CN1272464C - Magnetic and heating treatment method to improve magnetically driven reversible strain property of polycrystalline Ni2 MnGa - Google Patents

Magnetic and heating treatment method to improve magnetically driven reversible strain property of polycrystalline Ni2 MnGa Download PDF

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CN1272464C
CN1272464C CN02111523.0A CN02111523A CN1272464C CN 1272464 C CN1272464 C CN 1272464C CN 02111523 A CN02111523 A CN 02111523A CN 1272464 C CN1272464 C CN 1272464C
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magnetic
polycrystalline
mnga
thermomagnetic treatment
temperature
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CN1453388A (en
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徐祖耀
陈世朴
赵容斌
钱明
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Emerson Electric China Holdings Co Ltd
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
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Abstract

The present invention relates to a method for improving reversible magnetic drive dependent variable of polycrystalline Ni2MnGa by utilizing magnetic heat treatment, which comprises the following steps that a, Ni2MnGa alloy is prepared according to nonstoichiometry, wherein Ni content is 50.3 to 53.0 at%, and a ratio of Mn to Ga is 1.05 to 1.15; b, polycrystalline ingots are prepared from high-purity element Ni, Mn and Ga used as raw materials by electric arc melting in argon atmosphere; c, polycrystalline ingots are uniformly annealed for 1 to 3 days at a temperature of 1100 to 1200K; d, the test samples of the annealed polycrystalline ingots is processed by magnetic heat treatment for 20 to 30 minutes at a temperature of 340 to 350K or 360 to 460K in 0.7 T of magnetic field intensity H, and then processed by air cooling or water quenching in magnetic field. The present invention has the advantages that compared with alloy not processed by the magnetic heat treatment, the reversible magnetic drive dependent variable of the polycrystalline Ni2MnGa is increased by about 17% by utilizing the magnetic heat treatment.

