CN104357727B - A kind of Mn-Fe-P-Si magnetic refrigerating material and preparation method thereof - Google Patents
A kind of Mn-Fe-P-Si magnetic refrigerating material and preparation method thereof Download PDFInfo
- Publication number
- CN104357727B CN104357727B CN201410597188.2A CN201410597188A CN104357727B CN 104357727 B CN104357727 B CN 104357727B CN 201410597188 A CN201410597188 A CN 201410597188A CN 104357727 B CN104357727 B CN 104357727B
- Authority
- CN
- China
- Prior art keywords
- alloy
- preparation
- block
- magnetic
- magnetic refrigerating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention belongs to field of magnetic refrigeration material, disclose a kind of Mn Fe P Si magnetic refrigerating material and preparation method thereof, material composition is chosen as Mn1.15Fe0.85P0.52Si0.45B0.03.Preparation method is as follows: (1) mixes after Mn sheet, Fe block, FeP block, Si block and B block being weighed by the mass percent of element each in chemical formula, and wherein Mn adds the surplus of 5%；(2) raw material step (1) prepared loads in vacuum arc furnace ignition, utilizes high-purity argon gas protection melting to prepare alloy pig；(3) alloy pig is crushed, load melted alloy in vacuum quick quenching furnace, carry out copper mold casting；(4) copper mold casting alloy is sealed in quartz ampoule, is evacuated to 10‑4Below Pa, makes annealing treatment, and the most quickly quenches in cold water, prepares magnetic refrigerating material.Present invention process is simple, with low cost, the magnetic refrigerating material that available consistency is high, magnetic heating performance is excellent.
Description
Technical field
The invention belongs to the preparation field of magnetic refrigerating material, be specifically related to a kind of Mn-Fe-P-Si magnetic refrigerating material and system thereof
Preparation Method.
Background technology
Magnetic Refrigeration Technique is with magnetic material as working medium, utilizes the change of spin system magnetic entropy to realize a kind of complete of refrigeration
New Refrigeration Technique.Compared with Compressing Refrigeration, magnetic Refrigeration Technique has compact conformation, energy-efficient, non-environmental-pollution etc.
Many merits, is just becoming the focus of researcher research instantly.Magnetic Refrigeration Technique is at refrigerator, air-conditioning and large-scale food product refrigeration etc.
Field has wide practical use.But magnetic Refrigeration Technique to be achieved, also problems have to be solved, including magnetic field
Design, the selection of kind of refrigeration cycle, the selection of magnetic refrigeration working substance, heat transfer technology etc..It is currently room temperature magnetic refrigerating working material research
With the important stage of exploitation, only select and develop suitable magnetic refrigeration working substance could accelerate to advance the development of magnetic Refrigeration Technique to enter
Journey.
Common room temperature magnetic refrigerating material mainly has heavy rare earth class magnetic refrigerating material, LaFe13-xSixSeries alloy, class calcium titanium
Ore deposit type Mn oxide, Heusler type ferromagnetic material and MnFePSi series alloy.MnFePSi series alloy be the earliest by
MnFePAs alloy development, within 2002, Tegus is found that the giant magnetio-caloric effects of MnFePAs alloy, thus opens research
The gate of MnFePSi series alloy.MnFePSi series alloy is owing to without rare earth element, the prices of raw materials are cheap and source is wide
General, magnetic heating performance is excellent, Curie temperature at the many merits such as near room temperature is adjustable, be room temperature magnetic refrigerating optimal candidate material it
One.
The preparation of existing MnFePSi series alloy uses ball milling-sintering process or flash set technology, both mostly
Preparation technology is required for utilizing highly purified elemental powders as raw material, and this not only greatly improves raw-material cost,
And there is the problem that chemical property is active, oxidizable in powder.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is that offer is a kind of the most efficiently, becomes
This cheap Mn-Fe-P-Si series magnetic refrigerating material.
Another object of the present invention is to provide the preparation method of above-mentioned Mn-Fe-P-Si series magnetic refrigerating material, by moving back
Ignition technique controls the microscopic structure of alloy, thus controls the magnetic heating performance of alloy.
