CN107267839A - A kind of room temperature magnetic refrigerating alloy magneto-caloric material and preparation method and application - Google Patents
A kind of room temperature magnetic refrigerating alloy magneto-caloric material and preparation method and application Download PDFInfo
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- CN107267839A CN107267839A CN201710383978.4A CN201710383978A CN107267839A CN 107267839 A CN107267839 A CN 107267839A CN 201710383978 A CN201710383978 A CN 201710383978A CN 107267839 A CN107267839 A CN 107267839A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/02—Making non-ferrous alloys by melting
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- 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
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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- 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
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- 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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Abstract
The present invention relates to a kind of room temperature magnetic refrigerating alloy magneto-caloric material and preparation method and application, the chemical general formula of the material is MnCo1‑xTixGe, x is that the atomic percent of manganese element in 0.02 0.08, described material is 33.3~34.4% in formula, and the atomic percent of cobalt element is 32.8~33.3%, the atomic percent of titanium elements is 0.6~2.7%, and the atomic percent of Ge element is 30.2~32.7%；During preparation, reactive material is added in vacuum arc furnace ignition, vacuum arc stove evacuation is less than 10‑4Pa, is passed through high purity argon；By sample melt back 2~5 times；Sample cooling is taken out, sample is put into high temperature resistant quartz glass test tube, vacuumized, high purity argon is filled with and carries out gas washing, be put into stove formula case, sample annealing is taken out.Compared with prior art, alloy magneto-caloric material of the present invention is second-order phase transistion material, with the characteristics of heat stagnation is small, adjustable warm area is big, the heat stagnation problem that first order phase change material strips are come can be prevented effectively from, step of preparation process is simple, and condition controllability is good, with good application prospect.
Description
Technical field
The invention belongs to metallurgical technology field, be related to a kind of room temperature magnetic refrigerating alloy magneto-caloric material and preparation method thereof in should
With.
Background technology
With the pressure of a large amount of consumption, in addition environmental protection of traditional energy, the new energy such as development magnetic refrigeration has been compeled in eyebrow
Eyelash.For traditional vapor compression refrigeration, magnetic refrigeration is with efficiency high, noise is low, floor space is small and is using
The advantages of will not producing any pollution in journey, refrigeration is realized by the magnetothermal effect of magnetic material in itself, will necessarily turn into people
Class solves the important channel of the energy and environmental problem.But, compared with other refrigeration modes, magnetic refrigeration technology also less into
Ripe, particularly soon, Curie temperature and room temperature deviation are larger for the research ability ground zero of room temperature magnetic refrigerating, heat stagnation and magnetic hysteresis compared with
Greatly, and magnetothermal effect is smaller etc. is the key for restricting magnetic refrigeration development.Therefore, adjust how the Curie temperature of magnetic refrigerating material
Control reduces the heat stagnation and magnetic hysteresis of material near room temperature, and it is for a long time to obtain larger magnetothermal effect near room temperature
The problem of people endeavour to solve always.
Room temperature magnetic refrigerating development a key factor be exactly that Curie temperature is too high or too low, phase transformation nearby heat stagnation magnetic hysteresis compared with
Greatly, near room temperature magnetothermal effect is smaller, i.e., larger magnetothermal effect is obtained near room temperature.It is known that MnCoGe alloys are
Typical martensitic traoformation alloy, because its significant magnetic characteristic and magnetic heating performance be considered to be a kind of preferable magneto-caloric material it
One, alloy is in 650K recurring structure phase transformations, the orthogonal thereto TiNiSi structures of low temperature, and high temperature is in hexagonal Ni2In structures.In hexagonal structure
Curie temperature with orthogonal type structure is respectively 275K and 345K.But MnCoGe alloy structure phase transformations occur mainly in paramagnetic state,
Magnetization change is little, without obvious application value.Therefore, for how to regulate and control the Curie temperature of MnCoGe alloys to room
It is warm nearby to avoid being studied in the larger heat stagnation of near room temperature, the appearance of magnetic hysteresis and raising near room temperature magnetothermal effect again simultaneously
It is the key in room temperature magnetic refrigerating material design, preparation.
