CN102864356B - Rare earth-nickel material and preparation method and application thereof - Google Patents
Rare earth-nickel material and preparation method and application thereof Download PDFInfo
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- CN102864356B CN102864356B CN201110190323.8A CN201110190323A CN102864356B CN 102864356 B CN102864356 B CN 102864356B CN 201110190323 A CN201110190323 A CN 201110190323A CN 102864356 B CN102864356 B CN 102864356B
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- 239000000463 material Substances 0.000 title claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 238000005057 refrigeration Methods 0.000 claims abstract description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000010891 electric arc Methods 0.000 claims abstract description 6
- 230000006698 induction Effects 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract 1
- 230000007704 transition Effects 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 230000005415 magnetization Effects 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 229910017028 MnSi Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 241000238366 Cephalopoda Species 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052774 Proactinium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
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- Hard Magnetic Materials (AREA)
Abstract
本发明提供了一种稀土-镍材料及其制备方法和用途，该材料为以下通式化合物中的一种或它们的混合物：R3Ni2，其中R为Ho或Er；所述材料具有Er3Ni2型R心三角晶系结构。本发明还提供了制备上述稀土-镍材料的方法，该方法包括(1)按R3Ni2的化学式称料，将R、Ni原料混合，其中R为Ho或Er；(2)将混合得到的原料放入电弧炉或感应加热炉中，抽真空至3×10-3Pa以上，用氩气清洗并熔炼，熔炼温度为1500℃以上，冷却得到铸态合金；(3)对该铸态合金进行真空退火处理，然后快速冷却。所述稀土-镍材料可用于磁制冷，例如可作为磁制冷工质。
The invention provides a rare earth-nickel material and its preparation method and application. The material is one of the compounds of the following general formula or a mixture thereof: R 3 Ni 2 , wherein R is Ho or Er; the material has Er 3 Ni 2 -type R-centered triangular crystal structure. The present invention also provides a method for preparing the above-mentioned rare earth-nickel material, which method includes (1) weighing according to the chemical formula of R3Ni2 , mixing R and Ni raw materials, wherein R is Ho or Er; (2) mixing to obtain Put the raw materials into an electric arc furnace or an induction heating furnace, evacuate to above 3×10 -3 Pa, wash and melt with argon, the melting temperature is above 1500°C, and cool to obtain an as-cast alloy; (3) the as-cast alloy The alloy is vacuum annealed and then rapidly cooled. The rare earth-nickel material can be used for magnetic refrigeration, for example, it can be used as a magnetic refrigeration working medium.
Description
Technical field
The present invention relates to a kind of magnetic refrigerating material, relate in particular to a kind of rare earth-nickel material and its production and use.
Background technology
The world today, Refrigeration & Cryogenic Technique is related to numerous key areas of national economy, and mankind's energy has nearly 1/3rd to consume in refrigeration, and therefore the situation of Refrigeration Technique just seems very important to human survival and Sustainable development.Tradition gas compression Refrigeration Technique has been widely used in all trades and professions, but it exists, refrigerating efficiency is low, energy consumption large, destroy the shortcomings such as atmospheric environment.Magnetic Refrigeration Technique refers to a kind of New Refrigerating technology taking magneticsubstance as refrigeration working medium, its refrigeration principle is the magnetothermal effect by means of magnetic refrigerating material, under isothermal condition, in the time that magneticstrength increases (magnetization), the magnetic moment of magnetic refrigeration working substance is tending towards ordered arrangement, magnetic entropy reduces, to extraneous heat extraction; In the time that the specific magnetising moment weakens (demagnetization), magnetic moment is tending towards lack of alignment, and magnetic entropy increases, and magnetic refrigeration working substance absorbs heat from the external world, thereby reaches the object of refrigeration.Compared with traditional gas compression Refrigeration Technique, it has energy-efficient, environmental protection, the significant advantage such as reliable and stable, is described as high-new green refrigeration technology.
