CN103214042A - Superparamagnetic rare-earth intermetallic compound nano-particles and preparation method thereof - Google Patents
Superparamagnetic rare-earth intermetallic compound nano-particles and preparation method thereof Download PDFInfo
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Abstract
The purpose of the invention is to provide a novel superparamagnetic rare-earth intermetallic compound nano-particles, wherein the nano-particles are nano-particles of GdNi5, DyNi5, GdH2, and have superparamagnetic characteristic, wherein the nano-particles of GdNi5 and DyNi5 are of a typic shell-core structure; in other words, the nano-particle of GdNi5 is composed of Gd2O3 shell and GdNi5 core; and the nano-particle DyNi5 is composed of Dy2O3 shell and DyNi5 core. The nano-particle of GdH2 is single-phase GdH2 particle having the size at the nanometer scale. The three nano-particles have high magnetic entropy change in the temperature zone range of 5K so that the nano-particles become novel low-temperature magnetic refrigeration nano-materials; and the nano-materials are stable in air and can be directly used.
Description
Technical field
The invention belongs to the material field, relate to a kind of rare earth intermetallic compound DyNi5 with super paramagnetic feature, GdNi5, GdH2 nano particle and preparation method thereof, and as the application of hanging down the temperature magnetic refrigerating material aspect.
Background technology
Near determining, realize various superconduction environment, and the Bose-Einstein condensation environment all has very important physical significance to the low temperature environment of zero degree (0K) annex basic physical properties for research various materials itself.The magnetic Refrigeration Technique is to realize this approaching determining near a kind of important Refrigeration Technique of the low temperature environment zero degree (0K).The magnetic cooling technology mainly is to utilize paramagnetic material to have different magnetic entropies under changes of magnetic field to become, and then the variation that utilizes this magnetic entropy to become reaches the heat exchange between paramagnetic material itself and environment, realization low temperature magnetic refrigerating purpose.In recent years, in order to improve refrigerating efficiency, need the preparation nano materials with super paramagnetic as magnetic refrigerating working material, therefore, the nano material that preparation has high magnetic entropy change becomes the urgent day by day requirement of low temperature magnetic cooling material research more.
Early stage magnetic cooling material research comprises many materials, and brief introduction is as follows:
Patent 200610046215.2 discloses and has a kind ofly prepared RAl2(R=La with plasma body, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, the Er) method of metal nano material, this method utilize the plasma arc legal system to be equipped with the nano particle of Al2O3 parcel RAl2 intermetallic compound.
Patent 201110446792.1 discloses utilizes ball milling+sintering+high temperature annealing technology to prepare Mn (2-x) Fe (x) P (1-y) Ge (y), (scope of x is: 0.8～0.9, the scope of y is: material 0.2～0.25), its advantage is: prepared magnetic refrigerating material, high temperature annealing is grown up the crystal grain of material, has improved the magnetothermal effect of material, magnetic entropy becomes and increases, and can be applicable in the magnetic Refrigeration Technique.
Patent 201110397642.6 utilizes ball milling+sintering technology to prepare Mn (2-x) Fe (x) P (1-y) Ge (y) B (z), and (scope of x is: 0.8～0.9, the scope of y is: 0.2～0.27, the scope of z is: material 0.01～0.02), its advantage is: prepared magnetic refrigerating material, by adding the B element, form interstitial atom be present in Fe2P crystalline texture mutually in, stablized phase structure, improved the magnetothermal effect of material, its working temperature is improved, magnetic entropy becomes and increases, and can be applicable in the magnetic Refrigeration Technique.
Patent 201210169642.5 utilizes alloy cast ingot to carry out melt-spun under argon shield, gets rid of the band technology and prepares Gd base amorphous magnetic refrigerating material.Prepared magnetic refrigerating material can be prepared into amorphous can be prepared into compound again; This product shows second-order phase transition in magnetic history and magnetothermal effect is big; Preparation technology is simple, with low cost, be suitable for suitability for industrialized production.
