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CN107099698A - A kind of preparation method of superhigh intensity Ni Mn Ga Hf memorial alloys - Google Patents

A kind of preparation method of superhigh intensity Ni Mn Ga Hf memorial alloys Download PDF

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CN107099698A
CN107099698A CN201710477767.7A CN201710477767A CN107099698A CN 107099698 A CN107099698 A CN 107099698A CN 201710477767 A CN201710477767 A CN 201710477767A CN 107099698 A CN107099698 A CN 107099698A
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alloy
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superhigh intensity
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CN107099698B (en
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董桂馥
王通
王兴安
赵益民
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Dalian University
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Dalian University
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    • CCHEMISTRY; METALLURGY
    • 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
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • C22C1/023Alloys based on nickel
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon

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  • Materials Engineering (AREA)
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  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Investigating And Analyzing Materials By Characteristic Methods (AREA)
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Abstract

The present invention relates to a kind of preparation method of New Shape Memory Alloys, particularly a kind of preparation method of superhigh intensity Ni Mn Ga Hf memorial alloys.Marmem Ni prepared by the present invention53Mn25Ga21Hf1For the application extension thinking of high temperature high-ductility marmem.The Ni of the present invention53Mn25Ga21Hf1Prepared as follows:According to atomic percent feeding, vacuumize, melting plus Mn elements continue melting, clean, be incubated, carry out Homogenization Treatments in water of quenching, and by changing aging temp and aging time, that is, obtain superhigh intensity Ni53Mn25Ga21Hf1Alloy.Ni prepared by the present invention53Mn25Ga21Hf1Alloy has the advantages that good toughness, intensity are big.

