CN107267839B - A kind of room temperature magnetic refrigerating alloy magneto-caloric material and the preparation method and application thereof - Google Patents
A kind of room temperature magnetic refrigerating alloy magneto-caloric material and the preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The present invention relates to a kind of room temperature magnetic refrigerating alloy magneto-caloric material and the preparation method and application thereof, the chemical general formula of the material is MnCo1‑xTixGe, x is 0.02 0.08 in formula, and the atomic percent of manganese element is 33.3~34.4% in the material, 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 Germanium is 30.2~32.7%；When 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, is vacuumized, high purity argon is filled with and carries out gas washing, be put into stove formula case, takes out sample annealing.Compared with prior art, alloy magneto-caloric material of the present invention is second-order phase transistion material, has the characteristics that heat stagnation is small, adjustable warm area is big, it can effectively avoid the heat stagnation problem that first order phase change material strips are come, step of preparation process is simple, and condition controllability is good, has good application prospect.
Description
Technical field
The invention belongs to metallurgical technology field, it is related to a kind of room temperature magnetic refrigerating alloy magneto-caloric material and preparation method thereof in answering
With.
Background technology
With a large amount of consumption of traditional energy, the pressure of environmental protection, the new energy such as development magnetic refrigeration have been compeled in eyebrow in addition
Eyelash.For traditional vapor compression refrigeration, magnetic freezes with efficient, low noise, floor space is small and is using
The advantages that not will produce any pollution in journey realizes refrigeration by the magnetothermal effect of magnetic material itself, will necessarily become people
Class solves the important channel of energy and environmental problem.But compared with other refrigeration modes, magnetic refrigeration technology also less at
Ripe, especially 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
It is the key that restrict magnetic refrigeration development that greatly and magnetothermal effect is smaller etc..Therefore, how to make the Curie temperature tune of magnetic refrigerating material
Control reduces the heat stagnation and magnetic hysteresis of material, and it is for a long time to obtain larger magnetothermal effect near room temperature near room temperature
People endeavour to solve the problems, such as 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 ideal magneto-caloric material it
One, alloy is in hexagonal Ni in 650K recurring structure phase transformations, the orthogonal thereto TiNiSi structures of low temperature, high temperature2In 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 apparent 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 that in room temperature magnetic refrigerating material design, preparation.
Currently, a large amount of detailed research work has been done in home and abroad to design, the preparation etc. of MnCoGe alloys, master
It wants there are three types of technological means：It adulterates interstitial atom, the chemical composition for changing compound, substituted using transition group atom.Especially
Good magnetothermal effect is had been achieved in preparation to the replacement of MnCoGe alloy atoms.But since preparation method and raw material are pure
The limitations such as degree so that MnCoGe is still not satisfactory in the magnetothermal effect of near room temperature at present.This is because main research at present
The progress to work acquired by MnCoGe bases, mainly makes the structural phase transition of material be coupled with magnetic phase transition and has obtained huge magnetic thermal effect
It answers, but incident many still unresolved for room temperature magnetic refrigerating, if Curie temperature is excessively high or too low, near room temperature
Magnetothermal effect is smaller, first order phase change evident characteristic：Smaller 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
Wide and magnetothermal effect utilization 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, produce great influence.Related research is it has been shown that carry out MnCoGe alloys
Element substitution technology, can be promoted MnCoGe alloys magnetic Refrigeration Technique competitiveness.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 is all bigger, and but meet simultaneously near room temperature with larger magnetic thermal effect
Larger heat stagnation is avoided while answering again, this must just improve original technology of preparing, improve the microstructure of alloy, to subtract
Small heat stagnation and larger magnetothermal effect is obtained near room temperature.With the further investigation of MnCoGe alloys so that it is huge to prepare room temperature
The second-order phase transistion material of magnetothermal effect has become possibility, though there is the much research about 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) it compares, 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 near room temperature, available larger temperature controllable is wide again, is conducive to MnCo1-xTixGe freezes
Business promotion of the working medium in room temperature magnetic refrigerating field.
Invention content
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 the preparation method and application thereof, to solve the problems, such as that heat stagnation existing for MnCoGe base alloy materials in the prior art is prominent
Go out, Curie temperature is too high or too low, the wide smaller skill defect of temperature controllable.