Patent 201010536650.X utilizes melting and vacuum annealing treatment technology to prepare M1M2In(M1 to be among Gd, Tb, Dy, Ho and the Er any one, or any one combination among Ho and Gd, Tb, Dy and the Er) material is characterized in that: the magnetic refrigerating material magnetic entropy that this invention provides uprises, refrigeration capacity strong, have good magnetic, thermal reversibility matter.
Above-mentioned materials is near the magnetic refrigerating material of room temperature, and all exists with the metal blocks form.Therefore be badly in need of a kind of can be near 5K, realize near the magnetic refrigerating material of the cryogenic refrigeration 5K, and material is convenient to material quick heat radiating in process of refrigeration in nano-scale range, reach good refrigeration.
Summary of the invention
The object of the present invention is to provide compound nano-particle between a kind of novel super paramagnetic metal, this kind nano particle is respectively GdNi5, DyNi5, GdH2 nano particle, has super paramagnetic feature, GdNi5 wherein, the DyNi5 nano particle has typical core-shell structure: the GdNi5 nano particle is made up of Gd2O3 shell and GdNi5 kernel, and the DyNi5 nano particle is made up of Dy2O3 shell and DyNi5 kernel.The GdH2 nano particle is the particle that is of a size of nano level single-phase GdH2.More than three kinds of nano particles in 5K warm area scope, have very high magnetic entropy and become, make it become a kind of novel low temperature magnetic refrigeration nano material, and this nano material can existence stable in the air and directly use.
The present invention specifically provides a kind of rare earth intermetallic compound nano particle, it is characterized in that: described nano particle is that size is DyNi5, GdNi5 or the GdH2 particle of nano-level sphere.
Rare earth intermetallic compound nano particle of the present invention is characterized in that:
GdNi5 and DyNi5 nano particle have typical core-shell structure, and kernel is respectively DyNi5 and GdNi5, and shell is respectively Dy2O3 and Gd2O3, and the GdH2 nano particle does not have core-shell structure, and above-mentioned three kinds of nano particle diameters are distributed as 10-150nm.
The preparation method of rare earth intermetallic compound nano particle of the present invention is characterized in that: described rare earth intermetallic compound nano particle is to utilize the plasma electrically arc discharge technology, and in-situ preparing obtains under working gas;
Wherein: adopting the pure metal tungsten electrode is negative electrode, and Gd-Ni and Dy-Ni alloy are anode target material, keeps the distance of 2-30mm between negative electrode and the anode target material; The electric current of arc-over is 15～400A, and voltage is 10～60V; Described working gas is argon gas and hydrogen.
The preparation method of rare earth intermetallic compound nano particle of the present invention is characterized in that: the dividing potential drop of argon gas is 0.01-0.8MPa, and the dividing potential drop of hydrogen is 0.01-0.5MPa.
The preparation method of rare earth intermetallic compound nano particle of the present invention is characterized in that: described anode target material is the alloy Dy of rare earth metal and magnetic transition metal Ni
xNi
100-x(x=28-32), Gd
yNi
100-y(y=30-85), and anode target material is cylindrical alloy block, and its diameter is 1-5cm, and thickness is 1-4cm.
Using plasma arc-discharge technique among the present invention, electric arc produces very high temperature, plasma body is with Gd-Ni simultaneously, Gd in the Dy-Ni alloy and Ni atom (or Dy and Ni atom) are evaporated, in evaporative process, the mutual collision of Gd and Ni atom (or Dy and Ni atom) that is evaporated forms GdNi5 nano particle and DyNi5 nano particle respectively, and in passivating process, GdNi5 and DyNi5 nano grain surface Gd atom are oxidized to the Gd2O3 shell.Using plasma arc-discharge technique evaporation Gd-Ni alloy, when Gd content in the alloy surpasses 80at.%, and under high amounts of hydrogen, H atom and Gd atom form the GdH2 compound nano-particle.
The preparation method of rare earth intermetallic compound nano particle of the present invention is characterized in that: used water coolant water temperature is lower than 20 degrees centigrade.
The preparation method of rare earth intermetallic compound nano particle of the present invention, it is characterized in that: the optimal anode alloying constituent of preparation GdNi5 Nano capsule is GdyNi100-y(y=40-60), the optimal anode alloying constituent of preparation DyNi5 Nano capsule is Dy30Ni70, and the optimal alloy composition of preparation GdH2 nano particle is GdyNi100-y(y=75-85).
