CN110277211B - Preparation method of samarium-iron-nitrogen magnetic nanotube - Google Patents
Preparation method of samarium-iron-nitrogen magnetic nanotube Download PDFInfo
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Abstract
The invention relates to a preparation method of a samarium-iron-nitrogen magnetic nanotube, which is characterized in that porous alumina is used as a template, a pulse electrodeposition method is adopted to prepare a samarium-iron nanotube array under a vertical magnetic field, then the samarium-iron nanotube array is placed in a heat treatment furnace, and the samarium-iron-nitrogen magnetic nanotube array is obtained through nitriding orientation, annealing hydrogenation and nitriding. The samarium-iron-nitrogen magnetic nanotube array obtained by the method is a highly ordered nanotube array, and the outer diameter of the nanotube is consistent with the aperture of the porous alumina template; the samarium-iron-nitrogen magnetic nano array has excellent magnetic performance and magnetic anisotropy.
Description
Technical Field
The invention relates to a preparation method of a samarium-iron-nitrogen magnetic nanotube, belonging to the field of material preparation.
Background
The permanent magnetic material has large remanence, coercive force, magnetic energy and can keep constant magnetism after being magnetized. The permanent magnetic material is processed by carbon steel-AlNiCo-ferrite-SmCo5-Sm2Co17-Nd2Fe14B several major stages of development. The rare earth permanent magnet material is a novel permanent magnet material developed in the 60 s of the 20 th century, and comprises a first-generation rare earth permanent magnet 1: type 5 SmCo alloySecond-generation rare earth permanent magnet 2: type 17 SmCo alloys; the first and second generation rare earth permanent magnetic materials both contain rare earth element Co, which is a strategic material and is expensive, which limits their wide use to a great extent, and thus, the third generation Nd-Fe-B rare earth permanent magnetic materials are developed. Compared with the first and second generation rare earth permanent magnet materials, Nd-Fe-B has excellent magnetic performance, and the rare earth permanent magnet market is fast, so that the Nd-Fe-B has the reputation of "Magang". However, Nd-Fe-B is not perfect, and has the same obvious defects, such as high rare earth content, poor corrosion resistance, low Curie temperature at high temperature and the like. Therefore, people are actively searching for a new generation of rare earth permanent magnetic material. Sm-Fe-N is likely to replace Nd-Fe-B in terms of magnetic performance and production cost, and is expected to be a fourth generation rare earth permanent magnet material.
At present, the Sm-Fe-N is mainly prepared by a melt rapid quenching method (RQ), a mechanical alloying Method (MA), a powder metallurgy method (PM) and a hydrogenation-disproportionation-dehydrogenation-recrystallization method (HDDR). However, with the development of high technology in modern human society, the requirements for miniaturization and function compatibility integration of electronic devices are higher and higher. The Sm-Fe-N magnet prepared by the current process is difficult to meet high-end requirements, so that the development of Sm-Fe-N magnetic nano materials with high magnetic energy product and excellent magnetic anisotropy is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of samarium-iron-nitrogen magnetic nanotubes, wherein the samarium-iron-nitrogen magnetic nanotubes obtained by the preparation method are highly ordered nanotube arrays, and the outer diameter of the nanotubes is consistent with the aperture of a porous alumina template; samarium-iron-nitrogen magnetic nanotubes have high magnetic energy products and excellent magnetic anisotropy.
