CN108486469A - A kind of nanocrystalline La1-xRxFeySizThe manufacturing method of magnetothermal effect material - Google Patents

A kind of nanocrystalline La1-xRxFeySizThe manufacturing method of magnetothermal effect material Download PDF

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CN108486469A
CN108486469A CN201810413285.XA CN201810413285A CN108486469A CN 108486469 A CN108486469 A CN 108486469A CN 201810413285 A CN201810413285 A CN 201810413285A CN 108486469 A CN108486469 A CN 108486469A
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magnetothermal effect
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CN108486469B (en
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李玉平
熊桑
吴梦陵
黄叶
孔斌
许贝贝
查威
马颖涵
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Nanjing Institute of Technology
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Abstract

The invention belongs to magnetothermal effect field of material technology, and in particular to a kind of nanocrystalline La1‑xRxFeySizThe preparation method of magnetothermal effect material.Wherein, R is one or several kinds of mixtures in rare earth element, and rare earth element includes Ce, Pr, Nd, Sm, Te, Dy, Ho, Eu, Er, Tm；The compositing range of each element is：0≤x≤0.5,9≤y≤12.5,0.5≤z≤4.Preparation process includes the following steps：Melting process, fast quenching process are flushed with hydrogen ball milling process and heat treatment procedure, and wherein melting process, fast quenching process carries out under argon gas protection environment, and heat treatment procedure carries out under vacuum conditions.The La prepared through the invention1‑xRxFeySizMagnetothermal effect material has tiny, uniform nano-structure structure, therefore inhales exothermicity with good, and according to material composition and the difference for the treatment of process, the crystallite dimension of material is 20 80nm, and maximum entropy becomes 4.9 12.6J/kgK under the magnetic fields 1.5T.

