CN104962780B - 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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- CN104962780B CN104962780B CN201510275908.8A CN201510275908A CN104962780B CN 104962780 B CN104962780 B CN 104962780B CN 201510275908 A CN201510275908 A CN 201510275908A CN 104962780 B CN104962780 B CN 104962780B
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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, and in particular to a kind of repressed high temperature two-phase Ni-Mn-Ga- of γ phases
Gd alloys and preparation method thereof.
Background technology
Marmem has unique shape memory effect (SME) and super-elasticity, is a kind of intelligence of great prospect
Material, as the engineering fields such as Aero-Space, nuclear power, motor, fire-fighting, chemical industry, oil-gas exploration are generally needed more than 200 DEG C
At a temperature of work, but at present marmem its martensitic transformation temperature of exploitation comparative maturity is less than 120 DEG C, greatly
Limit greatly its application.Therefore, develop high temperature shape memory alloy be always marmem field primary study direction it
One.
Studying more high-temperature shape memory alloy at present mainly has：Ti-Ni-X (X=Pt, Pd, Au, Hf, Zr) base, Cu-
The high temperature shape memory alloy such as Al bases, Ni-Al bases, Ni-Mn bases, Co-Ni-Ga, Ta-Ru, Nb-Ru and Ti-Ta base and Ti-Nb bases.
On the whole, though Ti-Ni-X based alloys have preferable combination property, its addition element mostly is noble metal, expensive price
Limit its practical application.And Cu-Al bases and Ni-Al based alloy heat stability are poor, high-temperature shape-memory effect is with balance phase
Separate out and drastically deteriorate.Though Ta-Ru and Nb-Ru high temperature shape memory alloy phase transition temperature can more than 1000 DEG C, which is expensive, plus
Work difficult forming, high high-temp stability are not enough；Although Ti-Ta bases and Ti-Nb bases high temperature shape memory alloy with excellent plasticity and
Good machinability, but its thermal cycling stability is poor；And although Co-Ni-Ga has extraordinary non-oxidizability and stability,
But polycrystalline fragility significantly limit its practical application.
The Ni for having ferromagnetism and shape memory effect concurrently that people have found earliest2MnGa alloys, not only with big magnetic strength
Raw strain and high response frequency, and receive much concern with good shape memory effect and super-elasticity.Ukraine scholar
V.A.Cherenenko et al. is had found in series of experiments, by the chemistry of each element in appropriate change Ni-Mn-Ga alloys
Equivalent, the martensitic transformation temperature of alloy can be adjusted in a wide range.Ma Yunqing etc. is to Ni50+xMn25Ga25-x(x=2-
11) find when the microstructure of alloy and transformation behavior are studied, the martensitic transformation temperature of alloy is with the increasing of Ni contents
Plus 456.2 DEG C are increased to from 44.0 DEG C, its Reverse Martensitic Transformation Temperatures is increased to 520 DEG C from 50 DEG C, while also having good phase transformation steady
It is qualitative and cheap, it is a kind of potential high-temperature shape memory alloy.But when Ni contents are higher than 57at%, in alloy
The face-centered cubic γ phases with more mode of texturing will be produced, and increases γ phases with Ni contents and gradually be increased, but due to γ phases
Do not participate in martensite reverse transformation, and the size of γ phases, shape, volume and distribution can all hinder martensite variants to reset；While with
Ni contents increase limit stress needed for martensite variants are reset and increase, and this causes dislocation source to actuated in advance, can not so as to stay
Inverse metamorphism, deteriorates shape memory effect.Therefore how to suppress the γ phases in alloy, improve shape memory effect, it has also become high temperature
Memorial alloy application and the main direction of studying of development.
The content of the invention
The present invention suppresses martensite reverse transformation to solve γ phases in existing high temperature Ni-Mn-Ga suitable shape memory alloys,
And deteriorate the problem of shape memory effect, by rare earth doped element Gd in alloy, there is provided a kind of repressed height of γ phases
Warm two-phase Ni-Mn-Ga-Gd alloy.
