CN106270425B - A kind of magnetic refrigerating material mass production preparation method - Google Patents
A kind of magnetic refrigerating material mass production preparation method Download PDFInfo
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- CN106270425B CN106270425B CN201610656053.8A CN201610656053A CN106270425B CN 106270425 B CN106270425 B CN 106270425B CN 201610656053 A CN201610656053 A CN 201610656053A CN 106270425 B CN106270425 B CN 106270425B
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 41
- 239000000956 alloy Substances 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 230000006698 induction Effects 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005266 casting Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000005389 magnetism Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- 230000000171 quenching effect Effects 0.000 description 5
- 239000005457 ice water Substances 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 241000238366 Cephalopoda Species 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000007578 melt-quenching technique Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
-
- 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
-
- 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
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
-
- 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
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
Abstract
The invention discloses a kind of magnetic refrigerating material mass production preparation methods, comprise the following steps：(1) by 11~13%La, 5~6%Ce, 1~2%Mn, 4.5~5.5%Si, the mass percentage proportioning that surplus is Fe carries out dispensing, obtains LaCeFeMnSi alloys；(2) LaCeFeMnSi alloys are placed in vacuum induction rapid hardening furnace after melting, cast rapid hardening alloy thin band through chill roll speed；(3) rapid hardening alloy thin band after cooling is placed in vacuum tube furnace, is evacuated to 1 × 10‑4~1 × 10‑21000~1200 DEG C of 2~4h of heat treatment are heated to after Pa；(4) calandria is directly released to stopping heating, vacuum tube is carried out air-cooled to after room temperature, to the rapid hardening alloy thin band in step (3) be flushed with hydrogen processing to get with NaZn13Type structure, Curie temperature are 10~20 DEG C of magnetic refrigerating material.Present invention process step is simple, easily implements, and at low cost, efficient, yield is big, easily promotes.
Description
Technical field
The present invention relates to a kind of preparation methods of magnetic refrigerating material, are prepared more particularly, to a kind of magnetic refrigerating material mass production
Method.
Background technology
With increasingly sharpening for environmental pollution especially greenhouse effects, the getting worse of haze, there is a growing awareness that
The importance of environmental protection, energy consumption also increasingly allow people to feel the danger of lack of energy.And refrigeration industry
Energy consumption accounts for 15%~20% or so of social total energy consumption, and its refrigeration working medium produced pollution object causes temperature
Room effect.Not only efficiency is low for traditional compressor cooling, and noise is big, and seriously polluted.
And magnetic Refrigeration Technique then has environmentally friendly, energy-efficient, low noise etc. a little, is very promising solid-state system
Cold mode, alternative compressor cooling.Currently used magnetic refrigerating material mainly have LaFeSi systems alloy, Gd systems alloy,
MnFePAs systems alloy etc., wherein LaFeSi systems alloy become due to the features such as its preparation of low cost, nontoxic, easy most application
The magnetic refrigerating material of prospect.2006, LaFeSi systems magnetic refrigerating material was used for magnetic system by American National Astrotech Facility for the first time
In cold, its performance of the results show is better than traditional magnetic refrigerating material Gd.
Although LaFeSi systems magnetic refrigerating material self-discovery acts the research progress for having had the more than ten years, to its side of preparation
The research of method is always one of research emphasis of people.Patent of invention CN1140646C by vacuum arc furnace melting ingot casting, and
Will at alloy cast ingot again 900~1100 DEG C anneal a couple of days after in liquid nitrogen quenching obtain with due to metal gadolinium performance rare earth-
Iron-based (Rx(Fe1-yMy)100-x) compound.Patent of invention CN1236096C substitutes system by rare earth element and transition element
For La1-xRx(Fe1-yMy)13-zSizCαMagnetic refrigerating material, and heat treatment work is shortened using quick quenching furnace preparation for high C alloy
Skill.101554993 B of patent of invention CN adjust the Curie temperature of magnetic refrigerating material near room temperature by the method for hydrogenation.Hair
Bright patent CN101157484A by carrying out high temperature, short time heat treatment together for (1200~1400 DEG C) at very high temperatures by ingot casting
Sample obtains the LaFeSi systems magnetic refrigerating material with magnetothermal effect.
Although the above method can prepare LaFeSi systems magnetic refrigerating material, its preparation method is usually electric arc melting
It in high temperature long heat treatment and then is quenched in ice water or liquid nitrogen, is had after small ingot casting is carried out vacuum sealing tube afterwards
NaZn13The material of phase, material purity is high, heat treatment time length just determines that its is of high cost, efficiency is low, and in quenching process
The easy fragmentation of vacuum tube, yield rate are low.
