CN105861861B - A kind of memorial alloy of field drives deformation and preparation method thereof - Google Patents
A kind of memorial alloy of field drives deformation and preparation method thereof Download PDFInfo
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- CN105861861B CN105861861B CN201610204769.4A CN201610204769A CN105861861B CN 105861861 B CN105861861 B CN 105861861B CN 201610204769 A CN201610204769 A CN 201610204769A CN 105861861 B CN105861861 B CN 105861861B
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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
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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
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- 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
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- 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
- C22F1/006—Resulting in heat recoverable alloys with a memory effect
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- 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
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- 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
Abstract
The present invention provides a kind of memorial alloy of field drives deformation and preparation method thereof, belong to marmem field, there is the alloy external magnetic field under room temperature condition to control to produce the ability of deformation, be that a kind of can be changed at ambient temperature by external magnetic field drives martensitic twin circle to migrate and produced against migration a kind of magnetic control shape memory alloy of recoverable strain.The alloy formula is：CoxNiyAlzFej；Wherein, 28≤x≤42,25≤y≤32,23≤z≤37,0.5≤j≤10, x+y+z+j=100, x, y, z, j represent mole percent level.Magnetic control shape memory alloy of the present invention is compared with current material, there is Fe Co intermetallic compounds in its microstructure, make alloy that there is wider magneto-strain temperature range, there is important application in larger magneto-strain amount and good mechanical property, the field such as the high-precision driver and actuator that can use at room temperature.
Description
Technical field
The invention belongs to marmem field, and in particular to a kind of memorial alloy of field drives deformation and its preparation
Method.
Background technology
Magnetic control shape memory alloy is the new shape-memory material of a class, not only with conventional shape-memory alloy by temperature
The thermoelastic shape memory effect of field control, also with the magneto-shape-memory effect controlled by magnetic field, while also having big
Recoverable magnetic-field-induced strain, high response frequency and the overall characteristic such as accurately control.Current typical ferromagnetic shape memory
Alloy system has Ni-Mn-Ga, Ni-Fe-Ga, Fe based alloy (Fe-Pd, Fe-Ni-Co-Ti etc.) and Co based alloys (Co-Ni, Co-
Mn systems alloy etc.) etc..
At present in terms of the basic research and research for application and development of driver, magnetic control shape memory alloy is the most frequently used material
One of material.The AdaptaMat companies of current Finland are by Ni2MnGa alloys are applied to next-generation drive as driving sensitive material
Manufacture in.Nowadays both at home and abroad all in the performance characteristics and application of positive research and discussion magnetic control shape memory alloy, it is desirable to
Result in and further break through, its prospect is difficult to estimate, be expected to change the process of present world industry development.But it is conventional
There is monocrystalline segregation seriously in magnetic control shape memory alloy, polycrystalline poor toughness, and repeatability undesirable can lack with the relatively low grade of curie point
Fall into, greatly hinder the research and application of the alloy, it is therefore desirable for developing a kind of with preferable mechanical property, room temperature martensite
The novel magnetic controlled marmem of phase transition temperature and larger magneto-strain ability realizes its commercial introduction.
The content of the invention
In order to overcome drawbacks described above, the invention provides one kind can in the range of room temperature by external magnetic field control be deformed
Field drives deformation memorial alloy, while providing a kind of preparation method of the memorial alloy.
In order to realize foregoing invention purpose, the method for the memorial alloy of preparation field drives deformation of the invention, including with
Lower step：
Molar percentage x% Co, y% Ni, z% Al, j% Fe are placed in vacuum melting in crucible first, its
In, 28≤x≤42,25≤y≤32,23≤z≤37,0.5≤j≤10, x+y+z+j=100, its melting condition is：a.1×
10-2MPa to 1 × 10-3MPa low vacuum state；B. smelting temperature is 1300~1400 DEG C；C. fusion process is stirred using magnetic；
D. smelting time is 0.3~1.0 hour；
Then the alloy pig above-mentioned vacuum melting obtained carries out vacuum magnetic heat treatment, and treatment conditions are：Temperature 450~
650℃；Time：10~24 hours；Vacuum：1×10-2~1 × 10-3MPa；Apply magnetic field intensity：1×05~1 × 107A·
m-1；Magnetic field climbing speed is：800~1000Am-1·s-1；
Subsequent furnace cooling, cooling velocity scope is：0.01~1 DEG C of s-1；Magnetic field reduces speed：1000~
10000A·m-1·s-1；It is cooled to room temperature taking-up and obtains final magnetic control shape memory alloy.
