CN114566342A - Of special construction (Nd, Tb)2Fe14Preparation method of B/Co composite magnetic material - Google Patents

Of special construction (Nd, Tb)2Fe14Preparation method of B/Co composite magnetic material Download PDF

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CN114566342A
CN114566342A CN202210249267.9A CN202210249267A CN114566342A CN 114566342 A CN114566342 A CN 114566342A CN 202210249267 A CN202210249267 A CN 202210249267A CN 114566342 A CN114566342 A CN 114566342A
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magnetic material
ball milling
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composite magnetic
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吴琼
张磊
马翔宇
丛利颖
岳明
刘卫强
路清梅
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Beijing University of Technology
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    • 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
    • H01F1/0302—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity characterised by unspecified or heterogeneous hardness or specially adapted for magnetic hardness transitions
    • H01F1/0306—Metals or alloys, e.g. LAVES phase alloys of the MgCu2-type
    • 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

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Abstract

Of special construction (Nd, Tb)2Fe14A preparation method of B/Co composite magnetic material belongs to the field of rare earth magnetic materials, and comprises the steps of preparing (Nd, Tb) by using a surfactant to assist high-energy ball milling2Fe14B nanosheet hard magnetic phase core, and preparing (Nd, Tb) with core-shell structure by combining alcohol thermal method2Fe14B/Co composite magnetic particle, in the structure, (Nd, Tb)2Fe14The hard magnetic phase B is a core, the Co phase is a shell, and the soft magnetic phase can be uniformly distributed around the hard magnetic phase, thereby being beneficial to the exchange coupling effect between the soft magnetic phase and the hard magnetic phase, reducing the use of rare earth and greatly improving the magnetic performance. And after the external magnetic field is applied, the relative distribution of the soft magnetic phases and the hard magnetic phases is more beneficial to actual processing. Lays a foundation for the preparation of the bi-anisotropic bonded magnet and provides a new idea.

Description

Of special construction (Nd, Tb)2Fe14Preparation method of B/Co composite magnetic material
Technical Field
The invention relates to a preparation method of a composite magnetic material, in particular to a method for preparing (Nd, Tb) with a special structure by using a surfactant to assist high-energy ball milling and chemical precipitation2Fe14A preparation method of a B/Co composite magnetic material belongs to the field of rare earth magnetic materials.
Background
In the modern society, the permanent magnet material is widely applied in the fields of internal combustion engines, energy automobiles, computers, aerospace, biomedicine and the like. The development of society accelerates and amplifies the demand of people for permanent magnet materials. As is well known, the third generation of permanent magnet materials Nd2Fe14B is increasingly close to the theoretical energy product, and the content of rare earth elements on the earth is limited and becomes rare. Therefore, from the perspective of sustainable development and cost reduction, people look to the nano two-phase composite magnet, and have the advantages of high theoretical magnetic energy, lower cost and the like.
At present, two methods for preparing the nano two-phase composite magnet mainly comprise a bottom-up method and a top-down method. The top-down method is a method of miniaturizing a macroscopic material by physical means such as heating or plastic deformation, and is also called a physical method. The mechanical ball milling method is a main method for preparing a biphase composite magnetic material by a physical method, and comprises the steps of crushing an ingot, carrying out ball milling on soft and hard magnetic phase powder, and sintering and forming to obtain the biphase magnetic composite material. Although the method can be used for large-scale preparation, the particles are easy to agglomerate and oxidize, and influence is caused on the magnetic performance. The bottom-up method is a process of designing an oriented nano composite material by taking molecules or atoms as units and regulating and controlling the morphology structure and the like of the molecules or atoms through a certain chemical experimental design. The method combining liquid phase synthesis and Ca reduction and diffusion is one of the representatives of the bottom-up method and is often used as a main means for preparing magnets. The nano particles prepared by the method have uniform particle size and controllable appearance, but the temperature requirement is higher, and the mass production cannot be realized. Therefore, there is a need for a new method of preparing nanocomposite magnetic materials by combining physical and chemical methods.