For reaching above-mentioned purpose, what the present invention was realized in：A kind of repressed high temperature two-phase Ni-Mn-Ga-Gd of γ phases
Alloy, the general structure of the Ni-Mn-Ga-Gd alloys is Ni58Mn25Ga17-XGdX, x=0.1～0.5 in formula.
Non-modulation T-shaped martensite of the organizational structure of the alloy for tetragonal.
The present invention is also claimed the preparation method of above-mentioned Ni-Mn-Ga-Gd alloys, is characterized in that, including following step
Suddenly：
(1) Mn, Gd, Ga, Ni raw material of purity 99.9% is positioned over into vacuum according to order from the bottom to top successively non-certainly
In power pole electric arc furnace；
(2) 5 × 10 will be evacuated in electric arc furnace-3Pa, it is 2 × 10 to be re-filled with noble gas to vacuum in stove-2Pa,
2000～3000 DEG C, 18～20min of melting under melting 80～100A of electric current, make button shape sample, treat that its cooling is taken out；
(3) sample Jing mechanical polishinges remove surface impurity, are obtained using wire cutting method and require shape；
(4) it is 10 to enclose vacuum after being cleaned with acetone-1In the quartz ampoule of Pa, it is incubated under conditions of 800～850 DEG C
24h, then quench in water, obtain final product Ni-Mn-Ga-Gd high temperature two-phase memorial alloys.
Further, the noble gas described in step (2) is argon.
Further, for ensureing the uniformity of alloy composition in the fusion process in step (2), will be sample upset molten
Refining four times in addition magnetic are stirred.
With existing magnetic shape memory alloy Ni58Mn25Ga17Difference, the Ni of the present invention58Mn25Ga17-xGdxAlloy has
Advantages below：
1st, Ni prepared by the present invention58Mn25Ga17-xGdxIn alloy, γ phases are significantly reduced, than existing Ni58Mn25Ga17Alloy subtracts
Few about 80%～40%；
2nd, Ni prepared by the present invention58Mn25Ga17-xGdxThe martensitic transformation temperature of alloy is 387.5 DEG C～461.4 DEG C, temperature
Area's wide ranges, can meet the demand of different field；
3rd, needed raw material of the present invention is cheap, rich reserves, and the alloy material good toughness of preparation, intensity are big, processability
Can be good, variously-shaped use, preparation process is simple can be processed into as needed, it is easy to industrialized production, be high temperature high-ductility
The application extension of marmem new approaches.
Description of the drawings
Fig. 1 is the Ni of the present invention58Mn25Ga17-xGdxThe DSC curve figure of alloy, wherein curve 1-4 be cooling curve, curve
5-8 is heating curves, (a), x=0 in figure, (b), x=0.1, (c), x=0.2, (d), x=0.5；
Fig. 2 is the Ni of the present invention58Mn25Ga17-xGdxThe 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 the Ni of the present invention58Mn25Ga17-xGdxThe metallographic microstructure observation figure of alloy, wherein (a), x=0, (b),
X=0.2.
Specific embodiment
Present disclosure is described in detail below by embodiment, but is not used in and is limited the scope of the invention, such as nothing
Specified otherwise, experimental drug involved in the present invention and raw material it is commercially available, vacuum non-consumable electrode used in the present invention
Electric arc furnace is purchased from Shenyang tech equipment responsibility company limited.
