CN101693970B - Mn-Ni-Ga-Sn magnetic driving memory alloy - Google Patents

Mn-Ni-Ga-Sn magnetic driving memory alloy Download PDF

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Publication number
CN101693970B
CN101693970B CN2009103090117A CN200910309011A CN101693970B CN 101693970 B CN101693970 B CN 101693970B CN 2009103090117 A CN2009103090117 A CN 2009103090117A CN 200910309011 A CN200910309011 A CN 200910309011A CN 101693970 B CN101693970 B CN 101693970B
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alloy
memory alloy
molecular formula
magnetic driving
magnetic
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CN101693970A (en
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高智勇
吴迪
张婕
蔡伟
吴冶
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

A Mn-Ni-Ga-Sn magnetic driving memory alloy relates to a memory alloy, the invention solves the problem that a MnNiGa magnetic driving alloy is smaller than the delta M/ delta S value. The molecular formula of the Mn-Ni-Ga-Sn magnetic driving memory alloy is Mn50Ni25Ga25-*Sn*, and the * in the molecular formula is 1-2. Sn elements are added in the Mn-Ni-Ga-Sn magnetic driving memory alloy, thereby the aeolotropism of magnetocrystalline is increased, and the delta M/ delta S value is increased, which is beneficial to the phase change of martensite caused by the magnetic field in the Mn-Ni-Ga-Sn magnetic driving memory alloy, thereby obtaining the big output stress.

