CN112647098A

CN112647098A - Preparation method of reticular samarium-cobalt multilayer magnetic nanowire

Info

Publication number: CN112647098A
Application number: CN202110059543.0A
Authority: CN
Inventors: 杨杭福; 黄霞妮; 吴琼; 葛洪良
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-01-18
Filing date: 2021-01-18
Publication date: 2021-04-13

Abstract

The invention discloses a preparation method of a reticular samarium-cobalt multilayer magnetic nanowire, which is characterized in that a polycarbonate film (PC) template containing a 3D reticular structure channel is prepared by high-energy heavy ion beams, and a mesh (SmCo) is prepared by using a pulse electrodeposition technology_1‑xCu_xThe obtained nanowires are mutually connected in a net structure and can be directly used as a magnetic nano device, and then the comprehensive magnetic performance of the samarium cobalt nanowires is improved by introducing the non-magnetic nano layer Cu to enhance the demagnetization coupling interaction of the samarium cobalt.

Description

Preparation method of reticular samarium-cobalt multilayer magnetic nanowire

Technical Field

The invention relates to a preparation method of a samarium-cobalt magnet, in particular to a preparation method of a reticular samarium-cobalt multilayer magnetic nanowire, belonging to the technical field of permanent magnet materials.

Background

The one-dimensional nano magnetic material is used as the research foundation of other low-dimensional nano materials, is closely related to nano electronic devices and micro sensors, has wide application prospect in the aspects of developing nano electronic devices in the micro field and the like, and can be used as nano devices, needle points of scanning tunnel microscopes, optical fibers, sensitive materials, connecting lines of super-large-scale integrated circuits, micro drill bits, reinforcing agents of composite materials and the like. Samarium cobalt permanent magnet materials are still of great value as first and second generation permanent magnets due to their advantages of significant magnetic anisotropy, high curie temperature, etc. Samarium cobalt nanometer line is as one-dimensional material, and nanometer material has small size effect, surface effect, quantum size effect and macroscopic quantum tunnel effect etc. is the key material of nanometer assembly technique.

At present, the preparation method of samarium cobalt low-dimensional material mainly comprises vapor deposition, sputtering, spin coating, electrodeposition and the like, magnetron sputtering and the like have the defects of high cost, high process requirement and the like, and researchers try to find a process with low cost and simple operation. Electrodeposition is an excellent material preparation means, has the advantages of simple equipment, low cost, high production efficiency and the like, and researchers make attempts to prepare rare earth permanent magnetic materials by electrodeposition. Wherein the Hebei industry university utilizes electrodeposition and an AAO alumina template to prepare samarium cobalt nanowires, and the ratio of Sm to Co ions is adjusted to find that when the ratio of Sm to Co ions is 6: 1, the obtained magnetic performance is optimal, but the nanowire prepared by the method cannot stand and cannot be directly used as a device, so that the application of the nanowire as a nanometer device is limited to a certain extent, and the coercivity of the obtained SmCo nanowire is low due to the nanometer size effect.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a preparation method of a samarium-cobalt reticular multilayer magnetic nanowire.

In order to solve the problems, the technical scheme adopted by the invention is as follows:

a preparation method of the samarium-cobalt net-shaped magnetic nanowire comprises the following steps:

1. a preparation method of a samarium-cobalt net-shaped multilayer magnetic nanowire is characterized by comprising the following steps:

1) manufacturing a mesh PC channel template: the method comprises the steps of irradiating the surface of a polycarbonate film (PC) by using a high-energy heavy ion beam, taking the heavy ion beam as a normal line in the irradiation process, firstly adjusting the angle of the polycarbonate film to enable the irradiation angle of the polycarbonate film and the heavy ion beam to be alpha, then rotating the polycarbonate film to enable the irradiation angle of the carbonate film and the heavy ion beam to be-alpha, irradiating the polycarbonate film by using the heavy ion beam twice, forming a net-shaped nano-channel network in the polycarbonate film, putting the polycarbonate film into Na (OH) solution, expanding holes of the nano-channel network by using a chemical etching method to form a PC channel template with a 3D net-shaped structure, and finally plating a layer of Au/Pt film on the surface of the polycarbonate film by using an electronic evaporation method.

2) Chemical electrodeposition: preparing Sm with a certain concentration₂(SO₄)₃，CoSO₄And CuSO₄The mixed solution is used as a chemical electrodeposition solution, one or more of boric acid, citric acid and sodium citrate is used as a complexing agent, the reticular PC channel template obtained in the step 1 is placed into the electrodeposition solution, an electrochemical workstation is utilized, an Au/Pt film on the template is used as a cathode, Ag/AgCl is used as a reference electrode and Pt is used as a counter electrode, a pulse electrodeposition technology is adopted, the deposition potential is switched between-2V and-0.4V, -2.4V is used for depositing SmCo material, -0.4V is used for depositing Cu, the pulse duration of the-2.4 is 500 ms-1 s, the pulse duration of the-0.4V is 1 s-2 s, and a reticular (SmCo) is deposited in a polycarbonate film_1-xCu_xCu multilayer nanowire, where x is less than or equal to 0.05, (SmCo)_1-xCu_xThe thickness of the Cu nano layer is 10nm to 20nm, and the thickness of the Cu nano layer is 1nm to 2 nm.

3) Removing the template: the (SmCo) obtained in step 2_1-xCu_xPutting the polycarbonate film of the/Cu nanowire into a dichloromethane solution, and dissolving the polycarbonate film to obtain a net shape (SmCo)_1-xCu_xA Cu nanowire.

4) Sintering in a magnetic field: in the net shape (SmCo)_1-xCu_xApplying a 2T-7T magnetic field to the Cu nanowire along the direction of the nanowire, sintering for 0.5-3 h at 1220-1280 ℃ under the protection of argon, and cooling to 1180-1200 ℃ for solution treatmentAnd (5) quickly cooling and discharging after 0.5-2 h.

5) Aging treatment: the net shape (SmCo) obtained in the step 4_1-xCu_xCu nanowire at 600^oC~850 ^oAnd C, carrying out aging treatment for 2-4 h under the protection of nitrogen, and cooling to room temperature along with the furnace.

Specifically, the energy of the high-energy heavy ion beam in the step 1 is 5 MeV-10 MeV, the diameter of an irradiation area is 2cm, and the frequency is 1 Hz-2 Hz; the thickness of the polycarbonate film is 20-100 mu m; the irradiation angle alpha of the carbonate film and the heavy ion beam is 20^o~45^oThe diameter of the reticular nano channel obtained after the pore is opened is 50 nm-200 nm; the thickness of the Au/Pt film on the plated surface of the polycarbonate film is 500 nm-1 mu m.

Specifically, Sm described in step 2₂(SO₄)₃,CoSO₄And CuSO₄In the mixed solution, the atomic ratio of Sm to Co to Cu is 1: 5-8.5: 0.002-0.008.

Specifically, the concentration of the dichloromethane solution in the step 3 is 0.5 molL^-1~2 molL^-1。

Compared with the prior art, the invention has the following advantages and beneficial effects:

(1) through preparing a polycarbonate film (PC) three-dimensional nano-channel template, depositing samarium-cobalt reticular nanowires on the template, wherein the obtained nanowires form a mutually connected reticular structure and can be directly used as a magnetic nano device;

(2) according to the invention, the nonmagnetic nano-layer Cu is introduced into the samarium cobalt nanowire to form a SmCo/Cu multilayer nanowire structure, so that the demagnetization coupling interaction of samarium cobalt is enhanced, and the coercivity is improved;

(3) and sintering in a magnetic field, and diffusing the Cu ions of the Cu nano layer into the SmCo nanowire magnet to further improve the magnetic property of the samarium cobalt nanowire.

Detailed Description

The present invention will be further described with reference to the following specific embodiments and comparative examples.

Example 1

1) Manufacturing a mesh PC channel template: height of utilizationIrradiating the surface of a polycarbonate film (PC) with heavy ion beams at an energy of 5MeV and a frequency of 1Hz, wherein the thickness of the polycarbonate film (PC) is 30 μm, and during the irradiation process, the heavy ion beams are used as normal lines, and the angle of the polycarbonate film is firstly adjusted to ensure that the irradiation angle of the polycarbonate film and the heavy ion beams is 30^oRotating the polycarbonate film to make the irradiation angle between the polycarbonate film and the heavy ion beam be-30^oAfter the polycarbonate is irradiated by heavy ion beams twice, a reticular nano-channel network is formed inside, the polycarbonate film is put into Na (OH) solution, the pores of the nano-channel network are expanded by a chemical etching method to form a PC channel template with a 3D reticular structure, the pore diameter is 50nm, and finally, an Au film with the thickness of 700 nm is plated on the polycarbonate film by using an electronic evaporation method;

2) chemical electrodeposition: 0.5mol L of the mixture is prepared^-1Sm₂(SO₄)₃, 5 mol L^-1CoSO₄And 0.008 mol L^-1CuSO₄Putting the reticular PC channel template obtained in the step 1 into an electrodeposition solution by taking boric acid and sodium citrate as complexing agents as a chemical electrodeposition solution, using an electrochemical workstation, taking an Au film on the template as a cathode, Ag as a reference electrode and Pt as a counter electrode, adopting a pulse electrodeposition technology, switching the deposition potential between-2V and-0.4V, depositing SmCo material at-2.4V, depositing Cu at-0.4V, setting the pulse duration of-2.4 ms and the pulse duration of-0.4V at 1s, and depositing in a polycarbonate film to obtain a reticular (SmCo)_0.97Cu_0.03Cu multilayer nanowire, where x is less than or equal to 0.05, (SmCo)_0.97Cu_0.03The thickness of (2) is 10nm, and the thickness of the Cu nano layer is 1 nm;