At present, substantial amounts of detailed research work has been done in home and abroad to design, preparation of MnCoGe alloys etc., and it is led
Technological means is wanted there are three kinds：Adulterate interstitial atom, change compound chemical composition, utilize transition group atom substitute.Particularly
Replacement to MnCoGe alloy atoms has been achieved for good magnetothermal effect in preparation.But because preparation method and raw material are pure
The limitation such as degree so that current MnCoGe is still not ideal in the magnetothermal effect of near room temperature.Because, research main at present
The progress worked acquired by MnCoGe bases, the structural phase transition and magnetic phase transition for mainly making material, which are coupled, has obtained huge magnetic thermal effect
Should, but it is incident many still unresolved for room temperature magnetic refrigerating, such as Curie temperature is too high or too low, near room temperature
Magnetothermal effect is smaller, first order phase change evident characteristic：Less half-peak breadth and larger heat stagnation.Prepared by generally conventional method
MnCoGe based alloys are usually first order phase change material.And the magnetic entropy of first order phase change material becomes considerable, but in refrigeration temperature controllable
The utilization of wide and magnetothermal effect is often unsatisfactory.In recent years, second-order phase transistion material is special to material science research, including material
Property, new material synthesis and new diseases, generate material impact.Relevant research to MnCoGe alloys it has been shown that carry out
Element substitution technology, can lift competitiveness of the MnCoGe alloys in magnetic Refrigeration Technique.For room temperature magnetic refrigerating, refrigeration is improved
The key of efficiency is to obtain larger magnetothermal effect near room temperature first secondly have smaller heat stagnation and larger temperature controllable
It is wide.And for general material, magnetothermal effect but meets all than larger and has larger magnetic thermal effect near room temperature simultaneously
Larger heat stagnation is avoided again while answering, this must just improve original technology of preparing, improve the microstructure of alloy, so as to subtract
Small heat stagnation and obtain larger magnetothermal effect near room temperature.With the further investigation of MnCoGe alloys so that prepare room temperature huge
The second-order phase transistion material of magnetothermal effect has become possibility, though there are many researchs on MnCoGe based alloys both at home and abroad, but still
Lack research of the MnCoGe based alloys in room temperature magnetic refrigerating field to report.With MnCoGe1-x(0<X≤0.05) compare, Co doping
Micro Ti can regulate and control the Curie temperature of alloy near room temperature, and alloy is second-order phase transistion near Curie temperature, is had
Effect avoids heat stagnation problem, while it is wide to obtain larger temperature controllable again near room temperature, is conducive to MnCo1-xTixGe freezes
Business promotion of the working medium in room temperature magnetic refrigerating field.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide room temperature magnetic refrigerating alloy magnetic
Hot material and preparation method and application, to solve the problems, such as that the heat stagnation that MnCoGe base alloy materials are present in the prior art is dashed forward
Go out, Curie temperature is too high or too low, the wide less skill defect of temperature controllable.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of room temperature magnetic refrigerating alloy magneto-caloric material, the chemical general formula of the material is MnCo1-xTixX is 0.02- in Ge, formula
0.08, the atomic percent of manganese element is 33.3~34.4% in described material, the atomic percent of cobalt element for 32.8~
33.3%, the atomic percent of titanium elements is 0.6~2.7%, and the atomic percent of Ge element is 30.2~32.7%.
The Curie temperature of described material is promoted to 284K by 273.5K, and under 5T changes of magnetic field, maximum magnetic entropy variable is
3.16J·kg-1K-1,3.30J·kg-1K-1,3.28J·kg-1K-1,3.25J·kg-1K-1。
A kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material, this method specifically includes following steps：
Step (1)：Manganese powder, cobalt powder, titanium valve and germanium powder are weighed by a mole atomic percent, is well mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, progress vacuumizes gas washing processing；
Step (3)：It is on fire using 25~35A electric current, electrode is moved to directly over pre-reaction mixture, electric current is adjusted to
70~90A melts completely up to pre-reaction mixture, then electric current is down into 55~65A meltings 0.3~0.6 minute, treats that alloy is cold
But, bottom is turned into top, melt back 2~5 times；
Step (4)：It is transferred in quartz glass test tube, progress vacuumizes gas washing processing, then, is sealed and placed in stove formula case
It is middle to be heat-treated, that is, described room temperature magnetic refrigerating alloy magneto-caloric material is made.
