CN111292910B - Rapid preparation method of Co/SmCo composite magnetic material with special structure - Google Patents

Rapid preparation method of Co/SmCo composite magnetic material with special structure Download PDF

Info

Publication number
CN111292910B
CN111292910B CN202010094572.6A CN202010094572A CN111292910B CN 111292910 B CN111292910 B CN 111292910B CN 202010094572 A CN202010094572 A CN 202010094572A CN 111292910 B CN111292910 B CN 111292910B
Authority
CN
China
Prior art keywords
smco
phase
precursor
composite magnetic
magnetic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010094572.6A
Other languages
Chinese (zh)
Other versions
CN111292910A (en
Inventor
吴琼
丛利颖
岳明
刘卫强
张东涛
路清梅
张红国
李玉卿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN202010094572.6A priority Critical patent/CN111292910B/en
Publication of CN111292910A publication Critical patent/CN111292910A/en
Application granted granted Critical
Publication of CN111292910B publication Critical patent/CN111292910B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01F1/0551—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Soft Magnetic Materials (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

A method for quickly preparing Co/SmCo composite magnetic material with special structure belongs to the field of rare earth magnetic materials, and comprises using Co sea urchin cluster as core, Sm (OH)3The precursor attached to the sea urchin branches is subjected to incomplete calcium reduction reaction in a short time to prepare the Co/SmCo composite magnetic particles with the core-shell structure, wherein the Co phase is a core, the SmCo phase is a shell, and the hard magnetic phase is uniformly distributed around the soft magnetic phase, so that the exchange coupling effect is facilitated, the reaction time is greatly shortened, and a new idea is provided for the rapid preparation of the soft magnetic phase and hard magnetic phase composite material.