Description

Utilize thermomagnetic treatment to improve polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property
Technical field
The present invention relates to a kind of Ni that produces the magnetic control shape memory effect 2The MnGa functional materials more particularly, relates to and a kind ofly can improve polycrystalline Ni by thermomagnetic treatment 2The magnetic of MnGa drives the method for reversible strain property.
Background technology
Shape can take place under certain condition and recover as a kind of new-type functional material in shape memory alloy (SMA), produces macro-strain and restorer.Since people such as U.S. Buehler in 1963 find shape memory effect (SME) in the NiTi alloy first, all obtaining huge progress aspect fundamental research and the Application and Development, and at Aeronautics and Astronautics, medical treatment, engineering and daily life field widespread use is being arranged.Though traditional shape memory alloy such as NiTi, Cu base, Fe base alloy etc. have bigger recoverable strain and big restorer, owing to controlled by temperature, its response frequency is very low.In contrast to this, piezoelectricity known in the prior art and magnetostriction materials have much higher response frequency (~1000Hz), but reversible strain property has only 0.1% order of magnitude.
1996, Ullakko was at J.Mater.Eng.Perform. 5Propose a kind of in (1996) 405 with Ni 2MnGa is the novel magnetic control shape memory material and the mechanism of action thereof of representative, they can be under martensitic state (the rearranging of<martensite twin variant that 1T) causes (perhaps twin-plane boundary moves) brought out and produced the reversible macro-strain by not too high magnetic field.According to crystallographic reckoning, under the monocrystalline condition, the reversible strain of this kind field drives can reach 6~7%, and promptly the heat driving shape memory alloy with traditional is suitable, and has been achieved.And because no longer temperature dependent drives, its response frequency can surpass 5KHz, is a kind of transmitter or performer material that has application prospect.
Consider from economic angle, monocrystal material is applied to industry and the daily life field cost very high, and present Ni 2The prematurity still of MnGa single crystal preparation technology, for example the easy volatile of Mn and Ga element makes composition control difficulty, the device performance instability of making in preparation.
People such as Chu are at J.Appl.Phys. 87Disclosed Ni in (2000) 5777 2The MnGa monocrystalline cools off under magnetic field when martensitic transformation takes place, and according to the different orientation of magnetic field with respect to monocrystalline, can make the volume content of the martensite twin variant of a certain particular orientation reach 74%.
Although Ni 2The MnGa monocrystal material has fine prospect in the reversible strain of field drives, but is limited to technology and cost also is difficult to reach practical stage.If can adopt polycrystalline Ni 2The MnGa material will definitely promote the practicability of this new function material greatly.But, because parent grain and to bring out the martensite twin variant orientation of generation by simple heat chaotic in the polycrystalline material causes its magnetic to bring out the macro-strain amount and has only 10 -4The order of magnitude (being hundreds of ppm); Even make its parent phase be column crystal (parent phase texture) by methods such as directional freezes, also can only reach 120 * 10 -6The highest by 0.30%.
Summary of the invention
The objective of the invention is for can be at monocrystalline Ni 2Outside the technology of preparing of MnGa material, provide a kind of polycrystalline Ni again 2The technology of preparing of MnGa material is particularly introduced and is utilized thermomagnetic treatment to improve polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property.
For achieving the above object, the present invention describes a kind of thermomagnetic treatment of utilizing and improves polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, and this method comprises the following steps:
A) prepare Ni by the nonstoichiometry proportioning 2The MnGa alloy, the Ni that described nonstoichiometry proportioning is prepared 2The Ni that contains 50.3~53.0at% in the MnGa alloy, Mn/Ga is than=1.05~1.15;
By this proportioning, with the Ni of high pure element, Mn and Ga raw material carry out arc melting under argon shield, make polycrystalline ingot;
B) above-mentioned polycrystalline ingot being carried out homogenizing annealing handles;
C) polycrystalline ingot of handling through homogenizing is made the sample coupon of certain size, places pure iron yoke-permanent magnets assembly to carry out thermomagnetic treatment.
The thermomagnetic treatment of utilizing is as previously discussed improved polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, the polycrystalline Ni of described nonstoichiometry proportioning preparation 2The Ni that contains 50.3~53.0at% in the MnGa alloy, Mn/Ga is than=1.05~1.15.
The thermomagnetic treatment of utilizing is as previously discussed improved polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, and the annealing temperature that described polycrystalline ingot carries out the homogenizing annealing processing is 1100~1200K, and the time is 1~3 day.
The thermomagnetic treatment of utilizing is as previously discussed improved polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, and described thermomagnetic treatment is to be of a size of 2 * 4 * 8mm 3Sample coupon place pure iron yoke-NdFeB permanent magnets assembly to carry out, magneticstrength is H ≈ 0.7T, they with behind stove heating and the insulation certain hour, are taken out air cooling or shrend by simultaneously together.
The thermomagnetic treatment of utilizing is as previously discussed improved polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, and the Heating temperature of described thermomagnetic treatment should be 340~350K and (is higher than A fTemperature) or 360~460K (be higher than T cTemperature), soaking time is 20~30 minutes.
The thermomagnetic treatment of utilizing is as previously discussed improved polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, and the long side direction of sample coupon is parallel to the field direction of (L) permanent magnet assembly during described thermomagnetic treatment.
