CN103192069A - Rare earth-copper-aluminum nano particle for low-temperature magnetic refrigeration and preparing method of rare earth-copper-aluminum nano particle - Google Patents
Rare earth-copper-aluminum nano particle for low-temperature magnetic refrigeration and preparing method of rare earth-copper-aluminum nano particle Download PDFInfo
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Abstract
The invention provides a rare earth-copper-aluminum nano particle for low-temperature magnetic refrigeration and a preparing method of rare earth-copper-aluminum nano particle, and belongs to the field of magnetic nano materials. The rare earth-copper-aluminum nano particle is a compound expressed in following formula: RCuAl, wherein R is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, the rare earth-copper-aluminum nano particle is not provided with a core-shell structure, and size of the rare earth-copper-aluminum nano particle ranges from 10 to 40nm. A plasma arc discharging method is utilized to compress rare earth powder, copper powder and aluminum powder into blocks to be served as anode materials for a plasma electric-arc furnace, tungsten metal or niobium metal is utilized as a cathode material for the plasma electric-arc furnace, and the rare earth-copper-aluminum nano particle is obtained after the arc discharging reaction. The rare earth-copper-aluminum nano particle has great magnetic entropy change capability and high magnetic refrigeration capability in low-temperature areas, and the preparing method of the rare earth-copper-aluminum nano particle is simple and environmental-friendly.
Description
Technical field
The present invention relates to magnetic Nano material, especially relate to a kind of rare earth-copper-aluminium nano particle for low temperature magnetic refrigeration and preparation method thereof.
Background technology
Low-temperature refrigeration technology (T＜20 K) relates to fields such as national security and national economy at biologic medical, semi-conductor industry, the cryogenic gas energy, superconduction low temperature environment refrigeration, high energy acclerator low-temperature protection etc. the important use meaning.In the medium-term and long-term planning of science activities of China and the United States, low-temperature refrigeration technology all is listed in the primary study project in energy environment protection and environmentally conscious materials field.Low temperature magnetic Refrigeration Technique comes across the eighties in 20th century as an emerging low-temperature refrigeration technology, and the refrigeration scope can be from 20 K to μ K level, application promise in clinical practice is arranged aspect the green energy resource liquid hydrogen producing.The more important thing is that low temperature magnetic Refrigeration Technique has advantages such as reliability height, energy-efficient, noiselessness, non-environmental-pollution and work period be long, has become current domestic and international research focus.
The magnetic refrigeration is to utilize the magnetothermal effect of magnetic material to realize freezing.When magnetothermal effect referred to that the magnetic material thermal insulation adds magnetic, the magnetic moment order increased, and magnetic entropy reduces, and emits heat to external world; During adiabatic demagnetization, the magnetic moment order reduces, and magnetic entropy increases, and absorbs heat from the external world; Finish a Carnot cycle, thus the refrigeration of realization.At low-temperature space (T＜20 K), conduction electron warm-up movement and solid lattice vibration can be ignored, and the magnetic entropy of material becomes and is approximately equal to total Entropy Changes, thus the efficient of low temperature magnetic refrigeration to be higher than in high temperature magnetic refrigerating.The major parameter that characterizes the magnetic refrigerating material magnetic heating performance is that magnetic entropy becomes (), material more big, and refrigerating capacity and efficient are also just more high.Paramagnetic salt is the typical magnetic refrigerating material of low-temperature space, and these compounds mainly are the method acquisition utmost point low temperature by adiabatic demagnetization.In addition, because the poor thermal conductivity of paramagnetic salt is unfavorable to adiabatic demagnetization.Usually, the material with first order phase change character also can show big magnetothermal effect, but first order phase change also can be accompanied by the appearance of heat stagnation and magnetic hysteresis, thereby has reduced the refrigerating capacity of material.Though have the appearance that the material of second-order phase transistion character does not have heat stagnation and magnetic hysteresis, because its excellent refrigerating capacity only appears near the phase transition temperature, this has seriously restricted the temperature range of its application.