The purity of manganese powder, cobalt powder, titanium valve and germanium powder described in step (1) is >=99.9%.
The purity of described manganese powder is 99.9%, and the purity of described cobalt powder is 99.9%, and the purity of described titanium valve is
99.99%, the purity of described germanium powder is 99.99%.
The step of gas washing is handled that vacuumize described in step (2) be：It is first with mechanical pump that vacuum arc stove evacuation is low
In 5Pa, open molecular pump and be evacuated to again less than 10-4Pa, is subsequently passed air pressure 10Pa argon gas, repeats aforesaid operations 1~3
It is secondary.
The step of gas washing is handled that vacuumize described in step (4) be：It is evacuated to less than 5Pa, is poured using molecular pump
Argon gas carries out gas washing, repeats aforesaid operations 2~4 times.
The purity of described argon gas is 99.999%.
Process of thermal treatment condition described in step (4) is：Anneal 5~8 days, take out in 800~900 DEG C, it is placed in 5~
Annealed in 12 DEG C of cold water.
A kind of application of room temperature magnetic refrigerating alloy magneto-caloric material, described alloy magneto-caloric material is used to prepare refrigerating material.
The present invention proposes a kind of MnCo of Co doping trace Ti1-xTixGe alloys, at room temperature in hexagonal Ni2In is tied
Structure, doping of the structure by Ti to Co, alloy is obtained near room temperature, larger temperature controllable is wide and magnetothermal effect,
And near room temperature two grades of magnetic phase transitions occur for alloy, so as to preferably solve Curie temperature is too high or too low, heat stagnation is larger etc.
Problem.The present invention is capable of the crystal structure of more preferable controlled material, makes the Curie of alloy by adjusting the Ti content in magnetic material
Temperature is down near room temperature, and has larger temperature controllable wide near room temperature.
The temperature controllable for the room temperature magnetic refrigerating alloy magneto-caloric material that the present invention is prepared from is wider than conventional MnCoGe alloys, bright
It is aobvious alloy Curie temperature is down to room temperature, and have larger temperature controllable wide near room temperature.
Compared with prior art, the invention has the characteristics that：
1) the Co doping of MnCoGe compounds are shown, the Co doping is micro by survey calculation using trace Ti
Ti can make alloy Curie temperature be down near room temperature, and have larger temperature controllable wide and magnetothermal effect near room temperature；
2) alloy magneto-caloric material produced by the present invention is second-order phase transistion material, can be prevented effectively from what first order phase change material strips were come
Heat stagnation problem, favourable foundation is provided for MnCoGe systems alloy in the business application of room temperature magnetic refrigerating and development；
3) step of preparation process is simple, and condition controllability is good, obtained MnCo1-xTixGe materials have heat stagnation small, adjustable
The characteristics of warm area is big, preparation parameter is provided for the development of room temperature magnetic refrigerating, can be applied to the accurate instrument of high-energy physics, cryogenic engineering
Device, power industry, superconducting technology, medicine equipment etc. are related to numerous key areas of national economy.