The present invention also provides compound nano-particle between described super paramagnetic metal, and (the DyNi5 nano particle is in the 5-60K scope as the application of magnetic cooling material in the 5-100K scope, the GdNi5 nano particle is in the 5-100K scope, and the GdH2 nano particle is in the 5-80K scope).Material of the present invention is in 5-100K warm area scope, and maximum magnetic entropy variable can reach 13J/ (kgK), therefore can be used as the low temperature magnetic cooling material.
Description of drawings
Fig. 1 .Dy
xNi
100-xThe X ray diffracting spectrum of the nano particle of (x=17,30,40) anode alloy preparation;
Fig. 2. by Dy
30Ni
70Anode alloy prepares the pattern photo and the high-resolution-ration transmission electric-lens photo of DyNi5 nano particle;
Fig. 3. by Dy
30Ni
70Temperature-the magnetzation curve of the nano particle of anode alloy preparation;
Fig. 4. by Dy
30Ni
70Nano particle magnetic hysteresis loop under 5K of anode alloy preparation, wherein saturation magnetization 105Am
2/ kg, coercive force 0.547T;
Fig. 5. by Dy
30Ni
70The nano particle of anode alloy preparation, in the 5K-80K scope, under the 7T changes of magnetic field, magnetic entropy becomes temperature variant curve;
Fig. 6 .Gd
xNi
100-xThe X ray diffracting spectrum of the nano particle of (x=20,40,60) anode alloy preparation;
Fig. 7. by Gd
60Ni
40The transmission electron microscope photo shape appearance figure of the nano particle of anode alloy preparation;
Fig. 8. by Gd
60Ni
40The High-Resolution Map of the nano particle of anode alloy preparation;
Fig. 9. by Gd
60Ni
40Temperature-the magnetzation curve of the nano particle of anode alloy preparation;
Figure 10. by Gd
60Ni
40The nano particle of anode alloy preparation, in the 5K-180K scope, under the 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and wherein illustration is the magnetzation curve under the differing temps;
Figure 11. by Gd
60Ni
40The shape appearance figure of the transmission electron microscope photo of the nano particle of anode alloy preparation, wherein shell is the lattice image of Gd2O3, kernel is the GdNi5 lattice image;
The High-Resolution Map of Figure 12 .GdNi5 nano particle, wherein shell is the lattice image of Gd2O3, kernel is the GdNi5 lattice image;
Figure 13. by Gd
40Ni
60Temperature-the magnetzation curve of the nano particle of anode alloy preparation;
Figure 14. by Gd
40Ni
60The nano particle of anode alloy preparation, in the 5K-100K scope, under the 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and wherein illustration is the magnetzation curve under the differing temps;
Figure 15. by Gd
80Ni
20The X ray diffracting spectrum of the GdH2 nano particle of anode alloy preparation;
Figure 16. by Gd
80Ni
20The transmission electron microscope pattern photo of the GdH2 nano particle of anode alloy preparation;
Figure 17. by Gd
80Ni
20The high resolution lattice image of the GdH2 nano particle of anode alloy preparation;
Figure 18. by Gd
80Ni
20The GdH2 nano particle of anode alloy preparation from 5K to 80K between, the magnetic entropy under the 5T changes of magnetic field becomes and varies with temperature curve.
Embodiment
In following examples, as specified otherwise not, all adopting purity is that 99.9% tungsten electrode is a negative electrode, and used consumable anode target is cylindrical alloy pig.Used water coolant water temperature is lower than 20 degrees centigrade.
The plasma electrically arc discharge technology prepares the DyNi5 nano particle:
In gas ions arc-over cavity, used consumable anode target is that diameter 5cm thickness is the Dy of 3cm
xNi
100-x(x=30) alloy pig, the spacing of tungsten cathode and anode target material Dy30Ni70 alloy pig is 10mm.Gas ions arc-over cavity is led to water coolant, after cavity is vacuumized, feed argon gas and hydrogen respectively, wherein Ar:0.2MPa, H
2: 0.05MPa connects direct supply, regulating voltage is 15-30V, arc discharge takes place between anode target material and negative electrode, the electric current that produces arc-over is 60-100A, regulate working current and voltage keep relative stability (electric current is 80-90A) in the arc discharge process, prepare the DyNi5 nano particle, in passivating process subsequently, (be after arc-over finishes, in cavity, feed 0.02Mpa argon gas and 0.002MPa air, make the slowly oxidation of DyNi5 nano particle), the DyNi5 nano grain surface is oxidized to Dy2O3, finally forms the nano particle of Dy2O3 parcel DyNi5.