Embodiment 1
According to atomic percent take 58 parts Ni, 25 parts of Mn, Ga and 0.1～0.5 part of 16.5～16.9 parts of rare earth
Element Gd is sequentially placed in vacuum non-consumable electrode electric arc furnace in the following order：First Mn pieces be placed on melting kettle most under
Face, then places rare-earth Gd and Ga, closes vacuum drying oven, will be evacuated to 5 × 10 in electric arc furnace after finally placing Ni pieces-3Pa, then
It is 2 × 10 to be filled with noble gas to vacuum in stove-2Pa, the electric arc melting 20 minutes under the conditions of 2000 DEG C of temperature, melting electric current 80A,
The upset melting four times of each sample in addition magnetic are stirred, and melted sample is made button shape sample then, treats that its cooling takes
Go out.Then cut using wire cutting method, it is 10 that the alloy block cleaned after cutting with acetone encloses vacuum-1The stone of Pa
Ying Guanzhong, is incubated 24h under conditions of 850 DEG C, then quenches in water, obtains final product Ni-Mn-Ga-Gd high temperature two-phase marmems,
Its general structure is Ni58Mn25Ga17-xGdx, x=0.1,0.2 and 0.5, and with the increase of Gd contents, γ phases are significantly reduced.
By high temperature two-phase Ni manufactured in the present embodiment58Mn25Ga17-xGdx(x=0.1,0.2,0.5) alloy is in programming rate
For measuring heating DSC curve under conditions of 20K/min, cooling DSC curve is measured under conditions of cooling rate 20K/min, tie
Fruit is as shown in Figure 1.High temperature two-phase Ni prepared in present embodiment can be seen that by the DSC curve in figure58Mn25Ga17-xGdx
Alloy all only one of which in heating and the DSC curve for cooling down are absorbed heat and exothermic peak, illustrate high temperature two-phase Ni58Mn25Ga17-xGdx
Alloy is with the same thermoelastic martensitic transformation feature of same Ni-Mn-Ga ternary alloy three-partalloys.
By high temperature two-phase Ni manufactured in the present embodiment58Mn25Ga17-xGdx(x=0.1,0.2,0.5) alloy and
Ni58Mn25Ga17Alloy carries out the test of back scattering and metallographic microanalysis, test result as shown in Figures 2 and 3, the present embodiment
High temperature two-phase Ni of preparation58Mn25Ga17-xGdxIn alloy, γ phases are significantly reduced, and compare Ni58Mn25Ga17Reduce about 50% and also with
The increase γ phasors for Gd contents are gradually decreased.
Embodiment 2
According to atomic percent take 58 parts Ni, 25 parts of Mn, Ga and 0.1～0.5 part of 16.5～16.9 parts of rare earth
Element Gd is sequentially placed in vacuum non-consumable electrode electric arc furnace in the following order：First Mn pieces be placed on melting kettle most under
Face, then places rare-earth Gd and Ga, closes vacuum drying oven, will be evacuated to 5 × 10 in electric arc furnace after finally placing Ni pieces-3Pa, then
It is 2 × 10 to be filled with argon to vacuum in stove-2Pa, under 3000 DEG C of temperature, melting electric current 100A melting current conditions, electric arc melts
Refining 20 minutes, the upset melting four times of each sample in addition magnetic are stirred, and melted sample is made button shape sample then, is treated
Its cooling is taken out.Then cut using wire cutting, it is 10 that the alloy block after cutting after being cleaned with acetone encloses vacuum- 1In the quartz ampoule of Pa, 24h is incubated under conditions of 850 DEG C, then is quenched in water, obtain final product Ni-Mn-Ga-Gd high temperature two-phases shape note
Recall alloy, its general structure is Ni58Mn25Ga17-xGdx, x=0.1,0.2,0.3,0.4 and 0.5, and with the increasing of Gd contents
Plus, γ phases are significantly reduced.