Description

Rapid preparation method of Co/SmCo composite magnetic material with special structure
Technical Field
The invention relates to a preparation method of a magnetic material, in particular to a preparation method of a Co/SmCo composite magnetic material with a special structure by short-time incomplete calcium reduction, belonging to the field of rare earth magnetic materials.
Background
In the modern society, the permanent magnet material has wide application in the fields of energy, traffic, aerospace, medical treatment, computers and the like, and has wide application prospect. With the progress of society, the demand for permanent magnetic materials is also gradually increasing. The SmCo permanent magnet material has strong magnetocrystalline anisotropy and high Curie temperature, and is a preferred material in the fields of automobile engines, rocket launching and the like. But the low saturation magnetization of SmCo limits its development. In recent years, in order to compensate for this disadvantage, a two-phase composite material is formed by combining it with a soft magnetic material having a high saturation magnetization such as Fe or Co, and the magnetic properties thereof are improved.
At present, the preparation method of the biphase composite magnetic material mainly comprises a physical method and a chemical method. The method of preparing nanoparticles from bulk materials using physical processes is a "top-down" method; the method of preparing nanoparticles by recombining atoms by a chemical process is a "bottom-up" method. The mechanical ball milling method is a main method for preparing the biphase composite magnetic material by a physical method, and comprises the steps of crushing cast ingots, 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 chemical coating method is a main method for preparing a biphase composite magnetic material by a chemical method, and the specific flow is that firstly, a hard magnetic material is prepared, the hard magnetic material is taken as a core, and then a layer of soft magnetic phase is coated on the surface of the hard magnetic material by the chemical method. Although the method can control the microstructure of the particles, the phenomenon of uneven distribution of soft magnetic phase and hard magnetic phase is easy to occur, and the magnetic performance is influenced. The patent CN 107799252A of Beijing aerospace university mentions a method for preparing SmCo/Co nano composite magnetic material by microwave calcium thermal reduction, which solves the above problems to a certain extent, but has longer preparation time. Therefore, a method for preparing a Co/SmCo nanocomposite magnetic material in a short time is required.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a rapid preparation method of a Co/SmCo composite magnetic material with a special structure, which utilizes Co/Sm (OH)3The special structure of the precursor, which is published in Journal of Materials Chemistry C in 2018 of this group of subjects, A novel strategy to Synthesis and a novel and isomeric SmCo5 particles from Co/Sm(OH)3composition with specific morphology is mentioned in the article, where Sm (OH) is distributed on branches of Co-urchin clusters3This structural advantage produces a composition distribution by calcium reductionHomogeneous SmCo5Single phase particles. The invention utilizes the special structural advantage to reduce all Sm (OH) on the surface through calcium in an ultra-short time3Reducing to Sm and combining with partial Co nucleus to form SmCo5And Sm2Co17And (2) waiting for the hard magnetic phase, reserving a part of Co core, and preparing the composite magnetic particles taking the Co soft magnetic phase as the core and the SmCo hard magnetic phase as the shell, wherein the hard magnetic phase wraps the soft magnetic phase so that the soft magnetic phase and the hard magnetic phase are distributed more uniformly, the exchange coupling effect is facilitated, the magnetic performance is improved, and the reaction time is shortened to a great extent.
In order to achieve the above object, the technical solution of the present invention comprises the following steps:
s1, SmCl is adopted3·6H2Preparing Sm (OH) from O powder serving as a raw material by a hydrothermal method3A precursor;
s2, Sm (OH) prepared in step S13Preparing Co/Sm (OH) from the precursor, cobalt laurate and hexadecylamine by an alcohol heating method3A precursor;
s3, mixing the Co/Sm (OH) in the step S23And (3) fully mixing the precursor with CaO and Ca, and then carrying out short-time calcium reduction reaction to obtain the Co/SmCo composite magnetic particles with the core-shell structure and CaO generated in the reaction.
S4, dissolving unreacted Ca in the product obtained in the step S3 by using deionized water, adding acetic acid, pouring out supernatant after the pH of the solution is neutral or slightly acidic, centrifugally washing the dark gray powder for 2-3 times by using the deionized water to remove redundant acid, and centrifugally washing for 1-2 times by using absolute ethyl alcohol to obtain the Co/SmCo composite magnetic material.