Description

A kind of preparation method of superhigh intensity Ni-Mn-Ga-Hf memorial alloys
Technical field
The present invention relates to a kind of high intensity Ni-Mn-Ga-Hf memorial alloy preparation methods.
Background technology
Ni-Mn-Ga marmems are a class novel intelligent ferromagnetic shape memory materials, have thermo elastic martensite concurrently Phase transformation and ferromagnetic transition, not only with SME of the conventional shape-memory alloy by Temperature Field Control, but also can SME is produced under magnetic fields.The response frequency of its magneto-shape-memory effect is close to piezoelectric ceramics, and output should Become close to traditional temperature control marmem, be a kind of intellectual material of great future in engineering applications.Because its it is unique the characteristics of It is set also to be able to extensive use in terms of driver and sensor.
But, Ni-Mn-Ga block materials are remained fragility is big, low intensity and the shortcomings of small restoring force, significantly limit The engineer applied of the material and its development.These turn into the main bottleneck that magnetic driven memory alloy is applied and developed.So how The intensity of alloy is improved, fragility is reduced, improves alloy mechanical performance, big magnetic entropy is obtained and becomes and giant magnetoresistance effect, it has also become note Recall the main direction of studying of Alloyapplication and development.
The content of the invention
Big in order to solve existing Ni-Mn-Ga alloys fragility, the shortcomings of low intensity and small restoring force, we take timeliness Method increases the intensity of alloy and increases plasticity.It is strong to provide a kind of new superelevation by changing aging temp and time The Ni of degree53Mn25Ga21Hf1Memorial alloy preparation method.
The marmem of the present invention is prepared as follows:
(1) 53 parts of Ni, 25 parts of Mn, 21 parts of Ga and 1 part of Hf are taken to be put into vacuum intermediate-frequency induction melting furnace according to atomic percent In, raw material is sequentially placed in the following order:Hf is placed first, Ni is subsequently placed with, Ga is finally putting into, because the height of Mn elements is waved Mn, standby in material alloying device, close side fire door is placed on during charging by hair property in advance;
(2) before melting, 10 × 10 are evacuated down to-3-3×10-3Pa, is re-filled with noble gas to 1-0.2Pa, starts melting, control Monitor system is between 350-500Kw.Due to the Principle of Melting of Medium frequency induction itself, the metal liquid after thawing will be in electromagnetism Stirring is flowed in the presence of, is eventually adding aluminium alloy after the metal liquid being melted fully is mixed after Mn, 3-5min Body is poured into bar molds, obtains sample, treats that its cooling is taken out;
(3) sample is removed into surface impurity through wire cutting and mechanical polishing, it is 10 that vacuum is enclosed after cleaning-1Pa quartz Guan Zhong, is incubated 5 hours progress Homogenization Treatments under conditions of 1000 DEG C;Then by obtained alloy carry out 500-800 DEG C, 0.5-5h Ageing Treatment, you can obtain the Ni of superhigh intensity53Mn25Ga21Hf1Alloy.
Further, noble gas is high-purity argon gas in the step (2).
Further, acetone washed samples, then application of vacuum are used in the step (3).
Further, described vacuumize using equipment can be mechanical pump or lobe pump.
Another object of the present invention is claimed the above method and prepares superhigh intensity Ni-Mn-Ga-Hf memorial alloys Ni53Mn25Ga21Hf1
Alloying can significantly change alloy transformation temperature and improve its mechanical performance and physical property.Inventor by In Ni-Mn-Ga ternary alloy three-partalloys with ion electricity price is higher, radius is smaller, with compared with macroion field strength (ion electricity price and radius it Than) element Hf doping substitute part Ni member usually improve alloy mechanical property do not reduce or slightly reduction alloy martensite phase Phase transition temperature, to provide a kind of new high intensity Ni-Mn-Ga-Hf memorial alloys.Because Mn element saturated vapour pressures are higher, Volatile, in existing preparation method, Mn volatile quantity is difficult to control, it is impossible to which Mn content in exact alloy, inventor uses Hf is placed first, then puts Ni, Ga is subsequently placed into, Mn feed way is finally putting into, and solve that component content accurately controls asks Topic.
The high intensity Ni that inventor is prepared using vacuum intermediate-frequency induction melting furnace53Mn25Ga21Hf1Alloy, then to it Ageing Treatment is carried out, it is found that becoming of gradually increasing is presented with the increase of aging temp for the fracture strength and breaking strain of alloy Gesture, when aging temp is higher than 600 DEG C, quick increase, up to 7734MPa is presented in fracture strength;Breaking strain first quick increase After be slowly increased, highest breaking strain be 17.8%, this never Leader in NiMnGa alloys is crossed, this can turn into memory close Gold application and a kind of new material of development.Therefore shape memory aging alloy Ni53Mn25Ga21Hf1Development by material Using and expand open up new thinking.
Vacuum intermediate-frequency induction melting furnace is that eddy heating for heating is produced in metallic conductor using electromagnetic induction under vacuum Furnace charge is come the method that carries out melting.With melting small volume, pumpdown time and melting cycle are short, be easy to temperature, pressure control, The features such as being easily recycled Volatile Elements and accurate composition control.
The shape memory metal shape memorial alloy Ni that the inventive method is prepared53Mn25Ga21Hf1Different from using vacuum Ni-Mn-Ga alloys prepared by non-consumable smelting furnace, have the advantages that fracture strength height, toughness are big by comparison, and this method is grasped Make that alloy property that is simple, preparing is stable, be that new approaches have been expanded in the field of high intensity and high-ductility marmem.
Brief description of the drawings
The Ni that Fig. 1 is prepared for the present invention53Mn25Ga21Hf1The light micrograph of alloy;Wherein (a) figure is alloy in room Light micrograph under temperature, light micrograph of (b) figure alloy after 500 DEG C/3h Ageing Treatments, (c) figure is alloy warp Light micrograph after 600 DEG C/3h Ageing Treatments, (d) figure is that optics of the alloy after 700 DEG C/3h Ageing Treatments shows Micro- photo, (e) figure is light micrograph of the alloy after 800 DEG C/3h Ageing Treatments;