The present invention's has the marmem that field controllable is deformed, and is prepared by the above method, chemical formula is：
CoxNiyAlzFej；Wherein, 28≤x≤42,25≤y≤32,23≤z≤37,0.5≤j≤10, x+y+z+j=100, x, y, z,
J represents mole percent level；Fe-Co intermetallic compounds are formd in the γ phases of memorial alloy.
Alloy manufactured by the present invention has the ability that can be deformed in the range of room temperature by external magnetic field control, is one
The migration of driving martensitic twin circle can be changed by external magnetic field at ambient temperature and produce the magnetic control shape memory alloy strained by planting.
Fe-Co intermetallic compounds formed in magnetic material microstructure of the present invention have good mechanical property and magnetic behavior concurrently
Feature, promote alloy to realize the characteristics of having excellent mechanical property and magnetic behavior concurrently.
The present invention compared with prior art, with advantages below：
The present invention proposes a kind of memorial alloy of field drives deformation, and the alloy is closed relative to other magnetic control shape memories
Gold forms the Fe-Co intermetallic compounds for having magnetic property and good mechanical properties concurrently in the second phase, is keeping the second phase mechanics
Performance greatly improves its magnetic property simultaneously, alloy is had wider magneto-strain temperature range, has greatly widened this
The use scope of class alloy.
The marmem of the field controllable deformation of the present invention, deformation is produced with external magnetic field control under room temperature condition
Ability, is that a kind of can be changed at ambient temperature by external magnetic field drives the migration of martensitic twin circle to produce a kind of New Magnetic Field Controlled strained
Control marmem.Marmem of the present invention forms in the second phase compared with current material and has magnetic property and power concurrently
Fe-Co intermetallic compounds of good performance are learned, is keeping the second phase mechanical property to greatly improve its magnetic property simultaneously, is making
Alloy has wider magneto-strain temperature range, has expanded its application.
(1)：Larger magneto-strain：Solid solubility of the Fe elements in Co-Ni-Al ternary alloy three-partalloys is higher, is especially closing
In gold in the higher γ phases of Co contents, Fe solid solubility can be higher.Higher solid solubility can make most Fe be distributed in Co-
In Ni-Al alloys in richness Co γ phases, the Fe excessively concentrated can make in γ phases the supersaturation of Fe contents and with Co elements formation Fe-Co
Intermetallic compound, such intermetallic compound has compared with ferromagnetism, and the magnetic behavior and deformation that can greatly improve alloy drive
Power, makes the migration that alloy is easier to occur twin boundary under external magnetic field produce larger magneto-strain.
(2)：Higher magneto-strain temperature range：Because Fe is concentrated in γ phases, make the function phase of alloy (i.e.：β
Phase) in Fe contents reduce, reduce the flat fare electron concentration of β phases, and the part Fe and Co atoms being present in γ phases are formed
Fe-Co intermetallic compounds, also making the flat fare electron concentration of alloy γ phases further reduces, so that the martensite of alloy
Phase transition temperature and Curie temperature can be gradually increasing, and expand the temperature range of ferromagnetism twin crystal martensite presence, be made in external magnetic field
The migration that can occur twin boundary with lower ferromagnetism twin crystal martensite produces magneto-strain, so that alloy possesses higher mangneto and answered
Temperature scope.
