CN104962780A - Gamma phase-inhibited high temperature double-phase Ni-Mn-Ga-Gd alloy and preparation method thereof - Google Patents
Gamma phase-inhibited high temperature double-phase Ni-Mn-Ga-Gd alloy and preparation method thereof Download PDFInfo
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Abstract
The invention concretely relates to a gamma phase-inhibited high temperature double-phase Ni-Mn-Ga-Gd alloy and a preparation method thereof. The structural general formula of the alloy is represented by Ni58Mn25Ga17-xGdx, and x in the general formula is 0.1-0.5. The gamma phase of the Ni58Mn25Ga17-xGdx alloy obtained through material taking, arc melting, cleaning, heat insulation and quenching in water is obviously reduced, and is about 80-40% lower than that of present Ni58Mn25Ga17 alloy; and the martensite phase transition temperature of the Ni58Mn25Ga17-xGdx alloy is 387.5-461.4DEG C, and the temperature range is wide, so demands of different fields are met. Raw materials required in the invention are cheap and have abundant reserves, the alloy material prepared in the invention has the advantages of good toughness, large strength and good processing property, and can be processed to form various shapes as needed, and the preparation method has the advantages of simple process, easy industrial production, and development of a new idea for application of high-temperature and high-plasticity shape memory alloys.
Description
Technical field
The invention belongs to field of metal alloy technology, be specifically related to a kind of γ phase repressed high temperature two-phase Ni-Mn-Ga-Gd Alloy And Preparation Method.
Background technology
Shape memory alloy has unique shape memory effect (SME) and super-elasticity, it is a kind of intelligent material having prospect, due to the engineering fields such as aerospace, nuclear power source, motor, fire-fighting, chemical industry, oil-gas exploration usually need the temperature more than 200 DEG C under work, but its martensitic transformation temperature of shape memory alloy of exploitation comparative maturity is all no more than 120 DEG C at present, greatly limits its Application Areas.Therefore, develop high temperature shape memory alloy is one of the primary study direction in shape memory alloy field always.
The more high-temperature shape memory alloy of current research mainly contains: Ti-Ni-X (X=Pt, Pd, Au, Hf, Zr) high temperature shape memory alloy such as base, Cu-Al base, Ni-Al base, Ni-Mn base, Co-Ni-Ga, Ta-Ru, Nb-Ru and Ti-Ta base and Ti-Nb base.On the whole, though Ti-Ni-X base alloy has good over-all properties, its Addition ofelements mostly is precious metal, its practical application of expensive price limit.And Cu-Al base and Ni-Al base alloy poor heat stability, high-temperature shape-memory effect sharply worsens with the precipitation of equilibrium phase.Though Ta-Ru and Nb-Ru high temperature shape memory alloy transformation temperature can more than 1000 DEG C, it is expensive, machine-shaping is difficult, high high-temp stability is not enough; Although Ti-Ta base and Ti-Nb base high temperature shape memory alloy have excellent plasticity and good workability, its thermal cycling stability is poor; And although Co-Ni-Ga has extraordinary oxidation-resistance and stability, polycrystalline fragility significantly limit its practical application.
The Ni of what people found the earliest have concurrently ferromegnetism and shape memory effect
2mnGa alloy, not only has large magnetic-field-induced strain and high response frequency, and has good shape memory effect and super-elasticity and receive much concern.The people such as Ukraine scholar V.A.Cherenenko find in series of experiments, and by the chemical equivalent of each element in suitable change Ni-Mn-Ga alloy, the martensitic transformation temperature of alloy can regulate in very wide scope.Ma Yunqing etc. are to Ni
50+xmn
25ga
25-x(x=2-11) find when the microstructure of alloy and transformation behavior are studied, the martensitic transformation temperature of alloy is elevated to 456.2 DEG C from 44.0 DEG C along with the increase of Ni content, its Reverse Martensitic Transformation Temperatures is elevated to 520 DEG C from 50 DEG C, also there is good phase transformation stability simultaneously, and cheap, be a kind of potential high-temperature shape memory alloy.But when Ni content is higher than 57at%, the face-centered cubic γ phase with more mode of texturing will be produced in alloy, and increase gradually with Ni content increase γ phase, but because γ phase does not participate in martensite reverse transformation, and the size of γ phase, shape, volume and distribution all can hinder martensite variants to reset; Increase martensite variants with Ni content simultaneously and reset required critical stress increase, this causes dislocation source to actuated in advance, thus leaves irreversible deformation, worsens shape memory effect.Therefore how to suppress the γ phase in alloy, improve shape memory effect, become the main direction of studying of high temperature shape memory alloy application and development.