Professor Shull of NBS prophesy because non-interacting super paramagnetic nano particle has the magnetic behavior of high magnetic moment density and similar paramagnetic, has the magnetic entropy higher than paramagnetic salt at low temperatures and becomes (Δ S
M), and its magnetic entropy variate can reduce and increase gradually with temperature.Nano particle has very high surface area simultaneously, is conducive to improve heat transfer efficiency in the thermal cycle process, and therefore super paramagnetic nano particle will replace paramagnetic salt as the low temperature magnetic refrigeration working substance of a new generation.In recent years, synthetic super paramagnetic nano particle with the high magnetic entropy change of low temperature becomes the focus of research gradually.Evaporate rare earth and metal A l simultaneously, when forming intermetallic compound, because the molten boiling point of Al atom is lower than rare earth atom, in evaporation process, be adsorbed at formation compound particle surface and oxidized formation Al
2O
3Shell can be prepared the rare earth-Al compound/Al with core/shell structure
2O
3Nano capsule.RAl
2/ Al
2O
3(R=Gd, Tb, Dy, Ho) the serial nano capsule prepares (S. Ma, W.F. Li by the plasma-arc electric discharge, D. Li, D.K. Xiong, N.K. Sun, D.Y. Geng, W. Liu, Z.D. Zhang. Large cryogenic magnetocaloric effect in the blocking state of GdAl
2/ Al
2O
3Nanocapsules [J]
.Phys. Rev. B 2007,76:144404; W.S. Zhang, E. Br ü ck, Z.D. Zhang, O. Tegus, K.H.J. Buschow. Synthesis, structure and magnetic properties of DyAl
2Nanopartilces [J]. J. Alloys Compd. 2006,413:29; X.G. Liu, D.Y. Geng, J. Du, S. Ma, Z.D. Zhang. The large cryogenic magnetocaloric effect of TbAl
2Nanocapsules [J]
.Scr. Mater. 2008,59:340; X.G. Liu, B. Li, D.Y. Geng, Z.D. Zhang. Formation and large cryogenic magnetocaloric effect of HoAl
2/ Al
2O
3Nanocapsules [J]
.J. Phys. D 2009,42:045008).Under the changes of magnetic field of 7.5 K and 6 T, RAl
2/ Al
2O
3(R=Gd, Tb, Dy, Ho) change of the magnetic entropy of Nano capsule all is higher than 12 J/ (kgK).Find that by analyzing it is linear basically with the inverse of temperature that magnetic entropy becomes.As everyone knows, the cryogenic refrigeration material needs level and smooth heat conduction in the thermal cycle process, however Al
2O
3Be a kind of ceramic material with utmost point lower thermal conductivity, this has seriously restricted RAl
2/ Al
2O
3(R=Gd, Tb, Dy, Ho) the serial nano capsule is in low-temperature space magnetic refrigeration application.
Patent 201010515354.1 discloses rare earth-copper-aluminum that is used for the magnetic refrigeration and preparation method thereof.This block rare earth-copper-aluminum is to be prepared by vacuum melting and quick cooling synthesis, wherein HoCuAl is at Curie temperature 12K place, and under the 0-5 changes of magnetic field, obtaining maximum magnetic entropy variable is 23.9 J/ kgK, when but temperature was not 12K, it is very fast that its magnetic entropy becomes decline.
Patent 201110062394.X discloses low temperature magnetic refrigerating material of a kind of rare earth tinbase and preparation method thereof.The low temperature magnetic refrigerating material of this rare earth tinbase is to be prepared by vacuum melting method, wherein Ho
5Sn
4At Ne﹠1﹠el temperature 14K place, under the 0-5 changes of magnetic field, obtaining maximum magnetic entropy variable only is 7.95 J/ kgK
Patent 201110354855.0 discloses europium base ThCr
2Si
2Low temperature magnetic refrigerating material and the preparation method of structure.This rare-earth europium base ThCr
2Si
2The low temperature magnetic refrigerating material of structure is to be prepared by vacuum melting method, wherein EuCu
2P
2At Curie temperature 52K place, under the 0-5 changes of magnetic field, obtaining maximum magnetic entropy variable is 10.7 J/ kgK.