(3)：Lift mechanical property：The magnetic control shape memory alloy of the present invention forms Fe- in the good γ phases of toughness
Co intermetallic compounds.Because Fe-Co intermetallic compounds have good intensity and toughness concurrently, it is present in the γ phases of alloy
Invigoration effect is served to the overall mechanical property of alloy, the mechanical property of alloy is greatly improved.
(4)：Preparation method：The present invention uses vacuum crucible melting, in fusion process, because system is in vacuum state,
Avoiding alloy reduces its mechanics and magnetic performance because of surface oxidation.Compared with conventional method, this method, which also has, makes alloy
Internal melting defect strengthens the processing characteristics of material to the effect of surface aggregation, such as hole.Smelting temperature 1300~
Between 1400 DEG C, smelting time is 0.3~1.0 hour, both ensure that simple metal had time enough and temperature to be melted into alloy
Ingot, can ensure that Fe-Co intermetallic compounds can be formed in subsequent Cooling Process again；Avoid that temperature is too high, the time simultaneously
Long generation alloying component scaling loss.
(5)：Heat treatment method：Heat treatment uses vacuum magnetic heat treatment, on the one hand can be effectively prevented from alloy in height
Surface oxidation causes the reduction of its mechanical property and magnetic performance in warm processing procedure, for example：Alloy magnetic substance after oxidation should
Become can substantially reduce and martensitic transformation temperature change.On the other hand can be by applying magnetic field intensity 1 × 05~1 ×
107A·m-1, magnetic field climbing speed is 800~1000Am-1·s-1Magnetic-field heat treatment, make the magnetic magnetic domain in alloy to going out
In order, so as to cause induced anisotropy, the magnetocrystalline anisotropy of alloy is improved, without because of magnetic field intensity and magnetic in existing direction
Field climbing speed is excessive and occurs the scattered phenomenon of magnetic domain., on the one hand can be with then using furnace cooling and slow removal magnetic field
Low-alloyed internal stress is dropped by Slow cooling, the direction of magnetic domain in alloy on the other hand can be remained in cooling procedure
Preferentially property.
In summary, the present invention propose it is a kind of with field controllable deform marmem, the alloy relative to
Other magnetic control shape memory alloys have larger magneto-strain, higher magneto-strain temperature range and good mechanical property
The advantages of energy.
Brief description of the drawings
Fig. 1 is Co of the present inventionxNiyAlzFejSEM schemes alloy at room temperature；
Embodiment
The present invention is further described below by embodiment.
Fig. 1 is Co of the present inventionxNiyAlzFejSEM schemes alloy at room temperature, and accelerating potential is 2.0kV, beam spot size 3.0,
Operating distance 7.9mm, imaging pattern：Secondary electron image, 8000 times of multiplication factor；
Embodiment 1：
It is Co to prepare composition42Ni32Al25.5Fe0.5Have field controllable deform marmem, its preparation method
It is as follows：
(1) Co, Ni, Al, Fe that purity is 99.9% are weighed respectively；
(2) load weighted raw material is contained in crucible, using vacuum melting, its melting condition is：a.1×10-2MPa's
Vacuum state；B. smelting temperature is 1300 DEG C；C. fusion process is stirred using magnetic；D. smelting time is 1 hour.
(3) above-mentioned melted alloy pig is subjected to vacuum magnetic heat treatment, treatment conditions are：450 DEG C of temperature；Time：
24 hours；Vacuum：1×10-3Mpa；Apply magnetic field intensity：1×05A·m-1。
(4) then furnace cooling, cooling velocity scope is：0.01 DEG C/sec；Magnetic field reduces speed：1000A·m-1·s-1；It is cooled to room temperature taking-up and obtains final marmem.
The sample that Polycrystalline prepared by the above method cuts out 5 × 5 × 8mm with wire cutting carries out the various characteristics songs of detection
Line.