Summary of the invention
The present invention suppresses martensite reverse transformation to solve γ phase in existing high temperature Ni-Mn-Ga suitable shape memory alloy, and worsen the problem of shape memory effect, by to doped with rare-earth elements Gd in alloy, provide a kind of γ phase repressed high temperature two-phase Ni-Mn-Ga-Gd alloy.
For achieving the above object, the present invention is achieved in that a kind of γ phase repressed high temperature two-phase Ni-Mn-Ga-Gd alloy, and the general structure of described Ni-Mn-Ga-Gd alloy is Ni
58mn
25ga
17-Xgd
x, x=0.1 ~ 0.5 in general formula.
The weave construction of described alloy is the non-modulation T-shaped martensite of tetragonal.
The present invention also asks the preparation method protecting above-mentioned Ni-Mn-Ga-Gd alloy, and its technical essential comprises the following steps:
(1) Mn, Gd, Ga, Ni raw material of purity 99.9% is positioned in vacuum non-consumable electrode electric arc furnace according to order from the bottom to top successively;
(2) 5 × 10 are evacuated to by electric arc furnace
-3pa, then to be filled with vacuum tightness in noble gas to stove be 2 × 10
-2pa, at 2000 ~ 3000 DEG C, melting 18 ~ 20min under melting electric current 80 ~ 100A, makes button shape sample, treats that its cooling is taken out;
(3) sample removes surface impurity through mechanical polishing, adopts wire cutting method to obtain and requires shape;
(4) enclosing vacuum tightness after cleaning with acetone is 10
-1in the silica tube of Pa, under the condition of 800 ~ 850 DEG C, be incubated 24h, then quench in water, obtain Ni-Mn-Ga-Gd high temperature two-phase memorial alloy.
Further, the noble gas described in step (2) is argon gas.
Further, for ensureing the homogeneity of alloy composition in the fusion process in step (2), sample is overturn melting four times and in addition magnetic stirs.
With existing magnetic shape memory alloy Ni
58mn
25ga
17difference, Ni of the present invention
58mn
25ga
17-xgd
xalloy has the following advantages:
1, the Ni for preparing of the present invention
58mn
25ga
17-xgd
xin alloy, γ phase obviously reduces, than existing Ni
58mn
25ga
17alloy reduces about 80% ~ 40%;
2, the Ni for preparing of the present invention
58mn
25ga
17-xgd
xthe martensitic transformation temperature of alloy is 387.5 DEG C ~ 461.4 DEG C, and warm area wide ranges, can meet the demand of different field;
3, low in raw material price required for the present invention, rich reserves, preparation alloy material good toughness, intensity is large, processing characteristics is good, different shape can be processed into as required use, preparation technology is simple, being easy to suitability for industrialized production, is the application extension new approaches of high temperature high-ductility shape memory alloy.
Accompanying drawing explanation
Fig. 1 is Ni of the present invention
58mn
25ga
17-xgd
xthe DSC graphic representation of alloy, wherein curve 1-4 is cooling curve, and curve 5-8 is heating curve, (a), x=0 in figure, (b), x=0.1, (c), x=0.2, (d), x=0.5;
Fig. 2 is Ni of the present invention
58mn
25ga
17-xgd
xthe back scattering structure observation figure of alloy, wherein (a), x=0, (b), x=0.1, (c), x=0.2, (d), x=0.5;
Fig. 3 is Ni of the present invention
58mn
25ga
17-xgd
xthe metallographic microstructure of alloy observes figure, wherein (a), x=0, (b), x=0.2.