As from the foregoing, method of the present invention is that the thermomagnetic treatment technology is introduced polycrystalline Ni 2MnGa, the arrangement (magnetic texture) according to qualifications that is intended to produce martensite twin variant, thus can in the magnetic field that is parallel to the sample coupon length direction, under the condition of 360~460K insulation back air cooling, make polycrystalline Ni 2The magnetic of MnGa drives reversible strain and improves 17% from 180ppm, reaches 210ppm.
Description of drawings
Fig. 1 is the synoptic diagram of yoke-permanent magnet assembly of using of thermomagnetic treatment.Among the figure, 1 expression neodymium-iron-boron permanent magnet, 2 expression pure iron yokes.
When Fig. 2 is thermomagnetic treatment, the synoptic diagram of the lay mode of sample coupon in magnetic field.Among the figure, L-vertically handles, and the long side direction of expression sample is parallel with field direction; The T-lateral processes, the long side direction of expression sample is vertical with field direction.
Fig. 3 is that magnetic brings out strain measurement method, and sample coupon places electro-magnet, and the long side direction of sample coupon is parallel to field direction, and measures magnetic along long side direction and bring out strain.
To be same sample bring out the dependent variable comparison diagram through the magnetic that records after the identical thermal treatment to Fig. 4 under magnetic field (H ≈ 0.7T) and no magnetic field (H=0) condition.
Fig. 5 is that same sample coupon adopts laterally (T) mode and the vertically design sketch of (L) mode in thermomagnetic treatment, and promptly the magnetic of T1A-L and T1A-T (thermal treatment in vertical and horizontal magnetic field respectively) sample brings out the comparison of dependent variable ε and T1A-O (thermal treatment in zero magnetic field).
Fig. 6 a and 6b represent T respectively 1A-O (a) and T 1The thermomagnetic treatment of A-L (b) is to polycrystalline Ni 52Mn 25Ga 23The metallograph of material microstructure.Arrow among Fig. 6 b is represented the thermal treatment field direction.
Embodiment
Embodiment 1
Improve polycrystalline Ni according to the thermomagnetic treatment of utilizing of the present invention 2The magnetic of MnGa drives the method for reversible strain property, and this method comprises the following steps:
A) adopt nonstoichiometry to prepare Ni by described chemical formula 2The MnGa alloy wherein contains the Ni of 52at%, the Mn of 25at% and the Ga of 23at%;
By this proportioning, with the Ni of high pure element, Mn and Ga raw material place electric arc furnace, carry out the repeated multiple times melting under argon atmosphere, make polycrystalline ingot;
B) above-mentioned polycrystalline ingot is carried out homogenizing annealing and handle, annealing temperature is 1173K, and the time is 3 days;
C) make 2 * 4 * 8mm through the heat treated polycrystalline ingot of homogenizing 3Ni 52Mn 25Ga 23Sample coupon, place yoke-permanent magnet assembly as shown in Figure 1 to make thermomagnetic treatment, magneticstrength is H ≈ 0.7T, the length direction of described sample coupon sample coupon when thermomagnetic treatment (L-vertically handle) parallel or vertical (T-lateral processes) with field direction, as shown in Figure 2.Then, they are heated to temperature 413K (T with stove 1) (be higher than Curie temperature T c) insulation cooling in air (A) together after 30 minutes.
At Ni 52Mn 25Ga 23Interalloy contains the Ni a little more than 50at%, and has higher Mn/Ga ratio.This is in order to obtain to be higher than the martensitic transformation temperature of room temperature, and promptly material is a martensitic structure at room temperature, and the device of making can at room temperature be worked.
In the aforesaid method step c), same sample coupon is done identical thermal treatment in the magnetic field of zero magnetic field H=0 and H ≈ 0.7T, be expressed as respectively;
T 1A-O represents sample after 413K is incubated 30 minutes, and air cooling is to room temperature under H=0 condition (0).
T 1A-L represents sample after 413K is incubated 30 minutes, and (L) air cooling is vertically handled to room temperature in magnetic field under H ≈ 0.7T condition.
T 1A-T represents sample after 413K is incubated 30 minutes, and magnetic field lateral processes (T) air cooling is to room temperature under H ≈ 0.7T condition.
Embodiment 2
Utilize thermomagnetic treatment to improve polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, and this method adopts step similarly to Example 1, just Ni 52Mn 25Ga 23The thermomagnetic treatment of sample coupon adopts shrend mode (W) cooling.
In the present embodiment method steps, same sample coupon is done identical thermal treatment in the magnetic field of zero magnetic field H=0 and H ≈ 0.7T, be expressed as respectively:
T 1W-O represents sample after 413K is incubated 30 minutes, in H=0 condition (0) shrend down.
T 1W-L represents sample after 413K is incubated 30 minutes, and (L) shrend is vertically handled in magnetic field under H ≈ 0.7T condition.
T 1W-T represents sample after 413K is incubated 30 minutes, magnetic field lateral processes (T) shrend under H ≈ 0.7T condition.
The strain that each sample is measured along the sample longitudinal direction in electro-magnet variable magnetic field H=0~1T among the embodiment 1 and 2, and with identical heat-treat condition but magneticstrength is the magnetic of zero same sample coupon brings out dependent variable and compare, as shown in Figure 3.
Test-results is listed in table 1 (measuring result that two-wire is separated in the following form represents that same sample coupon is having or not dependent variable comparison under the magnetic field condition).
Table 1:T 1The heat treated Ni of=413K 52Mn 25Ga 23Magnetic brings out dependent variable (ppm)
Externally-applied magnetic field (T) T 1A-L T 1A-O T 1W-L T 1W-O T 1A-T T 1A-O T 1W-T T 1W-O
0.1 -35 -40 -20 -25 -20 -30 -20 -15
0.2 -70 -80 -45 -45 -35 -60 -40 -40
0.3 -100 -110 -65 -55 -50 -80 -60 -60
0.4 -125 -130 -80 -65 -60 -105 -65 -80
0.5 -145 -150 -90 -85 -65 -110 -75 -95
0.6 -165 -165 -100 -90 -65 -130 -80 -110
0.7 -180 -170 -105 -90 -70 -135 -83 -110
0.8 -190 -180 -110 -95 -75 -140 -83 -120
0.9 -200 -180 -110 -100 -75 -140 -83 -120
1.0 -210 -180 -110 -100 -75 -140 -83 -120
Magnetic according to the data creating that records of table 1 brings out the first half that the dependent variable comparison diagram is shown in Fig. 4.Show among Fig. 4 the different heat treatment mode to polycrystalline Ni51.9Mn25.1Ga23.0 sample longitudinally surveys dependent variable ε influence (near the magnetic that the same sample of two data representations records after the thermal treatment in zero magnetic field and 0.7T magnetic field of deceiving in vain bring out dependent variable).
