CN108060341A - A kind of high tenacity Ni50Mn25Ga25Memorial alloy and preparation method thereof - Google Patents

A kind of high tenacity Ni50Mn25Ga25Memorial alloy and preparation method thereof Download PDF

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Publication number
CN108060341A
CN108060341A CN201711422646.9A CN201711422646A CN108060341A CN 108060341 A CN108060341 A CN 108060341A CN 201711422646 A CN201711422646 A CN 201711422646A CN 108060341 A CN108060341 A CN 108060341A
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powder
alloy
high tenacity
memorial alloy
preparation
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CN108060341B (en
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董桂馥
吴蒙华
王珍
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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
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0433Nickel- or cobalt-based alloys
    • 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

Abstract

The present invention relates to a kind of memorial alloys and preparation method thereof, particularly a kind of high tenacity Ni50Mn25Ga25Memorial alloy and preparation method thereof, high tenacity Ni of the invention50Mn25Ga25Memorial alloy is prepared as follows:It according to atomic percent feeding, is uniformly mixed by mechanical agitation, then carries out ball milling, finally the powder of acquisition is put into graphite grinding tool and is sintered, high tenacity Ni is made50Mn25Ga25Memorial alloy.Ni prepared by the present invention50Mn25Ga25Alloy has higher fracture strength, breaking strain, and good toughness, intensity is big.