Similar techniques is many in addition, but these method complex process, reaction condition is harsh relatively, and operating process is loaded down with trivial details relatively, thereby has been subjected to restriction to a certain degree in actual applications.In addition, its maximum magnetic entropy variable is very sensitive to phase transition temperature, and when temperature changes a little, its magnetic entropy becomes to be significantly and descends.
Summary of the invention
The present invention overcomes the deficiencies in the prior art, and a kind of great magnetic entropy variation is provided, rare earth-copper-aluminium nano particle that is used for low temperature magnetic refrigeration of high magnetic refrigerating capacity and preparation method thereof, the simple and environmental friendliness of the preparation technology of this system nano material simultaneously.
Rare earth-copper-aluminium nano particle that the present invention is used for low temperature magnetic refrigeration is the compound of following general formula: RCuAl, and wherein R is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; Described rare earth-copper-aluminium nano particle does not have nucleocapsid structure, and its particle diameter is 10～40 nm.
As a kind of optimization, described rare earth-copper-aluminium nano particle is DyCuAl.
The preparation method of above-mentioned rare earth-copper-aluminium nano particle, adopt the plasma-arc electric discharge, purity is 99.9% (mass percent) rare earth powder, copper powder and aluminium powder are pressed into block as the anode material of plasma arc furnace under pressure 1Mpa～1Gpa, the shared atomic percent of described anode material middle rare earth is 50～52%, the shared atomic percent of copper is 44～45%, the shared atomic percent of Al is 3～6%, adopt tungsten metal or niobium metal as the cathode material of plasma arc furnace, quote argon gas as working gas, connect dc source, operating voltage is 10～40 V, operating current is 20～60 A, plays electric arc between anode and the negative electrode, powered-down behind maintenance 0.5～5 h, take out working gas, charge into passivation gas and carry out passivation, passivation time is 1h at least, after the end, open loam cake and collect the nano powder at plasma-arc furnace sidewall and loam cake position, namely get product rare earth-copper of the present invention-aluminium nano particle.
As a kind of optimization, described anode material middle rare earth is the dysprosium powder, and its atomic percent shared in anode material is 52%, and copper powder is 45%, aluminium powder is 3%, adopts the tungsten metal as cathode material, and described operating voltage is 10V, operating current is 20A, and the described working time is 5h, and passivation time is 4h.
Adopt arc discharge to produce the technology of preparing of plasma among the present invention, concrete principle is: the arc-plasma gas of Ar that has been ionization mainly in the preparation, it is made up of electronics, ion and neutral particle.Wherein the sum of electronics and ion is equal substantially, thereby is electroneutral as a whole, if in a single day separation of charge appears in plasma, will produce huge electric field immediately.In arc discharge process, the energy w that electronics obtains in electric field=electric weight * voltage, the quantity of electric charge of electronics is e=1.6 * 10-19 coulomb, when voltage V=2 volt, thereby can obtain 2eV=2 * 1.6 * 10-19 coulomb * volt=3.2 * 10-19 joule.According to the microcosmic definition of temperature, E=W=3/2 kT=2eV=3.2 * 10-19 joule just can obtain electron temperature T=23200 K to the Boltzmann constant substitution.This only is to consider independent electronic behavior.The very big temperature of electron energy is very high, but quantity seldom.When plasma state becomes normal state, temperature decrease, this provides condition for compound forming core between ternary metal.Because the particle diameter of nano particle is little, specific surface is big, the surface can be high, very easily oxidation in air, the oxide shell that forms on the surface.Because the conductibility of oxide shell is very poor, thereby be difficult to application at the magnetic refrigerating field.But utilize the metal bond energy of compound between ternary metal and the compensation relationship between the nano grain surface energy, can prepare rare earth-copper-aluminium nano particle, and oxide-free shell.