Embodiment 2：
It is Co to prepare composition41Ni32Al24Fe3Have field controllable deform marmem, its preparation method is such as
Under：
(1) Co, Ni, Al, Fe that purity is 99.9% are weighed respectively；
(2) load weighted raw material is contained in crucible, using vacuum melting, its melting condition is：a.9×10-3MPa's
Vacuum state；B. smelting temperature is 1350 DEG C；C. fusion process is stirred using magnetic；D. smelting time is 0.75 hour.
(3) above-mentioned melted alloy pig is subjected to vacuum magnetic heat treatment, treatment conditions are：500 DEG C of temperature；Time：
18 hours；Vacuum：8×10-3Mpa；Apply magnetic field intensity：1×106A·m-1。
(4) then furnace cooling, cooling velocity scope is：0.1 DEG C/sec；Magnetic field reduces speed：3000A·m-1·s-1；It is cooled to room temperature taking-up and obtains final marmem.
The sample that Polycrystalline prepared by the above method cuts out 5 × 5 × 8mm with wire cutting carries out the various characteristics songs of detection
Line.
Embodiment 3：
It is Co to prepare composition40Ni30Al24Fe6Have field controllable deform marmem, its preparation method is such as
Under：
(1) Co, Ni, Al, Fe that purity is 99.9% are weighed respectively；
(2) load weighted raw material is contained in crucible, using vacuum melting, its melting condition is：a.7×10-3MPa's
Vacuum state；B. smelting temperature is 1400 DEG C；C. fusion process is stirred using magnetic；D. smelting time is 0.6 hour.
(3) above-mentioned melted alloy pig is subjected to vacuum magnetic heat treatment, treatment conditions are：530 DEG C of temperature；Time：
15 hours；Vacuum：6×10-3Mpa；Apply magnetic field intensity：1×106A·m-1。
(4) then furnace cooling, cooling velocity scope is：0.3 DEG C/sec；Magnetic field reduces speed：5000A·m-1·s-1；It is cooled to room temperature taking-up and obtains final marmem.
The sample that Polycrystalline prepared by the above method cuts out 5 × 5 × 8mm with wire cutting carries out the various characteristics songs of detection
Line.
Embodiment 4：
It is Co to prepare composition35Ni28Al29Fe8Have field controllable deform marmem, its preparation method is such as
Under：
(1) Co, Ni, Al, Fe that purity is 99.9% are weighed respectively；
(2) load weighted raw material is contained in crucible, using vacuum melting, its melting condition is：a.5×10-3MPa's
Vacuum state；B. smelting temperature is 1400 DEG C；C. fusion process is stirred using magnetic；D. smelting time is 0.4 hour.
(3) above-mentioned melted alloy pig is subjected to vacuum magnetic heat treatment, treatment conditions are：550 DEG C of temperature；Time：
13 hours；Vacuum：4×10-3Mpa；Apply magnetic field intensity：1×106A·m-1。
(4) then furnace cooling, cooling velocity scope is：0.5 DEG C/sec；Magnetic field reduces speed：7000A·m-1·s-1；It is cooled to room temperature taking-up and obtains final marmem.
The sample that Polycrystalline prepared by the above method cuts out 5 × 5 × 8mm with wire cutting carries out the various characteristics songs of detection
Line.
Embodiment 5：
It is Co to prepare composition28Ni25Al37Fe10Have field controllable deform marmem, its preparation method is such as
Under：
(1) Co, Ni, Al, Fe that purity is 99.9% are weighed respectively；
(2) load weighted raw material is contained in crucible, using vacuum melting, its melting condition is：a.3×10-3MPa's
Vacuum state；B. smelting temperature is 1400 DEG C；C. fusion process is stirred using magnetic；D. smelting time is 0.3 hour.
(3) above-mentioned melted alloy pig is subjected to vacuum magnetic heat treatment, treatment conditions are：600 DEG C of temperature；Time：
10 hours；Vacuum：2×10-3Mpa；Apply magnetic field intensity：1×105A·m-1。
(4) then furnace cooling, cooling velocity scope is：0.8 DEG C/sec；Magnetic field reduces speed：8500A·m-1·s-1；It is cooled to room temperature taking-up and obtains final marmem.