The purpose of the present invention is achieved through the following technical solutions:
A kind of Mn-Fe-P-Si magnetic refrigerating material, chemical formula is Mn1.15Fe0.85P0.52Si0.45B0.03。
The preparation method of described Mn-Fe-P-Si magnetic refrigerating material, comprises the steps:
(1) mix after Mn sheet, Fe block, FeP block, Si block and B block being weighed by the mass percent of element each in chemical formula,
Wherein Mn adds the surplus (suitable with the amount of Mn loss in subsequent technique) of 5%；
(2) raw material step (1) prepared loads in vacuum arc furnace ignition, utilizes high-purity argon gas protection melting to prepare alloy
Ingot；
(3) alloy pig described in step (2) is crushed, take alloy pig and load melted alloy in vacuum quick quenching furnace, utilize copper
Die cast prepares Mn1.15Fe0.85P0.52Si0.45B0.03Alloy bar material；
(4) by the copper mold casting alloy described in step (3), it is sealed in quartz ampoule, is evacuated to 10-4Below Pa, seals
After sample under 1123～1423K, anneal 48～96h, the most quickly quench in cold water, prepare
Mn1.15Fe0.85P0.52Si0.45B0.03Magnetic refrigerating material.
Step (2) described vacuum arc furnace ignition is evacuated to 5 × 10-3Below Pa, is filled with the high-purity argon of 0.03～0.05MPa
Gas, melting number of times is 5 times.
Vacuum quick quenching furnace described in step (3) is evacuated to 8 × 10-4Below Pa, is filled with the high-purity argon of 0.03～0.05MPa
Gas, carries out sensing heating.
Described vacuum quick quenching furnace mode of heating is high-frequency induction heating, utilizes argon pressure reduction melted aluminium alloy spray to be arrived
In copper mold, argon pressure reduction is 0.08～0.1MPa.
The internal diameter of described copper mold is 2mm, and height is 120mm.
Annealing temperature described in step (4) is 1123K, 1223K, 1323K or 1423K, and annealing time is 48h.
Material purity is Fe > 99.8wt.%, Mn > 99.9wt.%, FeP > 98wt.%, Si > 99.9wt.%, B >
99.9wt.%.
The material of described FeP consists of Fe=71.5wt.%, P=26.5wt.%, Si=1.3wt.%, C=
0.36wt.%, Mn=0.31wt.%, S=0.03wt.%.
The present invention use melting-copper mold foundry engieering then use block materials as raw material, raw-material purity requirement
Well below ball milling-sintering or flash set technology.It is possible not only to each component uniform alloy during melt back, and
And have certain refining effect, smelting rear oxide inclusions to be mainly gathered in the surface of ingot casting, it is easy to remove.Melted ingot copper
Relatively fine tissue can be obtained after die cast, the size can organized by control by suitable annealing process, control material
The magnetic heating performance of material.
In actual application aspect, the MnFePSi series alloy bar prepared by melting-copper mold foundry engieering and ball milling-
The band that block materials prepared by sintering process is prepared with flash set technology is compared has obvious advantage.First, melting-copper
The defects such as alloy consistency prepared by die cast technology is higher, less hole make the decay resistance of alloy also be greatly improved；
Secondly, alloy bar material prepared by melting-copper mold foundry engieering is beneficial to clamping, can more conveniently load in magnetic refrigerator and use.
The present invention has such advantages as relative to prior art and effect:
(1) raw material sources used by the present invention is extensive, cheap, and without rare earth element and toxic element, business should
Considerable by prospect；
(2) raw material used by the present invention is block materials, and for dusty material, the cost of block materials is relatively
Low, chemical stability is preferable；
(3) present invention controls the microscopic structure of alloy by changing Technology for Heating Processing, thus prepares magnetic entropy and become big, Curie
Temperatures approach is in the magnetic refrigerating material of room temperature；
(4) present invention can regulate Curie temperature by the composition proportion changing alloy, magnetic entropy becomes and heat stagnation；
(5) the Mn-Fe-P-Si magnetic refrigerating material prepared by the present invention, by changing composition and Technology for Heating Processing, can adjust
Joint Curie temperature, heat stagnation and magnetic entropy become, and composition is Mn1.15Fe0.85P0.52Si0.45B0.03Alloy is annealed after 48h through 1423K, Curie
Temperature is that the magnetic entropy under 251K, 2T external magnetic field uprises and reaches 19.8J/ (kg K)；
(6) the Mn-Fe-P-Si magnetic refrigerating material consistency prepared by the present invention is higher, corrosion resistance preferable, beneficially business
Change application；
(7) preparation method technique of the present invention is simple, with low cost, favorable repeatability, is suitable for producing in enormous quantities.
