CN105390223A - Room temperature magnetic refrigeration alloy material and preparation method therefor - Google Patents

Room temperature magnetic refrigeration alloy material and preparation method therefor Download PDF

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CN105390223A
CN105390223A CN201510713559.3A CN201510713559A CN105390223A CN 105390223 A CN105390223 A CN 105390223A CN 201510713559 A CN201510713559 A CN 201510713559A CN 105390223 A CN105390223 A CN 105390223A
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room temperature
alloy material
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purity
temperature magnetic
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CN105390223B (en
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刘永生
司晓东
雷伟
徐娟
杜文龙
王玟苈
卢晓飞
李钊明
高湉
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/012—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials adapted for magnetic entropy change by magnetocaloric effect, e.g. used as magnetic refrigerating material
    • H01F1/015—Metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C22/00—Alloys based on manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

The invention discloses a room temperature magnetic refrigeration alloy material. The room temperature magnetic refrigeration alloy material is represented by the molecular formula of Mn1-XAlXCoGe; and the alloy material comprises 33.3-34.4% of manganese element, 0.6-2.7% of aluminum element, 32.8-33.3% of cobalt element, and 30.2-32.7% of germanium element in percentage by mass. The invention also provides a preparation method for the room temperature magnetic refrigeration alloy material. The preparation method comprises the steps of adding reactive materials into a vacuum arc furnace, vacuumizing until the pressure is lower than 10<-4>Pa, and pumping argon gas in; smelting the sample repeatedly; and taking out the sample and cooling the sample, putting the sample into a high-temperature-resistant quartz glass tube, vacuumizing, inflating the high-temperature-resistant quartz glass tube with high-purity argon for performing gas washing, then putting the high-temperature-resistant quartz glass tube into a furnace type box, taking the sample out and performing annealing to obtain the room temperature magnetic refrigeration alloy material. According to the preparation method, the Curie temperature of the alloy is obviously reduced to the temperature close to the room temperature, the thermal hysteresis phenomenon occurring close to phase change is effectively avoided, and a relatively wide adjustable temperature range close to the room temperature is obtained.

Description

A kind of room temperature magnetic refrigerating alloy material and preparation method
Technical field
The invention belongs to field of metallurgy, relate to the alloy magneto-caloric material in a kind of magnetic refrigerating field, particularly a kind of room temperature magnetic refrigerating alloy material and preparation method.
Background technology
Along with a large amount of consumption of traditional energy, the pressure of environmental protection in addition, the new forms of energy such as development magnetic refrigeration are extremely urgent.Relative to traditional vapor compression refrigeration etc., magnetic refrigeration has that efficiency is high, noise is low, floor space is little and in use can not produce the advantages such as any pollution.Realize refrigeration by the magneto-caloric effect of magnetic material itself, the important channel that the mankind solve the energy and environmental problem will inevitably be become.But compared with other refrigeration modes, the technology of magnetic refrigeration is also not overripened, particularly the research ability ground zero of room temperature magnetic refrigerating soon, Curie temperature and room temperature deviation are comparatively large, and heat stagnation and magnetic hysteresis are comparatively large, and magneto-caloric effect less etc. be the key of restriction magnetic refrigeration development.Therefore, how to make the Curie temperature regulation and control of magnetic refrigerating material near room temperature, reduce heat stagnation and the magnetic hysteresis of material, and near room temperature obtain larger magneto-caloric effect be for a long time people endeavour always solve problem, and a key factor of room temperature magnetic refrigerating development is exactly that Curie temperature is too high or too low, near phase transformation, heat stagnation magnetic hysteresis is comparatively large, and near room temperature magneto-caloric effect is less, namely obtains larger magneto-caloric effect near room temperature.We know, MnCoGe alloy is typical martensitic traoformation alloy, and because its significant magnetic characteristic and magnetic heating performance are considered to be one of a kind of desirable magneto-caloric material, alloy is in the phase transformation of 650K recurring structure, and the orthogonal thereto TiNiSi structure of low temperature, high temperature is hexagonal Ni 2in structure.275K and 345K is respectively at the Curie temperature of hexagonal structure and orthogonal type structure.But the phase transformation of MnCoGe alloy structure mainly occurs in paramagnetic state, magnetization change is little, does not have obvious using value.Therefore, for the Curie temperature how regulating and controlling MnCoGe alloy near room temperature avoid again simultaneously the larger heat stagnation of near room temperature, magnetic hysteresis appearance and to improve that near room temperature magneto-caloric effect carries out studying be key in room temperature magnetic refrigerating material design, preparation.
At present, a large amount of work that studies in great detail has been done in the design, preparation etc. of home and abroad to MnCoGe alloy, and its technical way has three kinds: doping interstitial atom, changes the chemical composition of compound, utilizes transition group atom to substitute.Particularly in preparation, good magneto-caloric effect is achieved to substituting of MnCoGe alloy atom.But due to the restriction such as preparation method and material purity, make current MnCoGe still not ideal in the magneto-caloric effect of near room temperature.This is because, the progress acquired by research work MnCoGe base main at present, mainly make the structural phase transition of material be coupled with magnetic phase transition and obtain giant magnetio-caloric effects, but it is incident many still unresolved for room temperature magnetic refrigerating, as Curie temperature is too high, or too low, near room temperature magneto-caloric effect is less, first order phase change evident characteristic: less half-peak breadth and larger heat stagnation.MnCoGe base alloy prepared by the method for general routine is generally first order phase change material.And the magnetic entropy of first order phase change material becomes considerable, but wide often unsatisfactory with utilization that is magneto-caloric effect at refrigeration temp. controllable.In recent years, second-order phase transistion material is studied material science, comprises material behavior, new material synthesis and new diseases, creates material impact.Relevant research shows, carries out element substitution technology to MnCoGe alloy, can promote the competitiveness of MnCoGe alloy in magnetic Refrigeration Technique.For room temperature magnetic refrigerating, the key improving refrigerating efficiency is first to obtain larger magneto-caloric effect near room temperature, and next has less heat stagnation and larger temp. controllable is wide.And for general material, magneto-caloric effect is all larger, and but meet simultaneously avoid larger heat stagnation while near room temperature has larger magneto-caloric effect, this just must improve original technology of preparing, improve the microstructure of alloy, thus reduce heat stagnation and obtain larger magneto-caloric effect near room temperature.Along with the further investigation of MnCoGe alloy, make the second-order phase transistion material preparing room temperature giant magnetio-caloric effects become possibility, though have much about the research of MnCoGe base alloy, but still lack the research report of MnCoGe base alloy in room temperature magnetic refrigerating field both at home and abroad.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of room temperature magnetic refrigerating alloy material and preparation method, described this room temperature magnetic refrigerating alloy material and preparation method solve in MnCoGe alloy of the prior art exists that larger heat stagnation problem, Curie temperature are too high, too low, the wide less technical problem of temp. controllable.
The invention provides a kind of room temperature magnetic refrigerating alloy material, its molecular formula is Mn 1-Xal xcoGe, in described room temperature magnetic refrigerating alloy material, the mass percent of manganese element is 33.3 ~ 34.4%, and the mass percent of aluminium element is 0.6 ~ 2.7%, the mass percent of cobalt element is 32.8 ~ 33.3%, and the mass percent of Ge element is 30.2 ~ 32.7%.
Further, X is 0.02 ~ 0.08.
Further, when the doping content of described Al is 0.02 ~ 0.08, Curie temperature is promoted to 301K by 271K, and under the changes of magnetic field of 5T, maximum magnetic entropy variable is: 3.21JKg -1k -1, 2.76JKg -1k -1, 2.4JKg -1k -1, 2.34JKg -1k -1, relative refrigerating capacity is: 242.2JKg -1, 109.1JKg -1, 102.2JKg -1, 101.8JKg -1, temp. controllable is wide: 75.5K, 79K, 85K, 87K.