The sample that Polycrystalline prepared by the above method cuts out 5 × 5 × 8mm with wire cutting carries out the various characteristics songs of detection
Line.
Embodiment 6：
It is Co to prepare composition30Ni31Al29Fe10Have field controllable deform marmem, its preparation method is such as
Under：
(1) Co, Ni, Al, Fe that purity is 99.9% are weighed respectively；
(2) load weighted raw material is contained in crucible, using vacuum melting, its melting condition is：a.1×10-3MPa's
Vacuum state；B. smelting temperature is 1400 DEG C；C. fusion process is stirred using magnetic；D. smelting time is 0.3 hour.
(3) above-mentioned melted alloy pig is subjected to vacuum magnetic heat treatment, treatment conditions are：650 DEG C of temperature；Time：8
Hour；Vacuum：1×10-3Mpa；Apply magnetic field intensity：1×105A·m-1。
(4) then furnace cooling, cooling velocity scope is：1 DEG C/sec；Magnetic field reduces speed：10000A·m-1·s-1；
It is cooled to room temperature taking-up and obtains final marmem.
The sample that Polycrystalline prepared by the above method cuts out 5 × 5 × 8mm with wire cutting carries out the various characteristics songs of detection
Line.Above-described embodiment 1-6 testing result is shown in Table 1.
The Co of the heterogeneity of table 1xNiyAlzFejMartensitic transformation temperature, Curie temperature, the maximum magneto-strain of material
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvement and the replacement of equivalents can also be made, these improvement
The technical scheme obtained with equivalent substitution should also belong to protection scope of the present invention.
Claims (2)
1. a kind of method for the memorial alloy for preparing field drives deformation, it is characterised in that this method comprises the following steps：First
Molar percentage x% Co, y% Ni, z% Al, j% Fe are placed in vacuum melting in crucible, wherein, 28≤x≤42,25≤
Y≤32,23≤z≤37,0.5≤j≤10, x+y+z+j=100, its melting condition is：a. 1×10-2MPa to 1 × 10-3MPa
Low vacuum state；B. smelting temperature is 1300 ~ 1400 DEG C；C. fusion process is stirred using magnetic；D. smelting time be 0.3 ~
1.0 hour；
Then the alloy pig above-mentioned vacuum melting obtained carries out vacuum magnetic heat treatment, and treatment conditions are：Temperature 450 ~ 650
℃；Time：10 ~ 24 hours；Vacuum：1×10-2~1×10-3MPa；Apply magnetic field intensity：1×105~1×107A·m-1；Magnetic
Climbing speed is：800~1000A·m-1·s-1；
Subsequent furnace cooling, cooling velocity scope is：0.01~1℃·s-1；Magnetic field reduces speed：1000~10000A·m-1·
s-1；It is cooled to room temperature taking-up and obtains final magnetic control shape memory alloy.
2. a kind of memorial alloy of field drives deformation, it is characterised in that the chemical formula of the memorial alloy is：CoxNiyAlzFej；
Wherein, 28≤x≤42,25≤y≤32,23≤z≤37,0.5≤j≤10, x+y+z+j=100, x, y, z, j represent Mole percent
Compare content；Fe-Co intermetallic compounds are formd in the γ phases of memorial alloy；Described memorial alloy is by claim 1 institute
The method stated is made.
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| CN110714141B (en) * | 2019-11-06 | 2021-03-23 | 四川大学 | Method for improving shape memory effect of cobalt-nickel base alloy |
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| CN103952615B (en) * | 2014-04-30 | 2016-03-30 | 东南大学 | There is magneticsubstance of field drives martensitic twin rearrangement and preparation method thereof |
| CN104018055B (en) * | 2014-06-17 | 2015-10-28 | 东南大学 | The rareearth magnetic material of high magnetocrystalline anisotropy and large magneto-strain and preparation method |
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