CN109108227A - A kind of high-throughput preparation method of LaFeSi base magnetic refrigerating material - Google Patents
A kind of high-throughput preparation method of LaFeSi base magnetic refrigerating material Download PDFInfo
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- CN109108227A CN109108227A CN201811163998.1A CN201811163998A CN109108227A CN 109108227 A CN109108227 A CN 109108227A CN 201811163998 A CN201811163998 A CN 201811163998A CN 109108227 A CN109108227 A CN 109108227A
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- refrigerating material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/22—Moulds for peculiarly-shaped castings
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C9/00—Moulds or cores; Moulding processes
- B22C9/06—Permanent moulds for shaped castings
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0068—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for particular articles not mentioned below
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
Abstract
The invention discloses a kind of high-throughput preparation methods of LaFeSi base magnetic refrigerating material.This method is during being cast into alloy pig for raw material melt, changes in gradient using wedge-shaped copper mold, therefore along the cooling rate of short transverse melt, obtains the wedge-shaped alloy pig with solidified superalloy tissue gradient, is then made annealing treatment, the NaZn of acquisition13The magnetothermal effect of the LaFeSi matrix body magnetic refrigerating material of type structure has gradient distribution.The microscopic structure obtained preferably by different cooling rate in scanning electron microscope iron-enriched yeast same sample, it is tested in conjunction with magnetic heating performance, different institutional frameworks, magnetothermal effect, the corresponding relationship between copper mold width are obtained, sample preparation parameters needed for can be used for quickly screening etc..
Description
Technical field
The present invention relates to technical field of magnetic materials, and in particular to a kind of high-throughput preparation of LaFeSi base magnetic refrigerating material
Method.
Background technique
With the development of modern society, Refrigeration Technique improve people's lives level and in terms of play to
Close important role.The electric refrigerators such as refrigerator and air conditioner have entered every household, and the annual energy consumption of refrigeration industry accounts for the whole society according to statistics
15% or more total energy consumption.The peak efficiency for the vapor compression refrigeration technology being commonly used is only 25%, and has discharge
The disadvantages of pernicious gas, noise is big, and volume is big.Therefore exploring environmental-friendly, energy-efficient New Refrigerating technology becomes current
Problem in the urgent need to address.
Magnetic Refrigeration Technique is one kind for being freezed by means of the magnetothermal effect of material itself using magnetic material as working media
Green refrigeration technology.Compared with traditional expansion of compressed gas Refrigeration Technique, magnetic Refrigeration Technique, which has the advantages that (1) not, to be made
With the refrigerants such as freon, ammonia, non-environmental-pollution；(2) magnetic refrigerating material is solid-state, and entropy density is much larger than gas, refrigeration effect
Rate is high；(3) freezed using magnetothermal effect, moved without significantly gas compression, avoid additional energy consumption, make simultaneously
Cold small volume runs smoothly reliably.Thus the Refrigeration Technique obtains global extensive concern.
In recent years, China, the U.S., Holland, Japan etc. have found that several classes have the material of giant magnetio-caloric effects in room temperature range,
Such as: Gd-Si-Ge, Ni-Mn-Ga, Mn-Fe-P-As, MnAs, La (Fe, Si)13Equal alloy systems.These material common features are magnetic
Along with the variation of significant crystal structure, magnetothermal effect is apparently higher than traditional magnetic refrigerating material Gd for phase transformation.It is novel at these
In magnetic refrigerating material, NaZn13The La (Fe, Si) of type structure13Compound is because its is nontoxic, lag is small, phase transformation driving field is low, former material
Expect that cheap, Curie temperature the advantages such as easily adjusts and becomes most by paying attention to one of magnetothermal effect material.
The Magnetic refrigerator in many laboratories has used La (Fe, Si) in world wide at present13Sill is as magnetic working medium.
It can be said that La (Fe, Si)13Magnetic refrigerating material has shown great application prospect, but forms single block NaZn13
Type structure La (Fe, Si)13Compound needs high annealing seven days or even several weeks, not only waste of energy, and production cycle overlength,
This greatlys restrict its industrial application.