Preferably Sm (OH)3The preparation process of the precursor comprises the following steps: adding 10-12mmol of SmCl into the hydrothermal kettle3·6H2Adding 30-40ml of deionized water, stirring uniformly, dropwise adding 20-30ml of 1.8-2mol/l NaOH solution, allowing 15-20% of NaOH to pass through, reacting at 180 ℃ for 2-3 hours after magnetic stirring for 30-40 minutes, cooling, centrifugally washing with deionized water for 2-3 times, centrifugally washing with absolute ethyl alcohol for 1-2 times at 6000-8000r/min for 5-8 minutes, dryingGrinding and storing.
Preferably, Co/Sm (OH)3The preparation process of the precursor comprises the following steps: adding Sm (OH) into the hydrothermal kettle in a molar ratio of 1:4-1:73And cobalt laurate in an amount of 1 to 1.5mmol of Sm (OH)3Adding 1.2-3.6mmol of hexadecylamine and 60-70ml of 1, 2-butanediol, fully stirring, performing ultrasonic water bath at 80 ℃ for 60-70 minutes, putting the mixture into a muffle furnace, heating to 250 ℃ at the heating rate of 8-10 ℃/min, keeping the temperature for 80-100 minutes, taking out, cooling, performing centrifugal washing for 2-3 times by using toluene at the rotating speed of 6000-8000r/min, and performing centrifugal time for 5-8 minutes each time.
Preferably, Co/Sm (OH) is added in each calcium reduction reaction30.2g of precursor, corresponding to 0.3-0.5g of CaO and 3-4g of Ca.
Preferably, the calcium reduction reaction is carried out in an argon-hydrogen mixed atmosphere (93% Ar + 7% H)2) Wherein the temperature is 840-870 ℃, the heating rate is 8-10 ℃/min, the heat preservation time is 8-15min, and the further optimization is 10 min.
Preferably, the phase compositions of the prepared Co/SmCo composite magnetic material are Co and SmCo5And Sm2Co17A composite phase is formed.
As a preferred scheme, the microstructure of the prepared Co/SmCo composite magnetic material takes Co soft magnetic phase as a core, and SmCo5And Sm2Co17The formed SmCo hard magnetic phase is a shell layer.
Compared with other prior art, the invention has the main advantages that:
the invention provides a method for preparing a Co/SmCo composite magnetic material with a special structure by utilizing the structural advantages of a precursor through short-time incomplete calcium reduction reaction, namely, a Co soft magnetic phase is taken as a core, a SmCo hard magnetic phase is taken as a shell layer, and the hard magnetic phase is uniformly distributed around the soft magnetic phase. The technology solves the problems of agglomeration and oxidation phenomena and uneven distribution of soft and hard magnetic phases in the prior art, and the prepared composite particles have even distribution of the soft and hard magnetic phases and are beneficial to exchange coupling effect. And the calcium reduction reaction time is short, the reaction time is greatly reduced, and the rapid preparation of the composite magnetic particles is realized.
Drawings
Fig. 1 is a left view showing phase results of XRD tests on the composite magnetic materials prepared in examples 1 to 4, and a right view showing magnetic results of example 1.
Fig. 2 is a phase result of XRD test for the magnetic material prepared in the comparative example at the left and a magnetic property result at the right.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
(1) 3.7580g of SmCl3·6H2O was dissolved in 40ml of deionized water and 1.4688g of NaOH was dissolved in 20ml of deionized water. Dropwise adding NaOH solution into SmCl under magnetic stirring3And (3) putting the solution into a muffle furnace after 30min, preserving the heat at 180 ℃ for 12 hours, and centrifugally washing the solution for 3 times by using deionized water when the temperature is reduced to room temperature, wherein the rotating speed is 6000 r/min. Air-blast drying at 60 ℃ for 12 hours, and grinding to obtain Sm (OH)3And (3) precursor.
(2) 0.2265g of Sm (OH) in step (1)3Adding 2.0589g of cobalt laurate and 0.5810g of hexadecylamine into a polytetrafluoroethylene lining filled with 60ml of 1, 2-butanediol, ultrasonically treating at 80 ℃ for 1 hour, putting the mixture into a muffle furnace, heating to 250 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 80min, cooling along with the furnace, pouring out supernatant, centrifugally washing for 3 times by using methylbenzene, and drying in a vacuum drying oven at room temperature for 30 minutes to obtain Co/Sm (OH)3A precursor of wherein nSm/nCo＝1:4。
(3) Mixing the Co/Sm (OH) prepared in the step (2)3After 0.2g of the precursor and 0.3g of CaO powder are mixed uniformly, 4g of Ca particles are added and mixed uniformly, and the mixture is put into a crucible and a tube furnace. Argon-hydrogen mixture (93% Ar + 7% H) was used2) Washing the furnace for 3 times, heating to 870 deg.C at a heating rate of 10 deg.C/min under the above mixed atmosphere, maintaining for 10min, and rapidly cooling to room temperature with fan.
(4) And (4) taking out the mixture in the crucible after the reaction in the step (3), putting the mixture into a beaker, adding deionized water, dropwise adding acetic acid while stirring when the Ca is fully dissolved, namely when the Ca is not bubbled, centrifugally washing twice by using the deionized water to remove redundant acid when the PH is approximately equal to 7, centrifugally washing twice by using absolute ethyl alcohol at the rotating speed of 6000r/min, and thus obtaining the Co/SmCo composite magnetic material.