Description

A kind of nanocrystalline La1-xRxFeySizThe manufacturing method of magnetothermal effect material
Technical field
The invention belongs to magnetothermal effect field of material technology, and in particular to a kind of preparation side of nanocrystalline magnetic fuel factor material Method.
Background technology
Currently, the refrigeration equipments such as refrigerator, air-conditioning mainly use traditional Technology of Compressor Refrigeration, need to use freon system There is the defects of destroying ozone layer, emission greenhouse effect gas in cryogen.Moreover, vapor compression refrigeration there is also efficiency low, energy consumption Big defect.In recent years, as global environmental protection consciousness gradually increases, room-temperature magnetic refrigeration technology is increasingly by the blueness of people It looks at.Room-temperature magnetic refrigeration technology as a kind of emerging green refrigeration technology, by suction of the magnetothermal effect material in the case where converting magnetic field, Exothermic effect is freezed to realize, without freon refrigerant, is not polluted with environment to air.Moreover, because magnetic cooling Technology is not necessarily to gas compressor, and moving component is few and movement is slow, not will produce excessive vibrations and noise, and energy consumption is small, uses Long lifespan has the advantages that reliable and stable.Therefore, mangneto refrigeration technique be current each colleges and universities, scientific research institutions, Corporation R ＆ D heat Point.
Since room-temperature magnetic refrigeration is by magnetothermal effect material to inhale heat release in the case where converting magnetic field to achieve the purpose that refrigeration, institute It is the key that magnetic cooling technical research with high-performance magnetism fuel factor material.Brown etc. [1] is found that metal material Gd can be with earliest It is used as room temperature magnetic refrigeration material.The material has prodigious Entropy Changes under the external magnetic field of 7T, therefore is being considered as once kind Very promising magnetic cooling material, but Gd is a kind of heavy rare earth element, it is expensive, and poor chemical stability, greatly Limit the application of its market.Hereafter, 1997 U.S.'s Ames Lab [2] be found that the Gd that Gd and Si, Ge are formed5Si2Ge2Tool There are giant magnetio-caloric effects, but this compound magnetic heating performance curve halfwidth is smaller, is unfavorable in the practical magnetic cooling circulatory system Middle use, and this material price is still more expensive, therefore fail to realize the marketization.Hereafter, Nanjing University it is all promising, in Institute of section CAS Institute of Physics Shen protect root, Japan H.Wada, S.Fujieda, Holland Tegues et al. be found that perovskite-like type respectively The magnetothermal effects material such as compound, MnAs compounds, LaFeSi compounds, MnFePAs compounds [3-6], these discoveries push away The development of magnetothermal effect Material Field is moved.But these materials still have some shortcomings (such as performance, cost), So that failing to introduce application to the market.
Invention content
To overcome above-mentioned shortcoming and defect of the existing technology, the purpose of the present invention is to provide a kind of nanocrystalline magnetic heat The preparation method of effect material, so that the nanocrystalline magnetic fuel factor material prepared has microscopic structure knot more tiny, evenly Structure, thus have more excellent performance.
The purpose of the present invention is what is be carried out by the following technical programs：
A kind of nanocrystalline La1-xRxFeySizThe manufacturing method of magnetothermal effect material, including the melting process of material, fast quenching work Sequence is flushed with hydrogen ball milling process and heat treatment procedure, and wherein melting process, fast quenching process carries out under argon gas protection environment, heat treatment Process carries out under vacuum conditions.The term " vacuum " of the present invention is the generic term of this field；Melting process, the choosing of fast quenching process It selects and uses argon gas protection environment, it is therefore an objective to prevent from aoxidizing.
Above-mentioned operation is also often used in other materials (such as nanocrystalline rare-earth permanent magnetic material) preparation[7], but it is specific to this Invention is needed to use the parameter and means different from previous technique, relevant art index is limited to due to the particularity of material In the range of the present invention allows, the performance that the present invention is declared can be just obtained, it is specific as follows：
(1) it is flushed with hydrogen in ball milling process, the hydrogen that when ball milling uses is pressed as 0.1-1MPa；Ball-milling Time is 4-25h；Ball and material Weight ratio be 10：1 to 30:1.Under the above parameters, alloy main phase is decomposed reaction, generates different nanometer phases, side Formula is as follows：
La1-xRxFeySi13-y+aH2=(1-x) LaH2a+xRH2a+(13-y)Fe2Si+(3y-26)Fe (1)
Under this process conditions, the crystallite dimension for obtaining each phase is generally 5-15nm, and average-size is about 10nm.
(2) in vacuum heat process, the material after decomposition is heat-treated at a temperature of 500-900 DEG C；At heat It is 10 minutes to 2 hours to manage the time.Under the above parameters, through being flushed with hydrogen the nanometer phase dehydrogenation of ball milling process generation and combining, again The main phase of alloy is generated, equation is as follows：
(1-x)LaH2a+xRH2a+(13-y)Fe2Si+ (3y-26) Fe=La1-xRxFeySi13-y+aH2 (2)
Under this process conditions, the main phase La that regenerates1-xRxFeySi13-yCrystallite dimension is 20-80nm, between crystal grain Grain boundary width be 1-3nm.
(3) in the present invention, R is one or several kinds of mixtures in rare earth element, rare earth element include Ce, Pr, Nd, Sm、Te、Dy、Ho、Eu、Er、Tm；La1-xRxFeySizThe compositing range of material each element is：0≤x≤0.5,9≤y≤12.5, 0.5≤z≤4。
The present invention basic principle be：Rare-earth iron series material can absorb hydrogen under certain condition, and it is anti-that chemical breakdown occurs It answers, the decomposition phase with fine grain size is generated, and relative to conventional rare-earth iron series material hydrogen abstraction reaction, in of the invention Material, which inhales hydrogen, to be completed by being flushed with hydrogen ball milling, and the broken dual thinning effect with ball mill crushing of hydrogen, the decomposition obtained are experienced Phase crystallite dimension is very tiny, only several nanometers.Moreover, because ball milling is to complete at normal temperatures, decomposing phase crystal grain will not It grows up.Just because of with above-mentioned tissue signature, in subsequent vacuum heat treatment process, can just obtain crystallite dimension is The nanocrystalline La of 20-80nm1-xRxFeySizMagnetothermal effect material.
Preferably, a kind of nanocrystalline La according to the present invention1-xRxFeySizThe manufacturing method of magnetothermal effect material, The hydrogen that is used when ball milling is pressed as 0.6-1MPa, and Ball-milling Time is preferably 10-15h, and the weight ratio of ball and material is 15：1 to 20：1. This is done to improve the efficiency of decomposition reaction, keep the material structure after reaction more tiny.
Preferably, a kind of nanocrystalline La according to the present invention1-xRxFeySizThe manufacturing method of magnetothermal effect material, In vacuum heat process, heat treatment temperature is 650-750 DEG C.According to the experiment repeatedly of inventor, under the above parameters, material Material can obtain more preferably tissue morphology, i.e. crystallite dimension is tiny, and the size difference between each crystal grain is smaller, uniformly Property is more preferable.