Accompanying drawing explanation
Fig. 1 is the Mn of embodiment 1 preparation1.15Fe0.85P0.52Si0.45B0.03Alloy XRD figure after different temperatures is annealed.
Fig. 2 is the Mn of embodiment 1 preparation1.15Fe0.85P0.52Si0.45B0.03Alloy metallographic structure after different temperatures is annealed is shone
Sheet, Fig. 2 (a), (b), (c), the annealing temperature of (d) correspondence are respectively 1123K, 1223K, 1323K, 1423K.
Fig. 3 is the Mn of embodiment 1 preparation1.15Fe0.85P0.52Si0.45B0.03Alloy liter gentleness fall after different temperatures is annealed
Temperature M-T curve (applying external magnetic field is 0.05T).
Fig. 4 is the Mn of embodiment 1 preparation1.15Fe0.85P0.52Si0.45B0.03Alloy Curie temperature after different temperatures is annealed is attached
Near isothermal magnetization curve, Fig. 4 (a), (b), (c), annealing temperature that (d) is corresponding be respectively 1123K, 1223K, 1323K,
1423K。
Fig. 5 is the Mn of embodiment 1 preparation1.15Fe0.85P0.52Si0.45B0.03Alloy Curie temperature after different temperatures is annealed
Neighbouring magnetic entropy becomes variation with temperature relation curve.
Fig. 6 is the Mn of embodiment 1 preparation1.15Fe0.85P0.52Si0.45B0.03Alloy polarization after 1223K and 1423K anneals
Curve (corrosive liquid is the NaCl solution of 3.5%).
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of Mn-Fe-P-Si magnetic refrigerating material, its preparation method is as follows:
(1) Mn sheet, Fe block, FeP block, Si block and B block are pressed Mn1.15Fe0.85P0.52Si0.45B0.03The atomic ratio of alloy is joined
Material.Wherein the quality of Mn sheet, Fe block, FeP block, Si block and B block be respectively 4.758g, 0.287g, 4.439g, 0.906g,
0.023g, weighs four parts；
(2) raw material prepared is loaded in vacuum arc furnace ignition, be evacuated to 5 × 10-3Below Pa, be filled with 0.03～
The high-purity argon gas of 0.05MPa, utilizes electric arc melting to prepare alloy pig.In order to ensure each component mix homogeneously, after often having melted once
Upset sample, melt back 5 times；
(3) crush after the alloy pig described in step (2) being removed surface scale, take 5g alloy pig loading lower end and have little
In the quartz ampoule in hole.Quartz ampoule is installed in vacuum quick quenching furnace, is evacuated to 8 × 10-4Below Pa, utilizes high-frequency induction heating
Melted alloy, by melted alloy, under the effect of argon pressure reduction (0.08～0.1MPa), quick spray to cast is to a diameter of 2mm, highly
For in the copper mold of 120mm, prepare Mn1.15Fe0.85P0.52Si0.45B0.03Alloy bar material；
(4) by the copper mold casting alloy described in step (3), it is sealed in quartz ampoule, is evacuated to 10-4Below Pa, seals
After sample (four parts) anneal under 1123K, 1223K, 1323K and 1423K 48h, the most quickly quench in cold water, prepare
Mn1.15Fe0.85P0.52Si0.45B0.03Magnetic refrigerating material (four parts).
Performance test
Mn prepared by above-described embodiment1.15Fe0.85P0.52Si0.45B0.03The structure of alloy and performance, use X-ray diffraction
Instrument, metallurgical microscope, comprehensive physical measurement system etc. characterize and analyze, and are described further below in conjunction with accompanying drawing.
Fig. 1 is Mn1.15Fe0.85P0.52Si0.45B0.03Alloy is after 1123K, 1223K, 1323K and 1423K annealing 48h
XRD figure is composed.Owing to the size of sample is less, so all using powder X-ray diffraction during test.As seen from the figure, the alloy after annealing is equal
Defining biphase, principal phase has hexagonal Mn1.9P-type phase structure, space group isDephasign is hexagonal Mn3Fe2Si3Phase, space
Group is P63/mcm.Along with the rising of annealing temperature, Mn1.9The diffraction peak intensity of p-type principal phase substantially increases, and it is worthy of note
The sample diffraction peak intensity of 1123K annealing is than the sample much weaker of other annealing temperatures, and diffraction maximum exists weak widthization phenomenon,
Illustrate that the sample that lower temperature is annealed exists a small amount of micron brilliant or nanocrystalline.Mn3Fe2Si3The relative amount of phase is with annealing temperature
Change do not change significantly.