The present invention has prepared rare earth-copper-aluminium nano particle by the plasma-arc electric discharge, has great magnetic entropy variation and high magnetic refrigerating capacity at low-temperature space.With respect to present low temperature magnetic refrigerating material of reporting and preparation method thereof, outstanding advantage of the present invention is:
1) rare earth-copper-aluminium nanometer purity height of this method preparation, productive rate is big, cost is low, simple to operate, generated time short;
2) the common solid-state sintering that adopts of the low temperature magnetic refrigerating material of the preparation of report at present, comparatively strict to required conditions such as heat treatment temperature, atmosphere and times, react later remaining residual, easily environment is produced and pollute, and the present invention is simple in the preparation process conditions needed, be easy to control, and environmentally safe, environmental protection;
3) the prepared rare earth-copper of the present invention-aluminium nano particle, surperficial oxide-free shell has light, stable, the good heat conductivity of quality and the excellent properties of great magnetic entropy variation, can satisfy the actual needs of relevant military project and the product for civilian use.
Description of drawings
Fig. 1 is the device schematic diagram of the low temperature magnetic refrigerating material of preparation rare earth-copper of the present invention-aluminium nano particle;
Wherein: 1, loam cake; 2, negative electrode; 3, valve; 4, target; 5, observation window; 6, baffle plate; 7, copper anode; 8, chuck; 9, copper crucible; 10, dc pulse power supply; A, cooling water; B, argon gas.
Fig. 2 is the room temperature X-ray diffraction spectra line chart of the embodiment of the invention 1 product D yCuAl nano particle.
Fig. 3 is the transmission electron microscope photo of the embodiment of the invention 1 product D yCuAl nano particle.
Fig. 4 is the null field cooling of the embodiment of the invention 1 product D yCuAl nano particle under 0.01T magnetic field and the thermomagnetization curve of a band cooling, and illustration is to be with relation curve between an intensity of magnetization derivative of cooling and temperature under the 0.01T magnetic field.
Fig. 5 is the hysteresis curve of the embodiment of the invention 1 product D yCuAl nano particle under 2 K and 28 K.Illustration is the amplifier section under the downfield.
Fig. 6 is the isothermal magnetization curve of the embodiment of the invention 1 product D yCuAl nano particle.
Fig. 7 is that the magnetic entropy of the embodiment of the invention 1 product D yCuAl nano particle under different externally-applied magnetic fields change becomes and the temperature relation curve.
Fig. 8 is the room temperature X-ray diffraction spectra line chart of the embodiment of the invention 2 product ErCuAl nano particles.
Fig. 9 is the transmission electron microscope photo of the embodiment of the invention 2 product ErCuAl nano particles.
Figure 10 is that the magnetic entropy of the embodiment of the invention 2 product ErCuAl nano particles under different externally-applied magnetic fields change becomes and the temperature relation curve.
Figure 11 is the room temperature X-ray diffraction spectra line chart of the embodiment of the invention 3 product HoCuAl nano particles.
Figure 12 is the transmission electron microscope photo of the embodiment of the invention 3 product HoCuAl nano particles.
Figure 13 is that the magnetic entropy of the embodiment of the invention 3 product HoCuAl nano particles under different externally-applied magnetic fields change becomes and the temperature relation curve.
The specific embodiment
The invention will be further described below in conjunction with accompanying drawing.
Fig. 2 is the X-ray diffraction spectra of embodiment 1 product product D yCuAl nano particle, and diffraction maximum is respectively (100), (001), (110), (200), (111), (201), (210), (300), (002) and (211), according to diffraction maximum, determine that it is the DyCuAl of ZrNiAl type hex crystal structure, its space group, lattice parameter a=7.009, c=4.019.