In order to achieve the purpose of the invention, the method comprises the following specific steps:
1) preparing a porous alumina template: selecting a 200nm bi-pass alumina template, carrying out magnetron sputtering on the back of the alumina template to form a gold film with the thickness of 1 mu m, and drying the gold film after ultrasonic cleaning by methyldimethoxysilane, ethanol and distilled water in sequence for later use;
2) and preparation of samarium-iron nanotubes: preparing samarium-iron nanotubes by adopting a pulse electrodeposition method under a magnetic field: preparing an alumina template as a working electrode, a mercury electrode as a counter electrode, an Ag/AgCl electrode as an auxiliary electrode, adding a deposition solution, performing pulse electrodeposition under stirring at 30-50 ℃, dissolving the porous alumina template by using 2 mol/L NaOH solution after deposition is finished, and then washing the porous alumina template to be neutral by using ethanol and distilled water;
the direction of the magnetic field is vertical to the growth direction of the nanotube, and the size of the magnetic field is 1-5T;
the deposition solution comprises the following solutes: SmCl3•6H2O、FeCl2•4H2O、Na3C6H5O7•2H2O、NaCl、H3BO3And ascorbic acid in a 2:1 solution of water and ethylene glycol;
the conditions of the pulse electrodeposition are as follows: the current density is 10-20 mA/cm2The pulse frequency is 1-10 Hz, and the pulse duty ratio is 0.1-0.5;
3) and nitriding orientation: placing a samarium-iron nanotube array in a heat treatment furnace, preserving heat for 1-5 h at 100-150 ℃, then introducing ammonia gas at a constant speed, applying a 0.5-1T magnetic field, and primarily nitriding for 5-10 h at 100-150 ℃;
4) annealing and hydrogenation: introducing high-purity argon at a constant rate, annealing at 400-600 ℃ for 1-5 h, introducing argon-hydrogen mixed gas containing 50% hydrogen at a constant rate, and hydrogenating at 300-400 ℃ for 10-24 h;
5) and nitriding: introducing high-purity nitrogen at a constant speed, nitriding at 300-400 ℃ for 2-20 h, cooling to room temperature, and taking out a sample to obtain the samarium-iron-nitrogen magnetic nanotube.
The technical effects are as follows: the invention utilizes the process conditions of vertical magnetic field, water and glycol mixed solvent and pulse electrodeposition to ensure that Sm is dissolved in water3+、Fe2+Can be co-deposited in the porous alumina pore canal to form the samarium-iron magnetic nanotube; the nanometer samarium iron nitrogen magnetic nanotube provides favorable conditions for nitridation through preliminary nitridation orientation and annealing hydrogenation, obtains the samarium iron nitrogen magnetic nanotube with higher nitrogen content, and ensures that the samarium iron nitrogen magnetic nanotube has excellent magnetic anisotropy.
Detailed Description
The present invention will now be described in detail with reference to examples to better understand the objects, features and advantages of the present invention. While the invention is described in conjunction with the specific embodiments, it is not intended that the invention be limited to the specific embodiments described. On the contrary, alternatives, modifications and equivalents may be included within the embodiments as may be included within the scope of the invention as defined by the claims. The process parameters not specifically mentioned can be carried out according to conventional techniques.
The method comprises the following specific steps:
1) preparing a porous alumina template: selecting a 200nm bi-pass alumina template, carrying out magnetron sputtering on the back of the alumina template to form a gold film with the thickness of 1 mu m, and drying the gold film after ultrasonic cleaning by methyldimethoxysilane, ethanol and distilled water in sequence for later use;
2) and preparation of samarium-iron nanotubes: preparing samarium-iron nanotubes by adopting a pulse electrodeposition method under a magnetic field: preparing an alumina template as a working electrode, a mercury electrode as a counter electrode, an Ag/AgCl electrode as an auxiliary electrode, adding a deposition solution, performing pulse electrodeposition under stirring at 30-50 ℃, dissolving the porous alumina template by using 2 mol/L NaOH solution after deposition is finished, and then washing the porous alumina template to be neutral by using ethanol and distilled water;
the direction of the magnetic field is vertical to the growth direction of the nanotube, and the size of the magnetic field is 1-5T;
the deposition solution comprises the following solutes: SmCl3•6H2O、FeCl2•4H2O、Na3C6H5O7•2H2O、 NaCl、H3BO3And ascorbic acid in a 2:1 solution of water and ethylene glycol;
the conditions of the pulse electrodeposition are as follows: the current density is 10-20 mA/cm2The pulse frequency is 1-10 Hz, and the pulse duty ratio is 0.1-0.5;
3) and nitriding orientation: placing a samarium-iron nanotube array in a heat treatment furnace, preserving heat for 1-5 h at 100-150 ℃, then introducing ammonia gas at a constant speed, applying a 0.5-1T magnetic field, and primarily nitriding for 5-10 h at 100-150 ℃;
4) annealing and hydrogenation: introducing high-purity argon at a constant rate, annealing at 400-600 ℃ for 1-5 h, introducing argon-hydrogen mixed gas containing 50% hydrogen at a constant rate, and hydrogenating at 300-400 ℃ for 10-24 h;
5) and nitriding: introducing high-purity nitrogen at a constant speed, nitriding at 300-400 ℃ for 2-20 h, cooling to room temperature, and taking out a sample to obtain the samarium-iron-nitrogen magnetic nanotube.