Conventionally, the parameter of measurement magnetic refrigerating material magnetic heating performance is mainly that magnetic entropy becomes and magnetic refrigerant capacity (be RC, refer to transferable heat in a refrigeration cycle).Divide by operation temperature area, magnetic refrigerating material can be divided into low temperature (15K is following), middle temperature (15K～77K) and high temperature (more than 77K) magnetic refrigerating material.Wherein, in, cold zone magnetic refrigerating material can be applicable to the aspect such as nitrogen, liquefaction of hydrogen and is subject to the extensive concern of domestic and international research institution and branch of industry because of it.Conventionally, the material with first-order phase transition character can show large magnetothermal effect, but meanwhile also can be accompanied by the appearance of heat stagnation and magnetic hysteresis, thereby has reduced the refrigeration capacity of material.Therefore, to have the New Magnetic Field Controlled refrigerating material of magnetic thermal reversibility and high refrigeration capacity under low temperature be the emphasis of studying from now in development.
At present, the magnetic refrigerating material of finding in this warm area research mainly comprises rare earth element monocrystalline, polycrystalline material, and as Nd, Er or Tm, and rare earth intermetallic compound, as RCoAl (R=Gd, Tb, Dy, Ho, Gd
0.5dy
0.25er
0.25), RNiAl (R=Gd, Tb, Dy, Ho, Gd
1-xer
x), TbCoC
2, and without intermetallic compound MnSi of rare earth element etc.But, because the magnetic heating performance of above-mentioned magnetic refrigerating material is also lower, its commercial applications is restricted.
Summary of the invention
The object of the invention is to overcome above-mentioned defect of the prior art, magnetic refrigerating material of a kind of magnetic heating performance excellence and its production and use is provided.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
The invention provides a kind of rare earth-nickel material, this material is a kind of in following general formula compound or their mixture: R
3ni
2, wherein R is Ho or Er.
As preferably, described rare earth-nickel material has Er
3ni
2type R heart trigonal system structure.
As preferably, described rare earth-nickel material is 1: 1～2 Ho by mass ratio
3ni
2and Er
3ni
2composition, the Ho that most preferably mass ratio is 2: 3
3ni
2and Er
3ni
2composition, can provide higher refrigeration capacity thus.
The present invention also provides the preparation method of described rare earth-nickel material, and the method comprises: (1) is by R
3ni
2chemical formula weighing, R, Ni raw material are mixed, wherein R is Ho or Er; (2) raw material being mixed to get is put into electric arc furnace or induction heater, be evacuated to 3 × 10
-3more than Pa, with argon gas cleaning melting, smelting temperature is more than 1500 DEG C, the cooling cast alloy that obtains; (3) this cast alloy is carried out to vacuum annealing processing, then cooling fast.
According to preparation method provided by the invention, wherein, preferably, the atomic percent that R raw material can excessive interpolation 4%～5% in described step (1), to compensate its volatilization and scaling loss in experimentation, thereby obtains single-phase.
According to preparation method provided by the invention, wherein, preferably, described step is evacuated to 2 × 10 in (2)
-3～3 × 10
-3pa; Smelting temperature is 1500 DEG C～1700 DEG C.In step (2), because rare earth element is oxidizable, material preparation should ensure to carry out under high vacuum environment as far as possible, otherwise may cause compound ratio mismatch, thereby affects into phase, is therefore evacuated to 3 × 10
-3pa all can realize the object of the invention above.For will be understood by those skilled in the art that, mentioned herein " 3 × 10
-3more than Pa " refer in fact numerical value lower than 3 × 10
-3the system pressure of Pa.Described vacuum tightness is preferably 2 × 10
-3to 3 × 10
-3between Pa.Meanwhile, the temperature of melting is also very important, because if temperature is inadequate, material can not fully melt, and can not prepare the compound needing, and smelting temperature need to be more than 1500 DEG C conventionally; If but excess Temperature may accelerate the volatilization of rare earth element, it between 1500～1700 DEG C, is therefore preferred temperature condition.Argon gas used in the present invention is preferably high-purity argon gas, for example, and the high-purity argon gas that purity is 99.999%.