(5) The phase composition of the product was analyzed by XRD, and the results are shown in the left panel of FIG. 1, where the sample consists of SmCo5Phase Sm2Co17Phase and Co phase (Sm is burnt in the reaction). Indicating that Co is not completely reacted in the reaction process and is remained. And the magnetic properties of the product were tested using VSM, the results of which are shown in the right panel of fig. 1.
Example 2
(1) 3.7580g of SmCl3·6H2O was dissolved in 40ml of deionized water and 1.4688g of NaOH was dissolved in 20ml of deionized water. Dropwise adding NaOH solution into SmCl under magnetic stirring3And (3) putting the solution into a muffle furnace after 30min, preserving the heat at 180 ℃ for 12 hours, and centrifugally washing the solution for 3 times by using deionized water when the temperature is reduced to room temperature, wherein the rotating speed is 6000 r/min. Air-blast drying at 60 ℃ for 12 hours, and grinding to obtain Sm (OH)3And (3) precursor.
(2) 0.2265g of Sm (OH) in step (1)3Adding 2.0589g of cobalt laurate and 0.5810g of hexadecylamine into a polytetrafluoroethylene lining filled with 60ml of 1, 2-butanediol, ultrasonically treating at 80 ℃ for 1 hour, putting the mixture into a muffle furnace, heating to 250 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 80min, cooling along with the furnace, pouring out supernatant, centrifugally washing for 3 times by using methylbenzene, and drying in a vacuum drying oven at room temperature for 30 minutes to obtain Co/Sm (OH)3A precursor of wherein nSm/nCo＝1:7。
(3) Mixing the Co/Sm (OH) prepared in the step (2)3After 0.2g of the precursor and 0.3g of CaO powder are mixed uniformly, 4g of Ca particles are added and mixed uniformly, and the mixture is put into a crucible and a tube furnace. Argon-hydrogen mixture (93% Ar + 7% H) was used2) Washing the furnace for 3 times, heating to 870 deg.C at a heating rate of 10 deg.C/min under the above mixed atmosphere, maintaining for 10min, and rapidly cooling to room temperature with fan.
(4) And (4) taking out the mixture in the crucible after the reaction in the step (3), putting the mixture into a beaker, adding deionized water, dropwise adding acetic acid while stirring when Ca is fully dissolved, namely the bubbling phenomenon of the solution is stopped, centrifugally washing twice by using the deionized water to remove redundant acid when the PH is approximately equal to 7, and centrifugally washing twice by using absolute ethyl alcohol at the rotating speed of 6000r/min to obtain the Co/SmCo composite magnetic material.
(5) The phase composition of the product was analyzed by XRD, and the results are shown in the left panel of FIG. 1, where the sample consists of SmCo5Phase Sm2Co17Phase and Co phase. Indicating that Co is not completely reacted in the reaction process and is remained.
Example 3
(1) 3.7580g of SmCl3·6H2O was dissolved in 40ml of deionized water and 1.4688g of NaOH was dissolved in 20ml of deionized water. Dropwise adding NaOH solution into SmCl under magnetic stirring3And (3) putting the solution into a muffle furnace after 30min, preserving the heat at 180 ℃ for 12 hours, and centrifugally washing the solution for 3 times by using deionized water when the temperature is reduced to room temperature, wherein the rotating speed is 6000 r/min. Air-blast drying at 60 ℃ for 12 hours, and grinding to obtain Sm (OH)3And (3) precursor.
(2) 0.1294g of Sm (OH) in step (1)3Adding 2.0589g of cobalt laurate and 0.5810g of hexadecylamine into a polytetrafluoroethylene lining filled with 60ml of 1, 2-butanediol, ultrasonically treating at 80 ℃ for 1 hour, putting the mixture into a muffle furnace, heating to 250 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 80min, cooling along with the furnace, pouring out supernatant, centrifugally washing for 3 times by using methylbenzene, and drying in a vacuum drying oven at room temperature for 30 minutes to obtain Co/Sm (OH)3A precursor of wherein nSm/nCo＝1:4。
(3) Mixing the Co/Sm (OH) prepared in the step (2)3After 0.2g of the precursor and 0.3g of CaO powder are mixed uniformly, 4g of Ca particles are added and mixed uniformly, and the mixture is put into a crucible and a tube furnace. Argon-hydrogen mixture (93% Ar + 7% H) was used2) Washing the furnace for 3 times, heating to 840 ℃ at a heating rate of 10 ℃/min under the mixed atmosphere, preserving heat for 10min, and then rapidly cooling to room temperature by using a fan.
(4) And (4) taking out the mixture in the crucible after the reaction in the step (3), putting the mixture into a beaker, adding deionized water, dropwise adding acetic acid while stirring when the Ca is fully dissolved, namely the solution is not foamed, centrifugally washing twice by using the deionized water to remove redundant acid when the pH is approximately equal to 7, centrifugally washing twice by using absolute ethyl alcohol at the rotating speed of 6000r/min, and thus obtaining the Co/SmCo composite magnetic material.
(5) The phase composition of the product is analyzed by XRD, and the main phase of the sample is Sm2Co17Phase and Co phase. Indicating that Co is not completely reacted in the reaction process and is remained.
Example 4