Some researchs point out that fast solidification technology can shorten La (Fe, Si)13The manufacturing cycle of magnetic refrigerating material, but for
The research of cooling rate is only limitted to the research under fixed curing condition, that is, to the solidification under a kind of cooler environment of fixation
Once studied, but the preparation method inefficiency of a this furnace, and the melt element under different melting environment
Volatilization is also different, be easy to cause comparing result unreliable.Therefore, it how efficiently, is with high throughput obtained in the same sample
The preparation method of different-alloy organization and performance becomes one of current urgent problem to be solved.
Summary of the invention
Technical purpose of the invention is to provide a kind of high-throughput preparation method of LaFeSi base magnetic refrigerating material, utilizes this
The solidification features of LaFeSi base magnetic refrigerating material made from method and magnetothermal effect have gradient distribution.
To realize the above-mentioned technical purpose, the technical solution adopted by the present invention is that: a kind of height of LaFeSi base magnetic refrigerating material
Flux preparation method, the LaFeSi base magnetic refrigerating material have NaZn13Type structure phase, the preparation method include following step
It is rapid:
(1) raw material is configured according to the chemical formula of the LaFeSi base magnetic refrigerating material；
(2) melt casting is used, the uniform alloy pig of ingredient is obtained；
(3) alloy pig is made annealing treatment, obtaining includes NaZn13The LaFeSi matrix body magnetic refrigeration material of type structure
Material；
It is characterized in that: using wedge-shaped copper mold, obtaining wedge-shaped alloy pig in the step (2).
The wedge-shaped copper mold refers to from copper mold bottom, along the short transverse of copper mold, the cross-sectional area of copper mold by
It is cumulative big or be gradually reduced.The cross-sectional shape of the wedge shape copper mold is unlimited, including rectangle, circle etc..
Preferably, the chemical formula of the LaFeSi base magnetic refrigerating material is La1+xFe13-ySiy, wherein 0 < x≤1,1.0
≤y≤1.8。
Preferably, carrying out melt casting under high purity inert gas protection in the step (2).
Preferably, institute's melt is blown casting with high purity inert gas, obtains wedge-shaped alloy pig in the step (2).
Preferably, raw material is placed in electric arc or induction melting furnace, is vacuumized, and with high-purity in the step (2)
Inert gas is cleaned, then carries out melting under high purity inert gas protection, obtains alloy pig.The high purity inert gas packet
It includes but is not limited to He and/or Ar gas.As further preferred, vacuum degree is evacuated to 5 × 10-3Pa or less.
As a kind of implementation, in the step (2), the alloy pig of institute's melting is placed on to the quartz of lower ending opening
Guan Zhong melts under high purity inert gas protection, and blows to be cast into wedge-shaped copper mold by alloy melt with high purity inert gas and solidify,
Obtain the wedge-shaped alloy pig.The high purity inert gas includes but is not limited to He and/or Ar gas.Preferably, melted alloy
The temperature of ingot is 1400 DEG C -1600 DEG C, and blowing casting air pressure is 0.03-0.06MPa.
Preferably, annealing under high purity inert gas protection in the step (3).
Preferably, annealing temperature is 1000-1200 DEG C in the step (3), annealing time is 5-30 minutes.
Compared with prior art, the present invention uses during melt casting when preparing LaFeSi base magnetic refrigerating material
Wedge-shaped copper mold, has the following beneficial effects:
(1) width due to wedge-shaped copper mold along its cross section of short transverse changes in gradient, when melt cast to wedge-shaped copper
In mould, the cooling rate along short transverse melt changes in gradient, and in the smaller height of cross-sectional width, melt has higher
Cooling rate, for example, being located at the cooling speed of the alloy melt of copper mold most tip (i.e. cross-sectional width is minimum) in wedge-shaped copper mold
Rate is 2500-4500K/s, and the cooling rate for being located at the alloy melt of copper mold bottommost (i.e. cross-sectional width is maximum) is 50-
250K/s.Therefore, the present invention efficiently realizes that in same sample, different height has a different cooling rates, and different cold
But rate obtains a series of solidified superalloy tissues, that is, primary Fe-rich phase dendrite size is along copper mold short transverse in same sample
Change of gradient, in the smaller height of cross-sectional width, primary Fe-rich phase interdendritic is away from more refining, so that magnetic heat be furthermore achieved
The gradient distribution of effect, that is, in the smaller height of cross-sectional width, the magnetothermal effect of material is better.