Embodiment 3
According to atomic percent take 58 parts Ni, 25 parts of Mn, Ga and 0.1～0.5 part of 16.5～16.9 parts of rare earth
Element Gd is sequentially placed in vacuum non-consumable electrode electric arc furnace in the following order：First Mn pieces be placed on melting kettle most under
Face, then places rare-earth Gd and Ga, closes vacuum drying oven, will be evacuated to 5 × 10 in electric arc furnace after finally placing Ni pieces-3Pa, then
It is 2 × 10 to be filled with noble gas to vacuum in stove-2Pa, the electric arc melting 18 minutes under the conditions of 2500 DEG C of temperature, melting electric current 100A,
The upset melting four times of each sample in addition magnetic are stirred, and melted sample is made button shape sample then, treats that its cooling takes
Go out.Then cut using wire cutting, it is 10 that the alloy block after cutting after being cleaned with acetone encloses vacuum-1The quartz of Pa
Guan Zhong, is incubated 24h under conditions of 800 DEG C, then quenches in water, obtains final product Ni-Mn-Ga-Gd high temperature two-phase marmems, its
General structure is Ni58Mn25Ga17-xGdx, x=0.1,0.2,0.3,0.4 and 0.5, and with the increase of Gd contents, γ phases are bright
It is aobvious to reduce.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope of present disclosure, technology according to the present invention scheme and its
Inventive concept equivalent or change in addition, should all be included within the scope of the present invention.
Claims (5)
1. a kind of repressed high temperature two-phase Ni-Mn-Ga-Gd alloy of γ phases, it is characterised in that the Ni-Mn-Ga-Gd alloys
General structure be Ni58Mn25Ga17-XGdX, x=0.2～0.5 in formula；
The preparation method of Ni-Mn-Ga-Gd alloys：
(1) Mn, Gd, Ga, Ni raw material of purity 99.9% is positioned over into vacuum non-consumable electricity according to order from the bottom to top successively
In pole electrical arc stove；
(2) 5 × 10 will be evacuated in electric arc furnace-3Pa, it is 2 × 10 to be re-filled with noble gas to vacuum in stove-2Pa, 2000～
3000 DEG C, 18～20min of melting under melting 80～100A of electric current, make button shape sample, treat that its cooling is taken out；
(3) sample Jing mechanical polishinges remove surface impurity, are obtained using wire cutting method and require shape；
(4) it is 10 to enclose vacuum after being cleaned with acetone-1In the quartz ampoule of Pa, 24h is incubated under conditions of 800～850 DEG C, then
Quench in water, obtain final product Ni-Mn-Ga-Gd high temperature two-phase memorial alloys.
2. the repressed high temperature two-phase Ni-Mn-Ga-Gd alloy of γ phases according to claim 1, it is characterised in that described
Alloy organizational structure for tetragonal non-modulation T-shaped martensite.
3. a kind of γ phases as claimed in claim 1 are suppressed the preparation method of high temperature two-phase Ni-Mn-Ga-Gd alloy, its feature
It is to comprise the following steps：
(1) by purity 99.9% atomic percent take 25 parts Mn, 0.2～0.5 part of rare earth Gd, 16.5～16.8 parts
Ga and 58 part of Ni is according to being positioned in vacuum non-consumable electrode electric arc furnace according to order from the bottom to top successively；
(2) 5 × 10 will be evacuated in electric arc furnace-3Pa, it is 2 × 10 to be re-filled with noble gas to vacuum in stove-2Pa, 2000～
3000 DEG C, 18～20min of melting under melting 80～100A of electric current, make button shape sample, treat that its cooling is taken out；
(3) sample Jing mechanical polishinges remove surface impurity, are obtained using wire cutting method and require shape；
(4) it is 10- to enclose vacuum after being cleaned with acetone1In the quartz ampoule of Pa, 24h is incubated under conditions of 800～850 DEG C, then
Quench in water, obtain final product Ni-Mn-Ga-Gd high temperature two-phase memorial alloys.
4. γ phases according to claim 3 are suppressed the preparation method of high temperature two-phase Ni-Mn-Ga-Gd alloy, and its feature exists
In the noble gas described in step (2) is argon.
5. γ phases according to claim 3 are suppressed the preparation method of high temperature two-phase Ni-Mn-Ga-Gd alloy, and its feature exists
In for ensureing the uniformity of alloy composition in the fusion process in step (2), sample being overturn melting four times and in addition magnetic
Stirring.
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