The purpose of the present invention can be achieved through the following technical solutions：
The chemical general formula of a kind of room temperature magnetic refrigerating alloy magneto-caloric material, the material is MnCo1-xTixGe, x is 0.02- in formula
0.08, the atomic percent of manganese element is 33.3~34.4% in the material, 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 Germanium is 30.2~32.7%.
The Curie temperature of the material is promoted to 284K by 273.5K, and under the changes of magnetic field of 5T, 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 include following steps：
Step (1)：Manganese powder, cobalt powder, titanium valve and germanium powder are weighed by a mole atomic percent, is uniformly mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, carries out vacuumizing gas washing processing；
Step (3)：It is on fire using the electric current of 25~35A, electrode is moved to right over pre-reaction mixture, electric current is adjusted to
70~90A melts completely up to pre-reaction mixture, then electric current is down to 55~65A meltings 0.3~0.6 minute, waits for 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, carries out vacuumizing gas washing processing, then, be sealed and placed in stove formula case
In be heat-treated, obtain the room temperature magnetic refrigerating alloy magneto-caloric material.
The purity of manganese powder, cobalt powder, titanium valve and germanium powder described in step (1) is >=99.9%.
The purity of the manganese powder is 99.9%, and the purity of the cobalt powder is 99.9%, and the purity of the titanium valve is
99.99%, the purity of the germanium powder is 99.99%.
Described in step (2) vacuumize gas washing processing the step of be：It is first with mechanical pump that vacuum arc stove evacuation is low
In 5Pa, opens molecular pump and be evacuated to again less than 10-4Pa is subsequently passed the argon gas of air pressure 10Pa, repeats aforesaid operations 1~3
It is secondary.
Described in step (4) vacuumize gas washing processing the step of 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 the argon gas is 99.999%.
Process of thermal treatment condition described in step (4) is：It anneals 5~8 days, takes out in 800~900 DEG C, it is placed in 5~
It anneals in 12 DEG C of cold water.
A kind of application of room temperature magnetic refrigerating alloy magneto-caloric material, the alloy magneto-caloric material are used to prepare refrigerating material.
The present invention proposes a kind of MnCo of Co doping trace Ti1-xTixGe alloys are in hexagonal Ni at room temperature2In is tied
Structure, doping of the structure by Ti to Co, so that alloy is obtained near room temperature, larger temperature controllable is wide and magnetothermal effect,
And near room temperature two level magnetic phase transition occurs for alloy, 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 is wider than conventional MnCoGe alloys, bright
It is aobvious that alloy Curie temperature is made to be down to room temperature, and have larger temperature controllable wide near room temperature.
Compared with prior art, the invention has the characteristics that：
1) it utilizes trace Ti to the Co doping of MnCoGe compounds, shows that the Co doping is micro by survey calculation
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 effectively avoid what first order phase change material strips were come
Heat stagnation problem provides advantageous foundation 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, MnCo obtained1-xTixGe materials have heat stagnation small, adjustable
The big feature of warm area provides preparation parameter for the development of room temperature magnetic refrigerating, can be applied to high-energy physics, cryogenic engineering precision instrument
Device, power industry, superconducting technology, medical instrument etc. are related to numerous key areas of national economy.
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-xTixThe M-T that Ge (x=0.02,0.04,0.06,0.08) alloys are 0.02T in magnetic field schemes；
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.