(1) 3.7580g of SmCl3·6H2O was dissolved in 40ml of deionized water and 1.4688g of NaOH was dissolved in 20ml of deionized water. Dropwise adding NaOH solution into SmCl under magnetic stirring3And (3) putting the solution into a muffle furnace after 30min, preserving the heat at 180 ℃ for 12 hours, and centrifugally washing the solution for 3 times by using deionized water when the temperature is reduced to room temperature, wherein the rotating speed is 6000 r/min. Air-blast drying at 60 ℃ for 12 hours, and grinding to obtain Sm (OH)3And (3) precursor.
(2) 0.1294g of Sm (OH) in step (1)3Adding 2.0589g of cobalt laurate and 0.5810g of hexadecylamine into a polytetrafluoroethylene lining filled with 60ml of 1, 2-butanediol, ultrasonically treating at 80 ℃ for 1 hour, putting the mixture into a muffle furnace, heating to 250 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 80min, cooling along with the furnace, pouring out supernatant, centrifugally washing for 3 times by using methylbenzene, and drying in a vacuum drying oven at room temperature for 30 minutes to obtain Co/Sm (OH)3A precursor of wherein nSm/nCo＝1:7。
(3) Mixing the Co/Sm (OH) prepared in the step (2)3After 0.2g of the precursor and 0.3g of CaO powder are mixed uniformly, 4g of Ca particles are added and mixed uniformly, and the mixture is put into a crucible and a tube furnace. Argon-hydrogen mixture (93% Ar + 7% H) was used2) Washing the furnace for 3 times, heating to 840 ℃ at a heating rate of 10 ℃/min under the mixed atmosphere, preserving heat for 10min, and then rapidly cooling to room temperature by using a fan.
(4) And (4) taking out the mixture in the crucible after the reaction in the step (3), putting the mixture into a beaker, adding deionized water, dropwise adding acetic acid while stirring when the Ca is fully dissolved, namely the solution is not foamed, centrifugally washing twice by using the deionized water to remove redundant acid when the pH is approximately equal to 7, centrifugally washing twice by using absolute ethyl alcohol at the rotating speed of 6000r/min, and thus obtaining the Co/SmCo composite magnetic material.
(5) By XRD on the productThe phase composition is analyzed, the result is shown in the left picture of figure 1, and the main phase of the sample is Sm2Co17Phase and Co phase. Indicating that Co is not completely reacted in the reaction process and is remained.
Comparative example
(1) 3.7580g of SmCl3·6H2O was dissolved in 40ml of deionized water and 1.4688g of NaOH was dissolved in 20ml of deionized water. Dropwise adding NaOH solution into SmCl under magnetic stirring3And (3) putting the solution into a muffle furnace after 30min, preserving the heat at 180 ℃ for 12 hours, and centrifugally washing the solution for 3 times by using deionized water when the temperature is reduced to room temperature, wherein the rotating speed is 6000 r/min. Air-blast drying at 60 ℃ for 12 hours, and grinding to obtain Sm (OH)3And (3) precursor.
(2) 0.1294g of Sm (OH) in step (1)3Adding 2.0589g of cobalt laurate and 0.5810g of hexadecylamine into a polytetrafluoroethylene lining filled with 60ml of 1, 2-butanediol, ultrasonically treating at 80 ℃ for 1 hour, putting the mixture into a muffle furnace, heating to 250 ℃ at a heating rate of 10 ℃/min, preserving the temperature for 80min, cooling along with the furnace, pouring out supernatant, centrifugally washing for 3 times by using methylbenzene, and drying in a vacuum drying oven at room temperature for 30 minutes to obtain Co/Sm (OH)3A precursor of wherein nSm/nCo＝1:4。
(3) Mixing the Co/Sm (OH) prepared in the step (2)3After 0.2g of the precursor and 0.3g of CaO powder are mixed uniformly, 4g of Ca particles are added and mixed uniformly, and the mixture is put into a crucible and a tube furnace. Argon-hydrogen mixture (93% Ar + 7% H) was used2) Washing the furnace for 3 times, heating to 870 deg.C at a heating rate of 10 deg.C/min under the above mixed atmosphere, maintaining for 90min, and rapidly cooling to room temperature with fan.
(4) Taking out the mixture in the crucible after the reaction in the step (3), putting the mixture into a beaker, adding deionized water, dropwise adding acetic acid while stirring when the Ca is fully dissolved, namely the solution is not foamed, centrifugally washing twice by using the deionized water to remove redundant acid when the pH is approximately equal to 7, centrifugally washing twice by using absolute ethyl alcohol at the rotating speed of 6000r/min, and thus obtaining SmCo5A magnetic material.
(5) The phase composition of the product was analyzed by XRD, and the result is shown in the left panel of FIG. 2, where the sample was SmCo5And (4) phase(s). And adopting VSM to pair the productsThe magnetic properties of the material were tested and the results are shown in the right panel of FIG. 2.
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 BDA0002384899080000101
In conclusion, the Co/SmCo sample with the core-shell structure can be successfully prepared by combining the incomplete calcium reduction reaction in a short time with the special structure of the precursor, and the hard magnetic phase is uniformly distributed around the soft magnetic phase, thereby being beneficial to the exchange coupling effect. Compared with a comparative example, the residual magnetization and the saturation magnetization under a 3T magnetic field are both improved, the reaction time is greatly shortened, the preparation method is simple, and a new idea is provided for the rapid preparation of the composite magnetic material.

