CN110277211A - A kind of preparation method of samarium iron nitrogen magnetic nanotube - Google Patents

A kind of preparation method of samarium iron nitrogen magnetic nanotube Download PDF

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CN110277211A
CN110277211A CN201910643628.6A CN201910643628A CN110277211A CN 110277211 A CN110277211 A CN 110277211A CN 201910643628 A CN201910643628 A CN 201910643628A CN 110277211 A CN110277211 A CN 110277211A
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nanotube
samarium iron
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magnetic field
electrode
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CN110277211B (en
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徐靖才
洪波
王新庆
彭晓领
金红晓
金顶峰
葛洪良
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China Jiliang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C23C8/24—Nitriding
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
    • H01F1/009—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity bidimensional, e.g. nanoscale period nanomagnet arrays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets

Abstract

The present invention relates to a kind of preparation methods of samarium iron nitrogen magnetic nanotube, the invention is using porous aluminas as template, samarium iron nanotube array is prepared using pulse electrodeposition method under vertical magnetic field, then samarium iron nanotube array is placed in heat-treatment furnace, obtains samarium iron nitrogen magnetic nano-tube array by nitriding orientation, annealing hydrogenation and nitridation.The samarium iron nitrogen magnetic nano-tube array that this method obtains is high-sequential nano-tube array, and the outer diameter of nanotube and the aperture of porous alumina formwork are consistent；Samarium iron nitrogen magnetic nano-array has excellent magnetic property and magnetic anisotropy.

Description

A kind of preparation method of samarium iron nitrogen magnetic nanotube
Technical field
The present invention relates to a kind of preparation methods of samarium iron nitrogen magnetic nanotube, belong to field of material preparation.
Background technique
Permanent-magnet material is that have larger remanent magnetism, coercivity, magnetic energy product and can keep constant magnetic material once magnetization. Permanent-magnet material experienced carbon steel-aluminum nickel cobalt-ferrite-SmCo5-Sm2Co17-Nd2Fe14The several main developing stage of B.Wherein Rare earth permanent-magnetic material is the novel permanent magnetic material to grow up in the 60's of 20th century, including first generation rare earth permanent magnet 1:5 Type SmCo alloy, second generation rare earth permanent magnet 2:17 type SmCo alloy；The first generation and second generation rare earth permanent-magnetic material all contain Have a rare earth element Co, and Co be strategic materials, it is expensive, which greatly limits being widely used for they, in It is to be developed third generation Nd-Fe-B rare earth permanent-magnetic material.Compared with the first and second generation rare earth permanent-magnetic material, the magnetic of Nd-Fe-B It has excellent performance, there is the good reputation of " magnetic king " in rapid rare-earth permanent magnet market.But Nd-Fe-B itself is simultaneously imperfect, and disadvantage is equally bright It is aobvious, such as Curie temperature is low when content of rare earth height, poor corrosion resistance and high temperature.Therefore people actively seek rare earth permanent magnet of new generation Material.Sm-Fe-N regardless of in terms of the magnetic property, or from production cost for, all very possible substitution Nd-Fe- B becomes the forth generation rare earth permanent-magnetic material of people's expectation.
Currently, the preparation method of Sm-Fe-N mainly has melt-quenching method (RQ), mechanical alloying method (MA), powder metallurgy Method (PM), hydrogenation-disproportionation-dehydrogenation-chemical combination method (HDDR) again.But with the high-tech development of modern humans society, electronic device Micromation, function it is compatible it is integrated require it is higher and higher.The Sm-Fe-N magnet that current process is prepared is difficult to meet high-end It needs, so being badly in need of the Sm-Fe-N magnetic Nano material that exploitation has high energy product and excellent magnetic anisotropy.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of samarium iron nitrogen magnetic nanotube, the samarium iron which obtains Nitrogen magnetic nanotube is high-sequential nano-tube array, and the outer diameter of nanotube and the aperture of porous alumina formwork are consistent；Samarium iron nitrogen Magnetic nanotube has high energy product and excellent magnetic anisotropy.