Example 1:
the method comprises the following steps:
1) preparing a porous alumina template: selecting a 200nm bi-pass alumina template, carrying out magnetron sputtering on the back of the alumina template to form a gold film with the thickness of 1 mu m, and drying the gold film after ultrasonic cleaning by methyldimethoxysilane, ethanol and distilled water in sequence for later use;
2) and preparation of samarium-iron nanotubes: preparing samarium-iron nanotubes by adopting a pulse electrodeposition method under a magnetic field: preparing an alumina template as a working electrode, a mercury electrode as a counter electrode, an Ag/AgCl electrode as an auxiliary electrode, adding a deposition solution, stirring at 50 ℃, performing pulse electrodeposition, dissolving the porous alumina template by using 2 mol/L NaOH solution after deposition is finished, and then washing the porous alumina template to be neutral by using ethanol and distilled water;
the direction of the magnetic field is vertical to the growth direction of the nanotube, and the size of the magnetic field is 5T;
the deposition solution comprises the following solutes: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid in a 2:1 solution of water and ethylene glycol;
the conditions of the pulse electrodeposition are as follows: the current density is 10 mA/cm2The pulse frequency is 10 Hz, and the pulse duty ratio is 0.5;
3) and nitriding orientation: placing a samarium-iron nanotube array in a heat treatment furnace, keeping the temperature at 150 ℃ for 4h, introducing ammonia gas at a constant speed, applying a 1T magnetic field, and primarily nitriding at 150 ℃ for 5 h;
4) annealing and hydrogenation: introducing high-purity argon at a constant rate, annealing at 400 ℃ for 4h, introducing argon-hydrogen mixed gas containing 50% of hydrogen at a constant rate, and hydrogenating at 400 ℃ for 20 h;
5) and nitriding: introducing high-purity nitrogen at a constant speed, nitriding at 400 ℃ for 10h, cooling to room temperature, and taking out a sample to obtain the samarium-iron-nitrogen magnetic nanotube.
XRD and TEM representation is carried out on the sample prepared in the embodiment 1, and a samarium iron nitrogen phase is detected, wherein the shape of the samarium iron nitrogen is an ordered nanotube array structure; VSM testing of the samarium-iron-nitrogen magnetic nanotube array shows that the samarium-iron-nitrogen magnetic nanotube array has higher magnetic energy product and excellent magnetic anisotropy.
Example 2:
the method comprises the following steps:
1) preparing a porous alumina template: selecting a 200nm bi-pass alumina template, carrying out magnetron sputtering on the back of the alumina template to form a gold film with the thickness of 1 mu m, and drying the gold film after ultrasonic cleaning by methyldimethoxysilane, ethanol and distilled water in sequence for later use;
2) and preparation of samarium-iron nanotubes: preparing samarium-iron nanotubes by adopting a pulse electrodeposition method under a magnetic field: preparing an alumina template as a working electrode, a mercury electrode as a counter electrode, an Ag/AgCl electrode as an auxiliary electrode, adding a deposition solution, stirring at 30 ℃, performing pulse electrodeposition, dissolving the porous alumina template by using 2 mol/L NaOH solution after deposition is finished, and then washing the porous alumina template to be neutral by using ethanol and distilled water;
the direction of the magnetic field is vertical to the growth direction of the nanotube, and the size of the magnetic field is 1T;
the deposition solution comprises the following solutes: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid in a 2:1 solution of water and ethylene glycol;
the conditions of the pulse electrodeposition are as follows: current density of20 mA/cm2The pulse frequency is 1Hz, and the pulse duty ratio is 0.1;
3) and nitriding orientation: placing the samarium-iron nanotube array in a heat treatment furnace, preserving heat for 5 hours at 100 ℃, then introducing ammonia gas at a constant speed, simultaneously applying a 0.5T magnetic field, and primarily nitriding for 5-10 hours at 100 ℃;
4) annealing and hydrogenation: introducing high-purity argon at a constant rate, annealing at 500 ℃ for 5h, introducing argon-hydrogen mixed gas containing 50% of hydrogen at a constant rate, and hydrogenating at 300 ℃ for 24 h;
5) and nitriding: introducing high-purity nitrogen at a constant speed, nitriding at 300 ℃ for 20h, cooling to room temperature, and taking out a sample to obtain the samarium-iron-nitrogen magnetic nanotube.
