CN103214042B - A kind of superparamagnetic rare earth intermetallic compound nano particle and preparation method thereof - Google Patents
A kind of superparamagnetic rare earth intermetallic compound nano particle and preparation method thereof Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims description 22
- 229910052761 rare earth metal Inorganic materials 0.000 title claims description 22
- 150000002910 rare earth metals Chemical class 0.000 title claims description 22
- 229910000765 intermetallic Inorganic materials 0.000 title claims description 21
- 230000005291 magnetic effect Effects 0.000 claims abstract description 56
- 239000011258 core-shell material Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 56
- 239000000956 alloy Substances 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 238000010891 electric arc Methods 0.000 claims description 34
- 239000013077 target material Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 23
- 229910052721 tungsten Inorganic materials 0.000 claims description 23
- 239000010937 tungsten Substances 0.000 claims description 23
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002826 coolant Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 4
- 239000002088 nanocapsule Substances 0.000 claims description 4
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- 150000003624 transition metals Chemical class 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 abstract description 13
- 238000005057 refrigeration Methods 0.000 abstract description 12
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002086 nanomaterial Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
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Abstract
The object of the present invention is to provide compound nano-particle between a kind of novel superparamagnetic metals, this kind of nano particle is respectively GdNi5, DyNi5, GdH2 nano particle, there is superparamagnetic feature, wherein GdNi5, DyNi5 nano particle has typical core-shell structure: GdNi5 nano particle is made up of Gd2O3 shell and GdNi5 kernel, and DyNi5 nano particle is made up of Dy2O3 shell and DyNi5 kernel.GdH2 nano particle is the particle being of a size of nano level single-phase GdH2.Above three kinds of nano particles have very high magnetic entropy and become within the scope of 5K warm area, become a kind of novel low temperature magnetic refrigeration nano material, and this nano material also directly can use in existence stable in the air.
Description
Technical field
The invention belongs to Material Field, relate to a kind of rare earth intermetallic compound DyNi5 with superparamagnetic feature, GdNi5, GdH2 nano particle and preparation method thereof, and as the application of low-temperature magnetic refrigeration material aspect.
Background technology
Close to certainly to the low temperature environment of zero degree (0K) annex for the basic physical properties of research various material itself, realize various superconduction environment, and Bose-Einstein condensation environment all has very important physical significance.Magnetic Refrigeration Technique realizes this kind of important Refrigeration Technique close to determining to low temperature environment near zero degree (0K).Magnetic cooling technology mainly utilizes paramagnetic material under changes of magnetic field, have the change of different magnetic entropy, and then the change utilizing this magnetic entropy to become reaches the heat exchange between paramagnetic material itself and environment, realizes the object of low temperature magnetic refrigeration.In recent years, in order to improve refrigerating efficiency, need prepare the nano material with superparamagnetic as magnetic refrigerating working material, therefore, preparation has the nano material that high magnetic entropy becomes becomes the day by day urgent requirement of low temperature magnetic material of cooling research more.
Early stage magnetic cooling material research comprises many materials, and brief introduction is as follows:
Patent 200610046215.2 discloses one plasma body and prepares RAl2(R=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er) method of metal nano material, the method utilizes plasma arc legal system to wrap up the nano particle of RAl2 intermetallic compound for Al2O3.
Patent 201110446792.1 discloses and 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, makes the crystal grain of material be grown up, improves the magnetothermal effect of material, magnetic entropy becomes and increases, and can be applicable in 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 B element, formed interstitial atom be present in Fe2P crystalline texture mutually in, stabilize phase structure, improve the magnetothermal effect of material, its working temperature is improved, magnetic entropy becomes and increases, and can be applicable in magnetic Refrigeration Technique.
Patent 201210169642.5 utilizes alloy cast ingot to carry out melt-spun under argon shield, gets rid of band technology and prepares Gd base amorphous magnetic refrigerating material.Prepared magnetic refrigerating material can be prepared into amorphous and can be prepared into compound again; This product shows second-order phase transition in magnetic history and magnetothermal effect is large; 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 for any one in Gd, Tb, Dy, Ho and Er, or Ho and Gd, any one combination in Tb, Dy and Er) material, it is characterized in that: the magnetic refrigerating material magnetic entropy that this invention provides uprises, refrigeration capacity strong, have good magnetic, heat reversible performance.