(2) there is gradient freeze tissue and gradient using LaFeSi base magnetic refrigerating material made from preparation method of the present invention
Magnetothermal effect, therefore can use different cooling rate in same sample made from scanning electron microscope iron-enriched yeast and obtain
Microscopic structure, in conjunction with magnetic heating performance test, institutional framework, magnetothermal effect and the copper of LaFeSi base magnetic refrigerating material can be obtained
The corresponding relationship of mode cross section width can be used for quickly screening alloy microstructure, optimal sample preparation parameters etc., can also be
In practical preparation, according to the institutional framework feature and performance of actually required LaFeSi base magnetic refrigerating material, correspondence pass is compareed
System, obtains the cross-sectional width of copper mold, cross-sectional width is referred to as referred to, to keep other preparation conditions in actual fabrication process
Constant, need to only control the cross-sectional width of actually used copper mold as this can be realized actually required LaFeSi base magnetic with reference to cross-sectional width
The preparation of refrigerating material.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the wedge-shaped copper mold in the embodiment of the present invention 1；
Fig. 2 is by obtaining LaFe in the embodiment of the present invention 111.6Si1.4The scanning electron microscopy of wedge-shaped alloy sample different parts
Mirror photo；
Fig. 3 is by obtaining LaFe in the embodiment of the present invention 111.6Si1.4The primary Fe-rich phase of wedge-shaped alloy sample different parts
Interdendritic is away from magnitude numerical value；
Fig. 4 is by obtaining LaFe in the embodiment of the present invention 111.6Si1.4Magnetic entropy becomes variation with temperature at sample top and tip
Curve；
Fig. 5 is by obtaining La in the embodiment of the present invention 21.7Fe11.6Si1.4The scanning electron of wedge-shaped alloy sample different parts is aobvious
Micro mirror photo；
Fig. 6 is by obtaining La in the embodiment of the present invention 21.7Fe11.6Si1.4The primary Fe-rich phase of wedge-shaped alloy sample different parts
Interdendritic away from magnitude numerical value；
Fig. 7 is by obtaining La in the embodiment of the present invention 21.7Fe11.6Si1.4Magnetic entropy becomes the change with temperature at sample top and tip
Change curve.
Specific embodiment
Present invention is further described in detail for embodiment with reference to the accompanying drawing, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Appended drawing reference in attached drawing 1 are as follows: 1- alloy melt；2- copper mold.
In the following example:
Electric arc furnaces used is Beijing WuKe opto-electrical Technology Co., Ltd WK series non-consumable arc furnace；Institute's use feeling is answered
Smelting furnace is that Japan produces the small-sized induction melting furnace of VF-HMF100；
Used scanning electron microscope model FEI Quanta FEG 250；Institute using measurement dendrite size software be
The Photoshop software of Adobe company of U.S. exploitation；
Using and leading quantum magnetometer is that U.S. Quantum Design company produces MPMS SQUID VSM.
It is apparent that those skilled in the art can also use other other equipment with the same function known in the art
Or software.
It in the following example, the use of material purity is La purity is 99.9%, Fe purity is 99.99%, Si purity
It is 99.999%, can be obtained from commercially available approach.