Preferably, a kind of nanocrystalline La according to the present invention1-xRxFeySizThe manufacturing method of magnetothermal effect material, R is one or several kinds of mixtures in rare earth element in alloy, is considered from material cost, rare earth material is preferably selected The light rare earths material such as Ce, Pr, Nd, Sm
Preferably, a kind of nanocrystalline La according to the present invention1-xRxFeySizThe manufacturing method of magnetothermal effect material, The compositing range of each element is：0.1≤x≤0.4,10≤y≤12.5,0.5≤z≤2.Inventor by testing discovery repeatedly, Within the above range, material, which has, preferably inhales exothermicity.
Advantages of the present invention：The La prepared through the invention1-xRxFeySizMagnetothermal effect material have it is tiny, uniformly receive Rice institutional framework, therefore exothermicity is inhaled with good, according to material composition and the difference for the treatment of process, the crystallite dimension of material For 20-80nm, maximum entropy becomes 4.9-12.6J/kgK under the magnetic fields 1.5T.
Specific implementation mode
With reference to embodiment, present disclosure is further illustrated.It should be appreciated that the implementation of the present invention is not limited to In the following examples, the accommodation in any form and/or change made to the present invention fall within the scope of the present invention.
In the present invention, if not refering in particular to, all equipment and raw material etc. are commercially available or the industry is common. Method in following embodiments is unless otherwise instructed the conventional method of this field.
Embodiment 1：
A kind of preparation method of nanocrystalline magnetic fuel factor material, including：
(1) alloy raw material is weighed by design proportion, it is La to be allowed to ingredient0.75R0.25Fe12Si1.2；
(2) by above-mentioned dispensing under protection of argon gas by being cast into alloy cast ingot after high-frequency induction melting, then 1150 DEG C annealing for 24 hours；
(3) under protection of argon gas by alloy melting, then the method for fast melt-quenching is used to prepare La0.75R0.25Fe12Si1.2Alloy casting piece；
(4) alloy casting piece is broken into the powder less than 1mm in protective atmosphere；
(5) alloy powder is subjected to ball milling under a hydrogen atmosphere, the air pressure of hydrogen is 0.6MPa, ratio of grinding media to material 20：1, ball milling Time is 15h.
(6) by powder after ball milling at a temperature of 750 vacuum heat 1 hour.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 35nm, Maximum entropy becomes 12.3J/kgK under the magnetic fields 1.5T.
Embodiment 2
Other are operated with embodiment 1 the present embodiment, the difference is that：The ingredient of alloy is LaFe12Si1.2；
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 37nm, Maximum entropy becomes 8.2J/kgK under the magnetic fields 1.5T.
Embodiment 3
Other are operated with embodiment 1 the present embodiment, the difference is that：The ingredient of alloy is La0.5R0.5Fe12Si1.2；
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 33nm, Maximum entropy becomes 10.1J/kgK under the magnetic fields 1.5T.
Embodiment 4
Other are operated with embodiment 1 the present embodiment, the difference is that：The ingredient of alloy is La0.75R0.25Fe9Si4；
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 35nm, Maximum entropy becomes 5.7J/kgK under the magnetic fields 1.5T.
Embodiment 5
Other are operated with embodiment 1 the present embodiment, the difference is that：The ingredient of alloy is La0.75R0.25Fe12.5Si0.5；
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 37nm, Maximum entropy becomes 5.7J/kgK under the magnetic fields 1.5T.
Embodiment 6
Other are operated with embodiment 1 the present embodiment, the difference is that：Hydrogen pressure is 0.1MPa
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 45nm, Maximum entropy becomes 9.3J/kgK under the magnetic fields 1.5T.
Embodiment 7
Other are operated with embodiment 1 the present embodiment, the difference is that：Hydrogen pressure is 1MPa
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 30nm, Maximum entropy becomes 12.6J/kgK under the magnetic fields 1.5T.
Embodiment 8
Other are operated with embodiment 1 the present embodiment, the difference is that：Ball-milling Time is 25h
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 30nm, Maximum entropy becomes 12.3J/kgK under the magnetic fields 1.5T.
Embodiment 9
Other are operated with embodiment 1 the present embodiment, the difference is that：Ball-milling Time is 10h
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 40nm, Maximum entropy becomes 11.5J/kgK under the magnetic fields 1.5T.
Embodiment 10
Other are operated with embodiment 1 the present embodiment, the difference is that：Ball-milling Time is 4h.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 72nm, Maximum entropy becomes 6.1J/kgK under the magnetic fields 1.5T.
Embodiment 11
Other are operated with embodiment 1 the present embodiment, the difference is that：Abrading-ball is 10 with material weight ratio：1.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 42nm, Maximum entropy becomes 9.5J/kgK under the magnetic fields 1.5T.
Embodiment 12
Other are operated with embodiment 1 the present embodiment, the difference is that：Abrading-ball is 15 with material weight ratio：1.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 40nm, Maximum entropy becomes 9.9J/kgK under the magnetic fields 1.5T.
Embodiment 13
Other are operated with embodiment 1 the present embodiment, the difference is that：Abrading-ball is 30 with material weight ratio：1.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 33nm, Maximum entropy becomes 10.9J/kgK under the magnetic fields 1.5T.
Embodiment 14
Other are operated with embodiment 1 the present embodiment, the difference is that：Heat treatment temperature is 500 DEG C of
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 20nm, Maximum entropy becomes 5.2J/kgK under the magnetic fields 1.5T.
Embodiment 15
Other are operated with embodiment 1 the present embodiment, the difference is that：Heat treatment temperature is 650 DEG C of
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 30nm, Maximum entropy becomes 11.6J/kgK under the magnetic fields 1.5T
Embodiment 16
Other are operated with embodiment 1 the present embodiment, the difference is that：Heat treatment temperature is 900 DEG C.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 80nm, Maximum entropy becomes 9.3J/kgK under the magnetic fields 1.5T.
Embodiment 17
Other are operated with embodiment 1 the present embodiment, the difference is that：Heat treatment temperature is 10 minutes.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 22nm, Maximum entropy becomes 6.4J/kgK under the magnetic fields 1.5T.
Embodiment 18
Other are operated with embodiment 1 the present embodiment, the difference is that：Heat treatment temperature is 2 hours.
The nanocrystalline magnetic fuel factor material that the present embodiment obtains is detected, and the average grain size of material is about 75nm, Maximum entropy becomes 6.2J/kgK under the magnetic fields 1.5T.
Above preferred embodiment is only intended to description and interpretation present disclosure, does not constitute the limit to the content of present invention System.Although inventor has been the present invention and has enumerated in more detail, those skilled in the art is according to invention content Part and the revealed content of embodiment can make described specific embodiment various modifications or/and supplement or adopt To substitute it is obvious with similar mode, and can realizes therefore the technique effect of the present invention no longer repeats one by one herein.This The term occurred in invention is not construed as limiting the invention for elaboration and understanding to technical solution of the present invention.