According to preparation method provided by the invention, wherein, preferably, in described step (3), the temperature of vacuum annealing processing is 600 DEG C～750 DEG C; The vacuum tightness of vacuum annealing processing is 1 × 10
-4～1 × 10
-5pa; The time of vacuum annealing processing is 3～30 days; Be cooled to fast and quench in liquid nitrogen or frozen water.In step (3), cast alloy stress after vacuum annealing is processed is discharged, physics and chemistry character will be more stable, and suitable anneal also contributes to material to become phase, therefore, other vacuum tightness, annealing temperature and the time that can achieve the above object well-known in the art also can be used; The present invention is vacuum annealing in the temperature range of 600～750 DEG C preferably, and more preferably vacuum annealing 3～30 days at this temperature.
By Ho provided by the invention
3ni
2and Er
3ni
2, or by the Ho making by preparation method provided by the present invention
3ni
2and Er
3ni
2, be mixed to get Ho according to 1: 1～2 mass ratio
3ni
2and Er
3ni
2mixture.After measured, the refrigeration capacity of this mixture has a distinct increment.Described mass ratio can be preferably 2: 3.
Rare earth-nickel material provided by the invention or the rare earth-nickel material making according to preparation method provided by the invention can freeze for magnetic, for example, can be used as magnetic refrigeration working substance.Therefore, the present invention also provides the purposes that the rare earth-nickel material making by described rare earth-nickel material or according to preparation method provided by the invention freezes for magnetic.
Compared with prior art, due to the existence of ferromagnetic-paramagnetic phase transformation, rare earth-nickel material provided by the invention is all presenting compared with great magnetic entropy variation near transformation temperature separately, thereby has larger magnetic refrigerant capacity.Ho
3ni
2and Er
3ni
2magnetic entropy become peak value under 0～5T changes of magnetic field, reach respectively 21.7J/kgK and 19.5J/kgK.The Ho that mass ratio is 2: 3 under 0～5T changes of magnetic field
3ni
2and Er
3ni
2the refrigeration capacity of mixture reaches 496J/kg.In addition, compound provided by the invention also has good magnetic, thermal reversibility matter simultaneously, and component is simple, cheap, ideal in, low-temperature magnetic refrigeration material.
Brief description of the drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 shows Ho prepared by the embodiment of the present invention 1
3ni
2the room temperature X-ray diffraction spectral line of crystalline compound;
Fig. 2 shows Ho prepared by the embodiment of the present invention 1
3ni
2null field cooling and band the cooling thermomagnetization curve of crystalline compound under downfield;
Fig. 3 shows Ho prepared by the embodiment of the present invention 1
3ni
2the isothermal magnetization curve of crystalline compound;
Fig. 4 shows Ho prepared by the embodiment of the present invention 1
3ni
2the Arrott curve of crystalline compound;
Fig. 5 shows Ho prepared by the embodiment of the present invention 1
3ni
2the isothermal magnetic entropy of crystalline compound becomes temperature curve;
Fig. 6 shows Er prepared by the embodiment of the present invention 2
3ni
2the room temperature X-ray diffraction spectral line of crystalline compound;
Fig. 7 shows Er prepared by the embodiment of the present invention 2
3ni
2null field cooling and band the cooling thermomagnetization curve of crystalline compound under downfield;
Fig. 8 shows Er prepared by the embodiment of the present invention 2
3ni
2the isothermal magnetization curve of crystalline compound;
Fig. 9 shows Er prepared by the embodiment of the present invention 2
3ni
2the Arrott curve of crystalline compound;
Figure 10 shows Er prepared by the embodiment of the present invention 2
3ni
2the isothermal magnetic entropy of crystalline compound becomes temperature curve;
Figure 11 shows the Ho that in the embodiment of the present invention 3, weight ratio is 2: 3
3ni
2and Er
3ni
2the isothermal magnetic entropy of mixture becomes temperature curve.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment providing is only in order to illustrate the present invention, instead of in order to limit the scope of the invention.
In following embodiment, utilize the D8Advance type X-ray diffractometer of German Bruker company to measure the X-ray diffraction spectral line of prepared crystalline compound, design parameter arranges as follows: pipe is pressed: 40kV; Guan Liu: 40mA; Scanning speed: stop 2s/step; Sweep limit 2 θ: 20 °～90 °; Step-length: 0.02 °.