In order to achieve the above-mentioned object of the invention, specific steps of the invention are as follows:
1), porous alumina formwork prepares: the alumina formwork that aperture is 200nm bilateral is chosen, in its back side magnetron sputtering one Layer is successively dried with a thickness of 1 μm of golden film after methyl dimethoxysilane, ethyl alcohol, distilled water ultrasonic cleaning with spare；
2), the preparation of samarium iron nanotube: pulse electrodeposition method is used to prepare samarium iron nanotube under magnetic field: is ready to the first step Alumina formwork is as working electrode, and mercury electrode is to electrode, and Ag/AgCl electrode is auxiliary electrode, is added after depositing liquid 30 ~ 50 DEG C of stirrings are lower to carry out pulse electrodeposition, and deposition is completed to be dissolved porous alumina formwork with the NaOH solution of 2 mol/L, Then it is cleaned with ethyl alcohol and distilled water to neutrality；
The direction in the magnetic field and the direction of growth of nanotube are vertical, and the size in magnetic field is 1 ~ 5 T；
The solute of the deposition liquid are as follows: SmCl3•6H2O、FeCl2•4H2O、Na3C6H5O7•2H2O、NaCl、H3BO3And Vitamin C Acid, solvent are the water and ethylene glycol solution of 2:1；
The condition of the pulse electrodeposition are as follows: current density is 10 ~ 20 mA/cm2, pulse frequency is 1 ~ 10 Hz, and pulse accounts for Sky is than being 0.1 ~ 0.5；
3), nitriding is orientated: samarium iron nanotube column being placed in heat-treatment furnace, in 100 ~ 150 DEG C of 1 ~ 5h of heat preservation, then with constant Rate is passed through ammonia, while applying the magnetic field of 0.5 ~ 1T, in 100 ~ 150 DEG C of 5 ~ 10h of preliminary nitriding；
4), annealing hydrogenation: being passed through high-purity argon gas with constant rate, and anneal 1 ~ 5h at 400 ~ 600 DEG C, then with constant speed Rate is passed through the argon hydrogen gaseous mixture containing 50% hydrogen, at 300 ~ 400 DEG C hydrogenate 10 ~ for 24 hours；
5) it, nitrogenizes: high pure nitrogen is passed through with constant rate, 2 ~ 20h is nitrogenized at 300 ~ 400 DEG C, be down to room temperature, take out sample Obtain samarium iron nitrogen magnetic nanotube.
Technical effect: the present invention utilizes the process conditions of vertical magnetic field, water and ethylene glycol mixed solvent and pulse electrodeposition, Make Sm3+、Fe2+The formation ferromagnetic nanotube of samarium in porous aluminas duct can be co-deposited；The samarium iron of nano-scale of the present invention is received Mitron, is hydrogenated by preliminary nitriding orientation, annealing, is provided advantage for nitridation, is obtained the higher samarium iron nitrogen magnetic of nitrogen content and receive Mitron makes samarium iron nitrogen magnetic nanotube have excellent magnetic anisotropy.
Specific embodiment
Here is that the present invention will be described in detail in conjunction with the embodiments, to more fully understand the purpose of the present invention, feature And advantage.Although the present invention is that the specific embodiment is combined to be described, it is not intended that the invention be limited to described tool Body embodiment.On the contrary, to may include in the claims in the present invention defined by embodiment in protection scope replace Generation, improvement and equivalent embodiment, belong to protection scope of the present invention.It can be by normal for the technological parameter not marked especially Rule technology carries out.