Fig. 2 is the Mn after different temperatures annealing1.15Fe0.85P0.52Si0.45B0.03Alloy through wang aqueous solution corrode after micro-
Tissue, it is seen that alloy is primarily present biphase, there is obvious dendrite, along with annealing temperature in the sample of 1123K and 1223K annealing
Rising, arborescent structure fades away, and organizes more uniform.
Fig. 3 is Mn1.15Fe0.85P0.52Si0.45B0.03Alloy liter gentleness cooling M-T curve under 0.05T external magnetic field, in order to
Ensure that alloy starts test when more stable, first stablize 300s after being cooled to 100K and apply magnetic field again and carry out heating-cooling
Test.Slowly, when being warming up to 350K, the intensity of magnetization does not also have the sample intensity of magnetization variation with temperature of visible 1123K annealing
Have and reach 0, illustrate that alloy is not the most completely converted into paramagnetic state.Additionally, the ferromagnetic-paramagnetic transition temperature of this alloy is also the most slow
Slowly.But, along with the rising of annealing temperature, rise gentle temperature lowering curve and all become more and more steep, illustrate that ferromagnetic-paramagnetic transition is more
Come the most obvious.Calculating shows, the Curie temperature of alloy is linearly increasing with the rising of annealing temperature, the 205K when 1123K anneals
It is increased to 251K during 1423K annealing.Rise gentleness cooling M-T curve misaligned, illustrate that alloy exists certain heat stagnation, alloy
Heat stagnation reduce with the rising of annealing temperature, along with annealing temperature is increased to 1423K by 1223K, heat stagnation is reduced to from 17K
10.5K.This is that the sample composition after annealing due to higher temperature is more uniform, defect is less, internal stress also decreases, so
Heat stagnation is relatively low.Mn1.15Fe0.85P0.52Si0.45B0.03The Curie temperature of alloy and the detailed data of heat stagnation are shown in Table 1.
Fig. 4 is Mn1.15Fe0.85P0.52Si0.45B0.03The isothermal magnetization curve of alloy, Fig. 4 (a), (b), (c), (d) are corresponding
Annealing temperature is respectively 1123K, 1223K, 1323K, 1423K.During test, TCNeighbouring temperature interval takes 2K, away from TCBetween place's temperature
Every taking 5K, 10K.As seen from the figure, alloy is at low temperatures in obvious ferromagnetism, and the intensity of magnetization tends to saturated under 2T substantially, with
The rising generation ferromagnetism temperature changes to paramagnetism.But, 1123K annealing sample ferromagnetic-paramagnetic transition slowly,
Complete paramagnetic state is not the most become when 270K.1323K annealing and the sample of 1423K annealing, occur near Curie temperature
Obvious field mutagens magnetic transition.
Fig. 5 is the Mn of different temperatures annealing1.15Fe0.85P0.52Si0.45B0.03Alloy is under 0-1T and 0-2T external magnetic field changes
(-Δ SM)-T curve.According to Maxwell relational expression can derive isothermal magnetic entropy become computing formula:Continuous integral is melted into discrete sum formula again, i.e. may utilize isothermal M-H curve meter
The magnetic entropy calculating alloy becomes.Increasing as it is shown in figure 5, the isothermal magnetic entropy of alloy becomes with the rising of annealing temperature, detailed data is listed in
Table 1.Under 2T external magnetic field, sample is after 1123K, 1223K, 1323K and 1423K anneal, and maximum isothermal magnetic entropy becomes respectively
0.6,5.0,19.1 and 19.8J kg-1K-1.The magnetic sample Entropy Changes of 1123K annealing is the least, but closes after higher temperature is annealed
The magnetic entropy of gold becomes and increases rapidly, and after annealing temperature is more than 1323K, magnetic entropy change is held essentially constant.XRD analysis table above
Bright, the alloy of different temperatures annealing is respectively provided with Mn1.9P-type hexagonal structure, although phase structure does not change, but magnetic entropy becomes but to be deposited
In the biggest difference, illustrating to may have occurred in annealing process the change of phase composition, the atom in principal phase and dephasign is in annealing process
In there occurs diffusion.