Fig. 1 provides the X ray diffracting spectrum of gained DyNi5 nano particle, and wherein the peak of marking is the feature crystal face diffraction peak of DyNi5, and the peak of round dot mark is the Ni characteristic diffraction peak.Fig. 2 is by Dy
30Ni
70The DyNi5 nano particle pattern photo and the high resolution photo of anode alloy preparation; nanoparticle size is distributed as 30-80nm shown in it; photo shows that also the DyNi5 nano particle has typical core-shell structure; kernel is DyNi5; shell is that Dy2O3 is not oxidized with the protection nano particle, and the Dy2O3 outer casing thickness is about 3.6nm.Fig. 3 indicates DyNi5 nano particle temperature-magnetzation curve, the cold curve of ZFC curve representation null field wherein, and the cold curve in FC curve representation field, the freezing temperature of 235K indication sample, 20K is the Curie temperature of DyNi5.Fig. 4 is DyNi5 nano particle magnetic hysteresis loop under 5K, wherein saturation magnetization 105Am
2/ kg, coercive force 0.547T.Fig. 5 indicates the DyNi5 nano particle in the 5K-80K scope, and under the 7T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 11.5J/ (kg K);
The plasma electrically arc discharge technology prepares the DyNi5 nano particle:
In gas ions arc-over cavity, used consumable anode target is that diameter 5cm thickness is the Dy of 4cm
xNi
100-x(x=30) alloy pig, the spacing of tungsten cathode and anode target material Dy30Ni70 alloy pig is 10mm.Gas ions arc-over cavity is led to water coolant, after cavity is vacuumized, feed argon gas and hydrogen respectively, wherein Ar:0.8MPa, H
2: 0.2MPa connects direct supply, regulating voltage is 18-35V, arc discharge takes place between anode target material and negative electrode, the electric current that produces arc-over is 300-400A, regulate working current and voltage keep relative stability (electric current is 350A) in the arc discharge process, prepare the DyNi5 nano particle, at passivating process subsequently (is after arc-over finishes, in cavity, feed 0.02Mpa argon gas and 0.002MPa air, making the slowly oxidation of DyNi5 nano particle) the DyNi5 nano grain surface is oxidized to Dy2O3, the final nano particle that forms Dy2O3 parcel DyNi5, nanoparticle size is distributed as 80-150nm.
Embodiment 3
The plasma electrically arc discharge technology prepares the GdNi5 nano particle:
In gas ions arc-over cavity, used consumable anode target is that diameter 4.5cm thickness is the Gd of 3cm
yNi
100-y(y=60) alloy pig, the spacing of tungsten cathode and anode target material Gd60Ni40 alloy pig is 15mm.Article on plasma body arc-over cavity leads to water coolant, after cavity is vacuumized, feeds argon gas and hydrogen respectively, wherein Ar:0.22MPa, H
2: 0.06MPa connects direct supply, regulating voltage is 12-35V, arc discharge takes place between anode target material Gd60Ni40 and tungsten cathode, the electric current that produces arc-over is 80-120A, adjusting working current and voltage keep relative stability (electric current is 80-100A) in the arc discharge process, prepare the GdNi5 nano particle.