Claims (8)

1. A rapid preparation method of a Co/SmCo composite magnetic material with a special structure is characterized by comprising the following steps:
s1, SmCl is adopted3·6H2Preparing Sm (OH) from O powder serving as a raw material by a hydrothermal method3A precursor;
s2, Sm (OH) prepared in step S13Preparing Co/Sm (OH) from the precursor, cobalt laurate and hexadecylamine by an alcohol heating method3A precursor;
s3, mixing the Co/Sm (OH) in the step S23The precursor is fully mixed with CaO and Ca and then subjected to a short-time calcium reduction reaction to obtain Co/SmCo composite magnetic particles with a core-shell structure and CaO generated in the reaction, wherein the calcium reduction reaction is carried out in an argon-hydrogen mixed atmosphere at the temperature of 840-870 ℃, the heating rate is 8-10 ℃/min, and the heat preservation time is 8-15 min;
s4, dissolving unreacted Ca in the product obtained in the step S3 by using deionized water, adding acetic acid, pouring out supernatant after the PH of the solution is neutral or slightly acidic, centrifugally washing the black and gray powder for 2-3 times by using the deionized water to remove redundant acid, and centrifugally washing for 1-2 times by using absolute ethyl alcohol to obtain the Co/SmCo composite magnetic material, wherein the composite magnetic particle takes a Co soft magnetic phase as a core and a SmCo hard magnetic phase as a shell.
2. The process of claim 1, wherein Sm (OH)3The preparation process of the precursor comprises the following steps: adding 10-12mmol of SmCl into the hydrothermal kettle3·6H2And O, adding 30-40ml of deionized water, stirring uniformly, dropwise adding 20-30ml of 1.8-2mol/l NaOH solution, reacting at 180 ℃ for 2-3 hours after magnetic stirring for 30-40 minutes, cooling, centrifugally washing with deionized water for 2-3 times, centrifugally washing with absolute ethyl alcohol, drying, grinding and storing.
3. The process of claim 1, wherein Co/Sm (OH)3The preparation process of the precursor comprises the following steps: adding Sm (OH) into the hydrothermal kettle in a molar ratio of 1:4-1:73And cobalt laurate in an amount of 1 to 1.5mmol of Sm (OH)3Adding 1.2-3.6mmol of hexadecylamine and 60-70ml of 1, fully stirring 2-butanediol, putting in an ultrasonic water bath at 80 ℃ for 60-70 minutes, putting in a muffle furnace, heating to 250 ℃ at the heating rate of 8-10 ℃/min, keeping the temperature for 80-100 minutes, taking out, cooling, and carrying out centrifugal washing by using toluene.
4. The method according to claim 1, wherein the calcium reduction reaction is carried out with each addition of Co/Sm (OH)30.2g of precursor, corresponding to 0.3-0.5g of CaO and 3-4g of Ca.
5. The method according to claim 1, wherein the incubation time for the calcium reduction reaction is 10 minutes; the argon-hydrogen mixed atmosphere is 93% Ar + 7% H2。
6. A method according to claim 1, wherein the Co/SmCo composite magnetic material produced has a phase composition of Co and SmCo5And Sm2Co17A composite phase is formed.
7. The microstructure of the prepared Co/SmCo composite magnetic material takes Co soft magnetic phase as a core, and SmCo5And Sm2Co17The formed SmCo hard magnetic phase is a shell layer.
8. A Co/SmCo composite magnetic material of particular structure when produced by a process as claimed in any one of claims 1 to 7.
CN202010094572.6A 2020-02-16 2020-02-16 Rapid preparation method of Co/SmCo composite magnetic material with special structure Active CN111292910B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010094572.6A CN111292910B (en) 2020-02-16 2020-02-16 Rapid preparation method of Co/SmCo composite magnetic material with special structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010094572.6A CN111292910B (en) 2020-02-16 2020-02-16 Rapid preparation method of Co/SmCo composite magnetic material with special structure