Brief description of the drawings
Fig. 1 is MnCo1-xTixGe (x=0.02,0.04,0.06,0.08) Alloy At Room Temperature XRD diffraction patterns；
Fig. 2 is MnCo1-xTixGe (x=0.02,0.04,0.06,0.08) alloys are schemed in magnetic field for 0.02T M-T；
Fig. 3 is MnCo1-xTixIsothermal magnetization of Ge (x=0.02,0.04,0.06,0.08) alloys near Curie temperature
Curve；
Fig. 4 is MnCo1-xTixGe (x=0.02,0.04,0.06,0.08) alloys are bent in the Arrott of near Curie temperature
Line；
Fig. 5 is MnCo1-xTixIsothermal of Ge (x=0.02,0.04,0.06,0.08) alloys under 2T and 5T changes of magnetic field
Magnetic entropy varied curve.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
The use of the purity of raw material is 99.9%Mn, 99.9%Co, 99.99%Ti, 99.99%Ge, according to mole atom hundred
Point than weighing each powder, the atomic percent of manganese element is 33.3~34.4%, the atomic percent of cobalt element for 32.8~
33.3%, the atomic percent of titanium elements is 0.6~2.7%, and the atomic percent of Ge element is 30.2~32.7%.
Alloy uses vacuum arc furnace melting method, and the high-purity powder mixture weighed is added in vacuum arc furnace ignition,
Before alloy melting, vacuumized first with mechanical pump less than 5Pa, open molecular pump and be evacuated to again less than 10-4Pa, is passed through gas
10Pa high purity argon (99.999%) is pressed, repeats to vacuumize with scrubbing operations step twice above, uses 30A or so electricity
Stream is on fire, and electrode is moved to directly over sample apart from sample 0.5cm or so, electric current slowly is adjusted into 80A or so until sample is complete
It is complete to melt, then electric current is down to 60A melting half a minute, treat that sample bottom is turned to top by alloy cooling, melt back four times with
Ensure the sample uniformity.Take out sample after cooling and be put into high-purity high temperature resistant quartz glass test tube, utilize hight atmospheric molecular pumping system
It is evacuated to less than 5Pa, is filled with high purity argon (99.999%) and carries out gas washing, repeat above step three times, sealed silica envelope,
It is put into stove formula case 850 DEG C of annealing 7 days to ensure good crystallinity, taking out sample, to be put into temperature rapidly cool for 10 DEG C or so
Is made annealing treatment in water
The present embodiment is prepared for MnCo by vacuum arc furnace melting method1-xTixGe alloys, x-ray diffraction experiment shows
The good orthogonal thereto TiNiSi structures main at room temperature of prepared alloy crystallinity.Physical measurement (PPMS-9T) result shows,
Ti incorporation can adjust the Curie temperature of alloy, make alloy near room temperature have larger temperature controllable wide and magnetic entropy become from
And larger refrigerating capacity is obtained, and alloy is mutually changed into second-order phase transistion near Curie temperature.
MnCo1-xTixGe (x=0.02,0.04,0.06,0.08) Alloy At Room Temperature XRD diffraction patterns are as shown in figure 1, all samples
Product crystallinity is good, and all samples are in mainly hexagonal Ni at room temperature2In structures, while being tied with a small amount of orthogonal TiNiSi
Structure.
Fig. 2 is magnetic variationization M-T (FC-ZFC) figure off field of alloy in 0.02T, and illustration is that the Ti contents of alloy are 0.02
When, the Curie temperature of alloy, alloy occurs by the ferromagnetic magnetic phase transition to paramagnetic near Curie temperature, and Curie temperature is schemed by M-T
Slope variation maximum is tried to achieve, as the increase Curie temperature of Ti doping contents by 273.5K rises to 284K.
Fig. 3 provides the isothermal magnetization curve M-H of alloy near Curie temperature under 0-7T changes of magnetic field, can by M-H figures
Know, it is larger in the magnetization change of near Curie temperature alloy, it is consistent with M-T analyses.
Fig. 4 is Arrott curve of the alloy near Curie temperature, further to analyze the magnetic property of alloy, from
It can be seen that all samples are on the occasion of showing that all samples exist near Curie temperature slope of a curve in Arrott curves
Two grades of magnetic phase transitions occur near Curie temperature, illustrate that all samples only have less heat stagnation near transformation temperature, effectively
The problem of heat stagnation is larger near first order phase change is avoided, the utilization ratio of the energy is improved.