Fig. 6 provides the X ray diffracting spectrum of gained B collection of illustrative plates indication by the GdNi5 nano particle of Gd60Ni40 alloy pig preparation, wherein diffraction peak is corresponding with GdNi5 standard diffraction peak among the figure, and wherein the diffraction peak of broad is indicating the GdNi5 nano particle to have the smaller particles radius.Fig. 7,8 indicates pattern photo and the high resolution photo that is prepared gained GdNi5 nano particle by Gd60Ni40, and nanoparticle size is distributed as 10-40nm shown in it, and photo also shows the lattice image of GdNi5 nano particle, and its corresponding crystal orientation is [101] direction.Fig. 9 indicates the temperature-magnetzation curve of GdNi5 nano particle, the cold curve of ZFC curve representation null field wherein, the cold curve in FC curve representation field, the freezing temperature of 145K indication sample, 40K is the Curie temperature of GdNi5, and Figure 10 indicates the GdNi5 nano particle in the 5K-180K scope, under the 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 13.8J/ (kg K);
The plasma electrically arc discharge technology prepares the GdNi5 nano particle:
In gas ions arc-over cavity, used consumable anode target is that diameter 4.5cm thickness is the Gd of 3cm
yNi
100-y(y=40) alloy pig, the spacing of tungsten cathode and anode target material Gd40Ni60 alloy pig is 22mm.Article on plasma body arc-over cavity leads to water coolant, after cavity is vacuumized, feeds argon gas and hydrogen respectively, wherein Ar:0.3MPa, H
2: 0.14MPa connects direct supply, regulating voltage is 15-45V, arc discharge takes place between anode target material Gd40Ni60 and tungsten cathode, the electric current that produces arc-over is 100-150A, regulate working current and voltage in the arc discharge process and keep relative stability (electric current is 120-130A), prepare the GdNi5 nano particle, in passivating process subsequently, the GdNi5 nano grain surface is oxidized to Gd2O3, finally forms the core-shell structure of Gd2O3 parcel GdNi5 nano particle.
Fig. 6 provides the X ray diffracting spectrum of gained A collection of illustrative plates indication by the GdNi5 nano particle of Gd40Ni60 alloy pig preparation, wherein diffraction peak is corresponding with GdNi5 standard diffraction peak among the figure, and wherein narrower diffraction peak is indicating the GdNi5 nano particle to have bigger particle radius.Figure 11,12 indicates pattern photo and the high resolution photo by the GdNi5 nano particle of Gd40Ni60 preparation, nanoparticle size is distributed as 30-80nm shown in it, photo shows that also the GdNi5 nano particle has typical core-shell structure, shell is Gd2O3, thickness is 0.312nm, kernel is the GdNi5 lattice image, and its corresponding crystal orientation is [101] direction.Figure 13 indicates the temperature-magnetzation curve of GdNi5 nano particle, the cold curve of ZFC curve representation null field wherein, the cold curve in FC curve representation field, the freezing temperature at different warm areas of 26K and 108K indication sample, 40K is the Curie temperature of GdNi5, and Figure 14 indicates the GdNi5 nano particle in the 5K-100K scope, under the 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 6J/ (kg K);
The plasma electrically arc discharge technology prepares the GdNi5 nano particle:
In gas ions arc-over cavity, used consumable anode target is that diameter 4.5cm thickness is the Gd of 4cm
yNi
100-y(y=40) alloy pig, the spacing of tungsten cathode and anode target material Gd40Ni60 alloy pig is 30mm.Article on plasma body arc-over cavity leads to water coolant, after cavity is vacuumized, feeds argon gas and hydrogen respectively, wherein Ar:0.8MPa, H
2: 0.14MPa connects direct supply, regulating voltage is 45-60V, arc discharge takes place between anode target material Gd40Ni60 and tungsten cathode, the electric current that produces arc-over is 350-400A, regulate working current and voltage keep relative stability (electric current is 350A) in the arc discharge process, prepare the GdNi5 nano particle, in passivating process subsequently, the GdNi5 nano grain surface is oxidized to Gd2O3, it is 80-150nm that the final core-shell structure that forms Gd2O3 parcel GdNi5 nano particle, resultant GdNi5 are received particle grain size distribution.