Embodiment 1:
In the present embodiment, the molecular formula of LaFeSi base magnetic refrigeration alloy material is LaFe11.6Si1.4。
The high throughput of above-mentioned LaFeSi base magnetic refrigerating material the preparation method is as follows:
Step 1: pressing molecular formula LaFe11.6Si1.4By raw material La, Fe, Si ingredient, specifically: alloy atom percentage is turned
It is changed to mass percent, weighs La, Fe and Si respectively in proportion, the purity of each raw material is all larger than 99%；
Step 2: the raw material prepared in step 1 being put into arc-melting furnace, 1 × 10 is evacuated to furnace body-5~5 ×
10-5It is 400~800mbar that argon gas to air pressure is filled with after mbar, heats melting raw material, after raw material is completely melt, continues melting 2
It~10 minutes, is subsequently cooled to solidify.It repeats melting 3~5 times, obtains the uniform alloy pig of ingredient；
Step 3: the alloy pig that step 2 is obtained is broken into fritter alloy, will be packed into lower ending opening after the cleaning of fritter alloy
Quartz glass tube in, be subsequently placed in the induction coil of induction melting furnace.It is evacuated to 5 × 10-3It is filled with after Pa appropriate high-purity
Argon gas is as protective gas, after adjusting electric current is completely melt to alloy, as shown in Figure 1, will using 0.03-0.06MPa draught head
The alloy melt 1 of melting is spurted into wedge-shaped copper mold, and the height of the copper mold 2 is about 50mm, and along short transverse, cross section is wide
Degree is linear to be increased, and the width of tip (i.e. cross-sectional width is minimum) is 0mm, and top is that internal diameter width is 4mm (i.e. cross-sectional width
It is maximum) square cast gate, be made height be about 50mm, the wide 4mm in top, the wedge-shaped alloy pig that tip width is 0mm；
Step 4: the LaFe that step 3 is obtained11.6Si1.4Wedge-shaped alloy pig is annealed under inert gas protection, annealing temperature
It is 1000-1200 DEG C, annealing time is 5-30 minutes, and liquid nitrogen or quenching-in water are obtained with NaZn13The magnetic refrigeration material of structure
Material.
Wedge shape alloy pig made from above-mentioned steps 3 is tested as follows:
(1) using wedge shape LaFe made from scanning electron microscope measurement above-mentioned steps 311.6Si1.4Alloy pig different parts
Tissue.In the present embodiment, select model FEI Quanta FEG 250 scanning electron microscope, using backscattered electron at
As mode, electron gun voltage is 20KV, and amplification factor is 400 times.It is from bottom to top respectively in distance that test results are shown in figure 2
The electron scanning micrograph that the position 0mm, 8mm, 16mm, 24mm and 32mm samples at wedge shaped sample tip, display are certainly wedge-shaped
Top to wedge shaped tip primary Fe-rich phase constantly refines, and shows it with continuous gradient alternative construction.
(2) wedge-like tip is measured to wedge shaped tip different parts primary Fe-rich phase interdendritic away from big with Photoshop software
It is small.Test results are shown in figure 3, shows from wedge-like tip to tip primary Fe-rich phase interdendritic away from being refined to 0.3 μm by 5 μm.
Magnetic refrigerating material made from above-mentioned steps 4 is tested as follows:
(1) the magnetic refrigerating material top is measured respectively using superconductive quantum interference vibrating specimen magnetometer MPMS (SQUID) VSM
The magnetization curve (M-H curve) at end and tip.According to Maxwell relation:
Magnetic entropy, which is calculated, from isothermal magnetization curve becomes Δ SM, as a result as shown in Figure 4.From fig. 4, it can be seen that the magnetic refrigerating material
With wide operating temperature range, belong to typical second-order phase transistion feature.Under 1T externally-applied magnetic field, magnetic refrigerating material top and point
End maximum magnetic entropy variable is respectively 4.9J/kgK and 4.6J/kgK, and corresponding Curie temperature is respectively 205.5K and 208.5K；Outside 2T
Add under magnetic field, magnetic refrigerating material top and tip maximum magnetic entropy variable are respectively 8J/kgK and 7.4J/kgK, corresponding Curie temperature point
It Wei not 205.5K and 208.5K.
In conclusion in LaFe11.6Si1.4In alloy system, blowing casting with wedge-shaped copper mold can realize not in same sample
It is prepared with cooling rate, obtains a series of gradient freeze tissues being distributed along copper mold height, it can be Bu Tong cold for research and application
But the sample of rate preparation provides easy preparation method.