Above-mentioned materials is near room temperature magnetic refrigerating material, and all exists with metal blocks form.Therefore be badly in need of one and can, near 5K, realize the magnetic refrigerating material of cryogenic refrigeration near 5K, and material be in nano-scale range, be convenient to material quick heat radiating in process of refrigeration, reach good refrigeration.
Summary of the invention
The object of the present invention is to provide compound nano-particle between a kind of novel superparamagnetic metals, this kind of nano particle is respectively GdNi5, DyNi5, GdH2 nano particle, there is superparamagnetic feature, wherein GdNi5, DyNi5 nano particle has typical core-shell structure: GdNi5 nano particle is made up of Gd2O3 shell and GdNi5 kernel, and DyNi5 nano particle is made up of Dy2O3 shell and DyNi5 kernel.GdH2 nano particle is the particle being of a size of nano level single-phase GdH2.Above three kinds of nano particles have very high magnetic entropy and become within the scope of 5K warm area, become a kind of novel low temperature magnetic refrigeration nano material, and this nano material also directly can use in existence stable in the air.
The present invention specifically provides a kind of rare earth intermetallic compound nano particle, it is characterized in that: DyNi5, GdNi5 or GdH2 particle of described nano particle to be size be nano-level sphere.
Rare earth intermetallic compound nano particle of the present invention, is characterized in that:
GdNi5 and DyNi5 nano particle has typical core-shell structure, and kernel is respectively DyNi5 and GdNi5, and shell is respectively Dy2O3 and Gd2O3, and GdH2 nano particle is without 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 utilizes plasma electrically arc discharge technology, and under working gas, original position prepares;
Wherein: adopt pure metal tungsten electrode to be negative electrode, Gd-Ni and Dy-Ni alloy is anode target material, keeps the distance of 2-30mm between negative electrode and positive electrode target; 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 in the present invention, electric arc produces very high temperature, plasma body is by Gd-Ni simultaneously, Gd and Ni atom (or Dy and Ni atom) in Dy-Ni alloy is evaporated, in evaporative process, Gd and the Ni atom (or Dy and Ni atom) that is evaporated mutually collision forms GdNi5 nano particle and DyNi5 nano particle respectively, and in passivating process, GdNi5 and DyNi5 nano grain surface Gd atom is oxidized to Gd2O3 shell.Using plasma arc-discharge technique evaporation Gd-Ni alloy, when in alloy, Gd content is more than 80at.%, and under high amounts of hydrogen, H atom and Gd atom form GdH2 compound nano-particle.
The preparation method of rare earth intermetallic compound nano particle of the present invention, is characterized in that: cooler-water temperature used is lower than 20 degrees Celsius.
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).
(DyNi5 nano particle is within the scope of 5-60K as the application of magnetic cooling material within the scope of 5-100K to present invention also offers compound nano-particle between described superparamagnetic metals, GdNi5 nano particle is within the scope of 5-100K, and GdH2 nano particle is within the scope of 5-80K).Material of the present invention is within the scope of 5-100K warm area, and maximum magnetic entropy variable can reach 13J/ (kgK), therefore can as low temperature magnetic material of cooling.
Accompanying drawing explanation
Fig. 1 .Dy
xni
100-xthe X ray diffracting spectrum of nano particle prepared by (x=17,30,40) anode alloy;
Fig. 2. by Dy
30ni
70anode alloy prepares 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 nano particle prepared by anode alloy;
Fig. 4. by Dy
30ni
70nano particle magnetic hysteresis loop, wherein saturation magnetization 105Am under 5K prepared by anode alloy
2/ kg, coercive force 0.547T;
Fig. 5. by Dy
30ni
70nano particle prepared by anode alloy, within the scope of 5K-80K, under 7T changes of magnetic field, magnetic entropy becomes temperature variant curve;
Fig. 6 .Gd
xni
100-xthe X ray diffracting spectrum of nano particle prepared by (x=20,40,60) anode alloy;
Fig. 7. by Gd
60ni
40the transmission electron microscope photo shape appearance figure of nano particle prepared by anode alloy;
Fig. 8. by Gd
60ni
40the High-Resolution Map of nano particle prepared by anode alloy;
Fig. 9. by Gd
60ni
40temperature-the magnetzation curve of nano particle prepared by anode alloy;
Figure 10. by Gd
60ni
40nano particle prepared by anode alloy, within the scope of 5K-180K, under 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and wherein illustration is the magnetzation curve under differing temps;
Figure 11. by Gd
60ni
40the shape appearance figure of the transmission electron microscope photo of nano particle prepared by anode alloy, its housing is the lattice image of Gd2O3, and kernel is GdNi5 lattice image;
The High-Resolution Map of Figure 12 .GdNi5 nano particle, its housing is the lattice image of Gd2O3, and kernel is GdNi5 lattice image;
Figure 13. by Gd
40ni
60temperature-the magnetzation curve of nano particle prepared by anode alloy;
Figure 14. by Gd
40ni
60nano particle prepared by anode alloy, within the scope of 5K-100K, under 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and wherein illustration is the magnetzation curve under differing temps;
Figure 15. by Gd
80ni
20the X ray diffracting spectrum of GdH2 nano particle prepared by anode alloy;
Figure 16. by Gd
80ni
20the transmission electron microscope pattern photo of GdH2 nano particle prepared by anode alloy;
Figure 17. by Gd
80ni
20the high resolution lattice image of GdH2 nano particle prepared by anode alloy;
Figure 18. by Gd
80ni
20gdH2 nano particle prepared by anode alloy is between 5K to 80K, and the magnetic entropy change under 5T changes of magnetic field varies with temperature curve.
Embodiment
In the examples below, as non-specified otherwise, all employing purity is the tungsten electrode of 99.9% is negative electrode, and consumable anode target used is cylindrical alloy pig.Cooler-water temperature used is lower than 20 degrees Celsius.
Embodiment 1
Plasma electrically arc discharge technology prepares DyNi5 nano particle:
In gas ions arc-over cavity, consumable anode target used is 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.Water coolant is led to gas ions arc-over cavity, after cavity is vacuumized, passes into argon gas and hydrogen respectively, wherein Ar:0.2MPa, H
2: 0.05MPa connects direct supply, regulating voltage is 15-30V, arc discharge is there is between anode target material and negative electrode, the electric current producing arc-over is 60-100A, working current and voltage is regulated to keep relative stability (electric current is 80-90A) in arc discharge process, prepare DyNi5 nano particle, in passivating process subsequently (after namely arc-over terminates, 0.02Mpa argon gas and 0.002MPa air is passed in cavity, DyNi5 nano particle is slowly oxidized), DyNi5 nano grain surface is oxidized to Dy2O3, final formation Dy2O3 wraps up the nano particle of DyNi5.
Fig. 1 provides the X ray diffracting spectrum of gained DyNi5 nano particle, and wherein marked peak is the feature crystallographic plane diffraction peak of DyNi5, and the peak of round dot mark is Ni characteristic diffraction peak.Fig. 2 is by Dy
30ni
70dyNi5 nano particle pattern photo prepared by anode alloy and high resolution photo; shown in it, nanoparticle size is distributed as 30-80nm; photo also shows DyNi5 nano particle and has typical core-shell structure; kernel is DyNi5; shell be Dy2O3 to protect nano particle not oxidized, Dy2O3 outer casing thickness is about 3.6nm.Fig. 3 indicates DyNi5 nano particle temperature-magnetzation curve, wherein the cold curve of ZFC curve representation null field, the cold curve in FC curve representation field, and 235K indicates the freezing temperature of sample, and 20K is the Curie temperature of DyNi5.Fig. 4 is DyNi5 nano particle magnetic hysteresis loop, wherein saturation magnetization 105Am under 5K
2/ kg, coercive force 0.547T.Fig. 5 indicates DyNi5 nano particle within the scope of 5K-80K, and under 7T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 11.5J/ (kgK);
Embodiment 2
Plasma electrically arc discharge technology prepares DyNi5 nano particle:
In gas ions arc-over cavity, consumable anode target used is 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.Water coolant is led to gas ions arc-over cavity, after cavity is vacuumized, passes into argon gas and hydrogen respectively, wherein Ar:0.8MPa, H
2: 0.2MPa connects direct supply, regulating voltage is 18-35V, arc discharge is there is between anode target material and negative electrode, the electric current producing arc-over is 300-400A, working current and voltage is regulated to keep relative stability (electric current is 350A) in arc discharge process, prepare DyNi5 nano particle, at passivating process subsequently (after namely arc-over terminates, 0.02Mpa argon gas and 0.002MPa air is passed in cavity, DyNi5 nano particle is slowly oxidized) DyNi5 nano grain surface is oxidized to Dy2O3, final formation Dy2O3 wraps up the nano particle of DyNi5, nanoparticle size is distributed as 80-150nm.
Embodiment 3
Plasma electrically arc discharge technology prepares GdNi5 nano particle:
In gas ions arc-over cavity, consumable anode target used is 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.Plasma arc-over cavity leads to water coolant, after vacuumizing, passes into argon gas and hydrogen respectively, wherein Ar:0.22MPa, H to cavity
2: 0.06MPa connects direct supply, regulating voltage is 12-35V, arc discharge is there is between anode target material Gd60Ni40 and tungsten cathode, the electric current producing arc-over is 80-120A, regulate working current and voltage to keep relative stability (electric current is 80-100A) in arc discharge process, prepare GdNi5 nano particle.
Fig. 6 provides the X ray diffracting spectrum that gained B collection of illustrative plates indicates the GdNi5 nano particle prepared by Gd60Ni40 alloy pig, wherein diffraction peak is corresponding with GdNi5 standard diffraction peak in figure, and wherein wider diffraction peak indicates GdNi5 nano particle and has less particle radius.Fig. 7,8 indicates pattern photo and the high resolution photo of being prepared gained GdNi5 nano particle by Gd60Ni40, and shown in it, nanoparticle size is distributed as 10-40nm, and photo also shows the lattice image of GdNi5 nano particle, and the crystal orientation of its correspondence is [101] direction.Fig. 9 indicates the temperature-magnetzation curve of GdNi5 nano particle, the wherein cold curve of ZFC curve representation null field, the cold curve in FC curve representation field, 145K indicates the freezing temperature of sample, 40K is the Curie temperature of GdNi5, and Figure 10 indicates GdNi5 nano particle within the scope of 5K-180K, under 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 13.8J/ (kgK);
Embodiment 4
Plasma electrically arc discharge technology prepares GdNi5 nano particle:
In gas ions arc-over cavity, consumable anode target used is 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.Plasma arc-over cavity leads to water coolant, after vacuumizing, passes into argon gas and hydrogen respectively, wherein Ar:0.3MPa, H to cavity
2: 0.14MPa connects direct supply, regulating voltage is 15-45V, arc discharge is there is between anode target material Gd40Ni60 and tungsten cathode, the electric current producing arc-over is 100-150A, regulate working current and voltage to keep relative stability (electric current is 120-130A) in arc discharge process, prepare GdNi5 nano particle, in passivating process subsequently, GdNi5 nano grain surface is oxidized to Gd2O3, and the final Gd2O3 that formed wraps up the core-shell structure of GdNi5 nano particle.
Fig. 6 provides the X ray diffracting spectrum that gained A collection of illustrative plates indicates the GdNi5 nano particle prepared by Gd40Ni60 alloy pig, wherein diffraction peak is corresponding with GdNi5 standard diffraction peak in figure, and wherein narrower diffraction peak indicates GdNi5 nano particle and has larger particle radius.Figure 11,12 indicates pattern photo and the high resolution photo of the GdNi5 nano particle prepared by Gd40Ni60, shown in it, nanoparticle size is distributed as 30-80nm, photo also shows GdNi5 nano particle and has typical core-shell structure, shell is Gd2O3, thickness is 0.312nm, kernel is GdNi5 lattice image, and the crystal orientation of its correspondence is [101] direction.Figure 13 indicates the temperature-magnetzation curve of GdNi5 nano particle, the wherein cold curve of ZFC curve representation null field, the cold curve in FC curve representation field, 26K and 108K indicates the freezing temperature at different warm area of sample, 40K is the Curie temperature of GdNi5, and Figure 14 indicates GdNi5 nano particle within the scope of 5K-100K, under 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 6J/ (kgK);
Embodiment 5
Plasma electrically arc discharge technology prepares GdNi5 nano particle:
In gas ions arc-over cavity, consumable anode target used is 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.Plasma arc-over cavity leads to water coolant, after vacuumizing, passes into argon gas and hydrogen respectively, wherein Ar:0.8MPa, H to cavity
2: 0.14MPa connects direct supply, regulating voltage is 45-60V, arc discharge is there is between anode target material Gd40Ni60 and tungsten cathode, the electric current producing arc-over is 350-400A, working current and voltage is regulated to keep relative stability (electric current is 350A) in arc discharge process, prepare GdNi5 nano particle, in passivating process subsequently, GdNi5 nano grain surface is oxidized to Gd2O3, final formation Gd2O3 wraps up the core-shell structure of GdNi5 nano particle, obtain GdNi5 to receive the size distribution of particle be 80-150nm.
Embodiment 6
Plasma electrically arc discharge technology prepares GdH2 nano particle:
In gas ions arc-over cavity, consumable anode target used is 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.Plasma arc-over cavity leads to water coolant, after vacuumizing, passes into argon gas and hydrogen respectively, wherein Ar:0.2MPa, H to cavity
2: 0.12MPa connects direct supply, regulating voltage is 12-35V, arc discharge is there is between anode target material Gd80Ni20 and tungsten cathode, the electric current producing arc-over is 85-125A, regulate working current and voltage to keep relative stability (electric current is 80-110A) in arc discharge process, prepare GdH2 nano particle.
Figure 15 provides the X ray diffracting spectrum of gained collection of illustrative plates instruction GdH2 nano particle, and wherein each diffraction peak is consistent with GdH2 diffraction peak, and wherein narrower diffraction peak indicates GdH2 nano particle and has larger particle radius.The pattern photo of Figure 16,17 instruction GdH2 nano particles and high resolution photo, shown in it, nanoparticle size is distributed as 30-80nm, and photo also shows the lattice image of GdH2 nano particle, and the crystal orientation of its correspondence is [111] direction.Figure 18 indicates GdH2 nano particle within the scope of 5K-80K, and under 5T changes of magnetic field, magnetic entropy becomes temperature variant curve, and magnetic entropy becomes maximum can reach 12.1J/ (kgK);
Embodiment 7
Plasma electrically arc discharge technology prepares GdH2 nano particle:
In gas ions arc-over cavity, consumable anode target used is 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.Plasma arc-over cavity leads to water coolant, after vacuumizing, passes into argon gas and hydrogen respectively, wherein Ar:0.7MPa, H to cavity
2: 0.5MPa connects direct supply, regulating voltage is 12-35V, arc discharge is there is between anode target material Gd85Ni15 and tungsten cathode, the electric current producing arc-over is 120-180A, working current and voltage is regulated to keep relative stability (electric current is 130A) in arc discharge process, prepare GdH2 nano particle, the size distribution of gained particle is 90-130nm.
Comparative example 1
In gas ions arc-over cavity, consumable anode target used is 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.Water coolant is led to gas ions arc-over cavity, after cavity is vacuumized, passes into argon gas and hydrogen respectively, wherein Ar:0.2MPa, H
2: 0.05MPa connects direct supply, regulating voltage is 15-30V, arc discharge is there is between anode target material Dy30Ni70 and tungsten cathode, the electric current producing arc-over is 60-100A, regulates working current and voltage to keep relative stability (electric current is 80-90A), can not obtain GdNi5 nano particle in arc discharge process, and Ni nano particle can only be prepared, in passivating process subsequently, Ni nano grain surface is oxidized to NiO, and the final NiO that formed wraps up the core-shell structure of Ni nano particle.In Fig. 1, SDN1 diffraction spectra provides gained Ni nano particle X ray diffracting spectrum, and wherein marked peak is the feature crystallographic plane diffraction peak of Ni.
Comparative example 2
In gas ions arc-over cavity, consumable anode target used is 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.Water coolant is led to gas ions arc-over cavity, after cavity is vacuumized, passes into argon gas and hydrogen respectively, wherein Ar:0.2MPa, H
2: 0.05MPa connects direct supply, regulating voltage is 15-30V, arc discharge is there is between anode target material Dy40Ni60 and tungsten cathode, the electric current producing arc-over is 60-100A, working current and voltage is regulated to keep relative stability (electric current is 80-90A) in arc discharge process, DyNi5 nano particle can not be obtained, and Dy2O3 oxide nano particles can only be prepared, this is mainly because in plasma discharge processes, Dy atom content in anode alloy is more, and vapour pressure is larger, cause evaporating in a large number in evaporative process, and resisted the evaporation of Ni atom, thus only form Dy nano particle, in passivating process subsequently, be oxidized to Dy2O3 nano particle.
Comparative example 3
In gas ions arc-over cavity, consumable anode target used is 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.Plasma arc-over cavity leads to water coolant, after vacuumizing, passes into argon gas and hydrogen respectively, wherein Ar:0.22MPa, H to cavity
2: 0.06MPa connects direct supply, regulating voltage is 12-35V, arc discharge is there is between anode target material Gd20Ni80 and tungsten cathode, the electric current producing arc-over is 80-120A, working current and voltage is regulated to keep relative stability (electric current is 80-100A) in arc discharge process, preparation can not obtain GdNi5 nano particle, and can only obtain Ni nano particle.Fig. 6 provides the X ray diffracting spectrum of gained C collection of illustrative plates instruction Ni nano particle, and wherein diffraction peak is corresponding with Ni standard diffraction peak in figure.The reason that can only obtain Ni nano particle is, in anode alloy, Ni content is far above the content of Gd, and the nano particle that causes being evaporated is Ni particle.Although the vapour pressure of Ni is less than the vapor pres-sure of Gd, due in Gd20Ni80 in anode alloy, Ni content is far longer than the content of Gd, and this makes in evaporative process, and what be evaporated is almost Ni atom.
Comparative example 4
In gas ions arc-over cavity, consumable anode target used is 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.Plasma arc-over cavity leads to water coolant, after vacuumizing, passes into argon gas and hydrogen respectively, wherein Ar:0.22MPa, H to cavity
2: 0.06MPa connects direct supply, regulating voltage is 12-35V, arc discharge is there is between anode target material Gd10Ni90 and tungsten cathode, the electric current producing arc-over is 80-120A, working current and voltage is regulated to keep relative stability (electric current is 80-100A) in arc discharge process, preparation can not obtain GdNi5 nano particle, and can only obtain Gd2O3 nano particle.This is mainly because in plasma discharge processes, Gd atom content in anode alloy is more, and vapour pressure is larger, cause evaporating in a large number in evaporative process, and resisted the evaporation of Ni atom, thus only form Gd nano particle, in passivating process subsequently, be oxidized to Gd2O3 nano particle.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (8)
1. a rare earth intermetallic compound nano particle, is characterized in that: the DyNi of described nano particle to be size be nano-level sphere
5or GdNi
5particle, DyNi
5and GdNi
5nano particle has typical core-shell structure, and kernel is respectively DyNi
5with GdNi
5, shell is respectively Dy
2o
3with Gd
2o
3, above-mentioned two kinds of nano particle diameters are distributed as 10-150nm.
2. a preparation method for rare earth intermetallic compound nano particle described in claim 1, is characterized in that: described rare earth intermetallic compound nano particle utilizes plasma electrically arc discharge technology, and under working gas, original position prepares;
Wherein: adopt pure metal tungsten electrode to be negative electrode, Gd-Ni and Dy-Ni alloy is anode target material, keeps the distance of 2-30mm between negative electrode and positive electrode target; The electric current of arc-over is 15 ~ 400A, and voltage is 10 ~ 60V; Described working gas is argon gas and hydrogen.
3. according to the preparation method of rare earth intermetallic compound nano particle described in claim 2, it is characterized in that: the dividing potential drop of argon gas is 0.01-0.8MPa, the dividing potential drop of hydrogen is 0.01-0.5MPa.
4. according to the preparation method of rare earth intermetallic compound nano particle described in claim 2, 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 is cylindrical alloy block, its diameter is 1-5cm, and thickness is 1-4cm.
5. according to the preparation method of the arbitrary described rare earth intermetallic compound nano particle of claim 2 ~ 4, it is characterized in that: lead to water coolant to gas ions arc-over cavity, cooler-water temperature used is lower than 20 degrees Celsius.
6. according to the preparation method of rare earth intermetallic compound nano particle described in claim 2, it is characterized in that: preparation GdNi
5the anode alloy composition of Nano capsule is Gd
yni
100-y, y=40-60, preparation DyNi
5the anode alloy composition of Nano capsule is Dy
30ni
70.
7. rare earth intermetallic compound DyNi described in a claim 1
5nano particle is as the application of low temperature magnetic cooling material under 5-60K.
8. rare earth intermetallic compound GdNi described in a claim 1
5nano particle is as the application of low temperature magnetic cooling material under 5-100K.
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