3) removing the template: subjecting the resulting network-containing (SmCo) obtained in step 2 to_0.97Cu_0.03A polycarbonate film of/Cu multilayer nanowire, 0.5mol L of^-1The polycarbonate film was sufficiently dissolved in the methylene chloride solution to obtain a network (SmCo)_0.97Cu_0.03A Cu multilayer nanowire;

4) sintering in a magnetic field: in the net shape (SmCo)_0.97Cu_0.03Nano-scale of/Cu nanowireApplying a 5T magnetic field in the direction of the line, sintering for 2h under the protection of 1250 ℃ argon, cooling to 1200 ℃ for solution treatment for 0.5h, and then rapidly cooling and discharging;

5) aging treatment: the (SmCo) obtained in step 4_0.97Cu_0.03the/Cu multilayer nanowire is 600^oC, carrying out aging treatment for 2 hours under the protection of nitrogen, and cooling to room temperature along with the furnace.

Prepared (SmCo)_0.97Cu_0.03The magnetic performance of a/Cu multilayer nanowire sample is tested by PPMS (polypropylene-random-Mass Spectrometry), and compared with samarium-cobalt nanowires prepared by AAO alumina templates in the literature, and the comparison result is shown in Table 1.

TABLE 1

Claims

1) manufacturing a mesh PC channel template: irradiating the surface of a polycarbonate film (PC) by using a high-energy heavy ion beam, taking the heavy ion beam as a normal line in the irradiation process, firstly adjusting the angle of the polycarbonate film, enabling the irradiation angle of the polycarbonate film and the heavy ion beam to be alpha, then rotating the polycarbonate film, enabling the irradiation angle of the carbonate film and the heavy ion beam to be-alpha, forming a reticular nano-channel network in the polycarbonate film after the polycarbonate film is irradiated by the heavy ion beam twice, putting the polycarbonate film into Na (OH) solution, expanding the holes of the nano-channel network by a chemical etching method, forming a PC channel template with a 3D reticular structure, and finally plating an Au/Pt film on the surface of the polycarbonate film by using an electronic evaporation method;

2) chemical electrodeposition: preparing Sm with a certain concentration₂(SO₄)₃，CoSO₄And CuSO₄Taking the mixed solution as a chemical electrodeposition solution, taking one or more of boric acid, citric acid and sodium citrate as a complexing agent, and putting the reticular PC channel template obtained in the step (1) into an electric precipitation wayIn the accumulated liquid, an electrochemical workstation is utilized, an Au/Pt thin film on a template is used as a cathode, Ag/AgCl is used as a reference electrode and Pt is used as a counter electrode, a pulse electrodeposition technology is adopted, the deposition potential is switched between-2V and-0.4V, -2.4V is used for depositing SmCo material, -0.4V is used for depositing Cu, the pulse duration of-2.4 is 500 ms-1 s, the pulse duration of-0.4V is 1 s-2 s, and a net shape (SmCo) is obtained by deposition in a polycarbonate thin film_1-xCu_xCu multilayer nanowire, where x is less than or equal to 0.05, (SmCo)_1- _xCu_xThe thickness of the Cu nano layer is 10nm to 20nm, and the thickness of the Cu nano layer is 1nm to 2 nm;

3) removing the template: the (SmCo) obtained in step 2_1-xCu_xPutting the polycarbonate film of the/Cu nanowire into a dichloromethane solution, and dissolving the polycarbonate film to obtain a net shape (SmCo)_1-xCu_xA Cu nanowire;

4) sintering in a magnetic field: in the net shape (SmCo)_1-xCu_xApplying a 2T-7T magnetic field to the Cu nanowire along the direction of the nanowire, sintering for 0.5-3 h at 1220-1280 ℃ under the protection of argon, cooling to 1180-1200 ℃ for solid solution treatment for 0.5-2 h, and then rapidly cooling and discharging;

5) aging treatment: the net shape (SmCo) obtained in the step 4_1-xCu_xthe/Cu nano-wire is 600-850^oAnd C, carrying out aging treatment for 2-4 h under the protection of nitrogen, and cooling to room temperature along with the furnace.

2. The method of making samarium cobalt reticulate multilayer magnetic nanowires of claim 1, wherein: the energy of the high-energy heavy ion beam is 5 MeV-10 MeV, the diameter of an irradiation area is 2cm, and the frequency is 1 Hz-2 Hz; the thickness of the polycarbonate film is 20-100 mu m; the irradiation angle alpha of the carbonate film and the heavy ion beam is 20^o~45^oThe diameter of the reticular nano channel obtained after the pore is opened is 50 nm-200 nm; the thickness of the Au/Pt film on the plated surface of the polycarbonate film is 500 nm-1 mu m.

3. The method of making samarium cobalt reticulate multilayer magnetic nanowires of claim 1, said Sm₂(SO₄)₃,CoSO₄And CuSO₄In the mixed solution, the atomic ratio of Sm to Co to Cu is 1: 5-8.5: 0.002-0.008; the concentration of the dichloromethane solution is 0.5mol L^-1~2 molL^-1。