XRD and TEM representation is carried out on the sample prepared in the embodiment 2, a samarium iron nitrogen phase is detected, and the shape of the samarium iron nitrogen is an ordered nanotube array structure; VSM testing of the samarium-iron-nitrogen magnetic nanotube array shows that the samarium-iron-nitrogen magnetic nanotube array has higher magnetic energy product and excellent magnetic anisotropy.
Example 3:
the method comprises the following steps:
1) preparing a porous alumina template: selecting a 200nm bi-pass alumina template, carrying out magnetron sputtering on the back of the alumina template to form a gold film with the thickness of 1 mu m, and drying the gold film after ultrasonic cleaning by methyldimethoxysilane, ethanol and distilled water in sequence for later use;
2) and preparation of samarium-iron nanotubes: preparing samarium-iron nanotubes by adopting a pulse electrodeposition method under a magnetic field: preparing an alumina template as a working electrode, a mercury electrode as a counter electrode, an Ag/AgCl electrode as an auxiliary electrode, adding a deposition solution, stirring at 40 ℃, performing pulse electrodeposition, dissolving the porous alumina template by using 2 mol/L NaOH solution after deposition is finished, and then washing the porous alumina template to be neutral by using ethanol and distilled water;
the direction of the magnetic field is vertical to the growth direction of the nanotube, and the size of the magnetic field is 2T;
the deposition solution comprises the following solutes: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid in a 2:1 solution of water and ethylene glycol;
the conditions of the pulse electrodeposition are as follows: the current density is 15 mA/cm2The pulse frequency is 8 Hz, and the pulse duty ratio is 0.3;
3) and nitriding orientation: placing a samarium-iron nanotube array in a heat treatment furnace, keeping the temperature at 120 ℃ for 3h, introducing ammonia gas at a constant speed, applying a 0.8T magnetic field, and primarily nitriding at 120 ℃ for 8 h;
4) annealing and hydrogenation: introducing high-purity argon at a constant rate, annealing at 600 ℃ for 1h, introducing argon-hydrogen mixed gas containing 50% of hydrogen at a constant rate, and hydrogenating at 400 ℃ for 10 h;
5) and nitriding: introducing high-purity nitrogen at a constant speed, nitriding at 400 ℃ for 10h, cooling to room temperature, and taking out a sample to obtain the samarium-iron-nitrogen magnetic nanotube.
XRD and TEM representation is carried out on the sample prepared in the embodiment 3, a samarium iron nitrogen phase is detected, and the shape of the samarium iron nitrogen is an ordered nanotube array structure; VSM testing of the samarium-iron-nitrogen magnetic nanotube array shows that the samarium-iron-nitrogen magnetic nanotube array has higher magnetic energy product and excellent magnetic anisotropy.