Embodiment
Content of the present invention is described in detail below by embodiment; but be not used in and limit the scope of the invention; if no special instructions; all commercially, vacuum non-consumable electrode electric arc furnace used in the present invention is purchased from Shenyang tech equipment responsibility company limited for experimental drug involved in the present invention and raw material.
Embodiment 1
Get the Ni of 58 parts, the Mn of 25 parts according to atomic percent, the rare earth Gd of 16.5 ~ 16.9 parts Ga and 0.1 ~ 0.5 part puts into vacuum non-consumable electrode electric arc furnace in the following order successively: the bottom first Mn sheet being placed on smelting pot, then rare-earth Gd and Ga is placed, close vacuum oven after finally placing Ni sheet, be evacuated to 5 × 10 by electric arc furnace
-3pa, then to be filled with vacuum tightness in noble gas to stove be 2 × 10
-2pa, arc melting 20 minutes under temperature 2000 DEG C, melting electric current 80A condition, each sample upset melting four times and in addition magnetic stir, then melted sample is made button shape sample, treats that its cooling is taken out.Then utilize wire cutting method cut, enclosing vacuum tightness with the alloy block after acetone cleaning cutting is 10
-1in the silica tube of Pa, be incubated 24h, then quench in water under the condition of 850 DEG C, obtain Ni-Mn-Ga-Gd high temperature two-phase shape memory alloy, its general structure is Ni
58mn
25ga
17-xgd
x, x=0.1,0.2 and 0.5, and along with the increase of Gd content, γ phase obviously reduces.
High temperature two-phase Ni prepared by the present embodiment
58mn
25ga
17-xgd
x(x=0.1,0.2,0.5) alloy records heating DSC curve under heat-up rate is the condition of 20K/min, and under the condition of cooling rate 20K/min, record cooling DSC curve, result as shown in Figure 1.The high temperature two-phase Ni prepared in present embodiment can be found out by the DSC curve in figure
58mn
25ga
17-xgd
xalloy all only has a heat absorption and release peak on the DSC curve of heating and cooling, and high temperature two-phase Ni is described
58mn
25ga
17-xgd
xalloy has the same thermoelastic martensitic transformation feature of same Ni-Mn-Ga ternary alloy.
High temperature two-phase Ni prepared by the present embodiment
58mn
25ga
17-xgd
x(x=0.1,0.2,0.5) alloy and Ni
58mn
25ga
17alloy carries out the test of back scattering and metallographic microanalysis, test result as shown in Figures 2 and 3, high temperature two-phase Ni prepared by the present embodiment
58mn
25ga
17-xgd
xin alloy, γ phase obviously reduces, and compares Ni
58mn
25ga
17decrease about 50% and reduce gradually along with the increase γ phasor of Gd content.
Embodiment 2
Get the Ni of 58 parts, the Mn of 25 parts according to atomic percent, the rare earth Gd of 16.5 ~ 16.9 parts Ga and 0.1 ~ 0.5 part puts into vacuum non-consumable electrode electric arc furnace in the following order successively: the bottom first Mn sheet being placed on smelting pot, then rare-earth Gd and Ga is placed, close vacuum oven after finally placing Ni sheet, be evacuated to 5 × 10 by electric arc furnace
-3pa, then to be filled with vacuum tightness in argon gas to stove be 2 × 10
-2pa, arc melting 20 minutes under temperature 3000 DEG C, melting electric current 100A melting current condition, each sample upset melting four times and in addition magnetic stir, then melted sample is made button shape sample, treats that its cooling is taken out.Then utilize Linear cut cut, enclosing vacuum tightness with the alloy block after cutting after acetone cleaning is 10
-1in the silica tube of Pa, be incubated 24h, then quench in water under the condition of 850 DEG C, obtain Ni-Mn-Ga-Gd high temperature two-phase shape memory alloy, its general structure is Ni
58mn
25ga
17-xgd
x, x=0.1,0.2,0.3,0.4 and 0.5, and along with the increase of Gd content, γ phase obviously reduces.