Fig. 5 is isothermal magnetic entropy varied curve of the series alloy under 2T and 5T changes of magnetic field, second-order phase transistion magnetic refrigerating material
Isothermal magnetic entropy, which becomes, to be obtained by Maxwell equations：
The numerical value in (1) in equation can be write as following formula with trapezoidal rule：
M in formulai+1And MiRespectively Ti+1And TiWhen the intensity of magnetization.Then, we combine Fig. 3 experimental result, and utilize
(2) formula calculates the isothermal magnetic entropy change that the sample is shown under different magnetic field.As a result show：Under 2T changes of magnetic field,
Maximum isothermal magnetic entropy is changed into:1.72J·kg-1K-1, 1.79Jkg-1K-1, 1.75Jkg-1K-1, 1.73Jkg-1K-1, in 5T
Changes of magnetic field under, maximum isothermal magnetic entropy is changed into:3.16J·kg-1K-1, 3.30Jkg-1K-1, 3.28Jkg-1K-1,
3.25J·kg-1K-1。
It can be seen that, by adjusting the content of the Ti in MnCoGe magnetic materials, the crystal structure of alloy can be better controled over,
It is effective the Curie temperature of alloy material is regulated and controled near room temperature and have larger temperature controllable wide and magnetic heat near room temperature
Effect.Compared with conventional MnCoGe alloys, it will be apparent that improve Curie temperature and the magnetothermal effect of magnetic material.And it is obtained
Alloy material is second-order phase transistion material, effectively avoids heat stagnation problem.
Embodiment 2：
The present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, the chemical general formula of the material is MnCo1-xTixX is in Ge, formula
0.02, the atomic percent of manganese element is 33.3% in material, and the atomic percent of cobalt element is 32.8%, the atom of titanium elements
Percentage is 1.2%, and the atomic percent of Ge element is 32.7%.
The Curie temperature of the present embodiment material is promoted to 284K by 273.5K, under 5T changes of magnetic field, maximum magnetic entropy variable
For 3.16Jkg-1K-1,3.30J·kg-1K-1,3.28J·kg-1K-1,3.25J·kg-1K-1。
The preparation method of the present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, specifically includes following steps：
Step (1)：Manganese powder, cobalt powder, titanium valve and germanium powder are weighed by a mole atomic percent, is well mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, progress vacuumizes gas washing processing；
Step (3)：It is on fire using 25A electric current, electrode is moved to directly over pre-reaction mixture, electric current is adjusted to 70A
Until pre-reaction mixture is melted completely, then electric current is down to 55A meltings 0.6 minute, treats that alloy is cooled down, bottom is turned into top
Portion, melt back 2 times；
Step (4)：It is transferred in quartz glass test tube, progress vacuumizes gas washing processing, then, is sealed and placed in stove formula case
It is middle to be heat-treated, that is, described room temperature magnetic refrigerating alloy magneto-caloric material is made.
The purity of manganese powder is 99.9% in step (1), and the purity of cobalt powder is 99.9%, and the purity of titanium valve is 99.99%, germanium
The purity of powder is 99.99%.
Vacuumizing the step of gas washing is handled in step (2) is：Vacuum arc stove evacuation is first less than 5Pa with mechanical pump,
Molecular pump is opened to be evacuated to again less than 10-4Pa, is subsequently passed air pressure 10Pa argon gas, repeats aforesaid operations 2 times.
Vacuumizing the step of gas washing is handled in step (4) is：It is evacuated to using molecular pump less than 5Pa, pours argon gas and enter
Row gas washing, repeats aforesaid operations 4 times.
Wherein, the purity of argon gas is 99.999%.
Process of thermal treatment condition is in step (4)：Anneal 8 days, take out in 800 DEG C, moved back in the cold water for being placed in 5 DEG C
Fire.
Room temperature magnetic refrigerating alloy magneto-caloric material made from the present embodiment is used to prepare refrigerating material.