And one of maximum factor for restricting its commercial applications, in addition to of high cost, small scale is also important original
Cause.Due to the limitation of arc-melting furnace in itself, sample preparation only has several grams to tens of grams.103540835 A of patent of invention CN
By electromagnetic induction melting alloy cast ingot, the magnetic refrigerating material of feather weight is obtained, is improved in scale, to magnetic system
The commercialization of cold material has stepped an important step again.
Patent of invention WO2004/03805A1 and CN100567543C obtains thin ribbon shaped sample by fast melt-quenching with chilling method
Product substantially reduce heat treatment time, improve efficiency.
In order to realize the commercialization of magnetic refrigerating material, it is of high cost, amount is small, heat treatment time is long, efficiency is low etc. be all there is an urgent need for
It solves the problems, such as.And it is quenched to after high temperature long heat treatment in liquid nitrogen or ice water and prepares magnetic refrigeration material for mass production
Material comes very difficult.
The content of the invention
The present invention is to solve of high cost, small, the hot place of amount present in the magnetic refrigerating material preparation method of the prior art
Manage that the time is long, the problem of efficiency is low, it is simple to provide a kind of processing step, easily implements, at low cost, efficient, yield is big, easily pushes away
Wide magnetic refrigerating material mass production preparation method.
To achieve these goals, the present invention uses following technical scheme：
A kind of magnetic refrigerating material mass production preparation method of the present invention, comprises the following steps：
(1) by 11~13%La, 5~6%Ce, 1~2%Mn, 4.5~5.5%Si, surplus is the mass percentage of Fe
Proportioning carries out dispensing, obtains LaCeFeMnSi alloys.
(2) LaCeFeMnSi alloys are placed in vacuum induction rapid hardening furnace after melting, cast rapid hardening alloy through chill roll speed
Strip.
(3) rapid hardening alloy thin band after cooling is placed in vacuum tube furnace, is evacuated to 1 × 10-4~1 × 10-2Add after Pa
Heat to 1000~1200 DEG C heat treatment 2~4h.Heat treatment time is substantially reduced in the present invention, improves production efficiency.
(4) calandria is directly released to stopping heating, vacuum tube is carried out it is air-cooled to after room temperature, to the speed in step (3)
Solidifying alloy thin band be flushed with hydrogen processing to get with NaZn13Type structure, Curie temperature are -10~20 DEG C of magnetic refrigerating material.Heat
Not using the form of ice water or Quenching in liquid nitrogen after processing, but directly calandria is released, stops heating, to vacuum tube into
Sector-style is cold, is ensureing to obtain NaZn13While type structure, reduce the possibility that product fragmentation is waste product.
Raw metal is directly using industrial pure material in the present invention, and raw material is easy to get and at low cost, passes through rapid casting technology
And heat treatment process can be mass magnetic refrigerating material, possess the features such as energy-efficient, inexpensive, mass production.
Preferably, in step (2), chill roll roller is fast for 40~50m/s, cooling velocity 103~104℃/s.In rapid hardening
In strip technology, different rollers speed and its microscopic structure of cooling velocity cause poor performance alienation notable there are larger difference, because
This, in rapid casting technique, it is important to rationally design roller speed and cooling velocity so as to the rapid casting of performance needed for acquisition.
Preferably, in step (2), the thickness of rapid hardening alloy thin band is 0.2~0.4mm.
Preferably, the addition of rapid hardening alloy thin band is controlled in 1~5Kg in vacuum tube furnace.
Therefore, the invention has the advantages that：
(1) directly using industrial pure material, raw material is easy to get and at low cost raw metal, passes through rapid casting skill in the present invention
Art and heat treatment process can be mass magnetic refrigerating material, have processing step simple, easily implement, at low cost, efficient, production
Amount is big, and the features such as easily popularization, the Curie temperature of product is -10~20 DEG C；
(2) not using the form of ice water or Quenching in liquid nitrogen after being heat-treated, but directly calandria is released, stops adding
Heat, it is air-cooled to vacuum tube progress, ensureing to obtain NaZn13While type structure, reduce the possibility that product fragmentation is waste product.
Description of the drawings
Fig. 1 is the XRD test results that magnetic refrigerating material is made in embodiment 1.
Fig. 2 is the M-H curves that magnetic refrigerating material is made in embodiment 1.
Fig. 3 is-△ S-T curves made from embodiment 1.
Fig. 4 is the XRD test results that magnetic refrigerating material is made in embodiment 2.
Fig. 5 is the M-H curves that magnetic refrigerating material is made in embodiment 2.
Fig. 6 is-△ S-T curves made from embodiment 2.
Fig. 7 is the XRD test results that magnetic refrigerating material is made in embodiment 3.
Fig. 8 is the M-H curves that magnetic refrigerating material is made in embodiment 3.
Fig. 9 is-△ S-T curves made from embodiment 3.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.