In above-mentioned method, if use two sample coupons, be sample 1 and sample 2 respectively under the condition of no magnetic field (H=0) under T1 temperature heating condition air cooling vertically handle air cooling to room temperature (T1A-O) with in H ≈ 0.7T magnetic field to room temperature (T1A-L), and at air cooling under the condition of no magnetic field (H=0) magnetic field lateral processes air cooling is to room temperature (T1A-T) under T1 temperature heating condition to room temperature (T1A-O) with in H ≈ 0.7T magnetic field, the relation curve that the magnetic that they record in electro-magnet magnetic field brings out between strain and the magneticstrength is shown in Fig. 5.
Can see that from table 1 all are through the polycrystalline Ni of vertical (L) mode thermomagnetic treatment 52Mn 25Ga 23Magnetic bring out dependent variable in various degree raising all arranged, wherein especially with T 1Temperature heating back air cooling (A) is more preferable than the effect of shrend (W), and dependent variable has been brought up to 210ppm by 180ppm, has improved 17%.This shows introduces polycrystalline Ni with the thermomagnetic treatment technology 2MnGa, the arrangement (magnetic texture) according to qualifications that has produced martensite twin variant.On the other hand, all are through the polycrystalline Ni of horizontal (T) mode thermomagnetic treatment 2The magnetic of MnGa brings out dependent variable all to be reduced.
Thermomagnetic treatment is to polycrystalline Ni 2The influence of MnGa material microstructure as shown in Figure 6.In Fig. 6, compare with the sample (a) of no thermomagnetic treatment, at polycrystalline Ni through thermomagnetic treatment 2In the MnGa material (b), martensite twin variant is preferred orientation, and the normal direction of its twining plane is tending towards arranging along field direction (representing with arrow among the figure) to a great extent, has promptly produced magnetic texture.Because Ni 2The magnetic of MnGa brings out strain and is produced by rearranging of martensite twin variant under the foreign field driving, by the polycrystalline Ni of thermomagnetic treatment generation described in the invention 2Form the martensite twin variant of favourable arrangement among the MnGa in the parent grain of different orientation, rearrange stack on beneficial direction under their outside magnetic field drive, caused the obvious increase of macro-strain amount.
Preliminary experiment shows, thermal treatment helps improving the mark of easy axle and the consistent monotropic body in outfield under the magnetic field, thereby useful to its magnetic control shape memory effect raising.
Embodiment 3
As the embodiment of shrend (W) and air cooling (A) method, use same step and material as embodiment 1 and 2, just the thermal treatment Heating temperature of annealing back sample coupon adopts 348K (T 2) (be higher than reverse transformation finishing temperature A f), same sample is at vertical (L) of zero magnetic field H=0 and H ≈ 0.7T or laterally do identical thermal treatment in (T) magnetic field, and air cooling or shrend are expressed as respectively: T 2A-L, T 2A-O, T 2W-L, T 2W-O, T 2A-T, T 2A-O, T 2W-T and T 2W-O.Each sample brings out strain along the magnetic that sample is vertically measured among the embodiment 3 in the electro-magnet of variable magnetic field H=0~1T, and test-results is listed in table 2.Correspondingly, bring out the dependent variable comparison diagram according to the magnetic of the data creating that records of table 2 and be shown in the latter half of of Fig. 4.
Table 2:T 2The heat treated Ni of=348K 52Mn 25Ga 23Magnetic brings out dependent variable (ppm)
Externally-applied magnetic field (T) T 2A-L T 2A-O T 2W-L T 2W-O T 2A-T T 2A-O T 2W-T T 2W-O
0.1 -25 -20 -45 -30 -20 -25 -30 -30
0.2 -50 -40 -85 -60 -40 -50 -65 -70
0.3 -70 -60 -110 -85 -50 -70 -85 -90
0.4 -85 -80 -120 -100 -65 -90 -105 -120
0.5 -100 -100 -140 -120 -75 -105 -115 -140
0.6 -110 -100 -155 -130 -80 -120 -125 -155
0.7 -115 -115 -160 -140 -80 -125 -135 -165
0.8 -120 -120 -165 -145 -85 -130 -140 -170
0.9 -125 -125 -170 -150 -90 -130 -140 -175
1.0 -125 -125 -170 -150 -90 -130 -140 -180
In above method, also use two sample coupons, promptly sample 1 and sample 2 respectively under the condition of no magnetic field (H=0) at T 2Temperature (is higher than A fTemperature) air cooling arrives room temperature (T under the heating condition 2A-O) and in H ≈ 0.7T magnetic field vertically handle air cooling to room temperature (T 2A-L), air cooling is to room temperature (T and under the condition of no magnetic field (H=0) 2A-O) and in H ≈ 0.7T magnetic field at T 2Lateral processes air cooling in magnetic field is to room temperature (T under the temperature heating condition 2A-T) magnetic that records brings out the relation between strain and the magneticstrength.Can see that from table 2 all are through the polycrystalline Ni of vertical (L) mode thermomagnetic treatment 52Mn 25Ga 23Magnetic bring out dependent variable and also improve.But all are through the polycrystalline Ni of horizontal (T) mode thermomagnetic treatment 2The magnetic of MnGa brings out dependent variable also all to be reduced.
With embodiment 1 and 2 and embodiment 3 compare, in the time of can finding that all sample coupon length directions when thermomagnetic treatment are parallel to field direction (L) and be higher than T c360~460K of temperature or at A fWith T c340~350K between temperature insulation is the sample coupon after air cooling or the shrend after 20~30 minutes, magnetic brings out dependent variable all has in various degree improvement than the same sample coupon of identical heat-treat condition under the no magnetic field, all are when the sample coupon length direction is perpendicular to field direction (T) when thermomagnetic treatment, and magnetic brings out dependent variable all in various degree decline.Particularly be parallel to field direction (L) and be higher than T at the sample coupon length direction c360~460K of temperature insulation after 20~30 minutes air cooling to carry out the effect of thermomagnetic treatment best, its magnetic can be brought out dependent variable and improve about 17%.
Simultaneously, magnetic field heat treatment process involved in the present invention is applied to monocrystalline Ni 2MnGa can not have the monocrystalline Ni of thermomagnetic treatment than simple use yet 2MnGa magnetic drives reversible strain property and is able to further raising.