The plasma electrically arc discharge technology prepares the GdH2 nano particle:
In gas ions arc-over cavity, used consumable anode target is that diameter 4.5cm thickness is the Gd of 3cm
yNi
100-y(y=80) alloy pig, the spacing of tungsten cathode and anode target material Gd80Ni20 alloy pig is 23mm.Article on plasma body arc-over cavity leads to water coolant, after cavity is vacuumized, feeds argon gas and hydrogen respectively, wherein Ar:0.2MPa, H
2: 0.12MPa connects direct supply, regulating voltage is 12-35V, arc discharge takes place between anode target material Gd80Ni20 and tungsten cathode, the electric current that produces arc-over is 85-125A, adjusting working current and voltage keep relative stability (electric current is 80-110A) in the arc discharge process, prepare the GdH2 nano particle.
Figure 15 provides the X ray diffracting spectrum of gained collection of illustrative plates indication GdH2 nano particle, and wherein each diffraction peak is consistent with the GdH2 diffraction peak, and wherein narrower diffraction peak is indicating the GdH2 nano particle to have bigger particle radius.The pattern photo and the high resolution photo of Figure 16,17 indication GdH2 nano particles, nanoparticle size is distributed as 30-80nm shown in it, and photo also shows the lattice image of GdH2 nano particle, and its corresponding crystal orientation is [111] direction.Figure 18 indicates the GdH2 nano particle in the 5K-80K scope, and under the 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 12.1J/ (kg K);
The plasma electrically arc discharge technology prepares the GdH2 nano particle:
In gas ions arc-over cavity, used consumable anode target is that diameter 4.5cm thickness is the Gd of 3.5cm
yNi
100-y(y=85) alloy pig, the spacing of tungsten cathode and anode target material Gd85Ni15 alloy pig is 15mm.Article on plasma body arc-over cavity leads to water coolant, after cavity is vacuumized, feeds argon gas and hydrogen respectively, wherein Ar:0.7MPa, H
2: 0.5MPa connects direct supply, regulating voltage is 12-35V, arc discharge takes place between anode target material Gd85Ni15 and tungsten cathode, the electric current that produces arc-over is 120-180A, regulate working current and voltage keep relative stability (electric current is 130A) in the arc discharge process, prepare the GdH2 nano particle, the gained particle grain size distribution is 90-130nm.
Comparative Examples 1
In gas ions arc-over cavity, used consumable anode target is that diameter 5cm thickness is the Dy of 3cm
xNi
100-x(x=17) alloy pig, the spacing of tungsten cathode and anode target material Dy17Ni83 alloy pig is 10mm.Gas ions arc-over cavity is led to water coolant, after cavity is vacuumized, feed argon gas and hydrogen respectively, wherein Ar:0.2MPa, H
2: 0.05MPa connects direct supply, regulating voltage is 15-30V, arc discharge takes place between anode target material Dy30Ni70 and tungsten cathode, the electric current that produces arc-over is 60-100A, and adjusting working current and voltage keep relative stability (electric current is 80-90A) in the arc discharge process, can not obtain the GdNi5 nano particle, and can only prepare the Ni nano particle, in passivating process subsequently, the Ni nano grain surface is oxidized to NiO, finally forms the core-shell structure of NiO parcel Ni nano particle.The SDN1 diffraction spectra provides gained Ni nano particle X ray diffracting spectrum among Fig. 1, and wherein the peak of marking is the feature crystal face diffraction peak of Ni.
Comparative Examples 2
In gas ions arc-over cavity, used consumable anode target is that diameter 5cm thickness is the Dy of 3cm
xNi
100-x(x=40) alloy pig, the spacing of tungsten cathode and anode target material Dy40Ni60 alloy pig is 12mm.Gas ions arc-over cavity is led to water coolant, after cavity is vacuumized, feed argon gas and hydrogen respectively, wherein Ar:0.2MPa, H
2: 0.05MPa connects direct supply, regulating voltage is 15-30V, arc discharge takes place between anode target material Dy40Ni60 and tungsten cathode, the electric current that produces arc-over is 60-100A, regulate working current and voltage keep relative stability (electric current is 80-90A) in the arc discharge process, can not obtain the DyNi5 nano particle, and can only prepare the Dy2O3 oxide nano particles, this mainly is because in the plasma discharge process, Dy atom content in anode alloy is more, and vapour pressure is bigger, cause evaporation in a large number in evaporative process, and the evaporation of having resisted the Ni atom, thereby the Dy nano particle only formed, in passivating process subsequently, be oxidized to the Dy2O3 nano particle.