The Ni that Fig. 2 is prepared for the present invention53Mn25Ga21Hf1The XRD spectrum of alloy;Wherein (a) figure be alloy through 700 DEG C/ Light micrograph after 0.5h Ageing Treatments, (b) figure is light micrograph of the alloy after 700 DEG C/1h Ageing Treatments, (c) figure is light micrograph of the alloy after 700 DEG C/3h Ageing Treatments, and (d) figure is alloy through 700 DEG C/5h Ageing Treatments Light micrograph afterwards;
The Ni that Fig. 3 is prepared for the present invention53Mn25Ga21Hf1Room temperature pressure of the memorial alloy after 800 DEG C/3h Ageing Treatments Stress under compression and strain curve;
The Ni that Fig. 4 is prepared for the present invention53Mn25Ga21Hf1Memorial alloy alloy after different aging temp Ageing Treatments Fracture strength changes;
The Ni that Fig. 5 is prepared for the present invention53Mn25Ga21Hf1Memorial alloy alloy after different aging temp Ageing Treatments Breaking strain changes;
Fig. 6 is Ni53Mn25Ga21Hf1The fracture strength of memorial alloy alloy after 700 DEG C of different time Ageing Treatments;
Fig. 7 is Ni53Mn25Ga21Hf1The change of memorial alloy breaking strain of alloy after 700 DEG C of different time Ageing Treatments Change.
Specific embodiment
The present invention is described in further detail below by embodiment, but not limited the scope of the invention.Such as without spy Different explanation, experimental method of the present invention is conventional method, and experiment equipment used, material, reagent etc. can be chemically Company buys.Vacuum intermediate-frequency induction melting furnace is purchased from Shanghai Twilight electric furnace Co., Ltd.
Embodiment 1
The high intensity Ni of the present embodiment53Mn25Ga21Hf1The preparation method of memorial alloy is prepared as follows:Press 53 parts of Ni, 25 parts of Mn, 21 parts Ga and 1 part of rare element Hf are taken to be put into vacuum intermediate-frequency induction melting furnace according to atomic percent, Raw material is sequentially placed in the following order:Rare element Hf is placed first, is subsequently placed with Ni pieces, is finally putting into Ga, it is pre- during charging First Mn is placed on it is standby in material alloying device, after Hf, Ni, Ga melt it is uniform after, add Mn.Before melting, using mechanical pump, Lobe pump is evacuated down to 6.67 × 10-3Pa, is re-filled with high-purity argon gas to 0.2Pa.Start melting, control monitor system 500Kw.When The metal liquid being melted is eventually adding Mn pieces after fully being mixed, 3-5min pours into alloy liquid in bar molds, obtains Φ 12mm × 60mm bar samples, treat that its cooling is taken out.Test material removes surface impurity through wire cutting and mechanical polishing, uses It is 10 that vacuum is enclosed after acetone cleaning-1In Pa quartz ampoule, insulation is carried out at homogenization for 5 hours under conditions of 1000 DEG C Reason;Obtain Ni53Mn25Ga21Hf1Marmem.
Embodiment 2
The high intensity Ni of the present embodiment53Mn25Ga21Hf1The preparation method of memorial alloy is prepared as follows:Press Carried out according to aging temp and aging time is changed, specific step is as follows:Aging time is fixed first, respectively heats sample In quenching within 3 hours water again to 500 DEG C, 600 DEG C, 700 DEG C and 800 DEG C insulations, that is, the superelevation for obtaining different aging time processing is strong Spend Ni53Mn25Ga21Hf1Marmem.
Embodiment 3
The present embodiment and the difference of embodiment 1 are, aging time is changed under conditions of 700 DEG C of holdings of aging temp are constant Respectively 0.5h, 1h, 3h and 5h.It is other identical with embodiment one.
Embodiment 4
53 parts of Ni, 25 parts of Mn, 21 parts Ga and 1 part of rare element Hf are taken to be put into vacuum intermediate-frequency sensing according to atomic percent In smelting furnace, rare element Hf being placed first, Ni pieces is subsequently placed with, is finally putting into Ga, Mn is placed on into alloy in advance during charging adds Expect standby in device, after Hf, Ni, Ga melt uniformly, add Mn.Before melting, 10 are evacuated down to using mechanical pump, lobe pump ×10-3Pa, is re-filled with high-purity argon gas to 0.2Pa.Start melting, control monitor system 350Kw.When the metal liquid quilt being melted Mn pieces are eventually adding after fully mixing, 3-5min pours into alloy liquid in bar molds, obtains the bar-shaped of Φ 12mm × 60mm Sample, treats that its cooling is taken out.Test material removes surface impurity through wire cutting and mechanical polishing, and vacuum is enclosed after being cleaned with acetone Spend for 10-1In Pa quartz ampoule, 5 hours progress Homogenization Treatments are incubated under conditions of 1000 DEG C;Then by obtained alloy In 800 DEG C of insulation 3h quench water again, that is, obtain Ni53Mn25Ga21Hf1Marmem.
Superhigh intensity Ni prepared by embodiment 2 and 353Mn25Ga21Hf1Alloy microstructure is analyzed, and Fig. 1 is superhigh intensity The light micrograph that alloy structure changes with aging temp, the precipitated phase in all alloys is at any time as seen in Figure 1 The increase of effect temperature first increases to be reduced afterwards.
Fig. 2 is the light micrograph that changes with aging time of superstrength alloy tissue, as can be seen from Figure 2 with And phase amount increase is separated out in the increase alloy of aging time.
Superstrength alloy prepared by the present invention carries out the test of fracture strength and breaking strain, test result such as Fig. 3 It is shown, Ni prepared by the present invention53Mn25Ga21Hf1Fracture strength is in 7734Mpa after 800 DEG C/3h Ageing Treatments for alloy, than not Ni through Ageing Treatment53Mn25Ga21Hf1Fracture strength be about 3300MPa.Ni prepared by the present invention53Mn25Ga21Hf1Alloy breaks Resistance to spalling increases with the increase of aging time, and 594834MPa is increased from 4684MPa, is improved about than existing Ni-Mn-Ga alloys 4000-5000Mpa。
By Ni resulting in the present embodiment 2-353Mn25Ga21Hf1Fracture strength and breaking strain with aging temp and The change test result of aging time is as shown in Figure 4 and Figure 5;Ni prepared by the present invention53Mn25Ga21Hf1The highest of alloy is broken Resistance to spalling is 7734MPa, and highest breaking strain is 18%, illustrates Ni prepared by the present invention53Mn25Ga21Hf1Alloy ductility is big. Ni prepared by the present invention53Mn25Ga21Hf1Alloy fracture intensity increases with the increase of aging temp, increases to from 4376MPa 7734MPa, about 3500-7000Mpa is improved than existing Ni-Mn-Ga alloys;Increase to 17.8% from 12.8%, than existing Ni- Mn-Ga alloys improve about 200%-350%;Ni prepared by the present invention53Mn25Ga21Hf1Alloy fracture is strained with aging time Increase first increases to be reduced afterwards, is increased to 16.7% from 12.8% and is dropped to 14.4, is improved about than existing Ni-Mn-Ga alloys 200%-350%.