Embodiment 2:
In the present embodiment, the molecular formula of LaFeSi base magnetic refrigeration alloy material is La1.7Fe11.6Si1.4。
Above-mentioned LaFeSi base magnetic refrigerating material the preparation method is as follows:
Step 1: pressing molecular formula La1.7Fe11.6Si1.4By raw material La, Fe, Si ingredient, specifically: by alloy atom percentage
Mass percent is converted to, weighs La, Fe and Si respectively in proportion, the purity of each raw material is all larger than 99%；
Step 2: the raw material prepared in step 1 being put in arc-melting furnace, 1 × 10 is evacuated to furnace body-5~5 × 10- 5It is 400~800mbar that argon gas to air pressure is filled with after mbar, heats melting raw material, after raw material is completely melt, continue melting 2~
It 10 minutes, is subsequently cooled to solidify, is repeated melting 3~5 times after being turned over rapidly, obtain the uniform alloy pig of ingredient；
Step 3: the alloy pig that step 2 is obtained is broken into fritter alloy, and blowing casting preparation using wedge-shaped copper mold has gradient
The La of solidified structure1.7Fe11.6Si1.4Alloy, specifically: the quartz glass tube of lower ending opening will be packed into after the cleaning of fritter alloy
In, it is subsequently placed in the induction coil of induction melting furnace.It is evacuated to 5 × 10-3Appropriate high-purity argon gas is filled with after Pa as protection
The alloy melt of melting is spurted into wedge using 0.03-0.06MPa draught head after adjusting electric current is completely melt to alloy by gas
In shape copper mold, the height of the copper mold is about 60mm, and along short transverse, cross-sectional width linearly increases, tip (i.e. cross section
Width is minimum) width be 1mm, top is that internal diameter width is that (the square cast gate of (i.e. cross-sectional width is maximum), is made 6mm
It is highly 60mm, the wedge-shaped alloy pig that the wide 6mm in top, tip width are 1mm；
Step 4: the La that step 3 is obtained1.7Fe11.6Si1.4Wedge-shaped alloy pig is annealed under inert gas protection, annealing temperature
Degree is 1000-1200 DEG C, and annealing time is 5-30 minutes, and liquid nitrogen or quenching-in water are obtained with NaZn13The magnetic refrigeration material of structure
Material.
Wedge shape alloy pig made from above-mentioned steps 3 is tested as follows:
(1) using wedge shape La made from scanning electron microscope measurement above-mentioned steps 31.7Fe11.6Si1.4Alloy pig difference portion
Bit organization.In the present embodiment, the scanning electron microscope of model FEI Quanta FEG 250 is selected, using backscattered electron
Imaging pattern, electron gun voltage are 20KV, and amplification factor is 400 times.Test results are shown in figure 5 be from bottom to top respectively away from
From the electron scanning micrograph that the position 0mm, 8mm, 16mm, 24mm and 32mm at wedge shaped sample tip samples, show from wedge
Shape top to wedge shaped tip primary Fe-rich phase constantly refines, and shows it with continuous gradient alternative construction.
(2) wedge-like tip is measured to wedge shaped tip different parts primary Fe-rich phase interdendritic away from big with Photoshop software
It is small.Test results are shown in figure 6, shows from wedge-like tip to tip primary Fe-rich phase interdendritic away from being refined to 0.3 μm by 5 μm.
Magnetic refrigerating material made from above-mentioned steps 4 is tested as follows:
(1) the magnetic refrigerating material top is measured respectively using superconductive quantum interference vibrating specimen magnetometer MPMS (SQUID) VSM
The magnetization curve (M-H curve) at end and tip.According to Maxwell relation:
Magnetic entropy, which is calculated, from isothermal magnetization curve becomes Δ SM, as a result as shown in Figure 7.From figure 7 it can be seen that the magnetic refrigerating material
Magnetothermal effect there is gradient distribution, the magnetothermal effect at top and tip has significant difference.Under 1T externally-applied magnetic field, magnetic refrigeration material
Material top and tip maximum magnetic entropy variable are respectively 7.6J/kgK and 9.6J/kgK, corresponding Curie temperature be respectively 184.5K and
187.5K；Under 2T externally-applied magnetic field, magnetic refrigerating material top and tip maximum magnetic entropy variable are respectively 11.0J/kgK and 14.6J/
KgK, corresponding Curie temperature is respectively 184.5K and 190.0K.
