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 PDFInfo
- 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
Links
- 239000000696 magnetic material Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000011575 calcium Substances 0.000 claims abstract description 32
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 239000006249 magnetic particle Substances 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 9
- OCDFTWVGTADYMH-UHFFFAOYSA-N cobalt dodecanoic acid Chemical compound [Co].CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O OCDFTWVGTADYMH-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 150000002910 rare earth metals Chemical class 0.000 abstract description 2
- 241000257465 Echinoidea Species 0.000 abstract 2
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 9
- 229940083957 1,2-butanediol Drugs 0.000 description 6
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000005415 magnetization Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000001808 coupling effect Effects 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Soft Magnetic Materials (AREA)
Abstract
一种具有特殊结构的Co/SmCo复合磁性材料的快速制备方法，属于稀土磁性材料领域，包括使用以Co海胆团簇为核心，Sm(OH)3附着于海胆枝杈中的前驱体，通过短时间不完全钙还原反应，制备具有核壳结构的Co/SmCo复合磁性颗粒，其结构中，Co相为核心，SmCo相为壳层，硬磁相均匀的分布在软磁相周围，有利于交换耦合作用，且极大的缩短了反应时间，为软磁相与硬磁相复合材料的快速制备提供了一种新思路。A rapid preparation method of a Co/SmCo composite magnetic material with a special structure, belonging to the field of rare earth magnetic materials, comprising using a Co sea urchin cluster as a core and Sm(OH) 3 attached to a precursor in a sea urchin branch, through a short time Co/SmCo composite magnetic particles with a core-shell structure were prepared by incomplete calcium reduction reaction. In the structure, the Co phase is the core, the SmCo phase is the shell, and the hard magnetic phase is uniformly distributed around the soft magnetic phase, which is conducive to exchange coupling. It can greatly shorten the reaction time, and provide a new idea for the rapid preparation of soft magnetic phase and hard magnetic phase composite materials.
Description
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
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.
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 (2)
| 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 |
| CN116786832B (en) * | 2023-01-03 | 2024-11-29 | 南京理工大学 | Double-phase composite rare earth iron cobalt magnetic powder with lamellar structure and preparation method thereof |
Citations (5)
| 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 preparation method of nanocrystalline Sm2Co17/Co dual-phase composite permanent magnet 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 |
-
2020
- 2020-02-16 CN CN202010094572.6A patent/CN111292910B/en active Active
Patent Citations (5)
| 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 preparation method of nanocrystalline Sm2Co17/Co dual-phase composite permanent magnet 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)
| 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) | A method for directly preparing samarium iron alloy powder by spray thermal decomposition reduction method | |
| CN111292910B (en) | Rapid preparation method of Co/SmCo composite magnetic material with special structure | |
| CN113149629B (en) | High-temperature-resistant transition metal high-entropy oxide wave-absorbing filler and preparation method thereof | |
| CN107488484B (en) | Method for preparing composite antiwear additive by grafting fatty acid | |
| CN107799252A (en) | A kind of method that microwave calciothermic reduction prepares SmCo/Co Nano-composite magnetic materials | |
| CN110358534A (en) | A kind of preparation method that carbon quantum dot combined oxidation is cuprous | |
| CN117809925A (en) | Nanocrystalline magnetic core material of high-frequency transformer and preparation method thereof | |
| CN105883934A (en) | Method for preparing water-soluble superparamagnetic Fe3O4 hollow spheres | |
| CN106997800B (en) | A kind of no rare earth MnAlCuC permanent-magnet alloy and preparation method thereof | |
| CN114898960B (en) | A method for preparing nano-scale SmFeN magnetic powder | |
| CN105290419B (en) | Herring-bone form nuclear shell structure nano monel powder and preparation method thereof | |
| CN115666115A (en) | Metal Organic Frameworks (MOFs) derived carbon-coated FeSi-based composite magnetic wave-absorbing material and preparation method thereof | |
| CN106745303A (en) | A kind of three-dimensional spherical lanthanum bismuth ferrite powder and its preparation method | |
| CN105702406A (en) | MnAlC-based high coercive force permanent magnetic material and preparation method thereof | |
| CN108746642A (en) | A kind of preparation method of the rare earth-transition metal nitride Magnaglo through surfacecti proteon processing | |
| CN109867310B (en) | In-situ preparation of SmCo5/Sm2Co17Method for preparing biphase composite magnetic nano particles with core-shell structure | |
| CN112479265A (en) | Preparation method of cobaltosic oxide nanoparticles | |
| CN113059179B (en) | Preparation method of magnetic cobalt particles | |
| CN107021520B (en) | A kind of yttrium oxide powder and preparation method thereof | |
| Wang et al. | Preparation of high-performance Nd–Fe–B magnetic powder by hydrothermal method assisted via ball milling | |
| CN116117152A (en) | Preparation method of iron-based micro powder with high magnetic conductivity and low high frequency loss | |
| CN110564365A (en) | Preparation method of graphene foam composite material loaded with magnetic hollow nanospheres | |
| CN114535591A (en) | Method for preparing alloy powder based on surface nanocrystallization treatment | |
| CN116730400B (en) | Iron-cobalt oxide core-shell magnetic particle and preparation method thereof | |
| CN110711586B (en) | A low-temperature preparation method of a magnetic bismuth-containing iron oxide photocatalyst |
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 |