CN111593261B - Lanthanum-cerium co-doped isotropic bonded magnetic powder and preparation method thereof - Google Patents
Lanthanum-cerium co-doped isotropic bonded magnetic powder and preparation method thereof Download PDFInfo
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- B22F1/0003—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—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
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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Abstract
A lanthanum-cerium co-doped neodymium iron boron isotropic bonded magnetic powder and a preparation method thereof are disclosed, wherein the chemical formula of the magnetic powder is represented by atomic percent: [ RE ]1‑x(LR)x]aFe100‑a‑b‑cMbBcWherein x is more than or equal to 0.05 and less than or equal to 0.7, a is more than or equal to 11 and less than or equal to 13, b is more than or equal to 0 and less than or equal to 1.55, c is more than or equal to 5.5 and less than or equal to 6.2, RE is Nd or the combination of Nd and any one or more rare earth elements except La and Ce, LR represents the rare earth elements La and Ce, and M is Al and/or Nb. Wherein the grain size of the magnetic powder is 20-70 nm. The invention uses the relatively surplus and cheap rare earth lanthanum and cerium to partially replace neodymium element in neodymium iron boron, inhibits the precipitation of alpha-Fe, reduces the irreversible loss of magnetic flux, improves the coercive force by regulating the ratio of lanthanum and cerium and the ratio of lanthanum, cerium and neodymium and adding a proper amount of Nb and/or Al element, saves the cost and keeps good magnetic performance by combining the rapid quenching process and the control of parameters, and ensures that the rare earth element is comprehensively and balanced utilized.
Description
Technical Field
The invention relates to the technical field of permanent magnet material processing, in particular to lanthanum-cerium co-doped isotropic bonded magnetic powder and a preparation method thereof.
Background
Since the Nd-Fe-B-based permanent magnetic material is discovered in the eighties of the last century, the excellent performance of the Nd-Fe-B-based permanent magnetic material has important and wide application in the fields of automobiles, electronic information, wind power generation and the like, but a large amount of medium-heavy rare earth such as Pr, Nd, Tb, Dy and the like is consumed, so that the resource is short and the price is soaring. Because rare earth ore is associated ore, and high-abundance rare earth La and Ce is heavily accumulated while a large amount of Pr, Nd, Tb and Dy is consumed, the high-abundance rare earth La and Ce is applied to permanent magnet materials in recent years to balance the utilization of rare earth resources and reduce the production cost, and the rare earth ore becomes the focus of attention in industrial production.
Disclosure of Invention
Objects of the invention
The invention aims to provide lanthanum-cerium co-doped isotropic bonded magnetic powder and a preparation method thereof, which can reduce the production cost, keep good magnetic performance and comprehensively and balancedly utilize rare earth elements.
(II) technical scheme
In order to achieve the purpose, the invention adopts the following technical scheme.
The first aspect of the invention provides a lanthanum-cerium co-doped isotropic bonded magnetic powder, the chemical formula of which is expressed by atomic percent: [ RE ]1-x(LR)x]aFe100-a-b-cMbBc；
Wherein x is more than or equal to 0.05 and less than or equal to 0.7, a is more than or equal to 11 and less than or equal to 13, b is more than or equal to 0 and less than or equal to 1.55, and c is more than or equal to 5.5 and less than or equal to 6.2;
RE is Nd or the combination of Nd and any one or more rare earth elements except La and Ce, LR represents the rare earth elements La and Ce, and M is Al and/or Nb;
the grain size of the magnetic powder is 20-70 nm.
Furthermore, the total atomic percentage of the rare earth element Ce in the LR and the LR ranges from 0.2 to 0.8;
preferably, the atomic percentage of La to Ce is 2:3, 1:1 or 3: 2.
Further, the magnetic powder comprises RE2Fe14Main phase R and crystal of B tetragonal structureA boundary phase L, wherein RE is a rare earth element.
Further, the average grain size of the main phase R is 30-70 nm; the average grain size of the grain boundary phase L is 5 to 20 nm.
Further, the atomic percentage of Ce distributed in the main phase R is 100%;
and/or La is distributed in the main phase R and the grain boundary phase L, wherein the atomic percentage of La distributed in the main phase R is 60-80%, and the rest of La enters the grain boundary phase L.
Further, the atomic percent of Nd atoms in RE is greater than 95%.
Furthermore, when RE is Nd, the atomic percentage of the total amount of La and Ce and the metal Nd is 0.2-0.5.
Another aspect of the present invention provides a method for preparing the lanthanum-cerium co-doped isotropic bonded magnetic powder, comprising the following steps:
(1) weighing raw materials according to the components in the magnetic powder, putting the raw materials into a furnace, smelting the raw materials into clear alloy liquid, and cooling the clear alloy liquid into an alloy ingot;
(2) crushing the alloy ingot smelted in the step (1), placing the crushed alloy ingot in an induction rapid quenching furnace, vacuumizing the rapid quenching furnace, introducing argon to positive pressure, and melting the crushed alloy in a crucible of the rapid quenching furnace until the crushed alloy is boiled to form alloy liquid;
(3) enabling the alloy liquid to flow into the edge of a rotating roller from a pouring gate, and rapidly cooling and solidifying the alloy liquid into a rapidly quenched thin strip under the cooling effect of the roller;
(4) carrying out heat treatment on the quick-quenched thin strip obtained in the step (3) and then quenching;
(5) and crushing the quenched thin strip into alloy powder.
Furthermore, the raw materials adopt single rare earth metal or mixed rare earth metal with determined proportion.
Further, the smelting in the step (1) is vacuum smelting; the smelting temperature is 100-300 ℃ above the melting point of the raw materials.
Further, the cooling of the alloy ingot in the step (1) is rapidly carried out under circulating cold water at the temperature of 15-25 ℃.
Further, the pressure of argon filled in the step (2) is 35-50 kPa.
Further, the casting in the step (3) is carried out by a high-vacuum single-roll spin quenching method; preferably, the speed of the rotary quenching roller is 15-30 m/s; further preferably, the cooling rate of the rotary quenching cooling is 105～106℃/s。
Further, the temperature of the heat treatment in the step (4) is 600-800 ℃, and the time of the heat treatment is 5-20 min; preferably, the heat treatment is carried out under a flowing argon atmosphere.
Further, water cooling quenching is adopted in the quenching in the step (4); preferably, the quenching is performed under flowing argon atmosphere; more preferably, the quenching time is 30-60 min.
Further, the average grain size of the alloy powder in the step (5) is 100-200 μm; preferably, the rapidly quenched thin strip is crushed into alloy powder with an average particle size of 100 to 200 μm by coarse crushing and grinding.
(III) advantageous effects
The technical scheme of the invention has the following beneficial technical effects:
1. the rare earth permanent magnet material is prepared by regulating the doping ratio of lanthanum and cerium and the ratio of the total doping amount of lanthanum and cerium to the amount of neodymium and combining the components with the conventional NdFeB rare earth permanent magnet material, the crystal grains are obviously refined, the morphology distribution is more uniform, and a single-phase structure is stabilized while good magnetic performance is maintained.
2. Relatively abundant light rare earth elements La and Ce are used for replacing Nd and Pr, so that the production cost is greatly reduced.
Drawings
FIG. 1 shows Nd as an alloy component12Fe82B6The TEM image and the grain size statistical chart of the permanent magnetic material;
FIG. 2 shows an alloy composition of [ Nd ]0.5(La0.6Ce0.4)0.5]12Fe82B6TEM images and statistical plots of grain size.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The invention provides lanthanum-cerium co-doped neodymium iron boron isotropic bonded magnetic powder, wherein the chemical formula of the material is represented by atomic percent: [ RE ]1-x(LR)x]aFe100-a-b-cMbBcWherein x is more than or equal to 0.05 and less than or equal to 0.7, a is more than or equal to 11 and less than or equal to 13, b is more than or equal to 0 and less than or equal to 1.55, c is more than or equal to 5.5 and less than or equal to 6.2, RE is Nd or the combination of Nd and any one or more rare earth elements except La and Ce, LR represents the rare earth elements La and Ce, and M is Al and/or Nb. Wherein the grain size of the magnetic powder is 20-70 nm.
The lanthanum-cerium co-doped isotropic bonded magnetic powder disclosed by the invention adopts the common doping of lanthanum and cerium to partially replace the Nd element of NdFeB alloy, and Nb and/or Al elements are doped simultaneously by regulating the doping proportion of lanthanum and cerium and the doping total amount of lanthanum and cerium and the proportion of the Nd element, so that the cost is reduced, and the magnetic powder has good magnetic performance, and the specific expression is as follows: in the rapid quenching NdFeB material, the doping of the La element can enhance the amorphous forming capability of the alloy, improve the microstructure, refine grains and concentrate the grain size distribution, and the discovery value is that on the basis of reducing the material cost, the energy cost can be reduced by reducing the speed of a rapid quenching wheel, the process controllability is improved, the uniformity of a thin strip is improved and the service life of equipment is prolonged. Meanwhile, a fine La-rich phase which is dispersedly distributed among main phase grains appears at the grain boundary, so that the pinning effect is achieved, and the phenomenon of coercive force reduction caused by LaCe codoping is compensated to a certain extent; on the other hand, the Ce element is doped to enable the alloy to maintain a single 2:14:1 structure, and the Ce element contains 4f electrons and has a certain anisotropy field, so that the phenomenon of magnetic property deterioration caused by single-doping NdFeB in La element without 4f electrons can be compensated. When La and Ce are doped together, the valence state of Ce can be regulated and controlled by doping the La. The above aspects interact with each other, so that the performance of the NdFeB co-doped with La and Ce is obviously better than that of the NdFeB singly doped with La and Ce under the same doping level.
Preferably, the total atomic percentage of the rare earth element Ce and L R in the LR is 0.2-0.8.
Preferably, the atomic percentage of La to Ce is 2:3, 1:1 or 3: 2.
In NdFeB materials, addition of La can refine the grains, but addition of excess La easily causes phase separation of the main phase structure. The La element does not contain 4f electrons, and the coercive force is sharply reduced due to the addition of excessive La; the doping of the element Ce can maintain the phase structure unchanged, and it contains 4f electrons, contributing to the coercive force. Therefore, the proper atomic mass ratio of La to Ce can refine crystal grains and obtain good magnetic performance under the condition of keeping the phase structure unchanged.
Preferably, the magnetic powder includes RE2Fe14B a main phase R with a tetragonal structure and a grain boundary phase L, wherein RE is a rare earth element.
Preferably, the average grain size of the main phase R phase is 30 to 70 nm; the average grain size of the grain boundary phase L is 5 to 20 nm.
Preferably, Ce enters RE2Fe14The atomic percentage of the main phase of the B tetragonal structure is 100 percent, and La enters RE2Fe14The atomic percentage of the main phase R of the tetragonal structure B is 60-80%, and the rest enters a grain boundary phase L.
The La element is added, and part of the La element enters the main phase, so that the La element has the effects of refining grains and improving the microstructure; the rest part exists in a crystal boundary L phase, and is distributed among main phase crystal grains in a fine and dispersed mode to play a pinning effect, so that the phenomenon of coercive force reduction caused by La and Ce codoping is compensated to a certain extent. And the addition of Ce element has the effect of stabilizing the phase structure. According to the invention, by adding a proper amount of lanthanum and cerium, the formation of a single main phase structure is promoted, and the average grain size of the permanent magnet material is 45.67nm compared with the average grain size of the initial neodymium iron boron, so that the permanent magnet material is greatly refined and is more uniformly distributed. The addition of lanthanum and cerium promotes the interphase exchange coupling effect, so that the remanence and the energy product of the magnet are increased.
Preferably, the atomic percentage of Nd atoms in RE is greater than 95%.
Preferably, when RE is Nd, the atomic percentage of the total amount of La and Ce and Nd is 0.2-0.5.
Nd atoms contribute most of coercive force, so in order to obtain good magnetic performance, the atomic mass ratio of the total amount of LaCe to the Nd atoms needs to be strictly regulated and controlled, so that the alloy of the components can meet the performance requirements, reduce the cost and balance the utilization of rare earth resources.
The invention utilizes the relatively surplus and cheap rare earth lanthanum and cerium to be jointly doped to replace Nd in neodymium iron boron, and the rare earth elements are comprehensively and balanced utilized while refining the main phase crystal grains and keeping good magnetic performance by regulating the doping proportion of lanthanum and cerium, the total doping amount of lanthanum and cerium and the proportion of neodymium elements and adding a proper amount of Nb and Al elements, thereby greatly reducing the production cost of the magnet.
Preferably, the magnetic powder adopts a nanocrystalline bonded permanent magnet material preparation process to introduce lanthanum and cerium elements into the neodymium iron boron magnet.
The invention also provides a preparation method of the lanthanum-cerium co-doped isotropic bonded magnetic powder, which comprises the following steps:
(1) weighing raw materials according to the components in the magnetic powder, placing the raw materials in a furnace to be melted into clear alloy liquid, and cooling the alloy liquid into an alloy ingot;
(2) crushing the alloy ingot smelted in the step (1), placing the crushed alloy ingot in an induction rapid quenching furnace, vacuumizing the rapid quenching furnace, introducing argon into the furnace to positive pressure, melting the crushed alloy in a crucible in the rapid quenching furnace to boiling to form alloy liquid, then flowing the alloy liquid into the edge of a rotating roller from a pouring gate, and rapidly cooling and solidifying the alloy liquid into a thin strip under the cooling action of the roller;
(3) and (3) carrying out heat treatment on the quick-quenched thin strip obtained in the step (2), quenching, and crushing the thin strip into alloy powder after quenching.
The rare earth needed by the raw materials is single rare earth metal or mixed rare earth metal with a determined proportion.
Preferably, the melting in the step (1) is vacuum melting.
Preferably, the high-temperature melting temperature is 100 to 300 ℃ or higher than the melting point of the raw material for producing the rapidly quenched ribbon, for example, 105 ℃, 115 ℃, 130 ℃, 150 ℃, 180 ℃, 210 ℃, 250 ℃, 270 ℃, 290 ℃ or higher than the melting point of the raw material.
Preferably, the cooling of the alloy ingot is performed rapidly under circulating cooling water at 15 to 25 ℃, and the water temperature is, for example, 17 ℃, 20 ℃, 22 ℃, 23 ℃ or the like.
Preferably, the casting is carried out by high vacuum single roll spinning.
Preferably, the pressure of the argon gas is 35-50 kPa.
Preferably, the rotary quenching roller speed is 15-30 m/s, such as 17m/s, 18m/s, 20m/s, 22m/s, 25m/s, 28m/s, etc.
Preferably, the cooling rate of the rotary quenching cooling is 105～106At 3X 10 deg.C/s, for example5、5*105、7*105、9*105And the like, the alloy is solidified at a high growth rate (more than or equal to 1-100 cm/s) under a large supercooling degree.
Due to different wheel speeds and different cooling rates of the rapid quenching process, the organizational structure, the thermodynamic and the kinetic changes in a solidification system can be changed differently. At low wheel speed, alpha-Fe is separated out; the wheel speed is too high, and the change of the atom space arrangement condition of the amorphous strip is obvious along with the increase of the rotating speed of the cooling roller, so that the saturation magnetic flux density Bs and the coercive force Hc both show a descending trend. The method rapidly cools the alloy liquid through the optimized wheel speed (cooling speed 10)5～106And/s) or suppressing the heterogeneous nucleation phenomenon in the cooling process, so that the alloy is solidified at a high growth rate (more than or equal to 1-100 cm/s) under a large supercooling degree, thereby preparing amorphous, quasicrystal and nano alloy materials, and obtaining an amorphous or nano crystal metastable state rapid quenching thin strip through rapid solidification.
Preferably, the heat treatment in step (3) is performed at a temperature of 600 to 800 deg.C, such as 630 deg.C, 660 deg.C, 700 deg.C, 730 deg.C, 760 deg.C, 790 deg.C, etc., and for a time of 5 to 20min, such as 7min, 9min, 11min, 13min, 15min, 17min, 19min, etc.
The rapidly quenched ribbon is a disordered material, is a ribbon prepared by a rapid quenching method, has a large amount of amorphous structures and a large amount of defects such as dislocation, vacancy and the like in the thickness of 20-40 mu m approximately, and therefore, an effective heat treatment needs to be carried out on a rapidly quenched sample in order to improve the magnetic performance of the material. This method requires the alloy to undergo extensive nucleation from a disordered amorphous state in a short time in order to obtain a nanocrystalline material of uniform size. Thermodynamic experiments show that the crystallization time of the experiment aiming at nucleation is shorter, generally 5-20 min is taken, and the heat treatment temperature is 600-800 ℃, which is beneficial to large-scale nucleation in a short time.
Preferably, the heat treatment is carried out under a flowing argon atmosphere.
Preferably, the quenching is water cooling quenching.
Preferably, the quenching is performed under a flowing argon atmosphere.
Preferably, the quenching time is 30-60 min, such as 30min, 35min, 40min, 45min, 50min, 55min, and the like.
Quenching and cooling are key steps of the heat treatment process, and directly influence the structure and the performance of a sample after heat treatment. The cooling speed is higher than the critical cooling speed during cooling so as to ensure that the alloy obtains a stable tissue structure; the quenching time is long enough to ensure that the alloy sample is fully water-cooled so as to avoid the re-growth of crystal grains and possible oxidation on the surface; when quenching is carried out under the flowing Ar atmosphere, the possibility that the sample is oxidized at high temperature can be prevented, partial heat can be taken away through Ar gas flow, and the cooling efficiency is improved.
Preferably, the average particle size of the alloy powder is 100 to 200. mu.m. For example, 110 μm, 125 μm, 140 μm, 150 μm, 160 μm, 180 μm, 190 μm, etc. The quick-quenched thin strip can be crushed into alloy powder with the average grain size of 100-200 mu m by coarse crushing and grinding.
Preferably, the method comprises the steps of:
(1) preparing materials: is prepared into [ Nd ]1-x(LR)x]aFe100-a-b-cMbBcWherein x is more than or equal to 0.05 and less than or equal to 0.7, y is more than or equal to 0.2 and less than or equal to 0.8, a is more than or equal to 11 and less than or equal to 13, and b is more than or equal to 0 and less than or equal to 1.5C is more than or equal to 5.5 and less than or equal to 6.2, LR represents rare earth elements La and Ce, M is Al and/or Nb, and the content of each element is atom percentage content;
(2) smelting a master alloy: the raw materials are placed in a furnace to be smelted into clear alloy liquid, and cooled into alloy ingots.
The high-temperature melting temperature is 100-300 ℃ above the melting point of the raw materials for preparing the quick-quenched thin strip, and the cooling of the alloy ingot is rapidly carried out under circulating cooling water at 15-25 ℃.
(3) Rapidly quenching to prepare a belt: and crushing the smelted alloy ingot, placing the crushed alloy ingot in an induction rapid quenching furnace, vacuumizing the rapid quenching furnace, introducing argon to positive pressure, melting the alloy in a crucible of the rapid quenching furnace to boil, flowing into the edge of a roller rotating at high speed from a pouring gate, and rapidly cooling and solidifying the alloy liquid under the cooling action of the roller to form a thin strip.
The speed of the rotary quenching roller is 15-30 m/s, and the cooling rate of the rotary quick quenching cooling is 105～106And (3) solidifying the alloy at a high growth rate (more than or equal to 1-100 cm/s) under a large supercooling degree at the temperature of DEG C/s.
With different wheel speeds of the rapid quenching process, the cooling rate is different, and the change of the organization structure, thermodynamics and kinetics in a solidification system is different. At low wheel speed, alpha-Fe is separated out; the wheel speed is too high, along with the increase of the rotating speed of the cooling roller, the atom space arrangement condition of the amorphous strip material is obviously changed, and both Bs and Hc are caused to show a descending trend. The method rapidly cools the alloy melt by optimizing the wheel speed (cooling speed 10)5～106And/s) or suppressing the heterogeneous nucleation phenomenon in the cooling process, so that the alloy is solidified at a high growth rate (more than or equal to 1-100 cm/s) under a large supercooling degree, thereby preparing amorphous, quasicrystal and nano alloy materials, and obtaining an amorphous or nano crystal metastable state rapid quenching thin strip through rapid solidification.
(4) And (3) heat treatment: the temperature of the heat treatment is 600-800 ℃, and the time of the heat treatment is 5-20 min.
The fast quenching thin strip belongs to a disordered material, has a large amount of amorphous structures and has a large amount of defects such as dislocation, vacancy and the like, so that effective heat treatment needs to be carried out on a fast quenching sample in order to improve the magnetic performance of the material. This experiment requires that the alloy be nucleated from a disordered amorphous state in large amounts in a short time in order to obtain a nanocrystalline material of uniform size. The thermodynamic experiment shows that the crystallization time of the experiment aiming at nucleation is shorter, and is generally 5-20 min.
(5) Water cooling quenching: the quenching process is to immerse the alloy subjected to heat treatment in cold water, and the quenching time is 30-60 min.
Quenching and cooling are key steps of the heat treatment process, and directly influence the structure and the performance of a sample after heat treatment. The cooling speed is higher than the critical cooling speed during cooling so as to ensure that the alloy obtains a stable tissue structure; the quenching time is long enough to ensure that the alloy sample is fully water-cooled so as to avoid the re-growth of crystal grains and possible oxidation on the surface; when quenching is carried out under the flowing Ar atmosphere, the possibility that the sample is oxidized at high temperature can be prevented, partial heat can be taken away through Ar gas flow, and the cooling efficiency is improved.
(6) Crushing: crushing the quick-quenched thin strip into alloy powder with the average grain size of 100-200 mu m by coarse crushing and grinding.
The preparation method of the lanthanum-cerium co-doped isotropic bonded magnetic powder provided by the invention adopts a high-vacuum single-roll spin quenching process to melt an alloy and then spray the alloy onto a roller rotating at a high speed, and rapidly cools an alloy melt (the cooling speed is 10.)5～106And/s) or suppressing the heterogeneous nucleation phenomenon in the cooling process, solidifying the alloy at a high growth rate (more than or equal to 1-100 cm/s) under a large supercooling degree to obtain a rapidly quenched thin strip with fine grains and even an amorphous structure, crushing and thermally treating the thin strip, and preparing the isotropic bonded magnet through subsequent steps. The crystal grains can be effectively refined in the experimental preparation process. The prepared magnet has a single 2:14:1 main phase structure, and the magnetic performance of the prepared magnetic powder is equivalent to that of the original NdFeB magnetic powder; the average grain size of the prepared lanthanum-cerium co-doped isotropic bonded magnetic powder is 25-35 nm, the preferred standard deviation is 4-8, compared with the initial NdFeB grains, the grain size is obviously refined, and the morphology distribution is more uniform.
The lanthanum-cerium co-doped isotropic bonded magnetic powder prepared by the method effectively avoids the growth of crystal grains in the bonding process, and can obtain a high-performance permanent magnet material with a nanocrystalline structure.
The invention utilizes the relatively surplus and cheap rare earth lanthanum and cerium to be jointly doped to replace Nd in neodymium iron boron, and the rare earth elements are comprehensively and balanced utilized while refining the main phase crystal grains and keeping good magnetic performance by regulating the doping proportion of lanthanum and cerium, the total doping amount of lanthanum and cerium and the proportion of neodymium elements and adding a proper amount of Nb and Al elements, thereby greatly reducing the production cost of the magnet.
For further illustration of the present invention, the following will describe the preparation method of a lanthanum-cerium co-doped isotropic bonded magnetic powder according to the present invention in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed implementation and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limiting the claims of the present invention, and the protection scope of the present invention is not limited to the following examples.
Example 1:
the permanent magnet material prepared by the embodiment has the following alloy components: [ Nd ]0.5(La0.6Ce0.4)0.5]11.9Fe81.1M1B6M is Al and/or Nb, and the content of each element is atom percentage content. The method comprises the following specific steps:
(1) the master alloy is prepared by the components, wherein raw materials of La, Ce and Nd are all blended in the form of pure metal, the phase morphology of B is BFe alloy containing 20 atomic percent of B and 80 atomic percent of Fe, and the residual Fe is blended in the form of pure metal. Then adopting the following process steps to manufacture the neodymium iron boron rare earth permanent magnet material.
(2) The raw materials are placed in a vacuum induction furnace to be smelted into clear alloy liquid, and the clear alloy liquid is quickly cooled into an alloy ingot under the condition of closing current and circulating cold water at the temperature of 20 ℃.
(3) Crushing the smelted alloy ingot, placing the crushed alloy ingot in an induction rapid quenching furnace, vacuumizing the rapid quenching furnace, and filling argon to positive pressure of 40kPaMelting the crushed alloy in a crucible of a quick quenching furnace until the alloy is boiled and flows into the edge of a roller rotating at high speed from a pouring gate, and carrying out quick rotary quenching on the alloy at 5 to 105And rapidly cooling and solidifying the alloy liquid at the temperature/s under the cooling action of the roller to form a thin strip. Wherein, the alloy liquid is sprayed on a roller rotating at a wheel speed of 25m/s to prepare the quick-quenched thin strip.
(4) And performing heat treatment on the quick-quenched thin strip, wherein the heat treatment temperature is 650 ℃, and the heat treatment time is 10 min.
(5) And (3) carrying out water-cooling quenching on the quickly quenched thin strip subjected to the heat treatment for 30min in an argon atmosphere, and crushing the quickly quenched thin strip into alloy powder with the average particle size of 100 mu m by coarse crushing and grinding methods to obtain the isotropic bonded magnetic powder containing lanthanum and cerium.
The magnetic properties of the magnetic powder were measured and shown in Table 1.
TABLE 1 magnetic Properties of the lanthanum cerium neodymium iron boron containing bonded permanent magnet powder of example 1
Example 2:
the permanent magnet material prepared by the embodiment has the following alloy components: [ Nd ]0.6(La0.8Ce0.2)0.4]11.9Fe81.1M1B6M is Al and/or Nb, and the content of each element is atom percentage content. The method comprises the following specific steps:
(1) the master alloy is prepared by the components, wherein raw materials of La, Ce and Nd are all blended in the form of pure metal, the phase morphology of B is BFe alloy containing 20 atomic percent of B and 80 atomic percent of Fe, and the residual Fe is blended in the form of pure metal. Then adopting the following process steps to manufacture the neodymium iron boron rare earth permanent magnet material.
(2) The raw materials are placed in a vacuum induction furnace to be smelted into clear alloy liquid, and the alloy liquid is quickly cooled into an alloy ingot under circulating cold water at 23 ℃ by closing current.
(3) Crushing the smelted alloy ingot, placing the crushed alloy ingot in an induction quick quenching furnace, vacuumizing the quick quenching furnace, and filling argon into the quick quenching furnaceGas is fed to positive pressure of 40kPa, the crushed alloy is melted to boiling in a crucible in a quick quenching furnace, flows into the edge of a roller rotating at high speed from a pouring gate, and is subjected to quick rotary quenching at 3 x 105And rapidly cooling and solidifying the alloy liquid at the temperature/s under the cooling action of the roller to form a thin strip. Wherein, the alloy liquid is sprayed on a roller rotating at a wheel speed of 23m/s to prepare the quick-quenched thin strip.
(4) And (3) carrying out heat treatment on the fast-quenched ribbon, wherein the heat treatment temperature is 700 ℃, and the heat treatment time is 15 min.
(5) And (3) carrying out water-cooling quenching on the quickly quenched thin strip subjected to the heat treatment for 30min in an argon atmosphere, and crushing the quickly quenched thin strip into alloy powder with the average particle size of 100 mu m by coarse crushing and grinding methods to obtain the isotropic bonded magnetic powder containing lanthanum and cerium.
The magnetic properties of the magnets were tested and the properties are shown in Table 2.
TABLE 2 magnetic Properties of the lanthanum cerium neodymium iron boron containing bonded permanent magnet powder of example 2
Example 3:
the permanent magnet material prepared by the embodiment has the following alloy components: [ Nd ]0.8(La0.4Ce0.6)0.2]11.9Fe81.1M1B6M is Al and/or Nb, and the content of each element is atom percentage content. The method comprises the following specific steps:
(1) the master alloy is prepared by the components, wherein raw materials of La, Ce and Nd are all blended in the form of pure metal, the phase morphology of B is BFe alloy containing 20 atomic percent of B and 80 atomic percent of Fe, and the residual Fe is blended in the form of pure metal. Then adopting the following process steps to manufacture the neodymium iron boron rare earth permanent magnet material.
(2) The raw materials are placed in a vacuum induction furnace to be smelted into clear alloy liquid, and the clear alloy liquid is quickly cooled into an alloy ingot under the condition of closing current and circulating cold water at the temperature of 20 ℃.
(3) Crushing the smelted alloy ingot, and placing the crushed alloy ingot in an induction quick quenching furnace to quickly quench the alloy ingotVacuumizing the quenching furnace, filling argon to positive pressure of 40kPa, melting the crushed alloy in a crucible of the rapid quenching furnace to boiling, flowing into the edge of a roller rotating at high speed from a pouring gate, and performing rapid rotary quenching at 3 × 105And rapidly cooling and solidifying the alloy liquid at the temperature/s under the cooling action of the roller to form a thin strip. Wherein, the alloy liquid is sprayed on a roller rotating at a wheel speed of 20m/s to prepare the quick-quenched thin strip.
(4) And carrying out heat treatment on the quick-quenched thin strip, wherein the heat treatment temperature is 665 ℃, and the heat treatment time is 15 min.
(5) And (3) carrying out water-cooling quenching on the quickly quenched thin strip subjected to the heat treatment for 30min in an argon atmosphere, and crushing the quickly quenched thin strip into alloy powder with the average particle size of 100 mu m by coarse crushing and grinding methods to obtain the isotropic bonded magnetic powder containing lanthanum and cerium.
The magnetic properties of the magnets were tested and the properties are shown in Table 3.
TABLE 3 magnetic Properties of the lanthanum cerium neodymium iron boron containing bonded permanent magnet powder of example 3
As can be seen from the above embodiments, the above-described examples of the present invention achieve the following technical effects: the rare earth permanent magnet material prepared by regulating the doping proportion of lanthanum and cerium and the proportion of the total doping amount of lanthanum and cerium and the amount of neodymium elements and combining the components with the conventional NdFeB rare earth permanent magnet material has the average grain size of 25-35 nm and the minimum standard deviation of 4.62, and is compared with the initial alloy component Nd12Fe82B6Has an average grain size of 38.57nm (as shown in FIG. 1) and a standard deviation of 7.74, wherein the alloy component is [ Nd ]0.5(La0.6Ce0.4)0.5]12Fe82B6The TEM image and the grain size statistics are shown in fig. 2, and comparing fig. 1, it can be seen that the co-doping of La and Ce makes the grain size significantly fine and the grain size distribution more concentrated. And La and Ce are doped together, so that good magnetic property is kept, and a single-phase structure is stabilized. Because of utilizing relatively rich light rare earth elements La and CeReplaces Nd and Pr, and greatly reduces the production cost.
Comparative example 1
Comparative example 1 a bonded magnetic powder differs from example 1 in that the amount of rare earth lanthanum doped is 0, and the other steps are the same as example 1.
Comparative example 2
Comparative example 2 a bonded magnetic powder differs from example 1 in that the amount of rare earth metal cerium doped is 0, and the same is applied to example 1.
Comparative example 3
Comparative example 3 a bonded magnetic powder differs from example 1 in that the doping ratio of lanthanum to cerium is 1:1, and the other steps are the same as example 1.
Comparative example 4
Comparative example 4 a bonded magnetic powder differs from example 1 in that the ratio of the total amount of doped lanthanum and cerium to the total amount of neodymium elements is 2:3, and the other steps are the same as example 1.
The results of the magnetic property tests of the permanent magnetic materials obtained in comparative examples 1 to 4 are shown in Table 4 below.
TABLE 4 magnetic Properties of the lanthanum cerium neodymium iron boron containing bonded magnet powders of comparative examples 1-4
From the results shown in table 4, it can be seen that, compared with comparative example 1 and comparative example 2, in the present invention, lanthanum and cerium are co-doped to replace neodymium, and each magnetic property of the bonded magnetic powder prepared under the same doping level is greatly improved compared with that of the bonded magnetic powder singly doped with lanthanum and cerium, wherein the magnetic energy product is improved by about 50% compared with that of the magnetic powder singly doped with cerium, and the grain size is refined and the grain size distribution is more concentrated.
Comparing with the comparison ratio 3, the doping ratio of lanthanum to cerium is limited to 3:2 in the embodiment 1, and compared with the ratio of 1:1 in the comparison example 3, the coercive force and the magnetic energy product are both improved, and the remanence is basically kept unchanged, so that the magnetic performance can be changed to a certain extent by properly regulating the ratio of lanthanum to cerium, and magnets with various performances suitable for downstream requirements can be produced.
Compared with the comparative example 4, the ratio of the total lanthanum-cerium doping amount to the total neodymium element amount in the embodiment 1 is 1:1, although the magnetic performance is slightly reduced, the reduction amplitude of the ratio of the limit of single lanthanum doping and single cerium doping to the neodymium content is much smaller, and the lanthanum and cerium can better compensate the performance deterioration problem caused by single lanthanum doping and single cerium doping under the combined action of lanthanum and cerium.
In summary, the invention provides a lanthanum-cerium co-doped neodymium iron boron isotropic bonded magnetic powder and a preparation method thereof, wherein the chemical formula of the magnetic powder is represented by atomic percent: [ RE ]1-x(LR)x]aFe100-a-b-cMbBcWherein x is more than or equal to 0.05 and less than or equal to 0.7, a is more than or equal to 11 and less than or equal to 13, b is more than or equal to 0 and less than or equal to 1.55, c is more than or equal to 5.5 and less than or equal to 6.2, RE is Nd or the combination of Nd and any one or more rare earth elements except La and Ce, LR is La and Ce, and M is Al and/or Nb. Wherein the grain size of the magnetic powder is 20-70 nm. The invention uses the relatively surplus and cheap rare earth lanthanum and cerium to partially replace neodymium element in neodymium iron boron, inhibits the precipitation of alpha-Fe, reduces the irreversible loss of magnetic flux, improves the coercive force by regulating the ratio of lanthanum and cerium and the ratio of lanthanum, cerium and neodymium and adding a proper amount of Nb and/or Al element, saves the cost and keeps good magnetic performance by combining the rapid quenching process and the control of parameters, and ensures that the rare earth element is comprehensively and balanced utilized.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (13)
1. A lanthanum-cerium co-doped isotropic bonded magnetic powder is characterized in that the chemical formula of the magnetic powder is [ Nd ]0.5(La0.6Ce0.4)0.5]11.9Fe81.1M1B6(ii) a Or
[Nd0.6(La0.8Ce0.2)0.4]11.9Fe81.1M1B6(ii) a Or
[Nd0.8(La0.4Ce0.6)0.2]11.9Fe81.1M1B6；
Wherein M is Al and/or Nb;
the content of each element is atom percentage content.
2. The lanthanum-cerium co-doped isotropic bonded magnetic powder according to claim 1, wherein the magnetic powder comprises RE2Fe14B a main phase R with a tetragonal structure and a grain boundary phase L, wherein RE is a rare earth element.
3. The lanthanum-cerium co-doped isotropic bonded magnetic powder according to claim 2, wherein the average grain size of the main phase R is 30 to 70 nm; the average grain size of the grain boundary phase L is 5 to 20 nm.
4. The lanthanum-cerium co-doped isotropic bonded magnetic powder according to any one of claims 2 to 3, wherein the atomic percentage of Ce distributed in the main phase R is 100%;
and/or La is distributed in the main phase R and the grain boundary phase L, wherein the atomic percentage of La distributed in the main phase R is 60-80%, and the rest of La enters the grain boundary phase L.
5. A method for preparing a lanthanum-cerium co-doped isotropic bonded magnetic powder according to any one of claims 1 to 4, comprising the steps of:
(1) weighing raw materials according to the components in the magnetic powder, putting the raw materials into a furnace, smelting the raw materials into clear alloy liquid, and cooling the clear alloy liquid into an alloy ingot;
(2) crushing the alloy ingot smelted in the step (1), placing the crushed alloy ingot in an induction rapid quenching furnace, vacuumizing the rapid quenching furnace, introducing argon to positive pressure, and melting the crushed alloy in a crucible of the rapid quenching furnace until the crushed alloy is boiled to form alloy liquid;
(3) enabling the alloy liquid to flow into the edge of a rotating roller from a pouring gate, and rapidly cooling and solidifying the alloy liquid into a rapidly quenched thin strip under the cooling effect of the roller;
(4) carrying out heat treatment on the quick-quenched thin strip obtained in the step (3) and then quenching;
(5) and crushing the quenched thin strip into alloy powder.
6. The method of claim 5, wherein the raw material is a single rare earth metal or a mixture of rare earth metals in a definite ratio.
7. The production method according to claim 5, wherein the melting in the step (1) is vacuum melting; the smelting temperature is 100-300 ℃ above the melting point of the raw materials.
8. The method according to claim 5, wherein the cooling of the alloy ingot in the step (1) is rapidly performed under circulating cooling water at 15 to 25 ℃.
9. The method according to claim 5, wherein the argon gas is introduced into the step (2) under a pressure of 35 to 50 kPa.
10. The method according to claim 5, wherein the casting in the step (3) is performed by high vacuum single roll spinning; the speed of the rotary quenching roller is 15-30 m/s; the cooling rate of the rotary quenching cooling is 105～106℃/s。
11. The method according to claim 5, wherein the heat treatment in step (4) is carried out at a temperature of 600 to 800 ℃ for 5 to 20 min; the heat treatment was performed under a flowing argon atmosphere.
12. The production method according to claim 5, wherein the quenching in the step (4) is water-cooled quenching; quenching is carried out in a flowing argon atmosphere; the quenching time is 30-60 min.
13. The method according to claim 5, wherein the average particle size of the alloy powder in the step (5) is 100 to 200 μm; crushing the quick-quenched thin strip into alloy powder with the average grain size of 100-200 mu m by coarse crushing and grinding.
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| JP2005093729A (en) * | 2003-09-17 | 2005-04-07 | Daido Steel Co Ltd | Anisotropic magnet, its manufacturing method, and motor using it |
| JP2017076680A (en) * | 2015-10-14 | 2017-04-20 | Tdk株式会社 | R-t-b based sintered magnet, and motor |
| CN108630371A (en) * | 2017-03-17 | 2018-10-09 | 有研稀土新材料股份有限公司 | A kind of rare earth permanent-magnetic material of high thermal stability, preparation method and the magnet containing it |
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