Specific steps of the invention are as follows:
1), porous alumina formwork prepares: the alumina formwork that aperture is 200nm bilateral is chosen, in its back side magnetron sputtering one Layer is successively dried with a thickness of 1 μm of golden film after methyl dimethoxysilane, ethyl alcohol, distilled water ultrasonic cleaning with spare；
2), the preparation of samarium iron nanotube: pulse electrodeposition method is used to prepare samarium iron nanotube under magnetic field: is ready to the first step Alumina formwork is as working electrode, and mercury electrode is to electrode, and Ag/AgCl electrode is auxiliary electrode, is added after depositing liquid 30 ~ 50 DEG C of stirrings are lower to carry out pulse electrodeposition, and deposition is completed to be dissolved porous alumina formwork with the NaOH solution of 2 mol/L, Then it is cleaned with ethyl alcohol and distilled water to neutrality；
The direction in the magnetic field and the direction of growth of nanotube are vertical, and the size in magnetic field is 1 ~ 5 T；
The solute of the deposition liquid are as follows: SmCl3•6H2O、FeCl2•4H2O、Na3C6H5O7•2H2O、 NaCl、H3BO3With it is anti-bad Hematic acid, solvent are the water and ethylene glycol solution of 2:1；
The condition of the pulse electrodeposition are as follows: current density is 10 ~ 20 mA/cm2, pulse frequency is 1 ~ 10 Hz, and pulse accounts for Sky is than being 0.1 ~ 0.5；
3), nitriding is orientated: samarium iron nanotube column being placed in heat-treatment furnace, in 100 ~ 150 DEG C of 1 ~ 5h of heat preservation, then with constant Rate is passed through ammonia, while applying the magnetic field of 0.5 ~ 1T, in 100 ~ 150 DEG C of 5 ~ 10h of preliminary nitriding；
4), annealing hydrogenation: being passed through high-purity argon gas with constant rate, and anneal 1 ~ 5h at 400 ~ 600 DEG C, then with constant speed Rate is passed through the argon hydrogen gaseous mixture containing 50% hydrogen, at 300 ~ 400 DEG C hydrogenate 10 ~ for 24 hours；
5) it, nitrogenizes: high pure nitrogen is passed through with constant rate, 2 ~ 20h is nitrogenized at 300 ~ 400 DEG C, be down to room temperature, take out sample Obtain samarium iron nitrogen magnetic nanotube.
Embodiment 1:
Step are as follows:
1), porous alumina formwork prepares: the alumina formwork that aperture is 200nm bilateral is chosen, in its back side magnetron sputtering one Layer is successively dried with a thickness of 1 μm of golden film after methyl dimethoxysilane, ethyl alcohol, distilled water ultrasonic cleaning with spare；
2), the preparation of samarium iron nanotube: pulse electrodeposition method is used to prepare samarium iron nanotube under magnetic field: is ready to the first step Alumina formwork is as working electrode, and mercury electrode is to electrode, and Ag/AgCl electrode is auxiliary electrode, is added after depositing liquid 50 DEG C of stirrings are lower to carry out pulse electrodeposition, and deposition is completed to be dissolved porous alumina formwork with the NaOH solution of 2 mol/L, then It is cleaned with ethyl alcohol and distilled water to neutrality；
The direction in the magnetic field and the direction of growth of nanotube are vertical, and the size in magnetic field is 5 T；
The solute of the deposition liquid are as follows: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1 mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid, solvent are the water and ethylene glycol of 2:1 Solution；
The condition of the pulse electrodeposition are as follows: current density is 10 mA/cm2, pulse frequency is 10 Hz, and pulse duty factor is 0.5；
3), nitriding is orientated: samarium iron nanotube column are placed in heat-treatment furnace, it is then logical with constant rate in 150 DEG C of heat preservation 4h Enter ammonia, while applying the magnetic field of 1T, in 150 DEG C of preliminary nitriding 5h；
4), annealing hydrogenation: high-purity argon gas is passed through with constant rate, anneal 4h at 400 DEG C, is then passed through with constant rate Argon hydrogen gaseous mixture containing 50% hydrogen, hydrogenates 20h at 400 DEG C；
5) it, nitrogenizes: high pure nitrogen being passed through with constant rate, nitrogenizes 10h at 400 DEG C, be down to room temperature, take out sample and obtain Samarium iron nitrogen magnetic nanotube.
XRD and TEM characterization is carried out to sample prepared by embodiment 1, detects samarium iron nitrogen object phase, the pattern of samarium iron nitrogen For ordered nano-tube array structure；To samarium iron nitrogen magnetic nano-tube array carry out VSM test, find its magnetic energy product with higher and Excellent magnetic anisotropy.