Description

The Mn-Ni-Ga-Sn magnetic driven memory alloy
Technical field
The present invention relates to a kind of memorial alloy.
Background technology
The essential characteristic of magnetic field driven martensitic transformation is that alloy is attended by antiferromagnetic (paramagnetic)-ferromagnetic magnetic phase transition when the A-M structural phase transition takes place, and externally-applied magnetic field has very strong constraint or promoter action to martensitic transformation.Externally-applied magnetic field can Zeeman can form the Gibus free energy of system is exerted an influence, thereby influence its martensitic transformation behavior, it is similar that its principle and stress field influence martensitic transformation.Externally-applied magnetic field can be used the Clausius-Clapayron equation to the influence of martensitic transformation:, wherein, dT/dH has characterized unit magnetic field to the influence of transformation temperature (also just having characterized the ability that phase driving force is changed in magnetic field into), Δ M is that the saturation magnetization between martensitic phase and the parent phase is poor, and Δ S is the Entropy Changes in the phase transition process; This shows if realize parent phase-martensitic transformation that bring out in magnetic field in a kind of magnetic driven memory alloy system, must satisfy high as much as possible, then need as much as possible little, that is to say, the magnetic that acquisition has a big value drives alloy and magnetic field just may take place brings out martensitic transformation, thereby obtains high output stress.And MnNiGa magnetic driving alloy ratio is little, is difficult to parent phase-martensitic transformation of realizing that magnetic field is brought out.
Summary of the invention
Technical problem to be solved by this invention is little in order to solve MnNiGa magnetic driving alloy ratio, and the very difficult problem that realizes parent phase-martensitic transformation that bring out in magnetic field provides a kind of Mn-Ni-Ga-Sn magnetic driven memory alloy.
The molecular formula of Mn-Ni-Ga-Sn magnetic driven memory alloy of the present invention is Mn 50Ni 25Ga 25-xSn x, the x value is 1～2 in the molecular formula.
The interpolation of Mn-Ni-Ga-Sn magnetic driven memory alloy of the present invention the Sn element, the increase of magnetocrystalline anisotropy and the rising of ratio have been caused, all help in the Mn-Ni-Ga-Sn magnetic driven memory alloy, obtaining the martensitic transformation that bring out in magnetic field, obtain big output stress.
Description of drawings
Fig. 1 be in the embodiment seven Sn content to Mn 50Ni 25Ga 25-xSn xThe influence curve of alloy martensite transformation temperature, expression Ms curve among the figure, expression Mf curve, expression As curve, expression Af curve; Fig. 2 is the Entropy Changes during martensitic transformation and the relation curve of Sn content in the embodiment seven; Fig. 3 is Sn content and Mn in the embodiment seven 50Ni 25Ga 25-xSn xThe relation curve comparison diagram of alloy parent phase and martensitic phase saturation magnetization, expression martensitic phase saturation magnetization curve among the figure, expression parent phase saturation magnetization curve; Fig. 4 is Mn in the embodiment seven 50Ni 25Ga 25-xSn xAlloy is the relation curve of saturation magnetization difference and Sn content under the cophasal state not; Fig. 5 is Mn in the embodiment seven 50Ni 25Ga 25-xSn xThe relation curve of alloy ratio and Sn content; Fig. 6 is Mn in the embodiment eight 50Ni 25Ga 25-xSn xAlloy solid solution is handled the DSC figure behind the 48h; Mn in Fig. 7 embodiment eight 50Ni 25Ga 25-xSn xAlloy
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the molecular formula of Mn-Ni-Ga-Sn magnetic driven memory alloy is Mn in the present embodiment 50Ni 25Ga 25-xSn x, the x value is 1～2 in the molecular formula.
The preparation method of Mn-Ni-Ga-Sn magnetic driven memory alloy is as follows in the present embodiment: be 5 * 10 in vacuum tightness respectively with electrolytic manganese, electrolytic nickel, tin and gallium one, -3Melting made manganese simple substance ingot casting, nickel simple substance ingot casting, tin simple substance ingot casting and gallium simple substance ingot casting in 2 minutes under the condition of Pa, respectively each simple substance ingot casting was pulverized, ultrasonic cleaning 20～30 minutes in acetone, obtained manganese particle, nickel particle, tin particle and gallium particle; Two, with manganese particle, nickel particle, tin particle and gallium particle according to 50: 25: (25-x): the mixed in molar ratio of x obtains compound, is 2 * 10 with compound in vacuum tightness -2The upset melting is four times under the condition of Pa, is cooled to room temperature then, obtains detaining the shape sample; Three, will detain the shape sample and clean once with acetone, enclosing vacuum tightness then is 1.33 * 10 -2Pa (10 -4Torr) in the silica tube, homogenizing annealing 48h under 800 ℃ condition in the frozen water of quenching again, promptly gets the Mn-Ni-Ga-Sn magnetic driven memory alloy.
The purity of used electrolytic manganese is 99.92% in the present embodiment, and the purity of electrolytic nickel is 99.95%, the purity of tin be 99.99% and the purity of gallium be 99.99%; Present embodiment adopts the WK-II non-consumable vacuum melting furnace of scientific instrument development center, Chinese Academy of Sciences Shenyang exploitation to prepare the Mn-Ni-Ga-Sn magnetic driven memory alloy under the condition of argon shield.
Embodiment two: what present embodiment and embodiment one were different is that the x value is 1.1～1.9 in the described molecular formula.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is that the x value is 1.2～1.8 in the described molecular formula.Other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is that the x value is 1.3～1.7 in the described molecular formula.Other is identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is that the x value is 1.4～1.6 in the described molecular formula.Other is identical with embodiment one.