Present invention also offers the preparation method of above-mentioned room temperature magnetic refrigerating alloy material, comprise the steps:
1) take high-purity manganese powder, aluminium powder, cobalt powder and germanium powder according to mass percent, the purity of above-mentioned substance all >=99.9%;
2) above-mentioned load weighted reactive material is joined in vacuum arc furnace ignition, with mechanical pump, vacuum arc furnace ignition sample cavity is vacuumized lower than 5Pa, open molecular pump and be again evacuated to lower than 10 -4pa, passes into the high purity argon of air pressure 10Pa, repeats above vacuumizing and scrubbing operations step 1 ~ 3 time;
3) use the electric current of 25 ~ 35A on fire, electrode is moved to distance sample 0.4 ~ 0.8cm directly over sample, electric current is adjusted to 70 ~ 90A until sample melts completely, then electric current is down to 55 ~ 65A melting 0.3 ~ 0.6 minute, treat that alloy cooling is to turning over, melt back 2 ~ 5 times;
4) sample cooling is taken out, sample is put into high temperature resistant quartz glass test tube, hight atmospheric molecular pumping system is utilized to be evacuated to lower than 5Pa, be filled with high purity argon and carry out gas washing, repeat above step 2 ~ 4 time, sealed silica envelope, put into 800 ~ 900 DEG C, stove formula case annealing 5 ~ 8 days, take out sample and put into the cold water annealing in process that temperature is 5 ~ 12 DEG C, obtain room temperature magnetic refrigerating alloy material.
Further, described manganese powder purity is 99.9%, and aluminium powder purity is 99.95%, and cobalt powder aluminium element purity is 99.95%, and the purity of germanium powder is 99.99%.
Further, the purity of described argon gas is 99.999%.
The present invention proposes the MnAlCoGe alloy of a kind of Mn position doping trace of Al, at room temperature orthogonal thereto TiNiSi structure, this structure is by the doping of Al to Mn position, make near room temperature obtain the wide and refrigerating capacity of larger temp. controllable and alloy near room temperature generation secondary magnetic phase transition, thus solve the difficult problems such as Curie temperature is too high, too low, heat stagnation is larger preferably.By the aluminium content in adjustment magnetic material, can the crystal structure of better controlled material, effectively make the Curie temperature of alloy be down near room temperature, and it is wide to have larger temp. controllable near room temperature.The temp. controllable of described room temperature magnetic refrigerating material is wide: 75.5K, 79K, 85K, 87K and conventional MnCoGe (343K, 5.8JKg -1k -1, 227JKg -1, 60K) and alloy phase ratio, significantly make alloy Curie temperature be down to room temperature and to have larger temp. controllable near room temperature wide.
Compared with prior art, its technological progress is significant in the present invention.The present invention utilizes trace of Al to adulterate to MnCoGe compound Mn position, shown by survey calculation, the Al of described Mn position doping trace significantly makes alloy Curie temperature be down near room temperature and to have larger temp. controllable near room temperature wide, and obtained alloy is second-order phase transistion material, effectively avoid the heat stagnation problem that first order phase change material brings, for MnCoGe system alloy provides favourable foundation in the development of room temperature magnetic refrigerating and application.
It is large that MnAlCoGe room temperature magnetic refrigerating alloy material of the present invention has little, the adjustable warm area of heat stagnation, prepare the advantages such as simple, preparation parameter can be provided for the development of room temperature magnetic refrigerating, can be applicable to as high-energy physics, cryogenic engineering precision instrument, power industry, superconducting technology, medicine equipment etc. relate to numerous key areas of national economy.
Accompanying drawing explanation
Fig. 1 Mn 1-xal xcoGe (x=0.02,0.04,0.06,0.08) Alloy At Room Temperature XRD diffraction pattern.
Fig. 2 Mn 1-xal xcoGe alloy is the M-T figure of 0.02T in magnetic field.
Fig. 3 Mn 1-xal xcoGe alloy is at the isothermal magnetization curve of near Curie temperature.
Fig. 4 Mn 1-xal xcoGe compound is at the Arrott curve of near Curie temperature.
Fig. 5 Mn 1-xal xthe isothermal magnetic entropy varied curve of CoGe alloy under 2T and 5T changes of magnetic field.
Embodiment
Embodiment 1
The purity using raw material is 99.9%Mn, 99.95%Al, 99.9%Co, 99.99%Ge, each powder is taken according to mass percent, the mass percent of manganese element is 33.3 ~ 34.4%, the mass percent of aluminium element is 0.6 ~ 2.7%, the mass percent of cobalt element is 32.8 ~ 33.3%, and the mass percent of Ge element is 30.2 ~ 32.7%.
Alloy adopts vacuum arc furnace melting method, joins in vacuum arc furnace ignition, before alloy melting, first vacuumize each element lower than 5Pa with mechanical pump, open molecular pump and be again evacuated to lower than 10 -4pa, pass into the high purity argon (99.999%) of air pressure 10Pa, repeat above vacuumizing and scrubbing operations step twice, use the electric current of about 30A on fire, electrode is moved to distance sample about 0.5cm directly over sample, slowly electric current is adjusted to about 80A until sample melts completely, then electric current is down to 60A melting half a minute, treat that alloy cooling will be turned over to top bottom sample, melt back four times is to ensure the sample uniformity.After taking out cooling, high-purity high temperature resistant quartz glass test tube put into by sample, hight atmospheric molecular pumping system is utilized to be evacuated to lower than 5Pa, be filled with high purity argon (99.999%) and carry out gas washing, repeat above step 3 time, sealed silica envelope, put into 850 DEG C, stove formula case and anneal 7 days to ensure good degree of crystallinity, take out sample and put into rapidly the cold water annealing in process that temperature is about 10 DEG C.
The present invention has prepared Mn by vacuum arc furnace melting method 1-xal xcoGe alloy, x-ray diffraction experiment shows the good at room temperature main orthogonal thereto TiNiSi structure of prepared alloy degree of crystallinity.Physical measurement (PPMS-9T) result shows, Al mixes the Curie temperature reducing alloy, make alloy near room temperature to have larger temp. controllable wide thus obtain larger refrigerating capacity, alloy becomes second-order phase transistion mutually near Curie temperature.
Mn 1-xal xas shown in Figure 1, all samples degree of crystallinity is good, and at room temperature the main orthogonal thereto TiNiSi structure of all samples, has a small amount of hexagonal Ni simultaneously for CoGe (x=0.02,0.04,0.06,0.08) Alloy At Room Temperature XRD diffraction pattern 2in structure.
Fig. 2 is magnetic variationization M-T after the match (FC-ZFC) figure of alloy at 0.02T, illustration is the Al content of alloy when being 0.08, the Curie temperature of alloy, alloy occurs by the ferromagnetic magnetic phase transition to paramagnetic near Curie temperature, Curie temperature is tried to achieve by M-T figure slope variation maximum, along with the increase Curie temperature of Al doping content rises to 301K by 271K.
Fig. 3 provides the isothermal magnetization curve M-H of alloy near Curie temperature under the changes of magnetic field of 0-7T, is schemed from M-H, comparatively large in the magnetization change of near Curie temperature alloy, analyzes consistent with M-T.
Fig. 4 is the Arrott curve of alloy near Curie temperature, to analyze the magnetic property of alloy further, can find out that from Arrott curve all samples are on the occasion of showing that all samples, near Curie temperature, secondary magnetic phase transition all occurs near Curie temperature slope of a curve, illustrate that all samples all only has less heat stagnation near transformation temperature, effectively avoid the problem that near first order phase change, heat stagnation is larger, improve the utilization ratio of the energy.
Fig. 5 is the isothermal magnetic entropy varied curve of series alloy under 2T and 5T changes of magnetic field, and the isothermal magnetic entropy of second-order phase transistion magnetic refrigerating material is become and can be obtained by Maxwell equation:
&Delta; S ( H , T ) = &Integral; 0 H ( &part; M ( H , T ) &part; T ) H d H - - - ( 1 )
Numerical value in (1) in equation trapezoidal rule can be write as following formula
&Delta;S M ( H , T ) = &Sigma; i M i + 1 ( H , T ) - M i ( H , T ) T i + 1 - T i &Delta;H i - - - ( 2 )
M in formula i+1and M ibe respectively T i+1and T itime the magnetization.So, the experimental result of our composition graphs 3, and isothermal magnetic entropy that this sample shows under different magnetic field becomes to utilize (2) formula to calculate.Result shows: under the changes of magnetic field of 2T, and maximum isothermal magnetic entropy becomes: 1.75JKg -1k -1, 1.48JKg -1k -1, 1.28JKg -1k -1, 1.23JKg -1k -1, under the changes of magnetic field of 5T, maximum isothermal magnetic entropy becomes: 3.21JKg -1k -1, 2.76JKg -1k -1, 2.4JKg -1k -1, 2.34JKg -1k -1.