Fig. 6 is 1223K and the Mn of 1423K annealing1.15Fe0.85P0.52Si0.45B0.03Alloy and pure Gd are at 3.5%NaCl solution
In polarization curve.Visible Mn1.15Fe0.85P0.52Si0.45B0.03The corrosion current density of alloy is well below pure Gd, from corrosion
Current potential is also high than pure Gd.Gd is E in 3.5%NaCl solutioncorrFor-1.493V, JcorrIt is 322.6 μ A/cm2, than pure Gd in distillation
Very different (the E of corrosion resistance in watercorr=-1.269V, Jcorr=1.072 μ A/cm2).The alloy of 1223K, 1423K annealing
EcorrAnd JcorrIt is respectively-0.372V, 0.904 μ A/cm2With-0.294V, 0.866 μ A/cm2.The alloy of 1423K annealing is corrosion-resistant
Increasing and be because after higher temperature is annealed, the tissue in alloy is more uniform, defect reduces.
Mn1.15Fe0.85P0.52Si0.45B0.03The corrosion resistance of alloy substantially can be comparable with general rustless steel, is the most promising
Room temperature magnetic refrigerating material.
The magnetic property data summarization of table 1 Mn-Fe-P-Si alloy
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (9)
1. the preparation method of a Mn-Fe-P-Si magnetic refrigerating material, it is characterised in that comprise the steps:
(1) Mn sheet, Fe block, FeP block, Si block and B block are pressed chemical formula Mn1.15Fe0.85P0.52Si0.45B0.03In the quality of each element
Percentage ratio mixes after weighing, and wherein Mn adds the surplus of 5%；
(2) raw material step (1) prepared loads in vacuum arc furnace ignition, utilizes high-purity argon gas protection melting to prepare alloy pig；
(3) alloy pig described in step (2) is crushed, take alloy pig and load melted alloy in vacuum quick quenching furnace, utilize copper mold to cast
Make prepared Mn1.15Fe0.85P0.52Si0.45B0.03Alloy bar material；
(4) by the copper mold casting alloy described in step (3), it is sealed in quartz ampoule, is evacuated to 10-4Below Pa, after sealing
Sample anneals 48～96h under 1123～1423K, the most quickly quenches in cold water, prepares Mn1.15Fe0.85P0.52Si0.45B0.03Magnetic
Refrigerating material.
Preparation method the most according to claim 1, it is characterised in that step (2) described vacuum arc furnace ignition is evacuated to 5 ×
10-3Below Pa, is filled with the high-purity argon gas of 0.03～0.05MPa, and melting number of times is 5 times.
Preparation method the most according to claim 1, it is characterised in that the vacuum quick quenching furnace described in step (3) is evacuated to 8
×10-4Below Pa, is filled with the high-purity argon gas of 0.03～0.05MPa, carries out sensing heating.
Preparation method the most according to claim 3, it is characterised in that described vacuum quick quenching furnace mode of heating is high-frequency induction
Heating, utilizes argon pressure reduction by melted aluminium alloy spray to copper mold, and argon pressure reduction is 0.08～0.1MPa.
Preparation method the most according to claim 1, it is characterised in that the internal diameter of described copper mold is 2mm, height is 120mm.
6. according to the preparation method described in claim 1 or 2 or 3 or 4 or 5, it is characterised in that the annealing temperature described in step (4)
Degree is 1123K, 1223K, 1323K or 1423K, and annealing time is 48h.
7. according to the preparation method described in claim 1 or 2 or 3 or 4 or 5, it is characterised in that material purity is Fe >
99.8wt.%, Mn > 99.9wt.%, FeP > 98wt.%, Si > 99.9wt.%, B > 99.9wt.%.
Preparation method the most according to claim 7, it is characterised in that the material of described FeP consists of Fe=
71.5wt.%, P=26.5wt.%, Si=1.3wt.%, C=0.36wt.%, Mn=0.31wt.%, S=0.03wt.%.