(a) is the pattern picture of the projection Electronic Speculum of embodiment 1 product D yCuAl nano particle among Fig. 3, for spherical, do not have nucleocapsid structure, and diameter is about 10-40 nm; (b) be the enlarged drawing of embodiment 1 product D yCuAl nano particle, in (b), measured wherein one group of interplanar distance; 0.264 nm=dDyCuAl (111) according to the d value, determines that it is DyCuAl (JCPDS21-0754).
Fig. 4 is the ZFC null field cooling of embodiment 1 product D yCuAl nano particle under the magnetic induction density B=0.01T of magnetic field and the thermomagnetization curve of a FC band cooling, and abscissa is T temperature [K], and ordinate is the M intensity of magnetization [Am
2/ kg], T shown in arrow among the figure
CCurie temperature is 24 K; Illustration is the dM/dT intensity of magnetization derivative [Am of a FC band cooling under the magnetic induction density B=0.01T of magnetic field
2/ kgK] and the T temperature between relation curve, 24 K of transition temperature shown in the arrow in the illustration.In addition, ZFC and FC curve overlap fully, show that material has good thermal reversibility.In addition, because the dimensional effect of nano particle, Curie temperature 24 K of DyCuAl nano particle are a little less than Curie temperature 28 K of block DyCuAl.
Fig. 5 is the hysteresis curve of embodiment 1 product D yCuAl nano particle under 2 K and 28 K.In Fig. 5, abscissa is B magnetic induction intensity [T], and ordinate is the M intensity of magnetization [Am
2/ kg]; Illustration is amplifier section under the low magnetic induction intensity; Can see that product demonstrates superparamagnetism when 2 K, demonstrate paramagnetism when 28 K.
Fig. 6 is the isothermal magnetization curve of embodiment 1 product D yCuAl nano particle between 2 K to 32 K, and abscissa is B magnetic induction intensity [T], and ordinate is the M intensity of magnetization [Am
2/ kg].
Based on the result of Fig. 6, according to Maxwell relation:, when Practical Calculation, the continuous integration of formula is changed into discrete summation, that is:.Calculate DyCuAl under different externally-applied magnetic fields change-magnetic entropy becomes [J/ (kgK)] and T temperature [K] relation curve, as shown in Figure 7.Wherein under 0-5 T changes of magnetic field, the maximum magnetic entropy variable of DyCuAl nano particle is 14.6 J/ (kgK).Owing to utilize permanent magnet NdFeB can easily obtain the magnetic field of 2T, so becoming, the magnetic entropy of the material under 0-2 T changes of magnetic field receives much attention, under 0-2 T changes of magnetic field, the Entropy Changes of DyCuAl nano particle is 6.4 J/ (kgK).In addition, we find that under identical externally-applied magnetic field changes magnetic entropy becomes along with temperature decline raises on the contrary; Under uniform temp, magnetic entropy becomes along with the externally-applied magnetic field increase and raises.This is different from the low temperature magnetic refrigerating material of block and only obtains big magnetic entropy change near Curie temperature or phase transition temperature.
Fig. 8 is the X-ray diffraction spectra of embodiment 2 product product ErCuAl nano particles, and diffraction maximum number marks with " ■ ".According to diffraction maximum, determine that it is the single-phase ErCuAl (JCPDS21-0755) of ZrNiAl type hex crystal structure, its space group, lattice parameter a=6.970, c=3.995.
Fig. 9 is the pattern picture of the projection Electronic Speculum of embodiment 2 product ErCuAl nano particles, for spherical, does not have nucleocapsid structure, and diameter is about 10-40 nm.
Figure 10 is embodiment 2 product ErCuAl nano particles under different externally-applied magnetic fields change-magnetic entropy becomes [J/ (kgK)] and T temperature [K] relation curve.Wherein under 0-5 T changes of magnetic field, the maximum magnetic entropy variable of ErCuAl nano particle is 16.6 J/ (kgK).Under 0-2 T changes of magnetic field, the Entropy Changes of ErCuAl nano particle is 7.8 J/ (kgK).In addition, we find that under identical externally-applied magnetic field changes magnetic entropy becomes along with temperature decline raises on the contrary; Under uniform temp, magnetic entropy becomes along with the externally-applied magnetic field increase and raises.
Figure 11 is the X-ray diffraction spectra of embodiment 3 product product HoCuAl nano particles, and diffraction maximum number marks with " ▼ ".According to diffraction maximum, determine that it is the single-phase HoCuAl (JCPDS21-0757) of ZrNiAl type hex crystal structure, its space group, lattice parameter a=6.977, c=4.006.
Figure 12 is the pattern picture of the projection Electronic Speculum of embodiment 3 product HoCuAl nano particles, for spherical, does not have nucleocapsid structure, and diameter is about 10-40 nm.
Figure 13 is embodiment 3 product HoCuAl nano particles under different externally-applied magnetic fields change-magnetic entropy becomes [J/ (kgK)] and T temperature [K] relation curve.Wherein under 0-5 T changes of magnetic field, the maximum magnetic entropy variable of HoCuAl nano particle is 17.8 J/ (kgK).Under 0-2 T changes of magnetic field, the Entropy Changes of HoCuAl nano particle is 7.4 J/ (kgK).In addition, we find that under identical externally-applied magnetic field changes magnetic entropy becomes along with temperature decline raises on the contrary; Under uniform temp, magnetic entropy becomes along with the externally-applied magnetic field increase and raises.
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to following embodiment.
Embodiment 1
Device loam cake 1 shown in Figure 1 is opened, making negative electrode 2 with tungsten is fixed on the chuck 8, the composition of institute's consumable anode target 4 is that purity is the 99.9%(mass percent) the block that is pressed into of dysprosium powder, copper powder and aluminium powder (atomic ratio 52:45:3), being placed on the copper anode 7 of logical cooling water, is copper crucible 9 between the copper anode that leads to cooling water and target.Lid mounted device loam cake 1 leads to cooling water a, after by valve 3 whole operating room being vacuumized, feeds argon gas, connects dc pulse power supply 10, and voltage is 10V, and operating current is 20A.Adjusting operating current and voltage keep relative stability in the arc discharge process, and the working time is 5h.Shown in Figure 15 is observation window, and shown in Figure 16 is baffle plate.Dysprosium powder, copper powder and aluminium powder fusing and evaporation and ionization in the arc discharge process form the DyCuAl nano particle, be deposited on sidewall and on cover.After finishing required arc discharge process, cut off the electricity supply, arc light extinguishes.Extract operating room's gas out, inject argon gas passivation nano particle, behind the passivation 4h, open loam cake collect sidewall and on the nano powder that covers.Its relevant characterization result is shown in Fig. 2～7.
Device loam cake 1 shown in Figure 1 is opened, making negative electrode 2 with niobium is fixed on the chuck 8, the composition of institute's consumable anode target 4 is that purity is the 99.9%(mass percent) the block that is pressed into of erbium powder, copper powder and aluminium powder (atomic ratio 50:44:6), being placed on the copper anode 7 of logical cooling water, is copper crucible 9 between the copper anode that leads to cooling water and target.Lid mounted device loam cake 1 feeds cooling water a, after by valve 3 whole operating room being vacuumized, feeds argon gas b, connects dc pulse power supply 10, and voltage is 40V, and operating current is 60A.Adjusting operating current and voltage keep relative stability in the arc discharge process, and the working time is 0.5 h.Erbium powder, copper powder and aluminium powder fusing and evaporation and ionization in the arc discharge process form the ErCuAl nano particle, be deposited on sidewall and on cover.After finishing required arc discharge process, cut off the electricity supply, arc light extinguishes.Extract operating room's gas out, inject the air passivation nano particle, behind the passivation 6h, open loam cake collect sidewall and on the nano powder that covers.Its relevant characterization result is shown in Fig. 8～10.