In addition, another important parameter evaluating magneto-caloric effect is the relative refrigerating capacity (RCP) of magneto-caloric material, and RCP can be expressed as:
R C P = - &Delta;S M ( H , T ) &times; &part; T F W H M - - - ( 3 )
According to above formula, we calculate Mn 1-xal xthe refrigerating capacity under magnetic field changes 5T condition of CoGe (x=0.02,0.04,0.06,0.08) alloy is respectively 242.2JKg -1, 109.1JKg -1, 102.2JKg -1, 101.8JKg -1, temp. controllable is wide: 75.5K, 79K, 85K, 87K.Visible, by the content of the Al in adjustment MnCoGe magnetic material, the crystal structure of alloy can be controlled better, effectively make the Curie temperature of alloy material be down near room temperature and near room temperature, there is the wide and larger refrigerating capacity of larger temp. controllable.With conventional MnCoGe (227JKg -1, 60K) and alloy phase ratio, significantly improve Curie temperature and the magneto-caloric effect of magnetic material.And obtained alloy material is second-order phase transistion material, effectively avoids heat stagnation problem.

Claims (6)

1. a room temperature magnetic refrigerating alloy material, is characterized in that: its molecular formula is Mn 1-Xal xcoGe, in described room temperature magnetic refrigerating alloy material, the mass percent of manganese element is 33.3 ~ 34.4%, and the mass percent of aluminium element is 0.6 ~ 2.7%, and the mass percent of cobalt element is 32.8 ~ 33.3%, and the mass percent of Ge element is 30.2 ~ 32.7%.
2. room temperature magnetic refrigerating alloy material according to claim 1, is characterized in that: x is 0.02 ~ 0.08.
3. room temperature magnetic refrigerating alloy material according to claim 1, is characterized in that: when the doping content of described Al is 0.02 ~ 0.08, Curie temperature is promoted to 301K by 271K, and under the changes of magnetic field of 5T, maximum magnetic entropy variable is: 3.21JKg -1k -1, 2.76JKg -1k -1, 2.4JKg -1k -1, 2.34JKg -1k -1, relative refrigerating capacity is: 242.2JKg -1, 109.1JKg -1, 102.2JKg -1, 101.8JKg -1, temp. controllable is wide: 75.5K, 79K, 85K, 87K.
4. the preparation method of room temperature magnetic refrigerating alloy material according to claim 1, is characterized in that comprising the steps:
1) take high-purity manganese powder, aluminium powder, cobalt powder and germanium powder according to mass percent, the purity of above-mentioned substance all >=99.9%;
2) above-mentioned load weighted reactive material is joined in vacuum arc furnace ignition, with mechanical pump by vacuum arc stove evacuation lower than 5Pa, open molecular pump and be again evacuated to lower than 10 -4pa, passes into the high purity argon of air pressure 10Pa, repeats above vacuumizing and scrubbing operations step 1 ~ 3 time;
3) use the electric current of 25 ~ 35A on fire, electrode is moved to distance sample 0.4 ~ 0.8cm directly over sample, electric current is adjusted to 70 ~ 90A until sample melts completely, then electric current is down to 55 ~ 65A melting 0.3 ~ 0.6 minute, treat that bottom is turned over to top by alloy cooling, melt back 2 ~ 5 times;
4) sample cooling is taken out, sample is put into high temperature resistant quartz glass test tube, hight atmospheric molecular pumping system is utilized to be evacuated to lower than 5Pa, be filled with high purity argon and carry out gas washing, repeat above step 2 ~ 4 time, sealed silica envelope, put into 800 ~ 900 DEG C, stove formula case annealing 5 ~ 8 days, take out sample and put into the cold water annealing in process that temperature is 5 ~ 12 DEG C, obtain room temperature magnetic refrigerating alloy material.
5. the preparation method of room temperature magnetic refrigerating alloy material according to claim 4, is characterized in that: the purity of described manganese powder is 99.9%, and the purity of aluminium powder is 99.95%, and the purity of cobalt powder is 99.9%, and the purity of germanium powder is 99.99%.
6. the preparation method of room temperature magnetic refrigerating alloy material according to claim 4, is characterized in that: the purity of described argon gas is 99.999%.
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Publication number Priority date Publication date Assignee Title
CN107267839A (en) * 2017-07-31 2017-10-20 上海电力学院 A kind of room temperature magnetic refrigerating alloy magneto-caloric material and preparation method and application
CN107760962A (en) * 2017-10-17 2018-03-06 上海电力学院 A kind of magnetic refrigeration alloy material and preparation method thereof
CN112430757A (en) * 2020-10-19 2021-03-02 北京工业大学 MnCoGe-based magnetic alloy capable of being used as magnetic refrigeration material

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