Claims (2)

1. one kind is utilized thermomagnetic treatment to improve polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, it is characterized in that, comprises the following steps:
A) prepare Ni by the nonstoichiometry proportioning 2The MnGa alloy, the Ni that described nonstoichiometry proportioning is prepared 2The Ni that contains 50.3~53.0at% in the MnGa alloy, Mn/Ga is than=1.05~1.15; By this proportioning, with the Ni of high pure element, Mn and Ga raw material carry out arc melting under argon shield, make polycrystalline ingot;
B) above-mentioned polycrystalline ingot being carried out homogenizing annealing handles; The annealing temperature that described polycrystalline ingot carries out the homogenizing annealing processing is 1100~1200K, and the time is 1~3 day;
C) polycrystalline ingot of handling through homogenizing is made the sample coupon of certain size, places pure iron yoke-permanent magnets assembly to carry out thermomagnetic treatment; The Heating temperature of described thermomagnetic treatment should be the 340~350K that is higher than the Af temperature or is higher than 360~460K of Tc temperature, and soaking time is 20~30 minutes; The long side direction of sample coupon is parallel to the field direction of permanent magnet assembly during described thermomagnetic treatment.
2. the thermomagnetic treatment of utilizing as claimed in claim 1 is improved polycrystalline Ni 2The magnetic of MnGa drives the method for reversible strain property, and its feature is that also described thermomagnetic treatment is to be of a size of 2 * 4 * 8mm 3Sample coupon place pure iron yoke-NdFeB permanent magnets assembly to carry out, magneticstrength is H ≈ 0.7T, they with behind stove heating and the insulation certain hour, are taken out air cooling or shrend by simultaneously together.
CN02111523.0A 2002-04-27 2002-04-27 Magnetic and heating treatment method to improve magnetically driven reversible strain property of polycrystalline Ni2 MnGa Expired - Fee Related CN1272464C (en)

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PCT/CN2003/000303 WO2003093520A1 (en) 2002-04-27 2003-04-24 PROCESS FOR INCREASING MAGNETIC-FIELD-INDUCED STRAIN IN POLYCRYSTALLINE Ni2MnGa BY MAGNETIC HEAT TREATMENT
AU2003236162A AU2003236162A1 (en) 2002-04-27 2003-04-24 PROCESS FOR INCREASING MAGNETIC-FIELD-INDUCED STRAIN IN POLYCRYSTALLINE Ni2MnGa BY MAGNETIC HEAT TREATMENT

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