Publications (2)

Publication Number Publication Date
CN111292910A CN111292910A (en) 2020-06-16
CN111292910B true CN111292910B (en) 2021-06-18

Family

ID=71024543

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010094572.6A Active CN111292910B (en) 2020-02-16 2020-02-16 Rapid preparation method of Co/SmCo composite magnetic material with special structure

Country Status (1)

Country Link
CN (1) CN111292910B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022024920A1 (en) * 2020-07-28 2022-02-03 国立研究開発法人産業技術総合研究所 Anisotropic magnet microparticles and production method therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61214503A (en) * 1985-03-20 1986-09-24 Daido Steel Co Ltd Manufacture of sm-co magnet
US4919734A (en) * 1984-09-29 1990-04-24 Kabushiki Kaisha Toshiba Compressed magnetic powder core
JP2010021541A (en) * 2008-06-12 2010-01-28 Toshiba Corp Permanent magnet and method of manufacturing the same, and permanent magnet for motor and permanent magnet motor
CN104762519A (en) * 2015-03-23 2015-07-08 北京工业大学 A preparing method of a nanocrystal Sm<2>Co<17>/Co double-phase composite permanent magnetic alloy
CN109867310A (en) * 2018-12-28 2019-06-11 北京航空航天大学 SmCo is prepared in situ in one kind5/Sm2Co17The method of core-shell structure two-phase composite magnetic nanoparticle