Specific implementation mode
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 is 32.8~
33.3%, the atomic percent of titanium elements is 0.6~2.7%, and the atomic percent of Germanium 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,
It before alloy melting, is vacuumized first less than 5Pa with mechanical pump, opens molecular pump and be evacuated to again less than 10-4Pa is passed through gas
The high purity argon (99.999%) of 10Pa is pressed, repetition is above to be vacuumized with scrubbing operations step twice, and the electricity of 30A or so is used
It flows on fire, electrode is moved to right over sample apart from sample 0.5cm or so, electric current is slowly adjusted to 80A or so until sample is complete
It is complete to melt, then electric current is down to 60A melting half a minute, wait for that sample bottom is turned to top by alloy cooling, melt back four times with
Ensure the sample uniformity.Sample is put into high-purity high temperature resistant quartz glass test tube after taking out cooling, utilizes hight atmospheric molecular pumping system
It is evacuated to and is less than 5Pa, be filled with high purity argon (99.999%) and carry out gas washing, repeat above step three times, sealed silica envelope,
850 DEG C of annealing is put into stove formula case 7 days to ensure good crystallinity, and it is 10 DEG C or so cool to take out sample and be put into temperature rapidly
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 show
The good main orthogonal thereto TiNiSi structures at room temperature of prepared alloy crystallinity.Physical measurement (PPMS-9T) the result shows that,
The incorporation of Ti 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 mutually becomes 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 near Curie temperature by the ferromagnetic magnetic phase transition to paramagnetic, and Curie temperature is schemed by M-T
Slope variation maximum value acquires, and 284K is risen to by 273.5K with the increase Curie temperature of Ti doping contents.
Fig. 3 provides the isothermal magnetization curve M-H of alloy near Curie temperature under the changes of magnetic field of 0-7T, 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 sample near Curie temperature slope of a curve is that positive value shows that all samples exist in Arrott curves
Two level magnetic phase transition occurs near Curie temperature, illustrates that all samples only have smaller heat stagnation near transformation temperature, effectively
The first order phase change larger problem of heat stagnation nearby 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
The change of isothermal magnetic entropy can 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 the experimental result of Fig. 3, and utilize
(2) formula calculates the isothermal magnetic entropy that the sample is shown under different magnetic field and becomes.The result shows that：Under the changes of magnetic field of 2T,
Maximum isothermal magnetic entropy becomes: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 becomes:3.16J·kg-1K-1, 3.30Jkg-1K-1, 3.28Jkg-1K-1,
3.25J·kg-1K-1。
As it can be seen that by adjusting the content of the Ti in MnCoGe magnetic materials, the crystal structure of alloy can be preferably controlled,
It is effective so that 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 chemical general formula of the present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, the material is MnCo1-xTixGe, x is in 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 Germanium is 32.7%.
The Curie temperature of the present embodiment material is promoted to 284K by 273.5K, under the changes of magnetic field of 5T, 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 uniformly mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, carries out vacuumizing gas washing processing；
Step (3)：It is on fire using the electric current of 25A, electrode is moved to right 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, waits for that alloy cools down, bottom is turned into top
Portion, melt back 2 times；
Step (4)：It is transferred in quartz glass test tube, carries out vacuumizing gas washing processing, then, be sealed and placed in stove formula case
In be heat-treated, obtain the room temperature magnetic refrigerating alloy magneto-caloric material.
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%.
The step of gas washing is handled is vacuumized 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 the argon gas of air pressure 10Pa, repeats aforesaid operations 2 times.
The step of gas washing is handled is vacuumized in step (4) is：Be evacuated to less than 5Pa using molecular pump, pour argon gas into
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)：It anneals 8 days in 800 DEG C, takes out, be placed in 5 DEG C of cold water and move back
Fire.
Room temperature magnetic refrigerating alloy magneto-caloric material made from the present embodiment is used to prepare refrigerating material.
Embodiment 3：
The chemical general formula of the present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, the material is MnCo1-xTixGe, x is in 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 Germanium is 30.2%.
The Curie temperature of the present embodiment material is promoted to 284K by 273.5K, under the changes of magnetic field of 5T, 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 uniformly mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, carries out vacuumizing gas washing processing；
Step (3)：It is on fire using the electric current of 35A, electrode is moved to right 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, waits for that alloy cools down, bottom is turned into top
Portion, melt back 5 times；
Step (4)：It is transferred in quartz glass test tube, carries out vacuumizing gas washing processing, then, be sealed and placed in stove formula case
In be heat-treated, obtain the room temperature magnetic refrigerating alloy magneto-caloric material.
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%.
The step of gas washing is handled is vacuumized 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 the argon gas of air pressure 10Pa, repeats aforesaid operations 3 times.
The step of gas washing is handled is vacuumized in step (4) is：Be evacuated to less than 5Pa using molecular pump, pour argon gas into
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)：It anneals 5 days in 900 DEG C, takes out, be placed in 12 DEG C of cold water and move back
Fire.