Utilize the MPMS-7 type superconducting quantum magnetometer of Quantum Design under the size of the magnetic field of 0.01T, to measure the thermomagnetization curve of prepared crystalline compound, within the scope of the changes of magnetic field of 0～5T, measure the isothermal magnetization curve of prepared crystalline compound.
embodiment 1
The present embodiment is used for illustrating Ho provided by the invention
3ni
2and preparation method thereof.
(1) press Ho
3ni
2chemical formula (being atomic ratio) weighing, mixes purity the wherein excessive interpolation 4% of Ho (atomic percent) higher than 99.9% commercially available rare earth metal Ho, Ni raw material;
(2) electric arc furnace put into by raw material step (1) being configured or induction heater vacuumizes, when vacuum tightness reaches 3 × 10
-3when Pa, the high-purity argon that is 99.999% by purity is cleaned after 1 time, again vacuum is evacuated to 3 × 10
-3when Pa, be filled with high-purity argon gas protection, furnace chamber internal gas pressure is 1 normal atmosphere, the melting 5 times of repeatedly overturning, and smelting temperature is 1550 DEG C;
(3) cooling acquisition cast alloy in copper crucible, wraps cast alloy with molybdenum foil, and being sealed in vacuum tightness is 1 × 10
-4in the silica tube of Pa, 600 DEG C of anneal 30 days, take out and quench fast in liquid nitrogen, obtain product Ho
3ni
2crystalline compound.
Utilize X-ray diffractometer to measure gained Ho
3ni
2the room temperature X-ray diffraction spectral line of crystalline compound, as shown in Figure 1.Result shows, product principal phase is Er
3ni
2the Ho of type R heart trigonal system structure
3ni
2, its spacer is
lattice parameter
with
at 31.6 ° of assorted peaks that occur unknown phase, in Fig. 1, mark with " * " number.
At the upper Ho measuring of magnetic measurement systems (SQUID)
3ni
2null field cooling (ZFC) and band cooling (FC) pyromagnetic (M-T) curve of crystalline compound under magneticstrength H=0.01T, as shown in Figure 2.From null field cooling M-T curve, can determine Ho
3ni
2the Transition Temperature of Spin Orientation T of crystalline compound
sRwith Curie temperature T
cbe respectively 10K and 36K; In addition, near Curie temperature, ZFC and FC curve overlap completely, show that material has good thermal reversibility.
The phase transition property of compound can be determined by the shape of its Arrott curve, conventionally near the Arrott slope of a curve of first-order phase transition material transformation temperature is for bearing or having flex point, and the Arrott curve of second-order phase transition material presents positive slope near transformation temperature.Fig. 3 is Ho
3ni
2the isothermal magnetization curve of crystalline compound between 5K to 41K, can obtain Arrott curve based on this curve, as shown in Figure 4.As can be seen from Figure 4, Curie temperature T
cnear curve is all positive slope, shows Ho
3ni
2crystalline compound is typical second-order phase transition material.The material of known generation second-order phase transition has good magnetic, thermal reversibility, and it is wider that magnetic entropy becomes peak, is conducive to its application in magnetic refrigerator.
Based on the result of Fig. 3, according to Maxwell relations:
can calculate magnetic entropy from this isothermal magnetzation curve becomes.Calculate Ho
3ni
2at T
cnear magnetic entropy become to temperature (| Δ S|-T) curve, as shown in Figure 5.As we know from the figure, compound is at T
cnear occur that huge magnetic entropy becomes, wherein under 0～5T changes of magnetic field, Ho
3ni
2the maximum magnetic entropy variable of crystalline compound is 21.7J/kgK.
Refrigeration capacity (RC) is to weigh another important parameter of material practical value.Usually, the area that its large I is surrounded for temperature range with peak width at half height by Entropy Changes-temperature curve calculates acquisition.Table 1 has been listed Ho
3ni
2the contrast of the rare earth based Compound D yCoAl performance that crystalline compound is close with its Curie temperature.Visible, under 0～5T changes of magnetic field, Ho
3ni
2the Entropy Changes peak value of the Entropy Changes peakedness ratio DyCoAl of crystalline compound is large 33%, compares TbCoC
2large 42%, be 6 times of MnSi.Ho
3ni
2the RC of crystalline compound reaches 333J/kg, with TbCoC
2quite, but be far superior to the result of MnSi.In general, Ho of the present invention
3ni
2crystalline compound has the magnetic heating performance better than DyCoAl, and component is simple, low price.
