CN101974707A - Ferromagnetic shape memory alloy material with giant magnetocaloric and magnetoresistance effect and application - Google Patents
Ferromagnetic shape memory alloy material with giant magnetocaloric and magnetoresistance effect and application Download PDFInfo
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- CN101974707A CN101974707A CN201010505099.2A CN201010505099A CN101974707A CN 101974707 A CN101974707 A CN 101974707A CN 201010505099 A CN201010505099 A CN 201010505099A CN 101974707 A CN101974707 A CN 101974707A
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- 239000000956 alloy Substances 0.000 title claims abstract description 39
- 230000005294 ferromagnetic effect Effects 0.000 title claims abstract description 36
- 230000000694 effects Effects 0.000 title claims abstract description 32
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 32
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 70
- 230000009466 transformation Effects 0.000 claims abstract description 69
- 230000005291 magnetic effect Effects 0.000 claims abstract description 48
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 229910052718 tin Inorganic materials 0.000 claims abstract description 20
- 230000001105 regulatory effect Effects 0.000 claims abstract description 19
- 229910052738 indium Inorganic materials 0.000 claims abstract description 18
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 16
- 229910001566 austenite Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 21
- 230000008859 change Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 230000005293 ferrimagnetic effect Effects 0.000 claims description 7
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000005298 paramagnetic effect Effects 0.000 claims description 6
- 230000008595 infiltration Effects 0.000 claims description 5
- 238000001764 infiltration Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000005290 antiferromagnetic effect Effects 0.000 claims description 4
- 229910003286 Ni-Mn Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 230000005303 antiferromagnetism Effects 0.000 abstract 1
- 230000005307 ferromagnetism Effects 0.000 abstract 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract 1
- 230000005415 magnetization Effects 0.000 abstract 1
- 230000005408 paramagnetism Effects 0.000 abstract 1
- 238000000137 annealing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910018645 Mn—Sn Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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Abstract
The invention relates to a ferromagnetic shape memory alloy material with a giant magnetocaloric and magnetoresistance effect, namely an alloy has a general formula of Ni-Mn-X (X is indium (In), stannum (Sn) or stibium (Sb)), in particular to the alloy with the general formula of Ni(40-60)Mn(40-60)X(5-20)Sn11 (X is In, Sn or Sb). The invention also relates to the application of the ferromagnetic shape memory alloy material with the giant magnetocaloric and magnetoresistance effect. In the ferromagnetic shape memory alloy material with the general formula of Ni-Mn-X (X is In, Sn or Sb), martensitic phase transformation temperature is regulated by regulating the element ratio, doping elements and infiltrating interstitial atoms to ensure that martensitic phase transformation or reverse martensitic phase transformation is generated among a weak magnetic state, a martensitic phase which comprises antiferromagnetism, paramagnetism and weak ferromagnetism, and a ferromagnetic austenite phase to obtain a great jump of magnetization intensity, and thus obtain a big magnetocaloric and magnetoresistance effect.
Description
Technical field
The invention belongs to the category of Material Physics, be specifically related to the magnetic alloy material that a class has wide application prospect: Ni-Mn-X (X=In, Sn, Sb) ferromagnetic shape memory alloys.Proposed several different methods and regulated martensitic transformation temperature in such alloy, and obtained excellent magnetic heat and magneto-resistance effect to specified operation temperature area.
Background technology
Ferromagnetic shape memory alloys is the novel shape-memory material of a class that last decade grows up, and is the intermetallic compound that has ferromegnetism and thermoelastic martensitic transformation feature simultaneously.Martensitic transformation in this class alloy can be driven by two kinds of factors of temperature and magnetic field, therefore they not only have the thermo-elasticity shape memory effect that the conventional shape-memory alloy is subjected to Temperature Field Control, and have ferromagnetic shape memory effect, a magneto-strain effect that is subjected to magnetic field control, magneto-resistance effect and magnetothermal effect etc. have broad application prospects.
(Sb) alloy is the novel ferromagnetic shape memory alloys of a class of discovered in recent years to Ni-Mn-X for X=In, Sn.In such alloy, have two kinds of structure phases, promptly the austenite under the high temperature mutually and the martensitic phase under the low temperature, the transformation between these two kinds of structures phases is violent first-order phase transition, and is accompanied by the sudden change of sample structure and resistivity.In these two kinds of structures, one has two kinds of magnetic state again, and the transformation between them is a second-order phase transition.Be that ferrimagnetic state (or antiferromagnetic state) in the martensitic phase is to the transformation of paramagnetic, with the transformation of the ferrimagnetic state of austenite in mutually to the paramagnetic attitude.In actual applications, in order to obtain bigger magneto-strain, magneto-resistor and magnetothermal effect, require martensitic transformation to be driven by foreign field, this just needs the martensite of phase transformation front and back and the difference that austenite has the huge specific magnetising moment.For reaching this purpose, people wish and can regulate martensitic transformation temperature by some means, and this phase transformation is occurred between the austenite of the martensite of weak magnetic attitude and ferrimagnetic state.(Sb) martensitic transformation temperature of alloy is quite responsive to composition and preparation technology for X=In, Sn for studies show that before: Ni-Mn-X.This phenomenon causes certain degree of difficulty to controlling its performance on the one hand, exchanges the performance of integrating gold on the other hand again convenience is provided.
Summary of the invention
The present invention seeks to: propose a kind of ferromagnetic shape memory alloys Martensitic Transformation Materials, can have the material and the application thereof of huge magnetic heat and magneto-resistance effect based on the adjusting of temperature; The present invention also aims to adopt respectively the adjusting element ratio, element doping, the infiltration of interstitial atom, means such as internal stress are regulated in thermal treatment, at Ni-Mn-X (X=In, Sn, Sb) in the alloy system, can successfully regulate martensitic transformation temperature, obtain huge magnetic heat and magneto-resistance effect.
Technical scheme of the present invention is: huge magnetic heat of ferromagnetic shape memory alloys and magneto-resistance effect material, its general formula is Ni-Mn-X (X=In, Sn, Sb) alloy.One Ni, Mn, X atomic ratio are 40-60: 40-60: 5-20.
Infiltrate minor radius atom H in the interstitial site of the lattice of material, N, C, B, the atomic ratio of minor radius atom and Ni atomic ratio are, less than 8: 40-60.
At Ni-Mn-X (X=In, Sn, Sb) in the ferromagnetic shape memory alloys material, by regulating element ratio, several means of the infiltration of element doping and interstitial atom are regulated martensitic transformation temperature, make martensitic transformation or contrary martensitic transformation occur in weak magnetic attitude, comprise antiferromagnetic, the austenite of paramagnetic and weak ferromagnetic martensitic phase and ferrimagnetic state mutually between, obtain the significantly jump of the specific magnetising moment, thereby obtain big magnetic heat and magneto-resistance effect.
Change responsive principle according to martensitic transformation temperature with lattice parameter, original element is substituted with an amount of same main group element, perhaps infiltrate minor radius H in the interstitial site of lattice, N, C, or B atom are under the prerequisite that does not change valence electron concentration, realize regulating martensitic transformation temperature, make it reach specified operation temperature area.
(Sb) ferromagnetic shape memory alloys realizes the method for great magnetic entropy variation and magneto-resistor to Ni-Mn-X for X=In, Sn.By regulating in the Ni-Mn-X alloy, the ratio of Ni-Mn element is regulated martensitic transformation temperature, makes it reach specified operation temperature area.Adopt melt-spun (can be described as again and get rid of band) to add heat treated preparation flow of later stage, regulate martensitic transformation temperature, make it reach specified operation temperature area.
The invention has the beneficial effects as follows: before this, the research of Ni-Mn-Sn alloy is mainly concentrated on the Ni that is just dividing
50Mn
50-xSn
x, as Ni
50Mn
39Sn
11Alloy, its martensitic transformation occur between the structure phase of two kinds of paramagnetic attitudes, and the specific magnetising moment is very little, therefore can't control with magnetic field.The present invention is by regulating Ni, and the ratio of Mn element has been studied the non-Ni that is just dividing
50-xMn
39+xSn
11The magnetic phase transition of (x=0,4,5,6,7) alloy is found the reduction along with the Ni-Mn ratio, and valence electron concentration also reduces thereupon, and martensitic transformation temperature significantly reduces simultaneously, and has obtained peak temperature and can become at huge low the magnetic entropy that 200K regulates in the 270K.Because this alloy is cheap, therefore become the comparatively ideal magnetic refrigeration working substance within this warm area.In addition, we have also obtained big magnetothermal effect by regulating the composition of Ni and Mn in the Ni-Mn-In alloy.
Utilize the principle of martensitic transformation temperature with the valence electron change in concentration, it is transition element doped to propose employing, regulates martensitic transformation temperature.We are with the non-Ni that is just dividing
43Mn
46Sn
11Be the basis, with Part of Co, Cu, Fe, units such as Cr usually substitute part Mn, with Part of Co element substitution Ni, with part Sb element substitution Sn, successful adjusting the temperature of martensitic transformation, widened the operation temperature area of this class alloy, and obtained austenitic phase transformation from the martensite of weak magnetic attitude to ferrimagnetic state as magnetic refrigerating material.Result of study shows, along with the Co that substitutes the Mn element, and Cu, Fe, and the raising of the Sn content of alternative Sb element, martensite transformation temperature all increases.
And if substitute Mn with Cr, or with Co element substitution Ni, then martensite transformation temperature reduces rapidly.These results all meet the Changing Pattern of aforesaid valence electron concentration.Especially at Ni
43Mn
46-xCo
xSn
11In, the adding of Co has improved martensite transformation temperature and austenite Curie temperature greatly, and the magnetic entropy that has improved material becomes, and makes it become 195K to the class magnetic refrigeration working substance that gets a good chance of between the 320K.In addition, at Ni
50Mn
39Sb
11In the alloy, we substitute the Ni atom by the Co atom, and successful is adjusted to its martensite transformation temperature near the room temperature, and have obtained big magnetic entropy change of low field and magneto-resistor.
Utilization substitutes with main group element or infiltrates the minor radius interstitial atom, changes lattice parameter, regulates martensitic transformation temperature.
The method of foregoing adjusting martensitic transformation is all based on the principle of regulating valence electron concentration.Ni-Mn-X (X=In, Sn, Sb) in the ferromagnetic shape memory alloys, the spacing of its martensitic transformation temperature and magnetic atom, particularly the spacing of Mn-Mn atom is closely related.Therefore, in the present invention, a certain component had the identical electronic structure but the different same main group element of atomic radius substitutes with another kind of, or infiltration minor radius interstitial atom (as H, N, B etc.), can be when valence electron concentration remains unchanged, by the change lattice parameter, thereby the spacing of change Mn-Mn atom can be regulated martensitic transformation temperature equally within the specific limits.Such as, at Ni
43Mn
46Sn
11-xGe
xIn, by doping and the same main group of Sn, but the smaller element Ge of atomic radius; At Ni
43Mn
46Sn
11In mix the B element of trace, make it to enter gap digit, all reached the purpose that improves martensitic transformation temperature, and obtained big magnetic entropy change effect.
Utilize melt-spun to add the preparation technology of post-processed, regulate unrelieved stress and grain size in the sample, thereby regulate martensitic transformation temperature.Studies show that (Sb) in the ferromagnetic shape memory alloys, its martensitic transformation temperature is subjected to unrelieved stress and the grain size in the sample to influence very big to Ni-Mn-X for X=In, Sn.Therefore, except above-mentioned three kinds of control methods, we propose the 4th kind of method, under the prerequisite of the chemical ingredients that does not change sample, regulate unrelieved stress and grain size in the sample by special preparation technology, thereby regulate martensitic transformation temperature.Earlier alloy cast ingot is got rid of into band with the method for melt-spun.Because it is solid-state that sample is cooled to rapidly from liquid state, so have higher unrelieved stress and less crystal grain.Then alloy strip is annealed under vacuum environment, and follow quenching.In this process, unrelieved stress obtains part and discharges, and crystal grain is grown up gradually simultaneously.By adjusting annealing temperature and annealing time, thereby reach the purpose of regulating transformation temperature.And big magnetic heat and magneto-resistance effect in this type of material, have also been obtained.
Description of drawings
Fig. 1 is Ni
43Mn
46-xCo
xSn
11The specific magnetising moment of (x=0,2,4,5) ferromagnetic shape memory alloys concerns with variation of temperature.The jump of the specific magnetising moment is corresponding to martensitic transformation among the figure.Along with the raising of Co content, martensitic transformation temperature raises fast.
Fig. 2 is Ni
43Mn
46-xCo
xSn
11The magnetic entropy of (x=0,2,4,5) alloy under 10kOe magnetic field becomes.
Fig. 3 (a) is Ni
50-xCo
xMn
39Sb
11The normalized resistance of ferromagnetic shape memory alloys 0 and 50kOe magnetic field under, concern with variation of temperature.The jump of resistance is corresponding to martensitic transformation among the figure.Along with the raising of Co content, martensitic transformation temperature reduces fast.(b) be this series alloy under 50kOe magnetic field, magneto-resistor concerns with variation of temperature.
Fig. 4 is Ni
40Mn
45X
5Sn
11The relation of the martensite transformation temperature of alloy and valence electron Konzentration/a, X=In, Sn, Sb.
Fig. 5 is Ni
43Mn
45Sn
11B
xThe magnetic entropy of alloy becomes the relation that varies with temperature.Along with the raising of the content of interstitial atom B, martensitic transformation temperature raises gradually.
Fig. 6 is Ni
44.1Mn
44.2Sn
11.7The quick quenching band of alloy, 1123K following annealing band and the 1173K specific magnetising moment of annealing band down vary with temperature relation.
Fig. 7 is Ni
44.1Mn
44.2Sn
11.7The magnetic heat and the magneto-resistance effect of the quick quenching band of alloy vary with temperature relation.
Fig. 8 is Ni
45Mn
44-xCr
xSn
11The magnetothermal effect of alloy varies with temperature relation.
Fig. 9 is Ni
45Mn
42Cr
2Sn
11The magneto-resistor of alloy varies with temperature relation.
Figure 10 is Ni
43Mn
46-xCu
xSn
11The magnetothermal effect of alloy varies with temperature curve.
Embodiment
The jump of the specific magnetising moment is corresponding to martensitic transformation: Ni among Fig. 1
43Mn
46-xCo
xSn
11The specific magnetising moment of (x=0,2,4,5) ferromagnetic shape memory alloys concerns with variation of temperature, along with the raising (Ni of Co content
43Mn
46-xCo
xSn
11Middle x from 0 to 5), along with the raising of Co content, martensitic transformation temperature raises fast.
Fig. 3 (a) is Ni
50-xCo
xMn
39Sb
11The normalized resistance of ferromagnetic shape memory alloys 0 and 50kOe magnetic field under, concern with variation of temperature.The jump of resistance is corresponding to martensitic transformation among the figure.Along with the raising of Co content, martensitic transformation temperature reduces fast.(b) be this series alloy under 50kOe magnetic field, magneto-resistor concerns with variation of temperature.
According to the principle of martensitic transformation temperature with the valence electron change in concentration, adopt Ni element or Mn element in an amount of transition element replacement Ni-Mn-X alloy, X=In, Sn or Sb make it reach specified operation temperature area.All can obtain Fig. 4 similar effects.
At Ni-Mn-X (X=In, Sn, Sb) great magnetic entropy variation that obtains in the ferromagnetic shape memory alloys and magneto-resistor, can regulate martensitic transformation temperature by several means, making martensitic transformation (or contrary martensitic transformation) occur in weak magnetic attitude (comprises antiferromagnetic, between the austenite phase of martensitic phase paramagnetic and weak ferromagnetic) and ferrimagnetic state, obtain the significantly jump of the specific magnetising moment, thereby obtain big magnetic heat and magneto-resistance effect.Ni among Fig. 4
40Mn
45X
5Sn
11The relation of the martensite transformation temperature of alloy and valence electron Konzentration/a, X=In, Sn, Sb.The X atomic ratio be 5-20 all can, the atomic ratio of Ni and Mn is 40-60: 40-60 all can.
Regulate Ni-Mn-X (X=In, Sn, Sb) processing method of martensitic transformation temperature in the ferromagnetic shape memory alloys.It is characterized in that according to martensitic transformation temperature sample unrelieved stress and the highstrung principle of grain size, adopt melt-spun (can be described as again and get rid of band) to add heat treated preparation flow of later stage, the per second temperature descends more than 100 degrees centigrade, can regulate martensitic transformation temperature, make it reach specified operation temperature area.Referring to Fig. 6 Ni
44.1Mn
44.2Sn
11.7The quick quenching band of alloy, 1123K following annealing band and the 1173K specific magnetising moment of annealing band down vary with temperature relation.
Claims (9)
1. huge magnetic heat of ferromagnetic shape memory alloys and magneto-resistance effect material is characterized in that general formula is Ni-Mn-X (X=In, a Sn or Sb) alloy.
2. huge magnetic heat of ferromagnetic shape memory alloys according to claim 1 and magneto-resistance effect material is characterized in that Ni, Mn, X atomic ratio are 40-60: 40-60: 5-20.
3. huge magnetic heat of ferromagnetic shape memory alloys according to claim 1 and magneto-resistance effect material is characterized in that Ni
40-60Mn
40-60X
5-20Sn
11In the alloy, X=In, Sn, Sb.
4. huge magnetic heat of ferromagnetic shape memory alloys according to claim 1 and magneto-resistance effect material is characterized in that the interstitial site infiltration minor radius atom H at the lattice of material, N, and C, B, the atomic ratio of minor radius atom and Ni atomic ratio are, less than 8: 40-60.
5. the application of huge magnetic heat of ferromagnetic shape memory alloys and magneto-resistance effect material, it is characterized in that (X=In at Ni-Mn-X, Sn or Sb) in the ferromagnetic shape memory alloys material, by regulating element ratio, several means of the infiltration of element doping and interstitial atom are regulated martensitic transformation temperature, make martensitic transformation or contrary martensitic transformation occur in weak magnetic attitude, comprise antiferromagnetic, between the austenite phase of paramagnetic and weak ferromagnetic martensitic phase and ferrimagnetic state, obtain the significantly jump of the specific magnetising moment, thereby obtain big magnetic heat and magneto-resistance effect.
6. the application of huge magnetic heat of ferromagnetic shape memory alloys according to claim 5 and magneto-resistance effect material, it is characterized in that changing responsive principle with lattice parameter according to martensitic transformation temperature, original element is substituted with an amount of same main group element, perhaps infiltrate minor radius H, N, C in the interstitial site of lattice, or B atom, under the prerequisite that does not change valence electron concentration, realize regulating martensitic transformation temperature, make it reach specified operation temperature area.