Embodiment 3：
The present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, the chemical general formula of the material is MnCo1-xTixX is in Ge, formula
0.05, the atomic percent of manganese element is 34.4% in material, and the atomic percent of cobalt element is 33.3%, the atom of titanium elements
Percentage is 2.1%, and the atomic percent of Ge element is 30.2%.
The Curie temperature of the present embodiment material is promoted to 284K by 273.5K, under 5T changes of magnetic field, maximum magnetic entropy variable
For 3.16Jkg-1K-1,3.30J·kg-1K-1,3.28J·kg-1K-1,3.25J·kg-1K-1。
The preparation method of the present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, specifically includes following steps：
Step (1)：Manganese powder, cobalt powder, titanium valve and germanium powder are weighed by a mole atomic percent, is well mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, progress vacuumizes gas washing processing；
Step (3)：It is on fire using 35A electric current, electrode is moved to directly over pre-reaction mixture, electric current is adjusted to 90A
Until pre-reaction mixture is melted completely, then electric current is down to 65A meltings 0.3 minute, treats that alloy is cooled down, bottom is turned into top
Portion, melt back 5 times；
Step (4)：It is transferred in quartz glass test tube, progress vacuumizes gas washing processing, then, is sealed and placed in stove formula case
It is middle to be heat-treated, that is, described room temperature magnetic refrigerating alloy magneto-caloric material is made.
The purity of manganese powder is 99.9% in step (1), and the purity of cobalt powder is 99.9%, and the purity of titanium valve is 99.99%, germanium
The purity of powder is 99.99%.
Vacuumizing the step of gas washing is handled in step (2) is：Vacuum arc stove evacuation is first less than 5Pa with mechanical pump,
Molecular pump is opened to be evacuated to again less than 10-4Pa, is subsequently passed air pressure 10Pa argon gas, repeats aforesaid operations 3 times.
Vacuumizing the step of gas washing is handled in step (4) is：It is evacuated to using molecular pump less than 5Pa, pours argon gas and enter
Row gas washing, repeats aforesaid operations 2 times.
Wherein, the purity of argon gas is 99.999%.
Process of thermal treatment condition is in step (4)：Anneal 5 days, take out in 900 DEG C, moved back in the cold water for being placed in 12 DEG C
Fire.
Room temperature magnetic refrigerating alloy magneto-caloric material made from the present embodiment is used to prepare refrigerating material.
Embodiment 4：
The present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, the chemical general formula of the material is MnCo1-xTixX is in Ge, formula
0.03, the atomic percent of manganese element is 34% in material, and the atomic percent of cobalt element is 33%, the atomic percent of titanium elements
It is 32% than the atomic percent for 1%, Ge element.
The Curie temperature of the present embodiment material is promoted to 284K by 273.5K, under 5T changes of magnetic field, maximum magnetic entropy variable
For 3.16Jkg-1K-1,3.30J·kg-1K-1,3.28J·kg-1K-1,3.25J·kg-1K-1。
The preparation method of the present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, specifically includes following steps：
Step (1)：Manganese powder, cobalt powder, titanium valve and germanium powder are weighed by a mole atomic percent, is well mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, progress vacuumizes gas washing processing；
Step (3)：It is on fire using 32A electric current, electrode is moved to directly over pre-reaction mixture, electric current is adjusted to 85A
Until pre-reaction mixture is melted completely, then electric current is down to 60A meltings 0.5 minute, treats that alloy is cooled down, bottom is turned into top
Portion, melt back 3 times；
Step (4)：It is transferred in quartz glass test tube, progress vacuumizes gas washing processing, then, is sealed and placed in stove formula case
It is middle to be heat-treated, that is, described room temperature magnetic refrigerating alloy magneto-caloric material is made.
The purity of manganese powder is 99.9% in step (1), and the purity of cobalt powder is 99.9%, and the purity of titanium valve is 99.99%, germanium
The purity of powder is 99.99%.
Vacuumizing the step of gas washing is handled in step (2) is：Vacuum arc stove evacuation is first less than 5Pa with mechanical pump,
Molecular pump is opened to be evacuated to again less than 10-4Pa, is subsequently passed air pressure 10Pa argon gas, repeats aforesaid operations 2 times.