Table 1
embodiment 2
The present embodiment is used for illustrating Er provided by the invention
3ni
2and preparation method thereof.
(1) press Er
3ni
2chemical formula (being atomic ratio) weighing, mixes purity the wherein excessive interpolation 5% of Er (atomic percent) higher than 99.9% commercially available rare earth metal Er, Ni raw material;
(2) electric arc furnace put into by raw material step (1) being configured or induction heater vacuumizes, when vacuum tightness reaches 2 × 10
-3when Pa, the high-purity argon that is 99.999% by purity is cleaned after 2 times, again vacuum is evacuated to 2 × 10
-3when Pa, be filled with high-purity argon gas protection, furnace chamber internal gas pressure is 1 normal atmosphere, the melting 3 times of repeatedly overturning, and smelting temperature remains on 1700 DEG C;
(3) cooling acquisition cast alloy in copper crucible, wraps cast alloy with molybdenum foil, and being sealed in vacuum tightness is 1 × 10
-5in the silica tube of Pa, 750 DEG C of anneal 3 days, take out and quench fast in liquid nitrogen, obtain product Er
3ni
2crystalline compound.
Utilize X-ray diffractometer to measure gained Er
3ni
2the room temperature X-ray diffraction spectral line of crystalline compound, as shown in Figure 6.Result shows, product principal phase is Er
3ni
2the Er of type R heart trigonal system structure
3ni
2, its spacer is
lattice parameter
with
at 29.0 °, 29.6 ° and the 32.0 ° assorted peaks that occur unknown phase, in Fig. 6, use respectively " * " number to mark.
At the upper Er measuring of magnetic measurement systems (SQUID)
3ni
2the null field cooling (ZFC) of crystalline compound and band cooling (FC) pyromagnetic (M-T) curve as shown in Figure 7.From M-T curve, can determine Er
3ni
2the Transition Temperature of Spin Orientation T of crystalline compound
sRwith Curie temperature T
cbe respectively 12K and 17K.Near Curie temperature, ZFC and FC thermomagnetization curve overlap completely, show that material has good thermal reversibility matter.
Er
3ni
2near the isothermal magnetization curve of crystalline compound transformation temperature as shown in Figure 8.Calculate Er according to this isothermal magnetzation curve
3ni
2crystalline compound is at T
cnear temperature, the Arrott curve of (being the scope of 5K to 30K), is shown in Fig. 9.As shown in Figure 9, Curie temperature T
cnear curve is all positive slope, shows Er
3ni
2crystalline compound is typical second-order phase transition material.
The Er obtaining according to the isothermal magnetization curve calculation of Fig. 8
3ni
2crystalline compound magnetic entropy becomes that curve as shown in figure 10 to temperature (| Δ S|-T).As can be seen from Figure 10, under 0～5T changes of magnetic field, Er
3ni
2the maximum magnetic entropy variable of crystalline compound reaches 19.5J/kgK.Reach 395J/kg by calculating its refrigeration capacity RC.
embodiment 3
The present embodiment is used for illustrating that mass ratio provided by the invention is the Ho of 2: 3
3ni
2and Er
3ni
2mixture and preparation method thereof.
First, embodiments of the invention 3 provide the Ho that a kind of preparation quality ratio is 2: 3
3ni
2and Er
3ni
2the method of mixture, comprises the following steps:
(1) obtain respectively Ho by step (1)～(3) in the step in embodiment 1 (1)～(3) and embodiment 2
3ni
2with Er
3ni
2crystalline compound;
(2) by the Ho obtaining
3ni
2and Er
3ni
2crystalline compound is mixed to get mass ratio as the Ho of 2: 3 taking the mass ratio of 2: 3
3ni
2and Er
3ni
2mixture.