7. the application of huge magnetic heat of ferromagnetic shape memory alloys according to claim 5 and magneto-resistance effect material, it is characterized in that (X=In at Ni-Mn-X, Sn, Sb) ferromagnetic shape memory alloys realizes the method for great magnetic entropy variation and magneto-resistor, by regulating in the Ni-Mn-X alloy, the ratio of Ni-Mn element is regulated martensitic transformation temperature, makes it reach specified operation temperature area.
8. the application of huge magnetic heat of ferromagnetic shape memory alloys according to claim 5 and magneto-resistance effect material is characterized in that at Ni
43Mn
46-xCo
xSn
11Middle x from 0 to 5, along with the raising of Co content, martensitic transformation temperature raises.
9. the application of huge magnetic heat of ferromagnetic shape memory alloys according to claim 5 and magneto-resistance effect material is characterized in that adopting melt-spun to regulate martensitic transformation temperature, makes it reach specified operation temperature area.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014227558A (en) * | 2013-05-20 | 2014-12-08 | Tdk株式会社 | Magnetic refrigeration apparatus magnetic working substance and magnetic refrigeration apparatus |
| US9255343B2 (en) | 2013-03-08 | 2016-02-09 | Ut-Battelle, Llc | Iron-based composition for magnetocaloric effect (MCE) applications and method of making a single crystal |
| CN104167488B (en) * | 2014-02-28 | 2017-02-15 | 南京大学 | Magneto-caloric Ni-Mn-based ferromagnetic-shape memory alloy and piezoelectric composite material and application thereof |
| CN106929740A (en) * | 2017-02-04 | 2017-07-07 | 河北科技大学 | A kind of preparation method of ferrous alloy and its application in test martensite start temperature |
| CN108286007A (en) * | 2018-02-07 | 2018-07-17 | 三峡大学 | A kind of Cr doping improve NiCoMnSn metamagnetism can Haas strangle alloy and preparation method thereof |
| CN108330372A (en) * | 2018-02-28 | 2018-07-27 | 华南理工大学 | A kind of Ni-Co-Mn-Sn magnetic refrigerating materials and preparation method thereof |
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| CN110484802A (en) * | 2019-08-30 | 2019-11-22 | 广州大学 | A kind of ferromagnetic shape memory alloy with nanometer Eutectic structure |
| CN115198123A (en) * | 2022-06-09 | 2022-10-18 | 中国科学院宁波材料技术与工程研究所 | Additive manufacturing method of nickel-manganese-tin shape memory alloy and nickel-manganese-tin shape memory alloy |
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2010
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| JP2014227558A (en) * | 2013-05-20 | 2014-12-08 | Tdk株式会社 | Magnetic refrigeration apparatus magnetic working substance and magnetic refrigeration apparatus |
| CN104167488B (en) * | 2014-02-28 | 2017-02-15 | 南京大学 | Magneto-caloric Ni-Mn-based ferromagnetic-shape memory alloy and piezoelectric composite material and application thereof |
| CN106929740A (en) * | 2017-02-04 | 2017-07-07 | 河北科技大学 | A kind of preparation method of ferrous alloy and its application in test martensite start temperature |
| CN106929740B (en) * | 2017-02-04 | 2018-04-17 | 河北科技大学 | A kind of preparation method of ferrous alloy and its application in test martensite start temperature |
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| CN110484802A (en) * | 2019-08-30 | 2019-11-22 | 广州大学 | A kind of ferromagnetic shape memory alloy with nanometer Eutectic structure |
| CN115198123A (en) * | 2022-06-09 | 2022-10-18 | 中国科学院宁波材料技术与工程研究所 | Additive manufacturing method of nickel-manganese-tin shape memory alloy and nickel-manganese-tin shape memory alloy |
| CN115198123B (en) * | 2022-06-09 | 2023-09-22 | 中国科学院宁波材料技术与工程研究所 | Additive manufacturing method of nickel-manganese-tin shape memory alloy and nickel-manganese-tin shape memory alloy |
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