Description

A kind of high tenacity Ni50Mn25Ga25Memorial alloy and preparation method thereof
Technical field
The invention belongs to field of memory alloy, and in particular to a kind of high tenacity Ni50Mn25Ga25Memorial alloy and its preparation side Method.
Background technology
Ni-Mn-Ga marmems are a kind of novel intelligent ferromagnetic shape memory materials, have thermo elastic martensite concurrently Phase transformation and ferromagnetic transition, not only with conventional shape-memory alloy shape memory effect temperature controlled, but also can be Shape memory effect is generated under magnetic fields.The response frequency of its magneto-shape-memory effect is strained close to piezoelectric ceramics, output It is a kind of intellectual material of great future in engineering applications close to traditional temperature control marmem.Because the characteristics of it is unique, makes It is also able to extensive use in terms of driver and sensor.But Ni-Mn-Ga block materials still have that brittleness is big, intensity is low With restoring force it is small the shortcomings of, significantly limit engineer application and its development of the material.These become magnetic driven memory alloy Using and development main bottleneck.Therefore so how to improve the intensity of alloy, brittleness is reduced, improves alloy mechanical performance, obtains The magnetic entropy obtained greatly becomes and giant magnetoresistance effect, it has also become memorial alloy is applied and the main direction of studying of development.
The content of the invention
In order to overcome existing Ni-Mn-Ga alloy systems brittleness big, the defects such as intensity is low, the present invention provides one kind and passes through powder The method that last metallurgical and hot pressed sintering is combined prepares Ni50Mn25Ga25The method of Magnetic Memory alloy, it is strong to the method achieve fine grain Change, significantly change alloy transformation temperature and improve its mechanical performance and physical property.
The technical solution adopted by the present invention to solve the technical problems is:A kind of high tenacity Ni50Mn25Ga25Memorial alloy Preparation method, the Ni powder, 25 parts of Mn powder, 25 parts of Ga powder for taking 50 parts according to atomic percent are mixed by mechanical agitation Even, the powder of acquisition is finally put into graphite grinding tool and is sintered, is made by ball milling when then progress 12-20 is small Ni50Mn25Ga25Memorial alloy;The grain size of powder is within 100 microns.
Further, the placement order of raw material is as follows:The Ga powder of low melting point is placed first, then places the Mn of high volatile Powder finally places Ni powder.
Further, the process conditions of sintering are:Pressure is 200 kilograms, vacuum degree 10-3-10-4Pa, temperature 1300 DEG C or 1400 DEG C or 1500 DEG C, the time be 10 minutes.
Further, the sintering method is vacuum heating-press sintering.
Another object of the present invention is that a kind of high tenacity Ni of above method preparation is claimed50Mn25Ga25Memorial alloy.
The process of hot-pressed material densification includes Plastic Flow, VISCOUS FLOW and diffusion and creep, when with plasticity and viscosity When densification mechanism is led based on flowing into, body of powder is able to quick densifying, and obtains controllable microstructure.The advantage of pressure sintering Although be equipment investment is small, pressure compared with isostatic pressed order of magnitude lower but due in hot press pressure-bearing material can attenuate, from And longitudinal heat flux is limited, improve the uniformity of workpiece temperature field, the material for greatly reducing energy consumption, major diameter being prepared Material, the densification process and quality that with IT technology observing and controlling hot presses, can effectively control material.Hot pressed sintering is to utilize thermal energy The process for being densified product with mechanical energy.The characteristic of this process is that sintering temperature can be burnt according to the size of impressed pressure than normal pressure Low about 200 DEG C -400 DEG C are tied, while additional energy causes the speed that product is densified to accelerate, therefore completely fine and close and crystal grain Careful product can be completed in relatively low temperature and in the shorter time;And using vacuum heating-press sintering, due in hot pressing Higher vacuum degree is maintained, can effectively further reduce the sintering temperature of product and efficiently excludes the gas in Minute pores Body, so as to further promote the densification process of hot-pressed material.
The polycrystal that Ni-Mn-Ga alloys are made of many crystal grain, experiment show that fine grain metal is than thick at normal temperatures Grained metals have higher intensity, hardness, plasticity and toughness.In addition, crystal grain is thinner, grain boundary area is bigger, and crystal boundary is more tortuous, more It is unfavorable for the extension of crackle.In general, not only intensity is high for fine grain sample, and toughness, refined crystalline strengthening can significantly change Become alloy transformation temperature and improve its mechanical performance and physical property.
The marmem Ni that the method for the present invention is prepared50Mn25Ga25Different from existing magnetic shape memory alloy Ni50Mn25Ga25, and has the following advantages by comparison:Ni prepared by the present invention50Mn25Ga25Alloy fracture intensity is in 1600- Between 1960MPa, than existing Ni50Mn25Ga25Alloy improves about 1000-1300Mpa;Ni prepared by the present invention50Mn25Ga25Alloy Crystallite dimension is tiny, about at 20-50 microns, and as the crystallite dimension of the increase alloy of sintering temperature is increased slightly;This hair The alloy fracture strain of bright preparation compares existing Ni50Mn25Ga25Alloy fracture strain improves 300-500%, that is to say, that bright Ni prepared by the present invention50Mn25Ga25Alloy ductility is big.
Description of the drawings
Fig. 1 (a) is the high tenacity Ni that alloy sintering temperature prepared by embodiment 1 is 1300 DEG C50Mn25Ga25Scanning electron Micrograph;
Fig. 1 (b) is the high tenacity Ni that alloy sintering temperature prepared by embodiment 2 is 1400 DEG C50Mn25Ga25Scanning electron Micrograph;
Fig. 1 (c) is the high tenacity Ni that alloy sintering temperature prepared by embodiment 3 is 1500 DEG C50Mn25Ga25Scanning electron Micrograph;
Fig. 2 is Ni50Mn25Ga25The XRD spectrum of alloy, wherein 1,2 and 3 represents sintering temperature as 1300 DEG C, 1400 respectively DEG C and the Ni for preparing of 1500 DEG C of whens50Mn25Ga25The XRD curves of alloy;
Fig. 3 is Ni50Mn25Ga25The DSC collection of illustrative plates of alloy, wherein 1,2 and 3 represents sintering temperature as 1300 DEG C, 1400 respectively DEG C and the Ni for preparing of 1500 DEG C of whens50Mn25Ga25The heating curves of the DSC of alloy;4,5 and 6 represent sintering temperature as 1300 respectively DEG C, Ni prepared by 1400 DEG C and 1500 DEG C whens50Mn25Ga25The cooling curve of the DSC of alloy;
Fig. 4 is Ni under different sintering temperatures50Mn25Ga25The room temperature compression strain curve of alloy.
Specific embodiment
Embodiment 1
High tenacity Ni50Mn25Ga25Memorial alloy is prepared as follows:50 parts of Ni is taken according to atomic percent Powder, 25 parts of Mn powder, 25 parts of Ga powder are put into ball mill, are placed the Ga powder of low melting point first, are subsequently placed with high volatile Mn powder, finally place Ni powder, carried out again after mixing by mechanical agitation ball milling 12-20 it is small when.Then by the mixing of acquisition Uniformly and powder of the grain size control within 100 microns is put into graphite grinding tool and is sintered.The technique of sintering is:Applying pressure is 200 kilograms, vacuum degree 10-4Pa, sintering temperature are 1300 DEG C, and sintering time is 10 minutes;Obtain high tenacity Ni50Mn25Ga25Memorial alloy.
Embodiment 2
High tenacity Ni50Mn25Ga25Memorial alloy is prepared as follows:50 parts of Ni is taken according to atomic percent Powder, 25 parts of Mn powder, 25 parts of Ga powder are put into ball mill, are placed the gallium powder of low melting point first, are subsequently placed with high volatile Manganese powder finally places nickel powder, carried out again after mixing by mechanical agitation ball milling 12-20 it is small when.Then by the mixing of acquisition Uniformly and powder of the grain size control within 100 microns is put into graphite grinding tool and is sintered.The technique of sintering is:Applying pressure is 200 kilograms, vacuum degree 10-3Pa, sintering temperature are 1400 DEG C, and sintering time is 10 minutes;Obtain high tenacity Ni50Mn25Ga25Memorial alloy.
Embodiment 3
High tenacity Ni50Mn25Ga25Memorial alloy is prepared as follows:50 parts of Ni is taken according to atomic percent Powder, 25 parts of Mn powder, 25 parts of Ga powder are put into ball mill, are placed the gallium powder of low melting point first, are subsequently placed with high volatile Manganese powder finally places nickel powder, carried out again after mixing by mechanical agitation ball milling 12-20 it is small when.Then by the mixing of acquisition Uniformly and powder of the grain size control within 100 microns is put into graphite grinding tool and is sintered.The technique of sintering is:Applying pressure is 200 kilograms, vacuum degree 10-3Pa, sintering temperature are 1500 DEG C, and sintering time is 10 minutes;Obtain high tenacity Ni50Mn25Ga25Memorial alloy.
Ni prepared by the present invention50Mn25Ga25Memorial alloy crystallite dimension is smaller, below 50 microns, martensitic traoformation Temperature is more than room temperature, and Ni prepared by the present invention50Mn25Ga25The existing Ni of alloy ratio50Mn25Ga25The fracture strength of alloy carries High about 1000-1300Mpa, breaking strain compare existing Ni50Mn25Ga25Alloy improves 300-500%.