Device loam cake 1 shown in Figure 1 is opened, making negative electrode 2 with tungsten is fixed on the chuck 8, the composition of institute's consumable anode target 4 is that purity is the 99.9%(mass percent) the block that is pressed into of holmium powder, copper powder and aluminium powder (atomic ratio 51:44:5), being placed on the copper anode 7 of logical cooling water, is copper crucible 9 between the copper anode that leads to cooling water and target.Lid mounted device loam cake 1 feeds cooling water a, after by valve 3 whole operating room being vacuumized, feeds argon gas b, connects dc pulse power supply 10, and voltage is 20V, and operating current is 40A.Adjusting operating current and voltage keep relative stability in the arc discharge process, and the working time is 2 h.Erbium powder, copper powder and aluminium powder fusing and evaporation and ionization in the arc discharge process form the HoCuAl nano particle, be deposited on sidewall and on cover.After finishing required arc discharge process, cut off the electricity supply, arc light extinguishes.Extract operating room's gas out, inject the air passivation nano particle, behind the passivation 5h, open loam cake collect sidewall and on the nano powder that covers.Its relevant characterization result is shown in Figure 11～13.
Claims (4)
1. one kind is used for rare earth-copper-aluminium nano particle that low temperature magnetic freezes, it is characterized in that, this rare earth-copper-aluminium nano particle is the compound of following general formula: RCuAl, wherein R is Y, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, described rare earth-copper-aluminium nano particle, do not have nucleocapsid structure, and particle diameter is 10～40 nm.
2. rare earth-copper-aluminium the nano particle for low temperature magnetic refrigeration as claimed in claim 1 is characterized in that described rare earth-copper-aluminium nano particle is DyCuAl.
3. the preparation method of the rare earth-copper-aluminium nano particle for low temperature magnetic refrigeration as claimed in claim 1, adopt the plasma-arc electric discharge, it is characterized in that, purity is the rare earth powder of 99.9% (mass percent), copper powder and aluminium powder are pressed into block as the anode material of plasma arc furnace under pressure 1Mpa～1Gpa, the shared atomic percent of described anode material middle rare earth is 50～52%, the shared atomic percent of copper is 44～45%, the shared atomic percent of Al is 3～6%, adopt tungsten metal or niobium metal as the cathode material of plasma arc furnace, quote argon gas as working gas, connect dc source, operating voltage is 10～40V, and operating current is 20～60A, play electric arc between anode and the negative electrode, powered-down behind maintenance 0.5～5h is taken out working gas, charges into passivation gas and carries out passivation, passivation time is 1h at least, after the end, open the nano powder that loam cake is collected plasma-arc furnace sidewall and loam cake position, namely get product rare earth-copper of the present invention-aluminium nano particle.
4. the preparation method of the rare earth-copper-aluminium nano particle for low temperature magnetic refrigeration as claimed in claim 3, it is characterized in that, described anode material middle rare earth is the dysprosium powder, and its atomic percent shared in anode material is 52%, and copper powder is 45%, aluminium powder is 3%, adopt the tungsten metal as cathode material, described operating voltage is 10V, and operating current is 20A, the described working time is 5h, and passivation time is 4h.
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| CN105127414A (en) * | 2015-09-29 | 2015-12-09 | 安徽工业大学 | Preparation method for silver-cladding nickel nano powder material adopting core-shell structure |
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| CN109087767A (en) * | 2018-08-08 | 2018-12-25 | 杭州电子科技大学 | A kind of crystal boundary spreads the neodymium iron boron magnetic body and preparation method thereof of nanoscale diffusate in situ |
| CN109692968A (en) * | 2018-12-28 | 2019-04-30 | 江苏博迁新材料股份有限公司 | A kind of production method of submicron order NdFeB alloyed powder |
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