Claims (5)

1. a kind of preparation method of superhigh intensity Ni-Mn-Ga-Hf memorial alloys, it is characterised in that comprise the following steps:
(1) take 53 parts of Ni, 25 parts of Mn, 21 parts of Ga and 1 part of Hf to be put into vacuum intermediate-frequency induction melting furnace according to atomic percent, press Raw material is sequentially placed according to following order:Hf is placed first, Ni is subsequently placed with, Ga is finally putting into, and Mn is placed on conjunction in advance during charging It is standby in golden feeding device, close side fire door;
(2) before melting, 10 × 10 are evacuated down to-3-3×10-3Pa, is re-filled with noble gas to 1-0.2Pa, starts melting, control melting Power is in 350-500Kw;Being eventually adding after metal liquid Ga, Hf, Ni for being melted fully are mixed after Mn, 3-5min will be mixed Alloy liquid after conjunction is poured into bar molds, obtains sample, treats that its cooling is taken out;
(3) sample is removed into surface impurity through wire cutting and mechanical polishing, it is 10 that vacuum is enclosed after cleaning-1Pa quartz ampoule In, 5 hours progress Homogenization Treatments are incubated under conditions of 1000 DEG C;Then obtained alloy is subjected to 500-800 DEG C, 0.5- 5h Ageing Treatment produces Ni53Mn25Ga21Hf1Marmem.
2. a kind of preparation method of superhigh intensity Ni-Mn-Ga-Hf memorial alloys according to claim 1, its feature exists In noble gas is high-purity argon gas in the step (2).
3. a kind of preparation method of superhigh intensity Ni-Mn-Ga-Hf memorial alloys according to claim 1, its feature exists In, using acetone washed samples in the step (3), then application of vacuum.
4. a kind of preparation method of superhigh intensity Ni-Mn-Ga-Hf memorial alloys according to claim 1, its feature exists In described vacuumize using equipment can be mechanical pump or lobe pump.
5. a kind of method as claimed in claim 1 prepares superhigh intensity Ni-Mn-Ga-Hf memorial alloys, it is characterised in that the note Alloy is recalled for Ni53Mn25Ga21Hf1
CN201710477767.7A 2017-06-20 2017-06-20 A kind of preparation method of superhigh intensity Ni-Mn-Ga-Hf memorial alloys Active CN107099698B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220448A (en) * 2008-02-03 2008-07-16 哈尔滨工业大学 Method for manufacturing toughening magnetic shape memory alloy
CN104947052A (en) * 2015-07-27 2015-09-30 大连大学 Method for preparing Ni52Mn24Ga24 alloy film through laser pulse sputtering deposition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101220448A (en) * 2008-02-03 2008-07-16 哈尔滨工业大学 Method for manufacturing toughening magnetic shape memory alloy
CN104947052A (en) * 2015-07-27 2015-09-30 大连大学 Method for preparing Ni52Mn24Ga24 alloy film through laser pulse sputtering deposition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
董桂馥: "时效Ni-Mn-Ga-Ti合金的相变和力学行为", 《中国博士学位论文全文数据库 工程科技I辑》 *

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