Comparative Examples 3
In gas ions arc-over cavity, used consumable anode target is that diameter 4.5cm thickness is the Gd of 3cm
yNi
100-y(y=20) alloy pig, the spacing of tungsten cathode and anode target material Gd20Ni80 alloy pig is 15mm.Article on plasma body arc-over cavity leads to water coolant, after cavity is vacuumized, feeds argon gas and hydrogen respectively, wherein Ar:0.22MPa, H
2: 0.06MPa connects direct supply, regulating voltage is 12-35V, arc discharge takes place between anode target material Gd20Ni80 and tungsten cathode, the electric current that produces arc-over is 80-120A, regulate working current and voltage keep relative stability (electric current is 80-100A) in the arc discharge process, preparation can not obtain the GdNi5 nano particle, and can only obtain the Ni nano particle.Fig. 6 provides the X ray diffracting spectrum of gained C collection of illustrative plates indication Ni nano particle, and wherein diffraction peak is corresponding with Ni standard diffraction peak among the figure.The reason that can only obtain the Ni nano particle is that Ni content is far above the content of Gd in the anode alloy, and the nano particle that causes being evaporated is the Ni particle.Although the vapour pressure of Ni is pressed less than the evaporation of Gd, because in the anode alloy among the Gd20Ni80, Ni content is far longer than the content of Gd, this makes in evaporative process, and what be evaporated is almost the Ni atom.
Comparative Examples 4
In gas ions arc-over cavity, used consumable anode target is that diameter 4.5cm thickness is the Gd of 3cm
xNi
100-x(x=90) alloy pig, the spacing of tungsten cathode and anode target material Gd10Ni90 alloy pig is 22mm.Article on plasma body arc-over cavity leads to water coolant, after cavity is vacuumized, feeds argon gas and hydrogen respectively, wherein Ar:0.22MPa, H
2: 0.06MPa connects direct supply, regulating voltage is 12-35V, arc discharge takes place between anode target material Gd10Ni90 and tungsten cathode, the electric current that produces arc-over is 80-120A, regulate working current and voltage keep relative stability (electric current is 80-100A) in the arc discharge process, preparation can not obtain the GdNi5 nano particle, and can only obtain the Gd2O3 nano particle.This mainly is because in the plasma discharge process, Gd atom content in anode alloy is more, and vapour pressure is bigger, cause evaporation in a large number in evaporative process, and resisted the evaporation of Ni atom, thereby only form the Gd nano particle, in passivating process subsequently, be oxidized to the Gd2O3 nano particle.
The foregoing description only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. rare earth intermetallic compound nano particle, it is characterized in that: described nano particle is that size is DyNi5, GdNi5 or the GdH2 particle of nano-level sphere.
2. according to the described rare earth intermetallic compound nano particle of claim 1, it is characterized in that:
GdNi5 and DyNi5 nano particle have typical core-shell structure, and kernel is respectively DyNi5 and GdNi5, and shell is respectively Dy2O3 and Gd2O3, and the GdH2 nano particle does not have core-shell structure, and above-mentioned three kinds of nano particle diameters are distributed as 10-150nm.
3. the preparation method of the described rare earth intermetallic compound nano particle of claim 1, it is characterized in that: described rare earth intermetallic compound nano particle is to utilize the plasma electrically arc discharge technology, and in-situ preparing obtains under working gas;
Wherein: adopting the pure metal tungsten electrode is negative electrode, and Gd-Ni and Dy-Ni alloy are anode target material, keeps the distance of 2-30mm between negative electrode and the anode target material; The electric current of arc-over is 15～400A, and voltage is 10～60V; Described working gas is argon gas and hydrogen.
4. according to the preparation method of the described rare earth intermetallic compound nano particle of claim 3, it is characterized in that: the dividing potential drop of argon gas is 0.01-0.8MPa, and the dividing potential drop of hydrogen is 0.01-0.5MPa.
5. according to the preparation method of the described rare earth intermetallic compound nano particle of claim 3, it is characterized in that: described anode target material is the alloy Dy of rare earth metal and magnetic transition metal Ni
xNi
100-x, x=28-32, Gd
yNi
100-y, y=30-85 and anode target material are cylindrical alloy block, and its diameter is 1-5cm, and thickness is 1-4cm.