Claims (5)

1. a kind of high tenacity Ni50Mn25Ga25The preparation method of memorial alloy, which is characterized in that take 50 parts according to atomic percent Ni powder, 25 parts of Mn powder, 25 parts of Ga powder be uniformly mixed by mechanical agitation, then carry out 12-20 it is small when ball milling, finally The powder of acquisition is put into graphite grinding tool and is sintered, Ni is made50Mn25Ga25Memorial alloy;The grain size of the powder exists Within 100 microns.
2. a kind of high tenacity Ni according to claim 150Mn25Ga25The preparation method of memorial alloy, which is characterized in that former The placement order of material is as follows:Ga powder is placed first, then places Mn powder, finally places Ni powder.
3. a kind of high tenacity Ni according to claim 150Mn25Ga25The preparation method of memorial alloy, which is characterized in that institute The process conditions for stating sintering are:Pressure is 200 kilograms, vacuum degree 10-3-10-4Pa, temperature for 1300 DEG C or 1400 DEG C or 1500 DEG C, the time is 10 minutes.
4. a kind of high tenacity Ni according to claim 150Mn25Ga25The preparation method of memorial alloy, which is characterized in that institute The sintering method stated is vacuum heating-press sintering.
5. a kind of high tenacity Ni50Mn25Ga25Memorial alloy, which is characterized in that be prepared according to method of claim 1 's.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950277A (en) * 2018-08-02 2018-12-07 大连大学 A kind of method of combustion reaction high―temperature nuclei NiMnGa Magnetic Memory alloy
CN109371473A (en) * 2018-11-20 2019-02-22 北京航空航天大学 A kind of method that twin in NiMnGa monocrystalline is eliminated in power thermal coupling
CN110923510A (en) * 2019-12-16 2020-03-27 大连大学 Preparation method of high preferred orientation NiMnGa magnetic memory alloy wire
CN110994516A (en) * 2019-12-27 2020-04-10 广东电网有限责任公司电力科学研究院 Drainage plate
CN110983134A (en) * 2019-12-18 2020-04-10 大连大学 Preparation method of Mn-Ni-Ga magnetic memory alloy with high saturation magnetization
CN111041259A (en) * 2019-12-18 2020-04-21 大连大学 Preparation method of high-strength Mn-Ni-Ga magnetic memory alloy

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001279357A (en) * 2000-03-29 2001-10-10 Toshiba Corp Magnetic shape memory alloy
CN102952982A (en) * 2012-11-20 2013-03-06 无锡常安通用金属制品有限公司 Low-temperature memory alloy and preparation method of low-temperature memory alloy

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001279357A (en) * 2000-03-29 2001-10-10 Toshiba Corp Magnetic shape memory alloy
CN102952982A (en) * 2012-11-20 2013-03-06 无锡常安通用金属制品有限公司 Low-temperature memory alloy and preparation method of low-temperature memory alloy

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108950277A (en) * 2018-08-02 2018-12-07 大连大学 A kind of method of combustion reaction high―temperature nuclei NiMnGa Magnetic Memory alloy
CN109371473A (en) * 2018-11-20 2019-02-22 北京航空航天大学 A kind of method that twin in NiMnGa monocrystalline is eliminated in power thermal coupling
CN110923510A (en) * 2019-12-16 2020-03-27 大连大学 Preparation method of high preferred orientation NiMnGa magnetic memory alloy wire
CN110983134A (en) * 2019-12-18 2020-04-10 大连大学 Preparation method of Mn-Ni-Ga magnetic memory alloy with high saturation magnetization
CN111041259A (en) * 2019-12-18 2020-04-21 大连大学 Preparation method of high-strength Mn-Ni-Ga magnetic memory alloy
CN110994516A (en) * 2019-12-27 2020-04-10 广东电网有限责任公司电力科学研究院 Drainage plate

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