9. the Mn-Fe-P-Si magnetic refrigerating material that method described in any one of claim 1～8 prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410597188.2A CN104357727B (en) | 2014-10-29 | 2014-10-29 | A kind of Mn-Fe-P-Si magnetic refrigerating material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410597188.2A CN104357727B (en) | 2014-10-29 | 2014-10-29 | A kind of Mn-Fe-P-Si magnetic refrigerating material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104357727A CN104357727A (en) | 2015-02-18 |
| CN104357727B true CN104357727B (en) | 2016-10-05 |
Family
ID=52525032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410597188.2A Expired - Fee Related CN104357727B (en) | 2014-10-29 | 2014-10-29 | A kind of Mn-Fe-P-Si magnetic refrigerating material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104357727B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190042679A (en) * | 2016-08-31 | 2019-04-24 | 바스프 에스이 | How to controllably change the parameters of a magnetocaloric material |
| CN108642355B (en) * | 2018-05-17 | 2019-11-22 | 内蒙古科技大学 | A kind of iron-based room temperature magnetic refrigerating material of manganese and preparation method thereof |
| CN110364324B (en) * | 2019-06-19 | 2021-07-06 | 南京理工大学 | Mn-Fe-P-Si based magnetic refrigeration material with low thermal hysteresis and preparation method thereof |
| CN110449585A (en) * | 2019-08-29 | 2019-11-15 | 华南理工大学 | A kind of Mn base magnetic refrigeration composite material and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881393B (en) * | 2012-09-11 | 2016-06-22 | 华南理工大学 | A kind of MnFePSi basal cell temperature magnetic refrigerating material and preparation method thereof |
-
2014
- 2014-10-29 CN CN201410597188.2A patent/CN104357727B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104357727A (en) | 2015-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103611896B (en) | A kind of method being prepared MnCoGe base and MnNiGe base alloy thin band by electric arc melting and fast melt-quenching | |
| CN104357727B (en) | A kind of Mn-Fe-P-Si magnetic refrigerating material and preparation method thereof | |
| CN109108227B (en) | High-flux preparation method of LaFeSi-based magnetic refrigeration material | |
| Zhou et al. | Hydrogen storage properties and thermal stability of V35Ti20Cr45 alloy by heat treatment | |
| CN103710605B (en) | A kind of ferromagnetic Martensitic Transformation Materials of MnCoGe base with big Entropy Changes and preparation method and purposes | |
| Wu et al. | Magnetocaloric effect of Fe25Co25Ni25Mo5P10B10 high-entropy bulk metallic glass | |
| CN108300882B (en) | Method for realizing magnetic structure coupling phase change in MnCoGe base alloy | |
| CN106917042A (en) | A kind of high frequency high magnetic flux density Fe-based nanocrystalline magnetically soft alloy and preparation method thereof | |
| CN106947925A (en) | A kind of Zr base block amorphous alloys and its preparation method and application | |
| Luo et al. | Magnetocaloric effect of melt-extracted high-entropy Gd19Tb19Er18Fe19Al25 amorphous microwires | |
| CN103502497B (en) | Magnetic refrigerating material | |
| Lu et al. | Excellent magnetocaloric effect of a Gd55Al20Co25 bulk metallic glass | |
| Wu et al. | LaFe11. 6Si1. 4/Pr40Co60 magnetocaloric composites for refrigeration near room temperature | |
| Dong et al. | Microstructure and magnetocaloric properties of melt-extracted La–Fe–Si microwires | |
| Liu et al. | Improving the refrigeration capacity of Gd-rich wires through Fe-doping | |
| Liu et al. | Near room-temperature magnetocaloric effect of Co-based bulk metallic glass | |
| Mo et al. | Table-like magnetocaloric effect and enhanced refrigerant capacity in crystalline Gd55Co35Mn10 alloy melt spun ribbons | |
| Alouhmy et al. | Effects of hydrogen implantation on the magnetocaloric properties of amorphous FeZr films | |
| CN101923933B (en) | Hydrogenated NiMn-based alloy magnetic refrigeration material and preparation method and use thereof | |
| CN103031501B (en) | Erbium base amorphous composite magnetic cold-storage material and preparation method thereof, Cryo Refrigerator | |
| CN110616386B (en) | High magnetocaloric effect rare earth based high-entropy amorphous alloy and preparation method thereof | |
| CN106191616A (en) | A kind of magnetic phase transition alloy | |
| CN106929775A (en) | Large-amorphous forming capacity magnetothermal effect gadolinium base block amorphous alloy high and preparation method | |
| Chen et al. | Microstructure evolution and accelerated magnetocaloric phase formation of LaFe13. 1Co0. 7Si1. 4 alloy by forging deformation at room temperature | |
| CN102978422B (en) | Preparation method and application of rare earth-nickel-silicon material with large magnetothermal effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161005 Termination date: 20211029 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |