CN111326303A - Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material - Google Patents

Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material Download PDF

Info

Publication number
CN111326303A
CN111326303A CN202010143114.7A CN202010143114A CN111326303A CN 111326303 A CN111326303 A CN 111326303A CN 202010143114 A CN202010143114 A CN 202010143114A CN 111326303 A CN111326303 A CN 111326303A
Authority
CN
China
Prior art keywords
alloy
magnetic powder
single crystal
rare earth
spherical
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.)
Pending
Application number
CN202010143114.7A
Other languages
Chinese (zh)
Inventor
唐少龙
董大舜
钱进
黄业
都有为
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.)
Nanjing University
Original Assignee
Nanjing University
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 Nanjing University filed Critical Nanjing University
Priority to CN202010143114.7A priority Critical patent/CN111326303A/en
Publication of CN111326303A publication Critical patent/CN111326303A/en
Priority to PCT/CN2021/078392 priority patent/WO2021175174A1/en
Pending legal-status Critical Current

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
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0558—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together bonded together
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B1/00—Single-crystal growth directly from the solid state
    • C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys
    • 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
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
    • 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
    • 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
    • H01F41/0266—Moulding; Pressing

Abstract

The invention provides a preparation method of <111> oriented rare earth giant magnetostrictive material and alloy spherical single crystal magnetic powder, which comprises the following steps: 1) preparing R-Fe-M alloy spherical magnetic powder; 2) uniformly mixing the R-Fe-M alloy spherical magnetic powder with an inert solid dispersing agent, and annealing at a temperature below the melting point of the R-Fe-M alloy to obtain R-Fe-M cubic Laves phase single crystal particles, wherein the annealing temperature is 50-200 ℃ below the melting point of the cubic Laves phase, and the preferred annealing time is 1-4 hours; 3) removing the solid dispersant to obtain the R-Fe-M cubic Laves phase spherical single crystal magnetic powder. The invention separates R-Fe-M alloy spherical magnetic powder by inert solid dispersant, and prepares spherical single crystal particles by the abnormal growth capacity of R-Fe-M cubic Laves phase crystal grains at high temperature. A bonded rare earth giant magnetostrictive material and a sintered rare earth giant magnetostrictive material having a high <111> orientation are prepared.

Description

Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material
Technical Field
The invention relates to a preparation method of rare earth giant magnetostrictive material and spherical single crystal magnetic powder suitable for <111> orientation, in particular to a preparation method of R-Fe-M alloy spherical single crystal magnetic powder in the fields of bonding rare earth giant magnetostrictive material and sintering rare earth giant magnetostrictive material.
Background
The rare earth-iron cubic Laves phase single crystal material shows a large magnetostriction effect and has important application in the fields of sonar, energy converters and the like. However, the preparation process of the rare earth-iron cubic Laves phase single crystal material is complex, the production cost is high, and the preparation of the single crystal material with large-size components and uniform performance is difficult. As an alternative method, the magnetostrictive bulk material can be prepared by preparing rare earth-iron cubic Laves phase single crystal powder and using the single crystal powder as a raw material. The single crystal powder can be oriented in a magnetic field and then is pressed and molded, and the sintered rare earth giant magnetostrictive material with certain orientation is prepared by high-temperature annealing. The single crystal powder can also be made into bonded rare earth giant magnetostrictive materials with other materials, such as epoxy resin, and the materials show magnetostrictive performance similar to that of bulk single crystal materials. For example, when a ferromagnetic single crystal magnetic powder is mixed with an epoxy resin and then molded under a magnetic field, a high degree of orientation can be obtained in the magnetic single crystal magnetic powder, and the bonded magnetostrictive material can exhibit a magnetostrictive property similar to that of a single crystal material.
The existing preparation method of rare earth-iron cubic Laves phase single crystal powder adopts a crushing method. There are two main ways: first, mechanical breaking of ingots or rapid-setting wafers (patent cn200410037611. x): annealing the ingot or the rapid hardening crystal plate at high temperature to grow crystal grains, and obtaining single crystal particles by a mechanical crushing method, wherein the particles are irregular flaky; the second is to prepare oriented crystals or single crystals and then to break the crystals to obtain single crystal powder (e.g. US 005792284A). At present, the defects of the two methods for preparing the single crystal particles still exist, which are mainly reflected in that the proportion of the single crystal particles in the powder is not high enough and the shapes of the particles are irregular. Although a magnetic intermetallic compound having a large brittleness is easily broken intergranularly upon mechanical fracture, a part of particles are broken intragranularly, and it is difficult to obtain a high proportion of single crystal particles in the powder. In addition, the powder after mechanical crushing has a large particle shape and is mostly in a sheet shape, has sharp water chestnuts, and is difficult to obtain high density when being mixed with other materials to prepare a super magnetostrictive adhesive material with high orientation degree. The reason is that when the magnetic field is applied for orientation, the flaky particles are greatly hindered by the surrounding powder and the dispersing agent, the rotational orientation of the particles is not easily realized, and when the density of the alloy particles is high, a high degree of orientation is difficult to obtain. If a high degree of orientation is to be obtained, the proportion of magnetic particles needs to be reduced, as in patent CN 201210034284.7. Reducing the proportion of magnetic particles affects the transfer of strain between the magnetic particles, reducing the magnitude of magnetostriction and the energy conversion efficiency.
The rare earth-iron cubic Laves phase alloy spherical single crystal particles can easily realize the rotational orientation of the particles when a magnetic field is applied externally, and obtain bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with good orientation degree and high magnetic metal particle density. The rare earth-iron cubic Laves phase alloy spherical single crystal magnetic powder is expected to develop bonded rare earth giant magnetostrictive materials and sintered rare earth giant magnetostrictive materials with high magnetostrictive effect.
Disclosure of Invention
The invention aims to provide a preparation method of cubic Laves phase R-Fe-M alloy spherical single crystal magnetic powder, in particular to a <111> oriented rare earth giant magnetostrictive material and a preparation method of alloy spherical single crystal magnetic powder.
The invention has the technical scheme that the preparation method of the cubic Laves phase R-Fe-M alloy spherical single crystal magnetic powder, in particular to the preparation method of the rare earth giant magnetostrictive material and the alloy spherical single crystal magnetic powder, comprises the following steps:
(1) preparing R-Fe-M alloy spherical magnetic powder;
(2) single crystallization treatment: uniformly mixing the R-Fe-M alloy spherical magnetic powder with an inert solid dispersing agent, and annealing at a temperature below the melting point of the R-Fe-M alloy to obtain R-Fe-M single crystal particles with a cubic Laves phase structure, wherein the annealing temperature is preferably 50-200 ℃ below the melting point of the R-Fe-M alloy, and the annealing time is preferably 1-4 hours;
(3) removing the solid dispersant to obtain the R-Fe-M cubic Laves phase spherical single crystal magnetic powder.
In the R-Fe-M alloy, R refers to rare earth elements including one or more of terbium, dysprosium, samarium, praseodymium, neodymium, cerium, holmium, erbium and the like, M refers to transition metal elements including one or more of cobalt, manganese, aluminum, gallium, chromium and the like, and the balance is iron.
The R-Fe-M rare earth alloy consists of 30-40% (atomic percent) of R, 0-20% (atomic percent) of M and the balance of Fe.
The preparation method of the R-Fe-M alloy spherical magnetic powder comprises the following steps: the method comprises the steps of firstly obtaining the R-Fe-M alloy by a smelting or chemical reduction method, and then carrying out annealing and spheroidization at a temperature higher than the melting point of the R-Fe-M alloy after separating R-Fe-M alloy particles by an atomization method, a liquid drop injection method, an electric spark method, a plasma spheroidization method or a solid dispersing agent.
The size of the R-Fe-M alloy spherical particles is less than 1mm, and the preferred size range is 10-300 mu M.
The R-Fe-M alloy magnetic powder is separated by inert solid dispersing agent, the solid dispersing agent comprises ceramic material powder (oxide ceramic, nitride ceramic, fluoride ceramic and their compound and mixture). The step of mixing materials is that the R-Fe-M alloy magnetic powder and a solid dispersant are mechanically mixed, or are uniformly mixed by stirring in organic liquid, or are uniformly mixed by the aid of the dispersant.
The solid dispersing agent can be in any size smaller than the particle size of the R-Fe-M alloy, the preferred size range is 1-10 mu M, and the morphology can be sheet-shaped, spherical, linear, tubular or other shapes.
The mass ratio of the rare earth giant magnetostrictive alloy spherical magnetic powder to the solid dispersant is such that the rare earth alloy spherical particles can be completely isolated by the solid dispersant.
The requirements for realizing single crystallization of R-Fe-M alloy particles by annealing treatment comprise: 1) annealing the mixed powder of the R-Fe-M alloy magnetic powder and the solid dispersant in high vacuum or inert gas; 2) the annealing temperature is lower than the melting point of the R-Fe-M alloy, the preferred annealing temperature is in the range of 50-200 ℃ lower than the melting point of the R-Fe-M alloy, and the preferred annealing time is 1-4 hours.
The method for removing the solid dispersant to obtain the R-Fe-M alloy spherical single crystal magnetic powder comprises the following steps: 1) after soaking in liquid, ultrasonically cleaning, and removing the solid dispersing agent to obtain R-Fe-M alloy single crystal magnetic powder; 2) separating ferromagnetic R-Fe-M alloy and nonmagnetic solid dispersant by adopting an external magnetic field method to obtain spherical single crystal magnetic powder of the R-Fe-M alloy; 3) the rare earth alloy cubic Laves phase spherical single crystal magnetic powder is obtained by a wind sorting method by utilizing the density difference between the rare earth alloy magnetic powder and a solid dispersing agent.
The size of the rare earth giant magnetostrictive alloy spherical single crystal particles is less than 1 mm. The preferred grain size of the R-Fe-M alloy spherical single crystal magnetic powder is in the range of 10 μ M to 300 μ M.
The <111> oriented rare earth giant magnetostrictive material is processed by taking rare earth giant magnetostrictive alloy spherical single crystal magnetic powder as a raw material (vacuum melting in an oriented magnetic field is a common technology). The preparation method comprises the steps of preparing R-Fe-M cubic Laves phase spherical single crystal magnetic powder with rare earth elements (hereinafter referred to as R), iron (Fe) and transition metal (M) as components into powder, and preparing a bonded rare earth giant magnetostrictive material and a sintered rare earth giant magnetostrictive material with a height <111> orientation by utilizing the magnetic anisotropy of the R-Fe-M cubic Laves phase single crystal and the characteristic of easy orientation of the spherical powder under a magnetic field. The raw material can form the rare earth giant magnetostrictive material with <111> orientation.
Has the advantages that: the invention separates R-Fe-M alloy spherical magnetic powder by inert solid dispersant, anneals at a certain temperature below the melting point of R-Fe-M alloy, and prepares single crystal particles by utilizing the abnormal growth capacity of R-Fe-M cubic Laves phase crystal grains at high temperature through the characteristic that R-Fe-M alloy and solid dispersant do not react and diffuse. According to the invention, the principle of preparing the R-Fe-M alloy single crystal magnetic powder is clear, the process method for preparing the R-Fe-M alloy single crystal magnetic powder is simple, the production efficiency is high, and the preparation method is simple and feasible and can be used for producing the R-Fe-M alloy single crystal magnetic powder in a large scale. The size of the prepared metal particles is less than 1mm, and the size of the metal single crystal particles is preferably in the range of 10-300 μm. The R-Fe-M alloy spherical particles have high single crystallinity, are particularly used for preparing bonding rare earth giant magnetostrictive materials and sintering rare earth giant magnetostrictive materials with the height <111> orientation, have particularly good orientation, and are shown in the attached drawings.
Drawings
FIG. 1 Tb obtained by the preparation method of the present invention0.35Dy0.65Fe1.9Scanning electron microscope pictures of cubic Laves phase spherical single crystal magnetic powder;
FIG. 2 Tb without magnetic field orientation0.35Dy0.65Fe1.9X-ray diffraction pattern of alloy (TDF) spherical powder and different Tb after magnetic field orientation0.35Dy0.65Fe1.9An x-ray diffraction pattern of the bonded magnetostrictive material in volume content of the alloy spherical powder.
Detailed Description
As described above, the inventors of the present application found that: mixing the R-Fe-M alloy magnetic powder with an inert solid dispersant to separate the R-Fe-M alloy spherical magnetic powder by the solid dispersant. Annealing at a certain temperature below the melting point of the R-Fe-M alloy, and preparing the spherical monocrystalline magnetic powder by utilizing the abnormal growth capacity of the crystal grains of the R-Fe-M cubic Laves phase at high temperature through the characteristic that the R-Fe-M alloy does not react with and diffuse with a solid dispersing agent. The method for producing the R-Fe-M alloy spherical single crystal magnetic powder of the present invention will be described in detail below.
The invention firstly prepares the R-Fe-M alloy spherical magnetic powder with the required size. The preparation method of the R-Fe-M alloy spherical magnetic powder is to obtain the R-Fe-M alloy by a smelting or chemical reduction method, and then to anneal and spheroidize the R-Fe-M alloy particles at a temperature higher than the melting point of the R-Fe-M alloy by an atomization method, a liquid drop injection method, an electric spark method, a plasma spheroidization method or a solid dispersing agent after separating the R-Fe-M alloy particles.
The R-Fe-M alloy spherical magnetic powder is uniformly mixed with a solid dispersing agent with proper size and quantity so as to achieve the purpose of separating the R-Fe-M alloy spherical magnetic powder by the solid dispersing agent. The mixing method comprises the following steps: 1) uniformly mixing by adopting a mechanical method; 2) in a liquid (e.g.: alcohol, acetone, etc.) and mixing them uniformly; 3) the uniform mixing is achieved by the dispersion aid of the dispersant.
Annealing the uniformly mixed R-Fe-M alloy spherical magnetic powder/solid dispersant mixed powder in high vacuum or inert atmosphere, wherein the temperature is as follows: is lower than the melting point of the R-Fe-M alloy, and the preferred temperature is 50-200 ℃ lower than the melting point of the R-Fe-M alloy.
And removing the solid dispersing agent in the annealed R-Fe-M alloy/solid dispersing agent to obtain the R-Fe-M alloy spherical single crystal magnetic powder. The cleaning method comprises the following steps: 1) in a liquid (e.g.: alcohol and other organic solvents, water), and ultrasonic cleaning to remove solid dispersant, and obtaining R-Fe-M alloy spherical single crystal magnetic powder; 2) separating the R-Fe-M alloy magnetic powder and the solid dispersant by an external magnetic field method to obtain R-Fe-M alloy spherical single crystal magnetic powder; 3) and separating the R-Fe-M alloy and the solid dispersing agent by a wind power separation method by utilizing the density difference of the metal and the solid dispersing agent to obtain the R-Fe-M alloy spherical single crystal particles.
The size of the spherical single crystal particles prepared by the preparation method of the R-Fe-M alloy spherical single crystal magnetic powder is less than 1mm, and the preferred size is 10-300 mu M.
The rare earth giant magnetostrictive alloy spherical single crystal magnetic powder prepared by the method is used for preparing a bonding rare earth giant magnetostrictive material and a sintering rare earth giant magnetostrictive material with <111> orientation.
Example 1
Preparation of Tb-Fe alloy cubic Laves phase spherical single crystal magnetic powder
TbFe is obtained by a smelting method1.95The alloy (subscript is atomic ratio) is mechanically crushed to obtain powder with the size of about 20-100 μm as a raw material. 50 g of TbFe is taken1.95Alloy powder and Ca of about 5 μm in size6Al2O9Powder ofThe weight ratio is 1:3, and the components are mechanically stirred and then uniformly mixed.
Mixing the TbFe1.95alloy/Ca6Al2O9Placing the powder into an annealing furnace, and vacuumizing to 1 × 10-3Pa, introducing argon to 0.06MPa, heating the annealing furnace to 1240 ℃ at 20 DEG/min (higher than TbFe)1.95Alloy melting point temperature), keeping the temperature for 10 minutes, then quickly cooling to 950 ℃, keeping the temperature for 2 hours, and then cooling to room temperature along with the furnace.
Soaking TbFe in alcohol1.95alloy/Ca6Al2O9Mixing the powders, and ultrasonically cleaning to obtain TbFe1.95Alloy magnetic powder. TbFe obtained1.95The size of the alloy magnetic powder particles is 20-100 mu m. EBSD results show that TbFe1.95The alloy particles are single crystal particles. After the single crystal particles are mixed with the epoxy resin (according to the volume ratio of 50:50), the mixture is cured or cured in a magnetic field orientation way, XRD research shows that TbFe1.95The crystal structure of the alloy is a cubic laves phase, and after comparison, TbFe is realized by an external magnetic field1.95Height of alloy<111>And (4) orientation. According to the production method of the present invention, it was confirmed that Tb-Fe cubic laves phase single crystal spherical powder could be produced.
Example 2
Preparing Sm-Fe alloy cubic Laves phase spherical single crystal magnetic powder, and preparing SmFe by atomization method1.85Alloy powder (subscript is atomic ratio) with the size of 50-100 μm is selected as raw material. Taking 100 g of SmFe1.85The alloy powder and CaO powder with the size of about 2 mu m are proportioned according to the weight ratio of 1:2, and are mechanically stirred and uniformly mixed.
Mixing SmFe1.85Placing the alloy/CaO powder into an annealing furnace, and vacuumizing to 1 × 10-3Pa, introducing argon to 0.1MPa, heating the annealing furnace to 860 ℃ at 20 ℃/min, preserving heat for 4 hours, and cooling to room temperature along with the furnace.
Soaking SmFe in alcohol1.85The alloy/CaO mixed powder is ultrasonically cleaned to obtain SmFe1.85Alloy magnetic powder. The scanning electron microscope shows that the particle size is 50-100 μm and is spherical. XRD results prove SmFe1.85The crystal structure of the alloy is a cubic laves phase. Mixing the spherical powderUniformly mixing the powder with epoxy resin according to the volume ratio of 50:50, and curing and molding the mixture in a 1T magnetic field to obtain SmFe1.85The Sm-Fe alloy cubic laves phase was found to have good properties<111>And orientation shows that the Sm-Fe alloy particles have good single crystallinity. According to the production method of the present invention, it was confirmed that Sm-Fe cubic laves phase single crystal spherical powder could be produced.
Example 3
Tb0.35Dy0.65Fe1.9Preparation of alloy cubic Laves phase spherical monocrystal magnetic powder and its use<111>Oriented magnetostrictive material obtained by smelting process to obtain Tb0.35Dy0.65Fe1.9The alloy (subscript is atomic ratio) is mechanically crushed to obtain powder with the size of about 20-200 μm as a raw material. 200 g of Tb0.35Dy0.65Fe1.9The alloy powder and CaO powder with the size of about 2 mu m are mixed according to the weight ratio of 1:3 and are mechanically stirred and evenly mixed.
Mixing Tb0.35Dy0.65Fe1.9Placing the alloy/CaO powder into an annealing furnace, and vacuumizing to 1 × 10-3Pa, introducing argon to 0.06MPa, heating the annealing furnace to 1290 deg.C (higher than Tb) at 20 deg.C/min0.35Dy0.65Fe1.9Alloy melting point temperature), keeping the temperature for 10 minutes, quickly cooling to 1100 ℃, keeping the temperature for 2 hours, and cooling to room temperature along with the furnace.
Soaking Tb in ethanol0.35Dy0.65Fe1.9alloy/CaO mixed powder is subjected to ultrasonic cleaning to obtain Tb0.35Dy0.65Fe1.9Alloy magnetic powder. FIG. 1 shows Tb obtained0.35Dy0.65Fe1.9The scanning electron microscope picture of the alloy magnetic powder shows that the size of the spherical particles is 20-200 mu m. A
Tb of the invention0.35Dy0.65Fe1.9EBSD pictures of the alloy particles can show that the particles are single crystals (not shown). According to the production method of the present invention, it was confirmed that Tb could be obtained0.35Dy0.65Fe1.9Cubic laves phase spherical single crystal powder.
Tb with spherical size distribution of 20-200 mu m0.35Dy0.65Fe1.9After the cubic laves phase single crystal powder and the epoxy resin are uniformly mixed according to different volume ratios, the mixture is cured and formed under a 1T magnetic field, figure 2 shows XRD of magnetic field orientation and non-orientation, and Tb can be seen after comparison under an external magnetic field0.35Dy0.65Fe1.9The alloy cubic Laves phase realizes good<111>Orientation to obtain a height<111>Tb of orientation0.35Dy0.65Fe1.9Resin bonded magnetostrictive material. When Tb0.35Dy0.65Fe1.9When the volume ratio of the alloy cubic laves phase single crystal powder to the epoxy resin is 55:45, the bonded magnetostrictive material has a magnetostrictive coefficient of 880 and a saturated magnetostrictive coefficient of more than 1500 at room temperature with a prestress of 10MP and a magnetic field of 1 kOe.
Tb with the size distribution of 20-200 mu m0.35Dy0.65Fe1.9Cubic laves phase spherical single crystal powder is pressed and formed after being oriented in a 1T magnetic field in a mould, and then is put into an annealing furnace and is vacuumized to 1 × 10-3Pa, heating to 1180 ℃ at a rate of 20 ℃/min, keeping the temperature for 2 hours, and cooling to room temperature along with the furnace to obtain the product with good quality<111>Tb of orientation0.35Dy0.65Fe1.9Sintering the magnetostrictive material. The sintered magnetostrictive material has a magnetostrictive coefficient of 1080 and a saturated magnetostrictive coefficient of more than 1600 at room temperature, a prestress of 8MP and a magnetic field of 1 kOe.
Example 4
Tb0.32Dy0.68Fe1.95Preparation of alloy cubic Laves phase spherical monocrystal magnetic powder and its use<111>Oriented bonded magnetostrictive material prepared by atomization method0.32Dy0.68Fe1.95The alloy (subscript is atomic ratio) has a particle size of about 30 to 100. mu.m. Taking 100 g of Tb0.32Dy0.68Fe1.95The alloy powder and CaO powder with the size of about 5 mu m are mixed according to the weight ratio of 1:2, and are mechanically stirred and then uniformly mixed.
Mixing Tb0.32Dy0.68Fe1.95Placing the alloy/CaO powder into an annealing furnace, and vacuumizing to 1 × 10-3Pa, introducing argon to 0.06MPa, and annealing at 20 deg/minHeating to 1150 deg.c, maintaining for 1 hr and cooling to room temperature.
Soaking Tb in ethanol0.32Dy0.68Fe1.95alloy/CaO mixed powder is subjected to ultrasonic cleaning to obtain Tb0.32Dy0.68Fe1.95Alloy magnetic powder. The scanning electron microscope shows that the particle size is 30-100 μm, the particle is spherical, and the EBSD result shows that the particle is single crystal. XRD results confirmed Tb0.32Dy0.68Fe1.95The crystal structure of the alloy is a cubic laves phase. Uniformly mixing spherical single crystal powder and epoxy resin according to a volume ratio of 69:31, and curing and molding under a 1T magnetic field to obtain Tb0.32Dy0.68Fe1.95Resin bonded magnetostrictive material. Tb in the bonded magnetostrictive material0.32Dy0.68Fe1.95The alloy has a height<111>Orientation, wherein the magnetostriction coefficient is 980 and the saturation magnetostriction coefficient is more than 1600 at room temperature, the prestress is 10MP and the magnetic field is 1 kOe.
Example 5
Tb0.5Dy0.5Fe1.9Mn0.5Preparation of alloy cubic Laves phase spherical monocrystal magnetic powder and its use<111>Oriented bonded magnetostrictive material obtained by smelting method to obtain Tb0.5Dy0.5Fe1.9Mn0.5The alloy (subscript is atomic ratio) is mechanically crushed to obtain powder with the size of 60-150 mu m as a raw material. Taking 100 g of Tb0.5Dy0.5Fe1.9Mn0.5The alloy powder and CaO powder with the size of about 5 mu m are mixed according to the weight ratio of 1:3, and are mechanically stirred and then uniformly mixed.
Mixing Tb0.5Dy0.5Fe1.9Mn0.5Placing the alloy/CaO powder into an annealing furnace, and vacuumizing to 1 × 10-3Pa, introducing argon gas to 0.1MPa, heating the annealing furnace to 1280 deg.C (higher than Tb) at 20 deg.C/min0.5Dy0.5Fe1.9Mn0.5Alloy melting point temperature), keeping the temperature for 10 minutes, quickly cooling to 1050 ℃, keeping the temperature for 2 hours, and cooling to room temperature along with the furnace.
Soaking Tb in ethanol0.5Dy0.5Fe1.9Mn0.5alloy/CaO mixed powder is subjected to ultrasonic cleaning to obtain Tb0.5Dy0.5Fe1.9Mn0.5Alloy magnetic powder. The scanning electron microscope shows that the particle size is 60-150 μm, the particle is spherical, and the EBSD result shows that the particle is single crystal. XRD results confirmed Tb0.5Dy0.5Fe1.9Mn0.5The crystal structure of the alloy is a cubic laves phase. Uniformly mixing spherical single crystal powder and epoxy resin according to a volume ratio of 65:35, and curing and molding under a 1T magnetic field to obtain Tb0.5Dy0.5Fe1.9Mn0.5Resin bonded magnetostrictive material. Tb in the bonded magnetostrictive material0.5Dy0.5Fe1.9Mn0.5The alloy has a height<111>Orientation, at room temperature, with a prestress of 10MP and a magnetic field of 1kOe, the magnetostriction coefficient is 1000, and the saturation magnetostriction coefficient is 1700 or more.
Example 6
Tb0.3Pr0.15Dy0.55Fe1.9Preparation of alloy cubic Laves phase spherical monocrystal magnetic powder and its use<111>Oriented bonded magnetostrictive material obtained by smelting method to obtain Tb0.3Pr0.15Dy0.55Fe1.9The alloy (subscript is atomic ratio) is mechanically crushed to obtain powder with the size of 50-120 mu m as a raw material. Taking 100 g of Tb0.3Pr0.15Dy0.55Fe1.9The alloy powder and CaO powder with the size of about 2 mu m are proportioned according to the weight ratio of 1:3, and are mechanically stirred and uniformly mixed.
Mixing Tb0.3Pr0.15Dy0.55Fe1.9Placing the alloy/CaO powder into an annealing furnace, and vacuumizing to 1 × 10-3Pa, introducing argon to 0.1MPa, heating the annealing furnace to 1260 ℃ (higher than Tb) at 20 °/min0.3Pr0.15Dy0.55Fe1.9Alloy melting point temperature), keeping the temperature for 10 minutes, then quickly cooling to 1000 ℃, keeping the temperature for 2 hours, and then cooling to room temperature along with the furnace.
Soaking Tb in ethanol0.3Pr0.15Dy0.55Fe1.9alloy/CaO mixed powder is subjected to ultrasonic cleaning to obtain Tb0.3Pr0.15Dy0.55Fe1.9Alloy magnetic powder. The scanning electron microscope shows that the particle size is 50-120 μm, the particle is spherical, and the EBSD result shows that the particle is single crystal. XRD results confirmed Tb0.3Pr0.15Dy0.55Fe1.9The crystal structure of the alloy is a cubic laves phase. Uniformly mixing spherical single crystal powder and epoxy resin according to a volume ratio of 69:31, and curing and molding under a 1T magnetic field to obtain Tb0.3Pr0.15Dy0.55Fe1.9Resin bonded magnetostrictive material. Tb in the bonded magnetostrictive material0.3Pr0.15Dy0.55Fe1.9The alloy has a height<111>Orientation, wherein the magnetostriction coefficient is 960 and the saturation magnetostriction coefficient is more than 1500 at room temperature, the prestress is 8MP and the magnetic field is 1 kOe.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it should be understood that any modification and improvement made by those skilled in the art within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The preparation method of the rare earth giant magnetostrictive alloy spherical single crystal magnetic powder is characterized by comprising the following steps:
(1) preparing R-Fe-M alloy spherical magnetic powder;
(2) uniformly mixing the R-Fe-M alloy spherical magnetic powder with an inert solid dispersing agent, and annealing at a temperature below the melting point of the R-Fe-M alloy to obtain R-Fe-M alloy single crystal particles with a cubic Laves phase structure, wherein the preferred annealing temperature is 50-200 ℃ below the melting point of the cubic Laves phase, and the annealing time is 1-4 hours;
(3) removing the solid dispersant to obtain the R-Fe-M cubic Laves phase spherical single crystal magnetic powder.
2. The method for preparing rare earth giant magnetostrictive spherical single crystal magnetic powder according to claim 1, characterized in that R is a rare earth element comprising one or more of terbium, dysprosium, samarium, praseodymium, neodymium, cerium, holmium and erbium, M is a transition metal element comprising one or more of cobalt, manganese, aluminum, gallium, chromium and the like, and the balance is iron; the R-Fe-M rare earth alloy consists of 30-40% (atomic percent) of R, 0-20% (atomic percent) of M and the balance of Fe.
3. The method for producing rare earth super magnetostrictive spherical single crystal magnetic powder according to claim 1 or 2, characterized in that:
preparing the R-Fe-M alloy spherical magnetic powder: the method comprises the steps of firstly obtaining the R-Fe-M alloy by a smelting or chemical reduction method, and then carrying out annealing and spheroidization at a temperature higher than the melting point of the R-Fe-M alloy after separating R-Fe-M alloy particles by an atomization method, a liquid drop injection method, an electric spark method, a plasma spheroidization method or a solid dispersing agent.
4. The method for producing R-Fe-M alloy spherical magnetic powder according to claim 2, wherein: the size of the spherical particles of the R-Fe-M alloy is less than 1mm, and the range is particularly between 10 and 300 mu M.
5. The method for producing a rare earth giant magnetostrictive spherical single crystal magnetic powder according to claim 3, characterized in that: separating the R-Fe-M alloy magnetic powder by using an inert solid dispersing agent, wherein the solid dispersing agent comprises ceramic material powder, including oxide ceramic, nitride ceramic, fluoride ceramic and compounds and mixtures thereof; the step of mixing materials is that the R-Fe-M alloy magnetic powder and a solid dispersant are mechanically mixed, or are uniformly mixed by stirring in organic liquid, or are uniformly mixed by the aid of the dispersant.
6. The method for preparing rare earth giant magnetostrictive spherical single crystal magnetic powder according to claim 5, characterized in that: the solid dispersing agent is in any size smaller than the size of R-Fe-M alloy particles, the preferable size range is 1-10 mu M, and the shape is sheet, spherical, linear, tubular or other shapes; the mass ratio of the rare earth giant magnetostrictive alloy spherical magnetic powder to the solid dispersant is such that the rare earth alloy spherical particles can be completely isolated by the solid dispersant.
7. The method for producing a rare earth giant magnetostrictive alloy spherical single crystal magnetic powder according to claim 1, characterized in that: the requirements for realizing single crystallization of R-Fe-M alloy particles by annealing treatment comprise: 1) annealing the mixed powder of the R-Fe-M alloy magnetic powder and the solid dispersant in high vacuum or inert gas; 2) the annealing temperature is lower than the melting point of the R-Fe-M alloy, the annealing temperature is 50-200 ℃ lower than the melting point of the R-Fe-M alloy, and the annealing time is 1-4 hours.
8. The method for producing a rare earth giant magnetostrictive alloy spherical single crystal magnetic powder according to claim 1, characterized in that: the method for removing the solid dispersant to obtain the R-Fe-M alloy spherical single crystal magnetic powder comprises the following steps: 1) after soaking in liquid, ultrasonically cleaning, and removing the solid dispersing agent to obtain R-Fe-M alloy spherical single crystal magnetic powder; 2) separating ferromagnetic R-Fe-M alloy and nonmagnetic solid dispersant by adopting an external magnetic field method to obtain spherical single crystal magnetic powder of the R-Fe-M alloy; 3) the R-Fe-M cubic Laves phase spherical single crystal magnetic powder is obtained by a wind power sorting method by utilizing the density difference between the rare earth alloy magnetic powder and the solid dispersing agent.
9. The method of preparing a <111> oriented rare earth giant magnetostrictive material according to any one of claims 1-8, characterized in that: the size of the rare earth giant magnetostrictive alloy spherical single crystal particles is less than 1 mm; the particle size of the preferred R-Fe-M alloy spherical single crystal magnetic powder is in the range of 10-300 mu M; the rare earth giant magnetostrictive material is prepared by taking the rare earth giant magnetostrictive alloy spherical single crystal magnetic powder as a raw material.
CN202010143114.7A 2020-03-04 2020-03-04 Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material Pending CN111326303A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202010143114.7A CN111326303A (en) 2020-03-04 2020-03-04 Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material
PCT/CN2021/078392 WO2021175174A1 (en) 2020-03-04 2021-03-01 Method for preparing rare earth alloy spherical single crystal magnetic powder, and rare earth giant magnetostrictive material having &lt;111&gt; orientation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010143114.7A CN111326303A (en) 2020-03-04 2020-03-04 Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material

Publications (1)

Publication Number Publication Date
CN111326303A true CN111326303A (en) 2020-06-23

Family

ID=71171317

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010143114.7A Pending CN111326303A (en) 2020-03-04 2020-03-04 Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material

Country Status (2)

Country Link
CN (1) CN111326303A (en)
WO (1) WO2021175174A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175174A1 (en) * 2020-03-04 2021-09-10 南京大学 Method for preparing rare earth alloy spherical single crystal magnetic powder, and rare earth giant magnetostrictive material having &lt;111&gt; orientation
US20220293310A1 (en) * 2021-03-15 2022-09-15 Tdk Corporation Rare-earth-based magnet powder, bonded magnet, bonded magnet compound, sintered magnet, method of manufacturing rare-earth-based magnet powder, and method of manufacturing rare-earth based permanent magnet

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1570187A (en) * 2004-04-27 2005-01-26 有研稀土新材料股份有限公司 Rare earth magnetostrictive material preparation method and the material
JP2005183503A (en) * 2003-12-17 2005-07-07 Chiba Inst Of Technology Material of permanent magnet
CN104259469A (en) * 2014-09-11 2015-01-07 南京大学 Manufacturing method of micron and nanometer metal spherical powder
CN108691007A (en) * 2018-06-07 2018-10-23 南京大学 The manufacturing method of metal single crystal particle

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4053328B2 (en) * 2002-03-27 2008-02-27 泰文 古屋 Polycrystalline FeGa alloy ribbon with giant magnetostrictive properties
JP2006213985A (en) * 2005-02-07 2006-08-17 Tdk Corp Method for producing magnetostriction element
CN102569638B (en) * 2012-02-15 2013-09-11 北京航空航天大学 Adhesive giant magnetostrictive material with laminated structure height (111) orientation and preparation method thereof
CN108550693A (en) * 2018-03-26 2018-09-18 北京科技大学 A kind of sintering terbium dysprosium ferrum magnetostriction materials and preparation method thereof
CN111326303A (en) * 2020-03-04 2020-06-23 南京大学 Method for manufacturing rare earth alloy spherical single crystal magnetic powder and <111> oriented rare earth giant magnetostrictive material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005183503A (en) * 2003-12-17 2005-07-07 Chiba Inst Of Technology Material of permanent magnet
CN1570187A (en) * 2004-04-27 2005-01-26 有研稀土新材料股份有限公司 Rare earth magnetostrictive material preparation method and the material
CN104259469A (en) * 2014-09-11 2015-01-07 南京大学 Manufacturing method of micron and nanometer metal spherical powder
CN108691007A (en) * 2018-06-07 2018-10-23 南京大学 The manufacturing method of metal single crystal particle

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021175174A1 (en) * 2020-03-04 2021-09-10 南京大学 Method for preparing rare earth alloy spherical single crystal magnetic powder, and rare earth giant magnetostrictive material having &lt;111&gt; orientation
US20220293310A1 (en) * 2021-03-15 2022-09-15 Tdk Corporation Rare-earth-based magnet powder, bonded magnet, bonded magnet compound, sintered magnet, method of manufacturing rare-earth-based magnet powder, and method of manufacturing rare-earth based permanent magnet

Also Published As

Publication number Publication date
WO2021175174A1 (en) 2021-09-10

Similar Documents

Publication Publication Date Title
KR101855530B1 (en) Rare earth permanent magnet and their preparation
KR20020033504A (en) Manufacturing method of an anisotropic magnet powder, precursory anisotropic magnet powder and bonded magnet
US5164104A (en) Magnetic material containing rare earth element, iron, nitrogen, hydrogen and oxygen and bonded magnet containing the same
WO2021175174A1 (en) Method for preparing rare earth alloy spherical single crystal magnetic powder, and rare earth giant magnetostrictive material having &amp;lt;111&amp;gt; orientation
CN111081443A (en) R-T-B series permanent magnetic material and preparation method and application thereof
US5486239A (en) Method of manufacturing magnetically anisotropic R-T-B-M powder material and method of manufacturing anisotropic magnets using said powder material
CN108691007B (en) Method for producing metal single crystal particle
JPH06235051A (en) Magnetic material
JPH1070023A (en) Permanent magnet and manufacture thereof
JP6179709B2 (en) R-T-B rare earth magnet powder, method for producing R-T-B rare earth magnet powder, and bonded magnet
JP3504735B2 (en) Method for producing RTMN based anisotropic bonded magnet
JPH05335120A (en) Anisotropic bonded manget manufacturing magnet powder coated with solid resin binder and manufacture thereof
JPH045740B2 (en)
JPH1092617A (en) Permanent magnet and its manufacture
US6592682B1 (en) Method for preparing a magnetic material by forging and magnetic material in powder form
JPH0682575B2 (en) Rare earth-Fe-B alloy magnet powder
KR900006533B1 (en) Anisotropic magnetic materials and magnets made with it and making method for it
CN116988137A (en) Preparation method of CoMnSi spherical single crystal particles
JPH045737B2 (en)
CN116174727A (en) Method for preparing CoMnSi-based alloy spherical single crystal particles by utilizing rapid quenching process
CN1104364A (en) 2:19(3:29) phase rare-earth iron nitride (carbide) permanent magnet and its preparation method
JPS646267B2 (en)
JPH06151137A (en) Powder of rare earth magnet material with excellent anisotropy
JP2730441B2 (en) Manufacturing method of alloy powder for permanent magnet
JPH07110965B2 (en) Method for producing alloy powder for resin-bonded permanent magnet

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200623