Embodiment six: what present embodiment and embodiment one were different is that the x value is 1.5 in the described molecular formula.Other is identical with embodiment one.
Embodiment seven: what present embodiment and embodiment one were different is that the x value is 0～2 in the described molecular formula.
(Sn content is to Mn by Fig. 1 50Ni 25Ga 25-xSn xThe influence curve of alloy martensite transformation temperature) as seen, along with the increase of Sn atomic percentage conc, Ms, Mf, As and Af all have obvious decline.
From Fig. 2 (relation curve of Entropy Changes during martensitic transformation and Sn content) as can be seen, Mn 50Ni 25Ga 25-xSn xEntropy Changes during the alloy martensite phase transformation descends along with the increase of Sn atomic percentage conc.The latent heat of phase change that Entropy Changes utilizes the DSC curve to measure among Fig. 2 calculates, and calculation formula is Δ S=Δ Q/Tm, and wherein Δ Q is a martensitic transformation latent heat, and Tm is the peak temperature of martensitic transformation.
From Fig. 3 (Sn content and Mn 50Ni 25Ga 25-xSn xThe relation curve comparison diagram of alloy parent phase and martensitic phase saturation magnetization) as can be seen, at the Sn atomic percentage conc less than 0.5% o'clock, no matter be under parent phase and martensitic state, Mn 50Ni 25Ga 25-xSn xThe saturation magnetization of alloy all raises rapidly with the increase of Sn atomic percentage conc; After the Sn atomic percentage conc surpasses 0.5%, Mn 50Ni 25Ga 25-xSn xThe saturation magnetization of alloy tends towards stability, and slightly raises along with the increase of Sn atomic percentage conc.
From Fig. 4 (Mn 50Ni 25Ga 25-xSn xAlloy is the relation curve of saturation magnetization difference and Sn content under the cophasal state not) can find the increase along with the Sn atomic percentage conc, Mn 50Ni 25Ga 25-xSn xAlloy austenite and martensitic saturation magnetization difference descend rapidly.
From Fig. 5 (Mn 50Ni 25Ga 25-xSn xThe relation curve of alloy ratio and Sn content) as can be known along with the increase of Sn content, Mn 50Ni 25Ga 25-xSn xThe ratio of alloy raises fast, show suitable interpolation Sn element, though can cause the austenite of alloy and the decline of martensitic saturation magnetization difference, but the increase of caused magnetocrystalline anisotropy and the rising of ratio simultaneously, all help in the Mn-Ni-Ga-Sn magnetic driven memory alloy, obtaining the martensitic transformation that bring out in magnetic field, obtain big output stress.
Martensitic transformation temperature adopts the Diamond DSC of U.S. PerkinElmer company to measure in the present embodiment.The weight of DSC sample is that 50mg～60mg, diameter are the disc thin slice of 3mm, and heating and cooling speed is 40 ℃/min.Mn 50Ni 25Ga 25-xSn xThe transformation temperature Ms of alloy, Mf, As, Ap, Af determine with tangent method.
(Physical Properties Measurement System QuantumDesign), is called for short PPMS to the Model 6000 type physical properties test macros at the measurement employing Harbin Institute of Technology condensed state science and technology center of magnetzation curve.The magnetic field size is ± 5T, and temperature measurement range is 1.9K～350K, and precision can reach 0.002mT in the following magnetic field of 1T, and the Magnetic Measurement precision can reach 2.5 * 10-5emu.
Embodiment eight: what present embodiment and embodiment one were different is that the x value is 0.5 in the described molecular formula.
As seen from Figure 6 heat up and temperature-fall period in polycrystalline Mn 50Ni 25Ga 25-xSn xAlloy has only an endotherm(ic)peak and exothermic peak, shows that the positive reverse transformation of thermic martensite of this alloy system is a step phase transformation, and promptly the Mn-Ni-Ga-Sn alloy has kept the typical step thermoelastic martensitic transformation of ternary Mn-Ni-Ga alloy.From Sn content to Mn 50Ni 25Ga 25-xSn xThe analysis of alloy phase change Temperature Influence as can be seen, Mn 50Ni 25Ga 25-xSn xAlloy is a martensitic state under 100K, and is in the parent phase state under 370K.By Fig. 7 (Mn 50Ni 25Ga 25-xSn xAlloy is at the magnetzation curve of 370K and 100K) as seen, Mn 50Ni 25Ga 25-xSn xAlloy all shows typical ferromegnetism behavior at parent phase and martensitic phase, but their saturation magnetic field (magnetocrystalline anisotropy field in other words) and saturation magnetization Ms are all inequality.For the parent phase austenite, its saturation magnetic field and saturation magnetization are respectively 3KOe and 25.7emu/g; For martensite, its value is respectively 17KOe and 35.2emg/g.Very obvious, Mn 50Ni 25Ga 25-xSn xThe magnetocrystalline anisotropy of alloy martensite phase is bigger than austenite, and this is closely-related with the two-phase lattice symmetry.

Claims (6)

1.Mn-Ni-Ga-Sn magnetic driven memory alloy is characterized in that the molecular formula of described Mn-Ni-Ga-Sn magnetic driven memory alloy is Mn50Ni25Ga25-xSnx, the x value is 1～2 in the molecular formula.
2. Mn-Ni-Ga-Sn magnetic driven memory alloy according to claim 1 is characterized in that the x value is 1.1～1.9 in the described molecular formula.
3. Mn-Ni-Ga-Sn magnetic driven memory alloy according to claim 1 is characterized in that the x value is 1.2～1.8 in the described molecular formula.
4. Mn-Ni-Ga-Sn magnetic driven memory alloy according to claim 1 is characterized in that the x value is 1.3～1.7 in the described molecular formula.
5. Mn-Ni-Ga-Sn magnetic driven memory alloy according to claim 1 is characterized in that the x value is 1.4～1.6 in the described molecular formula.
6. Mn-Ni-Ga-Sn magnetic driven memory alloy according to claim 1 is characterized in that the x value is 1.5 in the described molecular formula.
CN2009103090117A 2009-10-29 2009-10-29 Mn-Ni-Ga-Sn magnetic driving memory alloy Expired - Fee Related CN101693970B (en)

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