Disclosure of Invention
To understandIn order to solve the above problems, the present invention provides a (Nd, Tb) film having a specific structure2Fe14A method for preparing a B/Co composite magnetic material. Different (Nd, Tb) are prepared by using a surfactant-assisted ball milling combined with a chemical deposition method2Fe14Nano biphase composite particles with B/Co mass ratio. Prepared by a chemical deposition process of (Nd, Tb)2Fe14The phase composition of the B/Co composite magnetic material is (Nd, Tb)2Fe14B and Co; prepared (Nd, Tb)2Fe14The microstructure of the B/Co composite magnetic material is (Nd, Tb)2Fe14B is a core hard magnetic phase, and a soft magnetic phase consisting of Co nanowires is an outer shell layer; co nanowire pair (Nd, Tb)2Fe14B nano-sheet with different mass fractions coated or coated on (Nd, Tb)2Fe14B, growth load of the surface of the nanosheet; having anisotropy (Nd, Tb)2Fe14The c-axis (00l) direction of the B nano-sheet is parallel to the plane of the nano-sheet, so that the influence of the shape on the magnetic performance of the magnet is effectively reduced due to the benign orientation and distribution state, soft and hard magnetic phases can be distributed more uniformly after the magnetic field is oriented, the exchange coupling effect is more favorable, the magnetic performance is improved, and the consumption of rare earth (Nd, Tb) is reduced to a great extent. Lays a foundation for the preparation of the bi-anisotropic nano two-phase bonded magnet and provides a new idea.
In order to achieve the above object, the technical solution of the present invention comprises the following steps:
step 1: with CoCl2·6H2Preparing a cobalt laurate precursor by using O powder as a raw material through a hydrothermal method;
step 2: respectively weighing Nd, Tb, Fe and B raw materials according to the atomic ratio of Nd, Tb, Fe and B being 11.2:4.8:78: 6;
and step 3: putting the prepared raw materials into a suspension smelting furnace, vacuumizing, and smelting under the protection of argon to obtain an alloy ingot;
and 4, step 4: annealing the smelted alloy ingot under the protection of inert gas, and then carrying out quick cooling to prepare (Nd, Tb)2Fe14B；
And 5: step 4 (Nd, Tb)2Fe14B carry outMechanically crushing, adding surfactant, and ball milling to obtain (Nd, Tb)2Fe14B nanosheet;
step 6: mixing (Nd, Tb) obtained in step 52Fe14B nanosheet, cobalt laurate, hexadecylamine and RuCl3Prepared by alcohol heating method (Nd, Tb) after centrifugal ultrasonic treatment by deionized water2Fe14B/Co composite magnetic material.
As a preferred scheme, the preparation process of the cobalt laurate precursor in the step 1 comprises the following steps: adding 80-85mmol of NaOH into a three-neck flask filled with 80ml of deionized water, heating in a water bath to 60 ℃, adding 85-90mmol of lauric acid, and mechanically stirring to fully dissolve; taking 35-40mmol of CoCl2·6H2Dissolving O in 20ml of deionized water, dropwise adding the mixture into a three-necked flask, stirring for 30-40 minutes to change the solution from purple to pink, taking out and cooling to room temperature; then, ultrasonically centrifugally washing the mixture for 3 to 4 times by using deionized water and methanol, and then putting the mixture into a drying box, wherein the centrifugal speed is 6000-; grinding the dried product to obtain a cobalt laurate precursor; the dosage relation of the substances is increased or reduced proportionally according to needs;
preferably, step 3 (Nd, Tb)2Fe14The preparation process of the B alloy ingot comprises the following steps: smelting Nd-Tb-Fe-B alloy cast ingots in a suspension smelting mode; the vacuum degree of the suspension smelting furnace reaches 5 multiplied by 10-2Introducing pure argon after Pa, and circularly and repeatedly exhausting gas for 3-5 times; repeatedly smelting the raw materials for 3-5 times to ensure that the components of the cast ingot are uniform; in consideration of the problem of metal burning loss, respectively allocating additional burning loss such as 3 wt.%, 3 wt.% and 5 wt.% to Nd, Tb and FeB alloys according to corresponding stoichiometric ratio; and finally, homogenizing and annealing the cast ingot in a vacuum annealing furnace under the protection of inert gas.
Preferably, step 4 (Nd, Tb)2Fe14B annealing in a vacuum of 5X 10-2Pa, the annealing temperature is 1100-1200 ℃, and the annealing time is 24 h.
Preferably, step 5 (Nd, Tb)2Fe14The preparation process of the B nano sheet comprises the following steps: annealing (Nd, Tb)2Fe14B, removing oxide skin of the cast ingot, grinding the cast ingot through a 100-mesh sieve, and sieving the powder according to a ball-material ratio of 20: 1, putting the mixture into a ball milling tank, adding oleylamine and oleic acid serving as surfactants, and putting n-heptane serving as a ball milling medium into a high-energy ball mill for ball milling at different times and different energies; after the ball milling is finished, repeatedly carrying out ultrasonic treatment and centrifugation on the sample by using organic solvents such as alcohol, acetone, n-heptane and the like to remove the surfactant; finally drying under vacuum condition to obtain (Nd, Tb)2Fe14B nano-sheet.
Preferably, step 6 (Nd, Tb)2Fe14The preparation process of the B/Co nano composite magnetic material comprises the following steps: prepared in advance (Nd, Tb)2Fe14B nanosheet, 2-2.1g of cobalt laurate, 0.5771-0.5819g of Hexadecylamine (HDA), and 0.0035-0.004g of RuCl3Adding 60ml of 1, 2-butanediol into the inner liner of the high-pressure kettle, introducing argon protective gas for ultrasonic dispersion, then placing the mixture into the high-pressure kettle, and performing heating reaction by using a muffle furnace; the heating rate is 8-10 ℃/min, the reaction temperature is 250 ℃, and the heat preservation time is 80-100 min. Cooling to room temperature, centrifuging and washing with toluene and n-hexane for 3-5 times, and storing in n-hexane. Thus obtaining (Nd, Tb)2Fe14B/Co nano composite magnetic material.
In step 6, every 2-2.1g of cobalt laurate corresponds to 0.5771-0.5819g of Hexadecylamine (HDA) and 0.0035-0.004g of RuCl3And 60ml of 1, 2-butanediol to prepare a Co nanowire; according to the addition of different amounts of (Nd, Tb)2Fe14B nano-sheet can prepare Co nano-wires (Nd, Tb) with different coating amounts or loading amounts2Fe14B/Co nano composite magnetic material.
As a preferable example, in step 6 (Nd, Tb)2Fe14The B nano-sheet is processed under the conditions that the ball milling energy is 50-60V and the ball milling time is 0.5-7 h.
Further preferably: step 6 (Nd, Tb)2Fe14The mass ratio of the B nano sheet to the cobalt laurate is (0.5-2) to 1.
Compared with the prior art, the invention has the following beneficial effects:
hair brushThe method for preparing the (Nd, Tb) with a special structure by combining the surface active agent auxiliary ball milling with the alcohol thermal method is obviously provided2Fe14A process for preparing the magnetic B/Co composition (Nd, Tb)2Fe14The hard magnetic phase B is used as a core, and the soft magnetic phase Co is used as an outer shell layer, so that the soft magnetic phase can be uniformly distributed around the hard magnetic phase. The technology solves the problem of uneven distribution of soft and hard magnetic phases in the prior art, and the soft and hard magnetic phases in the composite particles prepared by the method are evenly distributed, thereby being beneficial to the exchange coupling effect between soft and hard magnetic phases. Magnetic properties are improved and consumption of rare earth (Nd, Tb) is reduced to a great extent. Favoring the bi-anisotropy (Nd, Tb)2Fe14And preparing the B/Co bonded magnet.
Drawings
Fig. 1 shows phase results of XRD tests on the composite magnetic materials prepared in examples 1 and 2 on the left, and magnetic results of example 1 on the right.
Fig. 2 is a scanning electron micrograph of the composite magnetic material prepared in example 1 on the left, and a scanning electron micrograph of the composite magnetic material prepared in example 2 on the right.
Fig. 3 shows phase results of XRD test of comparative example 1 on the left and magnetic test of comparative example 1 on the right.
Fig. 4 shows the phase results of XRD test of comparative example 2 on the left and the magnetic results of comparative example 2 on the right.
Detailed Description
In order to explain the technical content, the objects and the effects of the present invention in detail, the following description will be given with reference to the embodiments.
Example 1
(1) 84mmol NaOH is added into a three-neck flask filled with 80ml deionized water, 88mmol lauric acid is added after heating to 60 ℃ in a water bath, and the mixture is fully dissolved by mechanical stirring. 40mmol of CoCl was taken2·6H2O was dissolved in 20ml of deionized water and added dropwise to a three-necked flask, and after stirring for 30 minutes, the solution turned from purple to pink, and was taken out and cooled to room temperature. And then, ultrasonically centrifuging and washing the mixture for 4 times by using deionized water and methanol, and then putting the mixture into a drying box, wherein the centrifuging speed is 8000r/min, the centrifuging time is 5min, and the drying time is 10 h.And grinding the dried product to obtain the cobalt laurate precursor.
(2) And smelting Nd-Tb-Fe-B alloy cast ingots in a suspension smelting mode. The vacuum degree of the suspension smelting furnace reaches 5 multiplied by 10-2And (4) introducing high-purity argon after Pa, and circularly and repeatedly exhausting the gas for 5 times. The raw materials are repeatedly smelted for 3 times, so that the components of the cast ingot are uniform. In consideration of the problem of metal burning loss, Nd, Tb and FeB alloys were formulated with additional 3 wt.%, 3 wt.% and 5 wt.% burning loss, respectively, in the corresponding stoichiometric proportions. And finally, homogenizing and annealing the cast ingot in a vacuum annealing furnace under the protection of inert gas.
(3) Annealing (Nd, Tb)2Fe14And B, descaling the cast ingot, and grinding the cast ingot through a 100-mesh sieve. The powder after sieving is 20: 1, adding a proper amount of oleylamine and oleic acid serving as surfactants, and simultaneously taking n-heptane as a ball milling medium, putting the mixture into a high-energy ball mill, and performing ball milling at different times and different energies. After the ball milling is finished, the sample is repeatedly subjected to ultrasonic treatment and centrifugation by using organic solvents such as alcohol, acetone, n-heptane and the like, and the surfactant is removed. Finally drying under vacuum to obtain (Nd, Tb)2Fe14B nano-sheet.
(4) Mixing 2.16g (Nd, Tb) in the step (3)2Fe14B nanosheet and 2.07g cobalt laurate, 0.5809g Hexadecylamine (HDA), 0.0037g RuCl360ml of 1, 2-butanediol are added to the inner lining of a 100ml autoclave. Introducing argon protective gas for ultrasonic dispersion, then placing the mixture into a high-pressure kettle, and carrying out heating reaction by using a muffle furnace. The heating rate is 10 ℃/min, the reaction temperature is 250 ℃, and the heat preservation time is 80 min. After cooling to room temperature, the mixture was washed with toluene and n-hexane for 3 times by centrifugation and finally stored in n-hexane. Thus (Nd, Tb) with a Co content of 10% was obtained2Fe14B/Co nano composite magnetic material.
(5) The phase composition of the product was analyzed by XRD, and as a result, as shown in the left panel of FIG. 1, the sample consisted of (Nd, Tb)2Fe14The composition of the B phase and the Co phase indicates that Co is generated in the reaction, and the rare earth is burnt in the reaction. The magnetic properties of the product were tested using VSM and the results are shown in the right panel of FIG. 1. Using SEM for the productThe morphology of the nano-sheet is characterized, and the result is shown in the left graph of fig. 2, wherein the Co nano-wire is parallel to the surface of the nano-sheet.
Example 2
(1) 84mmol NaOH is added into a three-neck flask filled with 80ml deionized water, 88mmol lauric acid is added after heating to 60 ℃ in a water bath, and the mixture is fully dissolved by mechanical stirring. 40mmol of CoCl was taken2·6H2O was dissolved in 20ml of deionized water and added dropwise to a three-necked flask, and after stirring for 30 minutes, the solution turned from purple to pink, and was taken out and cooled to room temperature. And then, ultrasonically centrifuging and washing the mixture for 4 times by using deionized water and methanol, and then putting the mixture into a drying box, wherein the centrifuging speed is 8000r/min, the centrifuging time is 5min, and the drying time is 10 h. And grinding the dried product to obtain the cobalt laurate precursor.
(2) And smelting Nd-Tb-Fe-B alloy cast ingots in a suspension smelting mode. The vacuum degree of the suspension smelting furnace reaches 5 multiplied by 10-2And (4) introducing high-purity argon after Pa, and circularly and repeatedly exhausting the gas for 5 times. The raw materials are repeatedly smelted for 3 times, so that the components of the cast ingot are uniform. In consideration of the problem of metal burning loss, Nd, Tb and FeB alloys were formulated with additional 3 wt.%, 3 wt.% and 5 wt.% burning loss, respectively, in the corresponding stoichiometric proportions. And finally, homogenizing and annealing the cast ingot in a vacuum annealing furnace under the protection of inert gas.
(3) Annealing (Nd, Tb)2Fe14And B, descaling the cast ingot, and grinding the cast ingot through a 100-mesh sieve. The powder after sieving is 20: 1, adding a proper amount of oleylamine and oleic acid serving as surfactants, and simultaneously taking n-heptane as a ball milling medium, putting the mixture into a high-energy ball mill, and performing ball milling at different times and different energies. After the ball milling is finished, the sample is repeatedly subjected to ultrasonic treatment and centrifugation by using organic solvents such as alcohol, acetone, n-heptane and the like, and the surfactant is removed. Finally drying under vacuum condition to obtain (Nd, Tb)2Fe14B nano-sheet.
(4) Mixing 0.96g (Nd, Tb) in the step (3)2Fe14B nanosheets and 2.07g of cobalt laurate, 0.5809g of Hexadecylamine (HDA), 0.0037g of RuCl360ml of 1, 2-butanediol are added to the inner lining of a 100ml autoclave. Introducing argon protective gas for ultrasonic dispersion and then placing the mixture into a high-pressure kettleThe heating reaction was carried out using a muffle furnace. The heating rate is 10 ℃/min, the reaction temperature is 250 ℃, and the heat preservation time is 80 min. After cooling to room temperature, the mixture was washed with toluene and n-hexane for 3 times by centrifugation and finally stored in n-hexane. Thus obtained was 20% Co (Nd, Tb)2Fe14B/Co nano composite magnetic material.
(5) The phase composition of the product was analyzed by XRD, and as a result, as shown in the left panel of FIG. 1, the sample consisted of (Nd, Tb)2Fe14B phase and Co phase, rare earth burning loss in reaction. The peak intensity of Co phase is relatively increased compared to example 1, indicating that the Co content is changed during the reaction. The morphology of the product is characterized by SEM, and the result is shown in the right picture of FIG. 2, in which the content of Co nanowires is increased and the Co nanowires are more uniformly dispersed on the surface of the nanosheet.
Comparative example 1
(1) And smelting Nd-Tb-Fe-B alloy cast ingots in a suspension smelting mode. The vacuum degree of the suspension smelting furnace reaches 5 multiplied by 10-2And (4) introducing high-purity argon after Pa, and circularly and repeatedly exhausting the gas for 5 times. The raw materials are repeatedly smelted for 3 times, so that the components of the cast ingot are uniform. In consideration of the problem of metal burning loss, Nd, Tb and FeB alloys were formulated with additional 3 wt.%, 3 wt.% and 5 wt.% burning loss, respectively, in the corresponding stoichiometric proportions. And finally, homogenizing and annealing the cast ingot in a vacuum annealing furnace under the protection of inert gas.
(2) Annealing (Nd, Tb)2Fe14And B, descaling the cast ingot, and grinding the cast ingot through a 100-mesh sieve. The powder after sieving is 20: 1, adding a proper amount of oleylamine and oleic acid serving as surfactants, and simultaneously taking n-heptane as a ball milling medium, putting the mixture into a high-energy ball mill, and performing ball milling at different times and different energies. After the ball milling is finished, repeatedly carrying out ultrasonic treatment and centrifugation on the sample by using organic solvents such as alcohol, acetone, n-heptane and the like to remove the surfactant. Finally drying under vacuum condition to obtain (Nd, Tb)2Fe14B nano-sheet.
(3) The phase composition of the product was analyzed by XRD, and as a result, as shown in the left panel of FIG. 3, the sample consisted of (Nd, Tb)2Fe14Phase B, rare earth is burnt in the reaction. Using VSM pairsThe magnetic properties of the product were tested and the results are shown in the right panel of FIG. 3.
Comparative example 2
(1) 84mmol NaOH is added into a three-neck flask filled with 80ml deionized water, 88mmol lauric acid is added after heating to 60 ℃ in a water bath, and the mixture is fully dissolved by mechanical stirring. 40mmol of CoCl was taken2·6H2O was dissolved in 20ml of deionized water and added dropwise to a three-necked flask, and after stirring for 30 minutes, the solution turned from purple to pink, and was taken out and cooled to room temperature. And then, ultrasonically centrifuging and washing the mixture for 4 times by using deionized water and methanol, and then putting the mixture into a drying box, wherein the centrifuging speed is 8000r/min, the centrifuging time is 5min, and the drying time is 10 h. And grinding the dried product to obtain the cobalt laurate precursor.
(2) 2.07g of cobalt laurate, 0.5809g of Hexadecylamine (HDA), 0.0037g of RuCl in step (1)360ml of 1, 2-butanediol is added into a 100ml autoclave liner, argon protective gas is introduced for ultrasonic dispersion, and then the mixture is placed into an autoclave and heated to react by using a muffle furnace. Heating at a rate of 10 deg.C/min and a reaction temperature of 250 deg.C for 80min, cooling to room temperature, washing with toluene and n-hexane for 3 times, ultrasonically dispersing, and storing in n-hexane. Thus, Co nanowires were prepared.
(3) The phase composition of the product was analyzed by XRD, and as a result, as shown in the left panel of FIG. 4, the sample consisted of a Co phase, indicating that Co was formed in the reaction. The magnetic properties of the product were tested using VSM and the results are shown in the right panel of FIG. 4.
The magnetic property results of example 1 and comparative example were compared as shown in table 1.
Table 1: magnetic Property test results in examples of the present invention and comparative examples
Figure BDA0003545058460000061
In conclusion, the special structure of the nanosheets and the nanowires under the action of the external magnetic field can be successfully prepared by combining the surfactant-assisted ball milling and the alcohol-thermal method, so that the (Nd, Tb) with the core-shell structure2Fe14The samples of B/Co are taken as samples,the hard magnetic phase is uniformly distributed around the soft magnetic phase, so that the soft and hard magnetic phases can generate more effective exchange coupling effect. Compared with comparative example 1, the residual magnetization and the saturation magnetization under a 3T magnetic field are improved, the coercive force is greatly improved, the consumption of rare earth is reduced, a foundation is laid for the preparation of the bi-anisotropic bonded magnet, and a new idea is provided.

Claims (10)

1. Of special construction (Nd, Tb)2Fe14B/Co composite magnetic material, characterized in that (Nd, Tb)2Fe14The phase composition of the B/Co composite magnetic material is (Nd, Tb)2Fe14A composite phase consisting of B and Co; prepared (Nd, Tb)2Fe14The microstructure of the B/Co composite magnetic material is (Nd, Tb)2Fe14B is a core hard magnetic phase, and a soft magnetic phase consisting of Co nanowires is an outer shell layer; co nanowire pair (Nd, Tb)2Fe14B nano-sheet with different mass fractions coated or coated on (Nd, Tb)2Fe14B, growth load of the surface of the nanosheet; having anisotropy (Nd, Tb)2Fe14The c-axis (00l) direction of the B nano sheet is parallel to the nano sheet plane.
2. Of special construction (Nd, Tb) according to claim 12Fe14The preparation method of the B/Co composite magnetic material is characterized by comprising the following steps:
step 1: with CoCl2·6H2Preparing a cobalt laurate precursor by using O powder as a raw material through a hydrothermal method;
and 2, step: respectively weighing Nd, Tb, Fe and B raw materials according to the atomic ratio of Nd, Tb, Fe and B being 11.2:4.8:78: 6;
and step 3: putting the prepared raw materials into a suspension smelting furnace, vacuumizing, and smelting under the protection of argon to obtain an alloy ingot;
and 4, step 4: annealing the smelted alloy ingot under the protection of inert gas, and then carrying out quick cooling to prepare (Nd, Tb)2Fe14B；
And 5: step 4 (Nd, Tb)2Fe14B, after mechanical crushing, adding a surfactant for high-energy ball milling to obtain (Nd, Tb)2Fe14B nanosheet;
step 6: mixing (Nd, Tb) obtained in step 52Fe14B nanosheet, cobalt laurate, hexadecylamine and RuCl3Prepared by alcohol heating method (Nd, Tb) after centrifugal ultrasonic treatment by deionized water2Fe14B/Co composite magnetic material.
3. The method according to claim 2, wherein the cobalt laurate precursor of step 1 is prepared by: adding 80-85mmol of NaOH into a three-neck flask filled with 80ml of deionized water, heating in a water bath to 60 ℃, adding 85-90mmol of lauric acid, and mechanically stirring to fully dissolve; taking 35-40mmol of CoCl2·6H2Dissolving O in 20ml of deionized water, dropwise adding the mixture into a three-necked flask, stirring for 30-40 minutes to change the solution from purple to pink, taking out and cooling to room temperature; then, ultrasonically centrifugally washing the mixture for 3 to 4 times by using deionized water and methanol, and then putting the mixture into a drying box, wherein the centrifugal speed is 6000-; grinding the dried product to obtain a cobalt laurate precursor; the dosage relation of the substances is proportionally increased or reduced according to requirements.
4. A method according to claim 2, characterized in that in step 3 (Nd, Tb)2Fe14The preparation process of the B alloy ingot comprises the following steps: smelting Nd-Tb-Fe-B alloy cast ingots in a suspension smelting mode; the vacuum degree of the suspension smelting furnace reaches 5 multiplied by 10-2Introducing pure argon after Pa, and circularly and repeatedly exhausting gas for 3-5 times; repeatedly smelting the raw materials for 3-5 times to ensure that the components of the cast ingot are uniform; in consideration of the problem of metal burning loss, respectively allocating additional burning loss such as 3 wt.%, 3 wt.% and 5 wt.% to Nd, Tb and FeB alloys according to corresponding stoichiometric ratio; and finally, homogenizing and annealing the cast ingot in a vacuum annealing furnace under the protection of inert gas.
5. The method according to claim 2, wherein in step 4(Nd,Tb)2Fe14B annealing in a vacuum of 5X 10-2Pa, the annealing temperature is 1100-1200 ℃, and the annealing time is 24 h.
6. A method according to claim 2, characterized in that in step 5 (Nd, Tb)2Fe14The preparation process of the B nano sheet comprises the following steps: after annealing (Nd, Tb)2Fe14B, removing oxide skin of the cast ingot, grinding the cast ingot through a 100-mesh sieve, and sieving the powder according to a ball-material ratio of 20: 1, putting the mixture into a ball milling tank, adding oleylamine and oleic acid serving as surfactants, and putting n-heptane serving as a ball milling medium into a high-energy ball mill for ball milling at different times and different energies; after the ball milling is finished, repeatedly carrying out ultrasonic treatment and centrifugation on the sample by using organic solvents such as alcohol, acetone, n-heptane and the like to remove the surfactant; finally drying under vacuum condition to obtain (Nd, Tb)2Fe14B nano-sheet.
7. A method according to claim 2, characterized in that in step 6 (Nd, Tb)2Fe14The preparation process of the B/Co nano composite magnetic material comprises the following steps: prepared in advance (Nd, Tb)2Fe14B nanosheet and cobalt laurate, Hexadecylamine (HDA), RuCl3Adding 1, 2-butanediol into the inner liner of the high-pressure kettle, introducing argon protective gas for ultrasonic dispersion, then placing the mixture into the high-pressure kettle, and performing heating reaction by using a muffle furnace; the heating rate is 8-10 ℃/min, the reaction temperature is 250 ℃, and the heat preservation time is 80-100 min. Cooling to room temperature, centrifuging and washing with toluene and n-hexane for 3-5 times, and storing in n-hexane. Thus obtaining (Nd, Tb)2Fe14B/Co nano composite magnetic material.
8. The method according to claim 2, characterized in that in step 6, for every 2-2.1g of cobalt laurate, there are 0.5771-0.5819g of Hexadecylamine (HDA), 0.0035-0.004g of RuCl3And 60ml of 1, 2-butanediol to prepare a Co nanowire; according to the addition of different amounts of (Nd, Tb)2Fe14The B nano-sheet can prepare Co nano-wires (Nd) with different coating amounts or loading amounts,Tb)2Fe14B/Co nano composite magnetic material.
9. A method according to claim 2, characterized in that in step 6 (Nd, Tb)2Fe14The B nano-sheet is processed under the conditions that the ball milling energy is 50-60V and the ball milling time is 0.5-7 h.
10. A method according to claim 2, characterized in that in step 6 (Nd, Tb)2Fe14The mass ratio of the B nano sheet to the cobalt laurate is (0.5-2) to 1.
CN202210249267.9A 2022-03-14 2022-03-14 Of special construction (Nd, Tb)2Fe14Preparation method of B/Co composite magnetic material Pending CN114566342A (en)

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