Embodiment 2:
Step are as follows:
1), porous alumina formwork prepares: the alumina formwork that aperture is 200nm bilateral is chosen, in its back side magnetron sputtering one Layer is successively dried with a thickness of 1 μm of golden film after methyl dimethoxysilane, ethyl alcohol, distilled water ultrasonic cleaning with spare；
2), the preparation of samarium iron nanotube: pulse electrodeposition method is used to prepare samarium iron nanotube under magnetic field: is ready to the first step Alumina formwork is as working electrode, and mercury electrode is to electrode, and Ag/AgCl electrode is auxiliary electrode, is added after depositing liquid 30 DEG C of stirrings are lower to carry out pulse electrodeposition, and deposition is completed to be dissolved porous alumina formwork with the NaOH solution of 2 mol/L, then It is cleaned with ethyl alcohol and distilled water to neutrality；
The direction in the magnetic field and the direction of growth of nanotube are vertical, and the size in magnetic field is 1 T；
The solute of the deposition liquid are as follows: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1 mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid, solvent are the water and ethylene glycol of 2:1 Solution；
The condition of the pulse electrodeposition are as follows: current density is 20 mA/cm2, pulse frequency 1Hz, pulse duty factor is 0.1；
3), nitriding is orientated: samarium iron nanotube column are placed in heat-treatment furnace, it is then logical with constant rate in 100 DEG C of heat preservation 5h Enter ammonia, while applying the magnetic field of 0.5T, in 100 DEG C of 5 ~ 10h of preliminary nitriding；
4), annealing hydrogenation: high-purity argon gas is passed through with constant rate, anneal 5h at 500 DEG C, is then passed through with constant rate Argon hydrogen gaseous mixture containing 50% hydrogen, hydrogenates for 24 hours at 300 DEG C；
5) it, nitrogenizes: high pure nitrogen being passed through with constant rate, nitrogenizes 20h at 300 DEG C, be down to room temperature, take out sample and obtain Samarium iron nitrogen magnetic nanotube.
XRD and TEM characterization is carried out to sample prepared by embodiment 2, detects samarium iron nitrogen object phase, the pattern of samarium iron nitrogen For ordered nano-tube array structure；To samarium iron nitrogen magnetic nano-tube array carry out VSM test, find its magnetic energy product with higher and Excellent magnetic anisotropy.
Embodiment 3:
Step are as follows:
1), porous alumina formwork prepares: the alumina formwork that aperture is 200nm bilateral is chosen, in its back side magnetron sputtering one Layer is successively dried with a thickness of 1 μm of golden film after methyl dimethoxysilane, ethyl alcohol, distilled water ultrasonic cleaning with spare；
2), the preparation of samarium iron nanotube: pulse electrodeposition method is used to prepare samarium iron nanotube under magnetic field: is ready to the first step Alumina formwork is as working electrode, and mercury electrode is to electrode, and Ag/AgCl electrode is auxiliary electrode, is added after depositing liquid 40 DEG C of stirrings are lower to carry out pulse electrodeposition, and deposition is completed to be dissolved porous alumina formwork with the NaOH solution of 2 mol/L, then It is cleaned with ethyl alcohol and distilled water to neutrality；
The direction in the magnetic field and the direction of growth of nanotube are vertical, and the size in magnetic field is 2 T；
The solute of the deposition liquid are as follows: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1 mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid, solvent are the water and ethylene glycol of 2:1 Solution；
The condition of the pulse electrodeposition are as follows: current density is 15 mA/cm2, pulse frequency is 8 Hz, and pulse duty factor is 0.3；
3), nitriding is orientated: samarium iron nanotube column are placed in heat-treatment furnace, it is then logical with constant rate in 120 DEG C of heat preservation 3h Enter ammonia, while applying the magnetic field of 0.8T, in 120 DEG C of preliminary nitriding 8h；
4), annealing hydrogenation: high-purity argon gas is passed through with constant rate, anneal 1h at 600 DEG C, is then passed through with constant rate Argon hydrogen gaseous mixture containing 50% hydrogen, hydrogenates 10h at 400 DEG C；
5) it, nitrogenizes: high pure nitrogen being passed through with constant rate, nitrogenizes 10h at 400 DEG C, be down to room temperature, take out sample and obtain Samarium iron nitrogen magnetic nanotube.
XRD and TEM characterization is carried out to sample prepared by embodiment 3, detects samarium iron nitrogen object phase, the pattern of samarium iron nitrogen For ordered nano-tube array structure；To samarium iron nitrogen magnetic nano-tube array carry out VSM test, find its magnetic energy product with higher and Excellent magnetic anisotropy.
Embodiment 4:
Step are as follows:
1), porous alumina formwork prepares: the alumina formwork that aperture is 200nm bilateral is chosen, in its back side magnetron sputtering one Layer is successively dried with a thickness of 1 μm of golden film after methyl dimethoxysilane, ethyl alcohol, distilled water ultrasonic cleaning with spare；
2), the preparation of samarium iron nanotube: pulse electrodeposition method is used to prepare samarium iron nanotube under magnetic field: is ready to the first step Alumina formwork is as working electrode, and mercury electrode is to electrode, and Ag/AgCl electrode is auxiliary electrode, is added after depositing liquid 50 DEG C of stirrings are lower to carry out pulse electrodeposition, and deposition is completed to be dissolved porous alumina formwork with the NaOH solution of 2 mol/L, then It is cleaned with ethyl alcohol and distilled water to neutrality；
The direction in the magnetic field and the direction of growth of nanotube are vertical, and the size in magnetic field is 4 T；
The solute of the deposition liquid are as follows: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1 mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid, solvent are the water and ethylene glycol of 2:1 Solution；
The condition of the pulse electrodeposition are as follows: current density is 12 mA/cm2, pulse frequency is 3 Hz, and pulse duty factor is 0.5；
3), nitriding is orientated: samarium iron nanotube column are placed in heat-treatment furnace, it is then logical with constant rate in 100 DEG C of heat preservation 5h Enter ammonia, while applying the magnetic field of 1T, in 100 DEG C of preliminary nitriding 10h；
4), annealing hydrogenation: high-purity argon gas is passed through with constant rate, anneal 5h at 500 DEG C, is then passed through with constant rate Argon hydrogen gaseous mixture containing 50% hydrogen, hydrogenates 15h at 400 DEG C；
5) it, nitrogenizes: high pure nitrogen being passed through with constant rate, nitrogenizes 15h at 400 DEG C, be down to room temperature, take out sample and obtain Samarium iron nitrogen magnetic nanotube.
XRD and TEM characterization is carried out to sample prepared by embodiment 4, detects samarium iron nitrogen object phase, the pattern of samarium iron nitrogen For ordered nano-tube array structure；To samarium iron nitrogen magnetic nano-tube array carry out VSM test, find its magnetic energy product with higher and Excellent magnetic anisotropy.

Claims (1)

1. a kind of preparation method of samarium iron nitrogen magnetic nanotube, which is characterized in that comprise the steps of:
1), porous alumina formwork prepares: the alumina formwork that aperture is 200nm bilateral is chosen, in its back side magnetron sputtering one Layer is successively dried with a thickness of 1 μm of golden film after methyl dimethoxysilane, ethyl alcohol, distilled water ultrasonic cleaning with spare；
2), the preparation of samarium iron nanotube: pulse electrodeposition method is used to prepare samarium iron nanotube under magnetic field: is ready to the first step Alumina formwork is as working electrode, and mercury electrode is to electrode, and Ag/AgCl electrode is auxiliary electrode, is added after depositing liquid 30 ~ 50 DEG C of stirrings are lower to carry out pulse electrodeposition, and deposition is completed to be dissolved porous alumina formwork with the NaOH solution of 2 mol/L, Then it is cleaned with ethyl alcohol and distilled water to neutrality；
The direction in the magnetic field and the direction of growth of nanotube are vertical, and the size in magnetic field is 1 ~ 5 T；
The solute of the deposition liquid are as follows: SmCl3•6H2O、FeCl2•4H2O、Na3C6H5O7•2H2O、NaCl、H3BO3And Vitamin C Acid, solvent are the water and ethylene glycol solution of 2:1；
The condition of the pulse electrodeposition are as follows: current density is 10 ~ 20 mA/cm2, pulse frequency is 1 ~ 10 Hz, pulse duration Than being 0.1 ~ 0.5；
3), nitriding is orientated: samarium iron nanotube column being placed in heat-treatment furnace, in 100 ~ 150 DEG C of 1 ~ 5h of heat preservation, then with constant Rate is passed through ammonia, while applying the magnetic field of 0.5 ~ 1T, in 100 ~ 150 DEG C of 5 ~ 10h of preliminary nitriding；
4), annealing hydrogenation: being passed through high-purity argon gas with constant rate, and anneal 1 ~ 5h at 400 ~ 600 DEG C, then with constant speed Rate is passed through the argon hydrogen gaseous mixture containing 50% hydrogen, at 300 ~ 400 DEG C hydrogenate 10 ~ for 24 hours；
5) it, nitrogenizes: high pure nitrogen is passed through with constant rate, 2 ~ 20h is nitrogenized at 300 ~ 400 DEG C, be down to room temperature, take out sample Obtain samarium iron nitrogen magnetic nanotube.
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