Embodiment 3
Get the Ni of 58 parts, the Mn of 25 parts according to atomic percent, the rare earth Gd of 16.5 ~ 16.9 parts Ga and 0.1 ~ 0.5 part puts into vacuum non-consumable electrode electric arc furnace in the following order successively: the bottom first Mn sheet being placed on smelting pot, then rare-earth Gd and Ga is placed, close vacuum oven after finally placing Ni sheet, be evacuated to 5 × 10 by electric arc furnace
-3pa, then to be filled with vacuum tightness in noble gas to stove be 2 × 10
-2pa, arc melting 18 minutes under temperature 2500 DEG C, melting electric current 100A condition, each sample upset melting four times and in addition magnetic stir, then melted sample is made button shape sample, treats that its cooling is taken out.Then utilize Linear cut cut, enclosing vacuum tightness with the alloy block after cutting after acetone cleaning is 10
-1in the silica tube of Pa, be incubated 24h, then quench in water under the condition of 800 DEG C, obtain Ni-Mn-Ga-Gd high temperature two-phase shape memory alloy, its general structure is Ni
58mn
25ga
17-xgd
x, x=0.1,0.2,0.3,0.4 and 0.5, and along with the increase of Gd content, γ phase obviously reduces.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (5)
1. a γ phase repressed high temperature two-phase Ni-Mn-Ga-Gd alloy, is characterized in that, the general structure of described Ni-Mn-Ga-Gd alloy is Ni
58mn
25ga
17-Xgd
x, x=0.1 ~ 0.5 in general formula.
2. γ phase according to claim 1 repressed high temperature two-phase Ni-Mn-Ga-Gd alloy, is characterized in that, the weave construction of described alloy is the non-modulation T-shaped martensite of tetragonal.
3. a preparation method for γ phase as claimed in claim 1 suppressed high temperature two-phase Ni-Mn-Ga-Gd alloy, is characterized in that, comprise the following steps:
(1) Mn, Gd, Ga, Ni raw material of purity 99.9% is positioned in vacuum non-consumable electrode electric arc furnace according to order from the bottom to top successively;
(2) 5 × 10 are evacuated to by electric arc furnace
-3pa, then to be filled with vacuum tightness in noble gas to stove be 2 × 10
-2pa, at 2000 ~ 3000 DEG C, melting 18 ~ 20min under melting electric current 80 ~ 100A, makes button shape sample, treats that its cooling is taken out;
(3) sample removes surface impurity through mechanical polishing, adopts wire cutting method to obtain and requires shape;
(4) enclosing vacuum tightness after cleaning with acetone is 10
-1in the silica tube of Pa, under the condition of 800 ~ 850 DEG C, be incubated 24h, then quench in water, obtain Ni-Mn-Ga-Gd high temperature two-phase memorial alloy.
4. the preparation method of γ phase according to claim 3 suppressed high temperature two-phase Ni-Mn-Ga-Gd alloy, is characterized in that, the noble gas described in step (2) is argon gas.
5. the preparation method of γ phase according to claim 3 suppressed high temperature two-phase Ni-Mn-Ga-Gd alloy, it is characterized in that, for ensureing the homogeneity of alloy composition in fusion process in step (2), sample is overturn melting four times and in addition magnetic stirs.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115369288A (en) * | 2022-08-14 | 2022-11-22 | 南昌航空大学 | Dual-phase Ni-Mn-Ga shape memory alloy and preparation method thereof |
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2015
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115369288A (en) * | 2022-08-14 | 2022-11-22 | 南昌航空大学 | Dual-phase Ni-Mn-Ga shape memory alloy and preparation method thereof |
| CN115369288B (en) * | 2022-08-14 | 2023-05-26 | 南昌航空大学 | Diphase Ni-Mn-Ga shape memory alloy and preparation method thereof |
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