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919734A (en) * 1984-09-29 1990-04-24 Kabushiki Kaisha Toshiba Compressed magnetic powder core
JPS61214503A (en) * 1985-03-20 1986-09-24 Daido Steel Co Ltd Manufacture of sm-co magnet
JP2010021541A (en) * 2008-06-12 2010-01-28 Toshiba Corp Permanent magnet and method of manufacturing the same, and permanent magnet for motor and permanent magnet motor
CN104762519A (en) * 2015-03-23 2015-07-08 北京工业大学 A preparing method of a nanocrystal Sm<2>Co<17>/Co double-phase composite permanent magnetic alloy
CN109867310A (en) * 2018-12-28 2019-06-11 北京航空航天大学 SmCo is prepared in situ in one kind5/Sm2Co17The method of core-shell structure two-phase composite magnetic nanoparticle

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Anistropic nanostructured SmCo5 bonded magnets fabricated by magnetic-field-assisted liquid phase processing;Hongjian Li等;《Journal of Magnetism and Magnetic Materials》;20190801;全文 *
Magnetic properties of SmCo7/Co and Sm(Co,Fe)/α-(Fe，Co) Nanocomposite Magnets Prepared by Magnetic Annealing;B.Z.Cui等;《IEEE Transactions on Magnetics》;20030930;全文 *

Also Published As

Publication number Publication date
CN111292910A (en) 2020-06-16

Similar Documents

Publication Publication Date Title
CN108274016B (en) Method for directly preparing samarium-iron alloy powder by spray pyrolysis reduction method
CN107799252B (en) A kind of method that microwave calciothermic reduction prepares SmCo/Co Nano-composite magnetic materials
CN113149629B (en) High-temperature-resistant transition metal high-entropy oxide wave-absorbing filler and preparation method thereof
CN111825081A (en) Graphene-loaded MOF derivative aerogel and preparation method thereof
CN111292910B (en) Rapid preparation method of Co/SmCo composite magnetic material with special structure
CN111564305A (en) Preparation method of high-performance composite magnet
CN106745303A (en) A kind of three-dimensional flower ball-shaped cadmium ferrite bismuth meal body and preparation method thereof
CN112071543B (en) High-coercivity rare earth permanent magnet and preparation method thereof
CN111613901B (en) Graphene/metal oxide/metal ternary nano composite magnetic material and preparation method thereof
CN109867310B (en) In-situ preparation of SmCo5/Sm2Co17Method for preparing biphase composite magnetic nano particles with core-shell structure
CN114535591B (en) Method for preparing alloy powder based on surface nanocrystallization treatment
CN107021520B (en) A kind of yttrium oxide powder and preparation method thereof
CN113628824B (en) High-strength ceramic-coated iron-based composite soft magnetic material and preparation method thereof
CN110137346B (en) Manganese-doped holmium ferrite HoMn x Fe 1-x O 3 Preparation method of magnetoelectric material
Wang et al. Preparation of high-performance Nd–Fe–B magnetic powder by hydrothermal method assisted via ball milling
CN101698612B (en) Homodisperse ferrite magnetic manoparticles and preparation method thereof
CN114496442A (en) Nano magnetic particle, preparation method thereof and magnetic liquid
CN114566342A (en) Of special construction (Nd, Tb)2Fe14Preparation method of B/Co composite magnetic material
CN117736696A (en) 2:17 rare earth cobalt/graphite nano composite electromagnetic wave absorbing material and preparation method thereof
CN117809925B (en) Nanocrystalline magnetic core material of high-frequency transformer and preparation method thereof
CN116117152B (en) Preparation method of iron-based micro powder with high magnetic conductivity and low high frequency loss
CN113510247B (en) Ce 2 Fe 17 And Ce 2 Fe 17 N 3 Preparation method of alloy powder
CN115295266B (en) M-type strontium ferrite-based biphase composite permanent magnetic ferrite block and preparation method thereof
CN108470616A (en) It is a kind of to prepare Nd using neodymium iron boron solid waste2Fe14The method of the nano combined magnetic powders of B/ α-Fe
CN108806960A (en) A kind of liquid phase chemical combination method preparing Nd-Fe-B permanent magnetic nano-particle

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant