven martensitic transformation effect; Different is, uses specifically in the silica crucible, is heated by resistive the method growth, except that the seed rod speed of rotation is that 20 rev/mins, pulling growth speed are 10mm/ hour, all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, respective value sees Table 1.
Embodiment 3
Preparation consists of: Ni
48Co
6Mn
28Sb
18The magnetic alloy with magnetic field driven martensitic transformation effect; Removing the seed rod speed of rotation is 10 rev/mins, and pulling growth speed is outside 50mm/ hour, and all the other are with embodiment 1.Measure above-mentioned various character, obtain various characteristics curve as shown in drawings, respective value sees Table 1.
Preparation consists of Ni
53Co
5Mn
31Sb
11The magnetic alloy with magnetic field driven martensitic transformation effect; Removing the seed rod speed of rotation is 5 rev/mins, and pulling growth speed is outside 40mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
Embodiment 5
Preparation consists of: Ni
48Co
2Mn
37Sb
13The magnetic alloy with magnetic field driven martensitic transformation effect; Removing the seed rod speed of rotation is 15 rev/mins, and pulling growth speed is outside 45mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
Preparation consists of: Ni
49Co
5Mn
30Sb
16The magnetic alloy with magnetic field driven martensitic transformation effect; Removing the seed rod speed of rotation is 20 rev/mins, and pulling growth speed is outside 35mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
Embodiment 7
Preparation consists of: Ni
50Co
6Mn
32Sb
12The magnetic alloy with magnetic field driven martensitic transformation effect; Removing the seed rod speed of rotation is 25 rev/mins, and pulling growth speed is outside 25mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
Preparation consists of: Ni
43Co
12Mn
32Sb
13The magnetic alloy with magnetic field driven martensitic transformation effect; Removing the seed rod speed of rotation is 25 rev/mins, and pulling growth speed is outside 25mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
Embodiment 9
Preparation consists of: Ni
40Co
15Mn
33Sb
12The magnetic alloy with magnetic field driven martensitic transformation effect; Removing the seed rod speed of rotation is 35 rev/mins, and pulling growth speed is outside 25mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
Preparation consists of: Ni
40Co
17Mn
30Sb
13The magnetic alloy with magnetic field driven martensitic transformation effect; It is 60 rev/mins that its growth conditions removes the seed rod speed of rotation, and pulling growth speed is outside 80mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
Embodiment 11
Preparation consists of: Ni
35Co
13Mn
38Sb
14The magnetic alloy with magnetic field driven martensitic transformation effect; It is 40 rev/mins that its growth conditions removes the seed rod speed of rotation, and pulling growth speed is outside 15mm/ hour, and all the other measure above-mentioned various character with embodiment 1, obtain various characteristics curve as shown in drawings, and respective value sees Table 1.
It needs to be noted: the 1. magnetic alloy for preparing in the various embodiments described above, existing mono-crystalline structures also has polycrystalline structure; Though 2. be to prepare magnetic alloy under the condition of argon shield among the embodiment 1, the preparation magnetic alloy also can carry out in the vacuum environment of routine, as 1 * 10
-2To 5 * 10
-5Carry out under the vacuum state of Pa.
In addition, the magnetic alloy of preparation is annealed, help to improve the stability of magnetic alloy performance.
The Ni of table 1 heterogeneity
mCo
nMn
oSb
pThe dT/dH numerical value of material, magnetic strain (magnetostrain) value λ, magneto-resistor MR value and magnetic entropy become (Δ S) numerical value
| Composition | dT/dH (K/T) | λ (％) | MR (％) | ΔS (J/Kkg) |
| Ni 41Co 9Mn 39Sb 11 | 5 | 5.1 | 78 | 22.1 |
| Ni 40Co 11Mn 39Sb 10 | 4.7 | 5.0 | 80 | 24 |
| Ni 48Co 6Mn 28Sb 18 | 3.5 | 4.8 | 85 | 25 |
| Ni 53Co 5Mn 31Sb 11 | 3.1 | 4.9 | 75 | 23.5 |
| Ni 48Co 2Mn 37Sb 13 | 3.6 | 5.0 | 78 | 24 |
| Ni 49Co 5Mn 30Sb 16 | 4.2 | 4.9 | 82 | 24.7 |
| Ni 50Co 6Mn 32Sb 12 | 4.9 | 4.8 | 81 | 25 |
| Ni 43Co 12Mn 32Sb 13 | 10 | 4.8 | 80 | 23.6 |
| Ni 40Co 15Mn 33Sb 12 | 23.8 | 5.0 | 83 | 23.5 |
| Ni 40Co 17Mn 30Sb 13 | 33 | 5.1 | 80 | 25.1 |
| Ni 35Co 13Mn 38Sb 14 | 25 | 5.1 | 78 | 24.9 |
Claims (5)
1. magnetic material with magnetic field driven martensitic transformation effect, its chemical formula is:
Ni
mCo
nMn
oSb
pWherein, 35＜m＜55,2＜n＜17,28＜o＜42,10＜p＜18, m+n+o+p=100, m, n, o, p represent atom percentage content.