(3) according to test result, the institutional framework feature and performance and copper mold of the LaFeSi base magnetic refrigerating material are obtained
The corresponding relationship of cross-sectional width；
It is right according to the institutional framework feature and performance of actually required LaFeSi base magnetic refrigerating material in actually preparation
According to the corresponding relationship, the cross-sectional width of copper mold is obtained, referred to as refers to cross-sectional width；
In actual fabrication process, keep above-mentioned steps (1) other preparation conditions into step (4) constant, control is practical
The cross-sectional width of copper mold used is that this refers to cross-sectional width, and the preparation of actually required LaFeSi base magnetic refrigerating material can be realized.
Technical solution of the present invention is described in detail in embodiment described above, it should be understood that the above is only
For specific embodiments of the present invention, it is not intended to restrict the invention, all any modifications made in spirit of the invention,
Supplement or similar fashion substitution etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of high-throughput preparation method of LaFeSi base magnetic refrigerating material, the LaFeSi base magnetic refrigerating material has NaZn13
Type structure phase, the preparation method include the following steps:
(1) raw material is configured according to the chemical formula of the LaFeSi base magnetic refrigerating material；
(2) melt casting is used, the uniform alloy pig of ingredient is obtained；
(3) alloy pig is made annealing treatment, obtaining includes NaZn13The LaFeSi matrix body magnetic refrigerating material of type structure；
It is characterized in that: in the step (2), using wedge-shaped copper mold, from copper mold bottom, along the short transverse of copper mold, copper mold
Cross-sectional area is gradually increased or is gradually reduced, and obtains wedge-shaped alloy pig.
2. the high-throughput preparation method of LaFeSi base magnetic refrigerating material as described in claim 1, it is characterized in that: the LaFeSi
The chemical formula of base magnetic refrigerating material is La1+xFe13-ySiy, wherein 0 < x≤1,1.0≤y≤1.8.
3. the high-throughput preparation method of LaFeSi base magnetic refrigerating material as described in claim 1, it is characterized in that: the step
(2) in, melt casting is carried out under high purity inert gas protection；
Preferably, institute's melt is blown casting with high purity inert gas, wedge-shaped alloy pig is obtained.
4. the high-throughput preparation method of LaFeSi base magnetic refrigerating material as described in claim 1, it is characterized in that: the step
(2) in, raw material is placed in electric arc or induction melting furnace, is vacuumized, and cleaned with high purity inert gas, then high-purity lazy
Property gas shield under carry out melting, obtain alloy pig.
5. the high-throughput preparation method of LaFeSi base magnetic refrigerating material as described in claim 1, it is characterized in that: the step
(2) in, the alloy pig of institute's melting is placed in the quartz ampoule of lower ending opening, melts, is used in combination under high purity inert gas protection
Alloy melt is blown to be cast into wedge-shaped copper mold and be solidified by high purity inert gas.
6. the high-throughput preparation method of LaFeSi base magnetic refrigerating material as described in claim 1, it is characterized in that: melted alloy ingot
Temperature be 1400 DEG C -1600 DEG C, blow casting air pressure be 0.03-0.06MPa.
7. the high-throughput preparation method of LaFeSi base magnetic refrigerating material as described in claim 1, it is characterized in that: the step
(3) it in, anneals under high purity inert gas protection.
8. the high-throughput preparation method of LaFeSi base magnetic refrigerating material as described in claim 1, it is characterized in that: the step
(3) in, annealing temperature is 1000-1200 DEG C, and annealing time is 5-30 minutes.
9. the high-throughput preparation method of the LaFeSi base magnetic refrigerating material as described in any claim in claim 1 to 8,
Be characterized in: the LaFeSi base magnetic refrigerating material has gradient freeze alloy structure；The LaFeSi base magnetic refrigerating material has
Gradient magnetothermal effect.
10. the high-throughput preparation method of the LaFeSi base magnetic refrigerating material as described in any claim in claim 1 to 8,
It is characterized in that: further including following steps:
The microscopic structure obtained using different cooling rate in same sample made from scanning electron microscope iron-enriched yeast, is obtained
To the institutional framework feature of LaFeSi base magnetic refrigerating material and the corresponding relationship of performance and copper mold cross-sectional width；
According to the institutional framework feature and performance of actually required LaFeSi base magnetic refrigerating material, the corresponding relationship is compareed, is obtained
To the cross-sectional width of copper mold, cross-sectional width is referred to as referred to；
It in actual fabrication process, keeps other preparation conditions constant to step (3) with above-mentioned steps (1), controls actually used
The cross-sectional width of copper mold is that this refers to cross-sectional width, LaFeSi base magnetic refrigerating material needed for being made.
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| CN201811163998.1A CN109108227B (en) | 2018-10-04 | 2018-10-04 | High-flux preparation method of LaFeSi-based magnetic refrigeration material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112885549A (en) * | 2021-01-08 | 2021-06-01 | 哈尔滨工业大学 | Preparation method of magnetic phase change material of regenerator of magnetic refrigerator and magnetic refrigeration circulating system |
| CN113909455A (en) * | 2021-09-24 | 2022-01-11 | 北京科技大学 | Device and method for preparing sub-rapid solidification alloy in high flux |
| CN113969362A (en) * | 2021-10-27 | 2022-01-25 | 东北大学 | Continuous gradient aluminum alloy deformation material and preparation method thereof |
| CN114058798A (en) * | 2021-11-26 | 2022-02-18 | 上海大学 | Flash annealing process and device for La-Fe-Si series alloy |
| CN114453415A (en) * | 2022-02-11 | 2022-05-10 | 哈尔滨理工大学 | Non-uniform-thickness rolling method for metal plate with structure gradient structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277542A (en) * | 2011-09-21 | 2011-12-14 | 镇江忆诺唯记忆合金有限公司 | Quinary magnesium-based amorphous alloy |
| CN104694813A (en) * | 2015-03-04 | 2015-06-10 | 中国科学院宁波材料技术与工程研究所 | LaFeSi-based magnetic refrigeration material as well as preparation method and application thereof |
| CN105903931A (en) * | 2016-05-04 | 2016-08-31 | 上海大学 | High-flux preparation device and method for array type bulk amorphous alloys |
| CN106636843A (en) * | 2016-11-04 | 2017-05-10 | 北京工业大学 | MnNiSi-based magnetic alloy capable of serving as magnetic refrigeration material |
-
2018
- 2018-10-04 CN CN201811163998.1A patent/CN109108227B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102277542A (en) * | 2011-09-21 | 2011-12-14 | 镇江忆诺唯记忆合金有限公司 | Quinary magnesium-based amorphous alloy |
| CN104694813A (en) * | 2015-03-04 | 2015-06-10 | 中国科学院宁波材料技术与工程研究所 | LaFeSi-based magnetic refrigeration material as well as preparation method and application thereof |
| CN105903931A (en) * | 2016-05-04 | 2016-08-31 | 上海大学 | High-flux preparation device and method for array type bulk amorphous alloys |
| CN106636843A (en) * | 2016-11-04 | 2017-05-10 | 北京工业大学 | MnNiSi-based magnetic alloy capable of serving as magnetic refrigeration material |
Non-Patent Citations (1)
| Title |
|---|
| 林志平: "磁热材料LaCeFeSi和NiMnSn磁熵变性能研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112885549A (en) * | 2021-01-08 | 2021-06-01 | 哈尔滨工业大学 | Preparation method of magnetic phase change material of regenerator of magnetic refrigerator and magnetic refrigeration circulating system |
| CN112885549B (en) * | 2021-01-08 | 2022-09-20 | 哈尔滨工业大学 | Preparation method of magnetic phase change material of regenerator of magnetic refrigerator and magnetic refrigeration circulating system |
| CN113909455A (en) * | 2021-09-24 | 2022-01-11 | 北京科技大学 | Device and method for preparing sub-rapid solidification alloy in high flux |
| CN113969362A (en) * | 2021-10-27 | 2022-01-25 | 东北大学 | Continuous gradient aluminum alloy deformation material and preparation method thereof |
| CN114058798A (en) * | 2021-11-26 | 2022-02-18 | 上海大学 | Flash annealing process and device for La-Fe-Si series alloy |
| CN114453415A (en) * | 2022-02-11 | 2022-05-10 | 哈尔滨理工大学 | Non-uniform-thickness rolling method for metal plate with structure gradient structure |
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