Embodiment 1
(1) by 11%La, 5%Ce, 1%Mn, 4.5%Si, the mass percentage proportioning that surplus is Fe carries out dispensing, obtains
LaCeFeMnSi alloys；
(2) LaCeFeMnSi alloys are placed in vacuum induction rapid hardening furnace after melting, casting thickness through chill roll speed is
The rapid hardening alloy thin band of 0.2mm, chill roll roller are fast for 40m/s, cooling velocity 103℃/s；
(3) rapid hardening alloy thin band after cooling is placed in vacuum tube furnace, the addition 1Kg of rapid hardening alloy thin band takes out true
Sky is to 1 × 10-41000 DEG C of heat treatment 4h are heated to after Pa；
(4) calandria is directly released to stopping heating, vacuum tube is carried out it is air-cooled to after room temperature, to the speed in step (3)
Solidifying alloy thin band be flushed with hydrogen processing to get with NaZn13Type structure, Curie temperature are 16 DEG C of magnetic refrigerating material.
XRD tests are carried out to obtained magnetic refrigerating material, test result is as shown in Figure 1.
Magnetism testing is carried out to obtained magnetic refrigerating material using magnetism testing equipment SQUID, gained M-H curves are such as
It is as shown in Figure 3 according to Maxwell equations and the computable sample-△ S-T curves of M-H curves shown in Fig. 2.
According to institute's result of calculation, the Curie temperature of sample is 16 DEG C, and sample maximum magnetic entropy variable under 1T is
5.9J·kg-1·K-1, maximum magnetic entropy variable is 9.5Jkg under 2T-1·K-1。
Embodiment 2
(1) by 12.46%La, 5.44%Ce, 1.45%Mn, 5.04%Si, the mass percentage that surplus is Fe matches
Dispensing is carried out, obtains LaCeFeMnSi alloys；
(2) LaCeFeMnSi alloys are placed in vacuum induction rapid hardening furnace after melting, casting thickness through chill roll speed is
The rapid hardening alloy thin band of 0.3mm, chill roll roller speed are 45m/s, cooling velocity 5*103℃/s；
(3) rapid hardening alloy thin band after cooling is placed in vacuum tube furnace, the addition 3Kg of rapid hardening alloy thin band takes out true
Sky is to 1 × 10-31100 DEG C of heat treatment 3h are heated to after Pa；
(4) calandria is directly released to stopping heating, vacuum tube is carried out it is air-cooled to after room temperature, to the speed in step (3)
Solidifying alloy thin band be flushed with hydrogen processing to get with NaZn13Type structure, Curie temperature are 10 DEG C of magnetic refrigerating material.
XRD tests are carried out to obtained magnetic refrigerating material, test result is as shown in Figure 4.
Magnetism testing is carried out to obtained magnetic refrigerating material using magnetism testing equipment SQUID, gained M-H curves are such as
It is as shown in Figure 6 according to Maxwell equations and the computable sample-△ S-T curves of M-H curves shown in Fig. 5.It is tied according to calculating
Fruit understands that the Curie temperature of sample is 10 DEG C, and sample maximum magnetic entropy variable under 1T is 9.3Jkg-1·K-1, maximum magnetic flux under 2T
Entropy Changes is 13.4Jkg-1·K-1。
Embodiment 3
(1) by 13%La, 6%Ce, 2%Mn, 5.5%Si, the mass percentage proportioning that surplus is Fe carries out dispensing, obtains
LaCeFeMnSi alloys；
(2) LaCeFeMnSi alloys are placed in vacuum induction rapid hardening furnace after melting, casting thickness through chill roll speed is
The rapid hardening alloy thin band of 0.4mm, chill roll roller are fast for 50m/s, cooling velocity 104℃/s；
(3) rapid hardening alloy thin band after cooling is placed in vacuum tube furnace, the addition 5Kg of rapid hardening alloy thin band takes out true
Sky is to 1 × 10-21200 DEG C of heat treatment 4h are heated to after Pa；
(4) calandria is directly released to stopping heating, vacuum tube is carried out it is air-cooled to after room temperature, to the speed in step (3)
Solidifying alloy thin band be flushed with hydrogen processing to get with NaZn13Type structure, Curie temperature are -10 DEG C of magnetic refrigerating material.
XRD tests are carried out to obtained magnetic refrigerating material, test result is as shown in Figure 7.
Magnetism testing is carried out to obtained magnetic refrigerating material using magnetism testing equipment SQUID, gained M-H curves are such as
It is as shown in Figure 9 according to Maxwell equations and the computable sample-△ S-T curves of M-H curves shown in Fig. 8.It is tied according to calculating
Fruit understands that the Curie temperature of sample is -10 DEG C, and sample maximum magnetic entropy variable under 1T is 5.2Jkg-1·K-1, it is maximum under 2T
Magnetic entropy becomes 9.2Jkg-1·K-1。
Embodiment described above is a kind of preferable scheme of the present invention, and not the present invention is made in any form
Limitation also has other variants and remodeling on the premise of without departing from the technical solution recorded in claim.