2. the magnetic material with magnetic field driven martensitic transformation effect as claimed in claim 1 is characterized in that, described Ni
mCo
nMn
oSb
pThe form of magnetic material comprises mono-crystalline structures and polycrystalline structure.
3. one kind prepares claim 1 or 2 described methods with magnetic material of magnetic field driven martensitic transformation effect, comprises the steps:
(1) presses chemical formula Ni
mCo
nMn
oSb
pRaw materials weighing, wherein, 35＜m＜55,2＜n＜17,28＜o＜42,10＜p＜18, m+n+o+p=100, m, n, o, p represent atom percentage content;
(2) raw material that weighs up is contained in the crucible, adopts conventional Czochralski grown Ni
mCo
nMn
oSb
pMagnetic mono crystal or polycrystalline, its growth conditions is: the heating mentioned component former expect make it fusion; Its fusion environment is 1 * 10
-2To 5 * 10
-5The argon shield state of the vacuum state of Pa or 0.01～1MPa normal pressure; Fix a seed crystal in the seed rod lower end that rotates with 0.5～50 rev/min speed; Described seed crystal is composition monocrystalline identical or approaching, that have needed orientation or polycrystalline;
(3) raw material in making crucible kept under the temperature conditions of 1000～1330 ℃ fusion 10～30 minutes, liquid level with end in contact melt under the seed crystal, promote seed rod with 3～80mm/ hour uniform rate then, the monocrystalline or the polycrystalline of solidification and crystallization are upwards lifted, and make the monocrystalline of growth or polycrystalline diameter become big or keep certain;
(4) when the monocrystalline of growth or polycrystalline when reaching required size, monocrystalline or polycrystalline are lifted the raw material surface that breaks away from fusion, be cooled to room temperature, take out at last with 0.5～20 ℃/minute rate of temperature fall.
4. as a kind of method for preparing magnetic material as described in the claim 3, it is characterized in that, also comprise step (5): the above-mentioned magnetic alloy for preparing was annealed 0.01～100 hour again, and then be cooled to room temperature with 0.01～1000 ℃/second rate of temperature fall in 500～1200 ℃ temperature range.
5. as a kind of method for preparing magnetic material as described in the claim 3, it is characterized in that the growth mode of heating described in the above-mentioned steps (2) can adopt the radio frequency heating or the resistance heating mode of 50～245 KHz; Described crucible can be magnetic levitation cold crucible, graphite crucible or silica crucible.
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| CN100463081C CN100463081C (en) | 2009-02-18 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334043A (en) * | 2013-03-22 | 2013-10-02 | 中国科学院物理研究所 | Magnetic alloy serving as magnetic refrigeration material |
| CN104630568A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院物理研究所 | MnCoGe based ferromagnetic martensite phase-change material, preparation method and applications thereof |
| CN112961717A (en) * | 2021-02-03 | 2021-06-15 | 黑龙江科技大学 | Method for quickly hydrating and separating gas hydrate based on phase-change micro-nano fluid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3881741B2 (en) * | 1997-03-19 | 2007-02-14 | Ｎｅｃトーキン株式会社 | NiMnGa alloy |
| CN1310257C (en) * | 2004-09-24 | 2007-04-11 | 中国科学院物理研究所 | Magnetic material with bidirectional shape memory effect and single-crystal producing method thereof |
-
2007
- 2007-03-08 CN CNB2007100642821A patent/CN100463081C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334043A (en) * | 2013-03-22 | 2013-10-02 | 中国科学院物理研究所 | Magnetic alloy serving as magnetic refrigeration material |
| CN103334043B (en) * | 2013-03-22 | 2015-07-08 | 中国科学院物理研究所 | Magnetic alloy serving as magnetic refrigeration material |
| CN104630568A (en) * | 2013-11-07 | 2015-05-20 | 中国科学院物理研究所 | MnCoGe based ferromagnetic martensite phase-change material, preparation method and applications thereof |
| CN104630568B (en) * | 2013-11-07 | 2017-06-06 | 中国科学院物理研究所 | A kind of ferromagnetic Martensitic Transformation Materials of MnCoGe bases and its production and use |
| CN112961717A (en) * | 2021-02-03 | 2021-06-15 | 黑龙江科技大学 | Method for quickly hydrating and separating gas hydrate based on phase-change micro-nano fluid |
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