Room temperature magnetic refrigerating alloy magneto-caloric material made from the present embodiment is used to prepare refrigerating material.
Embodiment 4：
The chemical general formula of the present embodiment room temperature magnetic refrigerating alloy magneto-caloric material, the material is MnCo1-xTixGe, x is in 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
Than being 1%, the atomic percent of Germanium is 32%.
The Curie temperature of the present embodiment material is promoted to 284K by 273.5K, under the changes of magnetic field of 5T, 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 uniformly mixed, pre-reaction is made
Mixture；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, carries out vacuumizing gas washing processing；
Step (3)：It is on fire using the electric current of 32A, electrode is moved to right 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, waits for that alloy cools down, bottom is turned into top
Portion, melt back 3 times；
Step (4)：It is transferred in quartz glass test tube, carries out vacuumizing gas washing processing, then, be sealed and placed in stove formula case
In be heat-treated, obtain the room temperature magnetic refrigerating alloy magneto-caloric material.
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%.
The step of gas washing is handled is vacuumized 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 the argon gas of air pressure 10Pa, repeats aforesaid operations 2 times.
The step of gas washing is handled is vacuumized in step (4) is：Be evacuated to less than 5Pa using molecular pump, pour argon gas into
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)：It anneals 6 days in 860 DEG C, takes out, be placed in 10 DEG C of cold water and move back
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, which is characterized in that the chemical general formula of the material is MnCo1-xTixGe, in formula
X is 0.02-0.08, and for the material when preparing weighing, the atomic percent of manganese element is 33.3~34.4%, cobalt element
Atomic percent is 32.8~33.3%, and the atomic percent of titanium elements is 0.6~2.7%, and the atomic percent of Germanium is
30.2~32.7%.
2. a kind of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 1, which is characterized in that Curie's temperature of the material
Degree is promoted to 284K by 273.5K, under the changes of magnetic field of 5T,
As x=0.02, maximum magnetic entropy variable 3.16Jkg-1K-1；
As x=0.04, maximum magnetic entropy variable 3.30Jkg-1K-1；
As x=0.06, maximum magnetic entropy variable 3.28Jkg-1K-1；
As x=0.08, maximum magnetic entropy variable 3.25Jkg-1K-1。
3. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material as claimed in claim 1 or 2, which is characterized 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 uniformly mixed, pre-reaction mixing is made
Object；
Step (2)：Pre-reaction mixture is placed in vacuum arc furnace ignition, carries out vacuumizing gas washing processing；
Step (3)：It is on fire using the electric current of 25~35A, electrode is moved to right over pre-reaction mixture, electric current is adjusted to 70~
90A melts completely up to pre-reaction mixture, then electric current is down to 55~65A meltings 0.3~0.6 minute, waits for that alloy cools down, will
Bottom turns to top, melt back 2~5 times；
Step (4)：Be transferred in quartz glass test tube, vacuumize gas washing processing, then, be sealed and placed in stove formula case into
Row heat treatment, obtains the 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, which is characterized in that step
(1) purity of manganese powder, cobalt powder, titanium valve and germanium powder described in is >=99.9%.
5. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 4, which is characterized in that described
The purity of manganese powder be 99.9%, the purity of the cobalt powder is 99.9%, and the purity of the 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, which is characterized in that step
(2) described in vacuumize gas washing processing the step of be：Vacuum arc stove evacuation is first less than 5Pa with mechanical pump, opens and divides
Son pump is evacuated to again less than 10-4Pa is subsequently passed the argon gas of air pressure 10Pa, 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, which is characterized in that step
(4) described in vacuumize gas washing processing the step of be：It is evacuated to less than 5Pa using molecular pump, 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 described according to claim 6 or 7, which is characterized in that
The purity of the argon gas is 99.999%.
9. a kind of preparation method of room temperature magnetic refrigerating alloy magneto-caloric material according to claim 3, which is characterized in that step
(4) the process of thermal treatment condition described in is：It anneals 5~8 days in 800~900 DEG C, takes out, be placed in 5~12 DEG C of cold water
Annealing.
10. a kind of application of room temperature magnetic refrigerating alloy magneto-caloric material as claimed in claim 1 or 2, which is characterized in that described
Alloy magneto-caloric material is used to prepare refrigerating material.
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