Vacuumizing the step of gas washing is handled in step (4) is：It is evacuated to using molecular pump less than 5Pa, pours argon gas and enter
Row gas washing, repeats aforesaid operations 3 times.
Wherein, the purity of argon gas is 99.999%.
Process of thermal treatment condition is in step (4)：Anneal 6 days, take out in 860 DEG C, moved back in the cold water for being placed in 10 DEG C
Fire.
Room temperature magnetic refrigerating alloy magneto-caloric material made from the present embodiment is used to prepare refrigerating material.
Claims (10)
1. a kind of room temperature magnetic refrigerating alloy magneto-caloric material, it is characterised in that the chemical general formula of the material is MnCo1-xTixIn Ge, formula
X is 0.02-0.08, and the atomic percent of manganese element is 33.3~34.4%, the atomic percent of cobalt element in described material
For 32.8~33.3%, the atomic percent of titanium elements is 0.6~2.7%, the atomic percent of Ge element for 30.2~
32.7%.
2. a kind of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 1, it is characterised in that Curie's temperature of the material
Degree is promoted to 284K by 273.5K, and under 5T changes of magnetic field, maximum magnetic entropy variable is 3.16Jkg-1K-1,3.30J·kg-1K-1,
3.28J·kg-1K-1,3.25J·kg-1K-1。
3. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material as claimed in claim 1 or 2, it is characterised in that should
Method specifically includes following steps：
Step (1)：Manganese powder, cobalt powder, titanium valve and germanium powder are weighed by a mole atomic percent, is well mixed, pre-reaction mixing is made
Thing；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, progress vacuumizes gas washing processing；
Step (3)：It is on fire using 25~35A electric current, electrode is moved to directly over pre-reaction mixture, electric current is adjusted to 70~
90A melts completely up to pre-reaction mixture, then electric current is down into 55~65A meltings 0.3~0.6 minute, treats that alloy is cooled down, will
Bottom turns to top, melt back 2~5 times；
Step (4)：It is transferred in quartz glass test tube, progress vacuumizes gas washing processing, then, is sealed and placed in entering in stove formula case
Row heat treatment, that is, be made described room temperature magnetic refrigerating alloy magneto-caloric material.
4. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 3, it is characterised in that step
(1) purity of manganese powder, cobalt powder, titanium valve and germanium powder described in is >=99.9%.
5. the preparation method of a kind of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 4, it is characterised in that described
The purity of manganese powder be 99.9%, the purity of described cobalt powder is 99.9%, and the purity of described titanium valve is 99.99%, described
Germanium powder purity be 99.99%.
6. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 3, it is characterised in that step
(2) the step of gas washing is handled that vacuumize described in be：Vacuum arc stove evacuation is first less than 5Pa with mechanical pump, opens and divides
Sub- pump is evacuated to less than 10 again-4Pa, is subsequently passed air pressure 10Pa argon gas, repeats aforesaid operations 1~3 time.
7. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 3, it is characterised in that step
(4) the step of gas washing is handled that vacuumize described in be：It is evacuated to using molecular pump less than 5Pa, pours argon gas and carry out gas washing,
Repeat aforesaid operations 2~4 times.
8. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 6 or 7, it is characterised in that
The purity of described argon gas is 99.999%.
9. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 3, it is characterised in that step
(4) the process of thermal treatment condition described in is：Anneal 5~8 days, take out in 800~900 DEG C, in the cold water for being placed in 5~12 DEG C
Annealing.
10. a kind of application of room temperature magnetic refrigerating alloy magneto-caloric material as claimed in claim 1 or 2, it is characterised in that described
Alloy magneto-caloric material is used to prepare refrigerating material.
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| CN112226659A (en) * | 2020-10-29 | 2021-01-15 | 上海电力大学 | Near-room-temperature magnetic refrigeration manganese-germanium-based refrigeration material and preparation method thereof |
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