The Ho that under 0～5T changes of magnetic field, mass ratio is 2: 3
3ni
2and Er
3ni
2mixture magnetic entropy becomes that curve as shown in figure 11 to temperature (| Δ S|-T).As can be seen from Figure 11,, under 0～5T changes of magnetic field, the maximum magnetic entropy variable of this mixture reaches 15.0J/kgK.And the magnetic entropy varied curve that presents nearly platform-like in wider warm area, this is due to Ho
3ni
2and Er
3ni
2entropy Changes peak overlapping caused.Reach 496J/kg by calculating its refrigeration capacity RC, the data of this and DyNiAl (502J/kg) are suitable.
Claims (8)
1. for rare earth-nickel material of magnetic refrigeration, this rare earth-nickel material is a kind of in following general formula compound or their mixture: R
3ni
2, wherein R is Ho or Er; Described rare earth-nickel material has Er
3ni
2type R heart trigonal system structure;
The method of the rare earth-nickel material freezing for the preparation of described magnetic comprises:
(1) press R
3ni
2chemical formula weighing, R, Ni raw material are mixed, wherein R is Ho or Er;
(2) raw material being mixed to get is put into electric arc furnace or induction heater, be evacuated to 2 × 10
-3～3 × 10
-3pa, with argon gas clean and melting, smelting temperature more than 1500 DEG C, the cooling cast alloy that obtains;
(3) this cast alloy is carried out to vacuum annealing processing, then cooling fast, wherein the temperature of vacuum annealing processing is 600 DEG C～750 DEG C, and vacuum tightness is 1 × 10
-4～1 × 10
-5pa, the treatment time is 3～30 days.
2. rare earth-nickel material according to claim 1, wherein, the Ho that described rare earth-nickel material is 1:1～2 by mass ratio
3ni
2and Er
3ni
2composition.
3. rare earth-nickel material according to claim 1, wherein, the Ho that described rare earth-nickel material is 2:3 by mass ratio
3ni
2and Er
3ni
2composition.
4. according to the preparation method of the rare earth-nickel material for magnetic refrigeration described in any one in claims 1 to 3, the method comprises:
(1) press R
3ni
2chemical formula weighing, R, Ni raw material are mixed, wherein R is Ho or Er;
(2) raw material being mixed to get is put into electric arc furnace or induction heater, be evacuated to 2 × 10
-3～3 × 10
-3pa, with argon gas clean and melting, smelting temperature more than 1500 DEG C, the cooling cast alloy that obtains;
(3) this cast alloy is carried out to vacuum annealing processing, then cooling fast, wherein the temperature of vacuum annealing processing is 600 DEG C～750 DEG C, and vacuum tightness is 1 × 10
-4～1 × 10
-5pa, the treatment time is 3～30 days.
5. preparation method according to claim 4, wherein, the atomic percent of the excessive interpolation 4%～5% of R raw material in described step (1).
6. according to the preparation method described in claim 4 or 5, wherein, the smelting temperature in described step (2) is 1500 DEG C～1700 DEG C.
7. according to the preparation method described in claim 4 or 5, wherein, being cooled to fast of described step (3) quenched in liquid nitrogen or frozen water.
8. the purposes that in claims 1 to 3, the rare earth-nickel material described in any one freezes for magnetic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110190323.8A CN102864356B (en) | 2011-07-08 | 2011-07-08 | Rare earth-nickel material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110190323.8A CN102864356B (en) | 2011-07-08 | 2011-07-08 | Rare earth-nickel material and preparation method and application thereof |
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| EP0532001A1 (en) * | 1991-09-13 | 1993-03-17 | Mitsubishi Materials Corporation | Amorphous material for regenerator |
| CN101996720A (en) * | 2009-08-25 | 2011-03-30 | 中国科学院物理研究所 | Rare earth-gallium material for magnetic refrigeration and preparation method thereof |
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| EP0532001A1 (en) * | 1991-09-13 | 1993-03-17 | Mitsubishi Materials Corporation | Amorphous material for regenerator |
| CN101996720A (en) * | 2009-08-25 | 2011-03-30 | 中国科学院物理研究所 | Rare earth-gallium material for magnetic refrigeration and preparation method thereof |
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