Example 4:
the method comprises the following steps:
1) preparing a porous alumina template: selecting a 200nm bi-pass alumina template, carrying out magnetron sputtering on the back of the alumina template to form a gold film with the thickness of 1 mu m, and drying the gold film after ultrasonic cleaning by methyldimethoxysilane, ethanol and distilled water in sequence for later use;
2) and preparation of samarium-iron nanotubes: preparing samarium-iron nanotubes by adopting a pulse electrodeposition method under a magnetic field: preparing an alumina template as a working electrode, a mercury electrode as a counter electrode, an Ag/AgCl electrode as an auxiliary electrode, adding a deposition solution, stirring at 50 ℃, performing pulse electrodeposition, dissolving the porous alumina template by using 2 mol/L NaOH solution after deposition is finished, and then washing the porous alumina template to be neutral by using ethanol and distilled water;
the direction of the magnetic field is vertical to the growth direction of the nanotube, and the size of the magnetic field is 4T;
the deposition solution comprises the following solutes: 0.6 mol/L SmCl3•6H2O、0.1 mol/L FeCl2•4H2O、0.1mol/L Na3C6H5O7•2H2O、0.06 mol/L NaCl、0.6 mol/L H3BO3And ascorbic acid in a 2:1 solution of water and ethylene glycol;
the conditions of the pulse electrodeposition are as follows: the current density is 12 mA/cm2The pulse frequency is 3 Hz, and the pulse duty ratio is 0.5;
3) and nitriding orientation: placing a samarium-iron nanotube array in a heat treatment furnace, keeping the temperature at 100 ℃ for 5h, introducing ammonia gas at a constant speed, applying a 1T magnetic field, and primarily nitriding at 100 ℃ for 10 h;
4) annealing and hydrogenation: introducing high-purity argon at a constant rate, annealing at 500 ℃ for 5h, introducing argon-hydrogen mixed gas containing 50% of hydrogen at a constant rate, and hydrogenating at 400 ℃ for 15 h;
5) and nitriding: introducing high-purity nitrogen at a constant speed, nitriding at 400 ℃ for 15h, cooling to room temperature, and taking out a sample to obtain the samarium-iron-nitrogen magnetic nanotube.
XRD and TEM characterization is carried out on the sample prepared in the embodiment 4, a samarium iron nitrogen phase is detected, and the shape of the samarium iron nitrogen is an ordered nanotube array structure; VSM testing of the samarium-iron-nitrogen magnetic nanotube array shows that the samarium-iron-nitrogen magnetic nanotube array has higher magnetic energy product and excellent magnetic anisotropy.
Claims (1)
1. A preparation method of samarium-iron-nitrogen magnetic nanotubes is characterized by comprising the following steps:
1) preparing a porous alumina template: selecting a 200nm bi-pass alumina template, carrying out magnetron sputtering on the back of the alumina template to form a gold film with the thickness of 1 mu m, and drying the gold film after ultrasonic cleaning by methyldimethoxysilane, ethanol and distilled water in sequence for later use;
2) and preparation of samarium-iron nanotubes: preparing samarium-iron nanotubes by adopting a pulse electrodeposition method under a magnetic field: preparing an alumina template as a working electrode, a mercury electrode as a counter electrode, an Ag/AgCl electrode as an auxiliary electrode, adding a deposition solution, performing pulse electrodeposition under stirring at 30-50 ℃, dissolving the porous alumina template by using 2 mol/L NaOH solution after deposition is finished, and then washing the porous alumina template to be neutral by using ethanol and distilled water;
the direction of the magnetic field is vertical to the growth direction of the nanotube, and the size of the magnetic field is 1-5T;
the deposition solution comprises the following solutes: SmCl3•6H2O、FeCl2•4H2O、Na3C6H5O7•2H2O、NaCl、H3BO3And ascorbic acid in a 2:1 solution of water and ethylene glycol;
the conditions of the pulse electrodeposition are as follows: the current density is 10-20 mA/cm2The pulse frequency is 1-10 Hz, and the pulse duty ratio is 0.1-0.5;
3) and nitriding orientation: placing a samarium-iron nanotube array in a heat treatment furnace, preserving heat for 1-5 h at 100-150 ℃, then introducing ammonia gas at a constant speed, applying a 0.5-1T magnetic field, and primarily nitriding for 5-10 h at 100-150 ℃;
4) annealing and hydrogenation: introducing high-purity argon at a constant rate, annealing at 400-600 ℃ for 1-5 h, introducing argon-hydrogen mixed gas containing 50% hydrogen at a constant rate, and hydrogenating at 300-400 ℃ for 10-24 h;
5) and nitriding: introducing high-purity nitrogen at a constant speed, nitriding at 300-400 ℃ for 2-20 h, cooling to room temperature, and taking out a sample to obtain the samarium-iron-nitrogen magnetic nanotube.
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