Claims (3)
1. a kind of magnetic refrigerating material mass production preparation method, which is characterized in that comprise the following steps：
（1）By 11~13%La, 5~6%Ce, 1~2%Mn, 4.5~5.5%Si, the mass percentage that surplus is Fe matches
Dispensing is carried out, obtains LaCeFeMnSi alloys；
（2）LaCeFeMnSi alloys are placed in vacuum induction rapid hardening furnace after melting, cast rapid hardening alloy thin band through chill roll speed,
Chill roll roller speed is 40~50m/s, and cooling velocity is 103~104 DEG C/s；
（3）Rapid hardening alloy thin band after cooling is placed in vacuum tube furnace, is heated after being evacuated to 1 × 10-4~1 × 10-2Pa
To 1000~1200 DEG C of 2~4h of heat treatment；
（4）Calandria is directly released to stopping heating, vacuum tube is carried out it is air-cooled to after room temperature, to step（3）In rapid hardening close
Golden strip be flushed with hydrogen processing to get with NaZn13Type structure, Curie temperature are -10~20 DEG C of magnetic refrigerating material.
A kind of 2. magnetic refrigerating material mass production preparation method according to claim 1, which is characterized in that step（2）In, speed
The thickness of solidifying alloy thin band is 0.2~0.4mm.
3. a kind of magnetic refrigerating material mass production preparation method according to claim 1, which is characterized in that in vacuum tube furnace
The addition of rapid hardening alloy thin band is controlled in 1~5Kg.
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| CN108467928B (en) * | 2018-03-02 | 2020-01-10 | 横店集团东磁股份有限公司 | Method for improving half-height width of magnetic entropy variation curve of LaFeSi alloy magnetic refrigeration material |
| CN109023145A (en) * | 2018-08-08 | 2018-12-18 | 横店集团东磁股份有限公司 | A kind of the Curie temperature regulation method and preparation method of LaFeSi base magnetic refrigerating material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61248401A (en) * | 1985-04-25 | 1986-11-05 | Mitsubishi Steel Mfg Co Ltd | Heat treatment of magnetic material |
| CN1837393A (en) * | 2005-03-24 | 2006-09-27 | 株式会社东芝 | Magnetic refrigeration material and method of manufacturing thereof |
| CN101368243A (en) * | 2008-09-24 | 2009-02-18 | 上海大学 | Production method for magnetic refrigeration working medium material Y2Fe17 at room temperature |
| CN101554993A (en) * | 2009-05-19 | 2009-10-14 | 北京科技大学 | Method for preparing large magnetic entropy material hydride with main phase of NaZn13 type structure |
| CN101906563A (en) * | 2010-08-31 | 2010-12-08 | 沈阳理工大学 | Preparation method of MnAsP compound with efficient room temperature magnetic refrigeration performance |
| CN105314598A (en) * | 2015-11-24 | 2016-02-10 | 沈阳理工大学 | A high-pressure synthesis method for flaky La (Fe, si)13-based hydride bulk material with high-efficiency room-temperature magnetic refrigeration performance |
-
2016
- 2016-08-10 CN CN201610656053.8A patent/CN106270425B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61248401A (en) * | 1985-04-25 | 1986-11-05 | Mitsubishi Steel Mfg Co Ltd | Heat treatment of magnetic material |
| CN1837393A (en) * | 2005-03-24 | 2006-09-27 | 株式会社东芝 | Magnetic refrigeration material and method of manufacturing thereof |
| CN101368243A (en) * | 2008-09-24 | 2009-02-18 | 上海大学 | Production method for magnetic refrigeration working medium material Y2Fe17 at room temperature |
| CN101554993A (en) * | 2009-05-19 | 2009-10-14 | 北京科技大学 | Method for preparing large magnetic entropy material hydride with main phase of NaZn13 type structure |
| CN101906563A (en) * | 2010-08-31 | 2010-12-08 | 沈阳理工大学 | Preparation method of MnAsP compound with efficient room temperature magnetic refrigeration performance |
| CN105314598A (en) * | 2015-11-24 | 2016-02-10 | 沈阳理工大学 | A high-pressure synthesis method for flaky La (Fe, si)13-based hydride bulk material with high-efficiency room-temperature magnetic refrigeration performance |
Non-Patent Citations (1)
| Title |
|---|
| 熔体快淬LaFe11.5Si1.5的巨大熵变;谢鲲 等;《稀有金属材料与工程》;20051231;第2和第4节 * |
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