Claims (8)

1. a kind of nanocrystalline La1-xRxFeySizThe manufacturing method of magnetothermal effect material, it is characterised in that：Preparation section includes melting Process, fast quenching process are flushed with hydrogen ball milling process and heat treatment procedure, and wherein melting process, fast quenching process are under argon gas protection environment It carries out, heat treatment procedure carries out under vacuum conditions.
2. a kind of nanocrystalline La according to claim 1,1-xRxFeySizThe manufacturing method of magnetothermal effect material, feature It is：R is one or several kinds of mixtures in rare earth element, rare earth element include Ce, Pr, Nd, Sm, Te, Dy, Ho, Eu, Er、Tm；The compositing range of each element is：0≤x≤0.5,9≤y≤12.5,0.5≤z≤4.
3. a kind of nanocrystalline La according to claim 1,1-xRxFeySizThe manufacturing method of magnetothermal effect material, feature It is：Fine Texture of Material is made of main phase and crystal boundary, and wherein main phase grain size is 20-80nm, and group becomes La1-xRxFeySi13-y, grain boundary width, which is 1-3nm groups, becomes La1-xRxFeSi。
4. a kind of nanocrystalline La according to claim 1,1-xRxFeySizThe manufacturing method of magnetothermal effect material, feature It is：It is flushed with hydrogen in ball milling process, hydrogen pressure is 0.1-1MPa.
5. a kind of nanocrystalline La according to claim 1,1-xRxFeySizThe manufacturing method of magnetothermal effect material, feature It is：It is flushed with hydrogen in ball milling process, Ball-milling Time 4-25h.
6. a kind of nanocrystalline La according to claim 1,1-xRxFeySizThe manufacturing method of magnetothermal effect material, feature It is：It is flushed with hydrogen in ball milling process, the weight ratio of ball and material is 10:1 to 30:1.
7. a kind of nanocrystalline La according to claim 1,1-xRxFeySizThe manufacturing method of magnetothermal effect material, feature It is：In vacuum heat process, heat treatment temperature is 500-900 DEG C.
8. a kind of nanocrystalline La according to claim 1,1-xRxFeySizThe manufacturing method of magnetothermal effect material, feature It is：In vacuum heat process, heat treatment time is 10 minutes to 2 hours.
CN201810413285.XA 2018-05-03 2018-05-03 Nanocrystalline La1-xRxFeySizMethod for producing magnetocaloric effect material Expired - Fee Related CN108486469B (en)

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