6. according to the preparation method of the arbitrary described rare earth intermetallic compound nano particle of claim 3～5, it is characterized in that: used water coolant water temperature is lower than 20 degrees centigrade.
7. according to the preparation method of the described rare earth intermetallic compound nano particle of claim 3, it is characterized in that: the optimal anode alloying constituent of preparation GdNi5 Nano capsule is GdyNi100-y, y=40-60, the optimal anode alloying constituent of preparation DyNi5 Nano capsule is Dy30Ni70, the optimal alloy composition of preparation GdH2 nano particle is GdyNi100-y, y=75-85.
8. the described rare earth intermetallic compound DyNi5 of claim 1 nano particle is as the application of low temperature magnetic cooling material under the 5-60K.
9. the described rare earth intermetallic compound GdNi5 of claim 1 nano particle is as the application of low temperature magnetic cooling material under the 5-100K.
10. the described rare earth intermetallic compound GdH2 of claim 1 nano particle is as the application of low temperature magnetic cooling material under the 5-80K.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310152939.5A CN103214042B (en) | 2013-04-27 | 2013-04-27 | A kind of superparamagnetic rare earth intermetallic compound nano particle and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106180740A (en) * | 2015-05-27 | 2016-12-07 | 中国科学院金属研究所 | Co, Ni, FeCo, GdCo5nano capsule primary reconstruction nano chain and preparation thereof |
| CN112453417A (en) * | 2020-12-07 | 2021-03-09 | 沈阳翼源盟电器有限公司 | Method for preparing Ho-Al nano-scale alloy particles by direct current arc method |
| US11473171B1 (en) | 2022-05-31 | 2022-10-18 | Kunming University Of Science And Technology | Integrated method for purifying metal gadolinium and preparing gadolinium oxide nanomaterials by arc plasma |
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| CN1803816A (en) * | 2006-01-24 | 2006-07-19 | 北京工业大学 | Method for in-situ synthesizing preparation of high-purity GdH2 block material |
| CN101045547A (en) * | 2006-03-31 | 2007-10-03 | 中国科学院金属研究所 | Preparation method of rare earth RAl2 metal compound nano powder material |
| WO2010144746A2 (en) * | 2009-06-10 | 2010-12-16 | Genomatica, Inc. | Microorganisms and methods for carbon-efficient biosynthesis of mek and 2-butanol |
| CN102465225A (en) * | 2010-11-09 | 2012-05-23 | 中国科学院物理研究所 | Magnetic refrigerant material, its preparation method and application |
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| CN1803816A (en) * | 2006-01-24 | 2006-07-19 | 北京工业大学 | Method for in-situ synthesizing preparation of high-purity GdH2 block material |
| CN101045547A (en) * | 2006-03-31 | 2007-10-03 | 中国科学院金属研究所 | Preparation method of rare earth RAl2 metal compound nano powder material |
| WO2010144746A2 (en) * | 2009-06-10 | 2010-12-16 | Genomatica, Inc. | Microorganisms and methods for carbon-efficient biosynthesis of mek and 2-butanol |
| CN102465225A (en) * | 2010-11-09 | 2012-05-23 | 中国科学院物理研究所 | Magnetic refrigerant material, its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106180740A (en) * | 2015-05-27 | 2016-12-07 | 中国科学院金属研究所 | Co, Ni, FeCo, GdCo5nano capsule primary reconstruction nano chain and preparation thereof |
| CN106180740B (en) * | 2015-05-27 | 2019-02-12 | 中国科学院金属研究所 | Co, Ni, FeCo, GdCo5Nano capsule primary reconstruction nano chain and its preparation |
| CN112453417A (en) * | 2020-12-07 | 2021-03-09 | 沈阳翼源盟电器有限公司 | Method for preparing Ho-Al nano-scale alloy particles by direct current arc method |
| US11473171B1 (en) | 2022-05-31 | 2022-10-18 | Kunming University Of Science And Technology | Integrated method for purifying metal gadolinium and preparing gadolinium oxide nanomaterials by arc plasma |
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