CN113593882A - 2-17 type samarium-cobalt permanent magnet material and preparation method and application thereof - Google Patents
2-17 type samarium-cobalt permanent magnet material and preparation method and application thereof Download PDFInfo
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- CN113593882A CN113593882A CN202110827355.8A CN202110827355A CN113593882A CN 113593882 A CN113593882 A CN 113593882A CN 202110827355 A CN202110827355 A CN 202110827355A CN 113593882 A CN113593882 A CN 113593882A
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- 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
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- 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
Abstract
The invention discloses a 2-17 type samarium cobalt permanent magnet material and a preparation method and application thereof. The preparation method comprises the following steps: applying a metal Cu layer on the surface of the samarium cobalt sintered body, performing diffusion treatment, and performing aging treatment to obtain the samarium cobalt sintered body; wherein the samarium cobalt sintered body has a composition of RxFeyCo1‑x‑y‑p‑qCupMqWherein R is Sm, or R comprises Sm and one or more rare earth elements selected from La, Pr, Nd, Gd, Ho, Er, Dy and Tb; m is selected from one or more of Zr, Ti and Hf. The preparation method can effectively improve the Cu content in the magnet grain boundary, eliminate the demagnetization step of the magnet demagnetization curve, and ensure that the magnet has high remanence, higher coercive force and magnetic energy product and good squareness.
Description
Technical Field
The invention relates to a 2-17 type samarium cobalt permanent magnet material and a preparation method and application thereof.
Background
In the field of high comprehensive performance samarium cobalt permanent magnet materials, a formula with high Fe content and low Cu content is generally adopted, the high Fe content can improve the saturation magnetization of a main phase, so that higher remanence is obtained, and meanwhile, the low Cu content is beneficial to improving the proportion of the main phase in a magnet, so that the remanence is further enhanced.
However, in conventional 2-17 type samarium cobalt permanent magnet materials, the increase in Fe content and the decrease in Cu content make it difficult for the magnet to form a complete continuous cell structure upon aging, and in particular, the Cu-rich cell wall phase Sm (Co, Cu) constituting the cell structure5The proportion of (1:5H phase for short) is insufficient, the distribution is incomplete, and particularly in the area lean in copper at the magnet grain boundary.
The 1:5H phase with high intrinsic coercivity (Hcj) cannot be formed due to the lack of sufficient Cu element, so that the intrinsic coercivity (Hcj) of the magnet is greatly reduced, a demagnetization step occurs in the demagnetization curve of the magnet between-2 and-10 kOe, the squareness (SQ — Hk/Hcj) of the magnet is deteriorated, and the knee point coercivity (Hk), the magnetic induction coercivity (Hcb), and the magnetic energy product (BH) of the magnet are reduced.
Disclosure of Invention
The invention provides a 2-17 type samarium cobalt permanent magnet material and a preparation method and application thereof, aiming at solving the defects that in the prior art, Hcj, Hk, Hcb and BH of a 2-17 type samarium cobalt permanent magnet material with high Fe content and low Cu content are low and demagnetization steps exist. The preparation method of the 2-17 type samarium cobalt permanent magnet material can effectively improve the Cu content in the crystal boundary of the magnet, eliminate the demagnetization step of the demagnetization curve of the magnet, and ensure that the magnet has high remanence, high Hcj, high Hk, high Hcb and high BH and good squareness.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a 2-17 type samarium cobalt permanent magnet material, which comprises the following steps: applying a metal Cu layer on the surface of the samarium cobalt sintered body, performing diffusion treatment, and performing aging treatment to obtain the samarium cobalt sintered body;
wherein the samarium cobalt sintered body has a composition of RxFeyCo1-x-y-p-qCupMqWherein R is Sm, or R comprises Sm and one or more rare earth elements selected from La, Pr, Nd, Gd, Ho, Er, Dy and Tb; m is selected from one or more of Zr, Ti and Hf; 0.11<x<0.12，0.25<y<0.45，0.03<p<0.065，0.015<q<0.035, and satisfies 0.05<p+q<0.08，1.5<p/q<4.5，7.5<(1-x)/x<8.0; wherein x, y, p and q represent atomic ratios, and the total number of atoms of R, Fe, Co, Cu and M is represented as 1.
In the present invention, the range of x is preferably 0.114< x <0.118, e.g. 0.1132, 0.1145, 0.115, 0.1155 or 0.12.
In the present invention, the range of y is preferably 0.285< y <0.365, such as 0.305, 0.32 or 0.325.
In the present invention, the range of p is preferably 0.04< p <0.055, e.g. 0.042, 0.05 or 0.055.
In the present invention, the range of q is preferably 0.015< q <0.025, such as 0.017, 0.0185, 0.0215 or 0.0245.
In the present invention, the range of p + q is preferably 0.06< p + q <0.078, for example 0.0665 or 0.068.
In the present invention, the range of p/q is preferably 1.6< p/q <3.0, e.g. 1.7 or 2.0.
In the present invention, the range of (1-x)/x is preferably 7.65< (1-x)/x <7.85, for example 7.73.
In certain embodiments, the R is Sm and Nd; wherein, preferably, the atomic ratio of Sm is 0.1, and the atomic ratio of Nd is 0.0145; alternatively, the atomic ratio of Sm is 0.115 and the atomic ratio of Nd is 0.005.
In certain embodiments, the R is Sm and Dy; wherein, preferably, the atomic ratio of Sm is 0.1045 and the atomic ratio of Nd is 0.01.
In certain embodiments, the R is Sm, La, and Nd; wherein, preferably, the atomic ratio of Sm is 0.1045, and L isThe atomic ratio of a is 0.005 and the atomic ratio of Nd is 0.005. In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1145Fe0.285Co0.537Cu0.042M0.0215。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1Nd0.1045Fe0.285Co0.537Cu0.042Zr0.0215。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1045Dy0.01Fe0.285Co0.537Cu0.042Zr0.0215。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1045La0.005Nd0.005Fe0.28 5Co0.537Cu0.042Zr0.0215。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1145Fe0.285Co0.537Cu0.04 2Ti0.0215。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1145Fe0.285Co0.537Cu0.04 2Hf0.0215。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1155Fe0.305Co0.511Cu0.05Zr0.0185。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.1132Fe0.32Co0.4948Cu0.05 5Zr0.017。
In one embodiment of the present invention, the samarium cobalt sintered body has the composition Sm0.115Nd0.005Fe0.365Co0.438 5Cu0.055Zr0.0215。
In the present invention, the method of applying the metallic Cu layer may be conventional in the art, such as electroplating, PVD (physical vapor deposition) plating, evaporation, or coating.
In the present invention, the thickness of the metal Cu layer may be 5 to 50 μm, for example, 10 μm.
In the invention, the metal Cu layer may account for 0 to 3.0% by mass of the samarium cobalt sintered body, and is not 0, for example, 2.1%.
In the invention, the temperature of the diffusion treatment can be 880-1000 ℃, for example 950 ℃.
In the invention, the time of the diffusion treatment can be 2-20 h, such as 10 h.
In the invention, the samarium cobalt sintered body can have a thickness of 1 to 20mm, for example 2 mm.
In the present invention, the samarium cobalt sintered body may be prepared by methods conventional in the art, generally comprising the following steps in order: proportioning, smelting, casting, pulverizing, pressing, sintering, solid dissolving and cooling.
In the present invention, the melting may be performed by a method conventional in the art, for example, induction melting. Melting the metal material by adopting an induction melting mode, vacuumizing the interior of a furnace body before melting, then filling argon for atmosphere protection, simultaneously inhibiting volatilization of metal components in the melting process, and heating to melt the metal material into uniformly mixed molten alloy liquid. Wherein the pressure range of the argon gas is preferably 30-80 kPa, such as 70 kPa; the maximum temperature of the heating is preferably 1450-1600 ℃, for example 1520 ℃.
In the present invention, the casting may be performed by a method conventional in the art, such as a strip casting, a centrifugal casting, or a book-type casting. The casting of the melt-spun strip is carried out through a rotary cooling roller, the centrifugal casting is carried out through a rotary cooling ring wall, and the book-type casting adopts a water-cooling book-type casting mold. The casting is preferably performed by casting the molten alloy into an alloy ingot having a thickness of 5mm to 25 mm.
In the present invention, the milling may be carried out by a method conventional in the art, preferably comprising coarse crushing and jet milling in this order.
Wherein, the coarse crushing can be carried out under the protection of inert gas by adopting a common jaw crushing, disc type grinding crushing, airflow impact or ball milling crushing mode. The common jaw type crushing can be carried out by adopting a jaw type crusher, the material can be crushed to the diameter of 1mm-5mm, and the intermediate crushing procedures such as disc type grinding crushing, airflow impact or ball milling crushing and the like can be further carried out generally. The disc type grinding and crushing can be carried out by adopting a disc type grinder, and the materials can be crushed to be below 40 meshes.
The coarse powder obtained by said coarse crushing preferably has a particle size of less than 40 mesh, for example 80 mesh.
Wherein, the coarse powder obtained by the coarse crushing is crushed by an airflow mill. The jet mill preferably uses high purity nitrogen as a carrier gas. The sorting rotating speed of the jet mill is preferably 3000-3500 revolutions per minute, such as 3300 revolutions per minute. The fine powder obtained by the air flow milling has an average particle size of preferably 4 to 8 μm, for example 6.5 μm.
In the present invention, the pressing may be performed by a method conventional in the art, and preferably includes magnetic field orientation pressing and cold isostatic pressing in this order. The cold isostatic pressing may further densify the green body.
Wherein the magnetizing magnetic field for the magnetic field orientation pressing is preferably 1-1.5T, such as 1.2T; the pressure of the magnetic field orientation pressing is preferably 8-20T, such as 10T.
Wherein the pressure of the cold isostatic pressing is preferably 150 to 300MPa, for example 200 MPa.
In the present invention, the sintering may be performed by a method conventional in the art. The sintering temperature can be 1195-1230 ℃, preferably 1205-1215 ℃, such as 1210 ℃; the sintering time can be 2-8 h, and preferably 3-6 h.
In the present invention, the solid solution may be performed by a method conventional in the art. And after sintering, slowly cooling to the temperature required by solid solution, and then preserving heat. The solid solution temperature can be 1175-1195 ℃, and is preferably 1180-1190 ℃; the solid solution time can be 5-10 h.
In the present invention, after the solid solution is completed, the magnet at the solid solution temperature may be cooled. The coolingThe rate of cooling is preferably greater than 120 deg.C/min, for example 150 deg.C/min. The cooling speed can ensure the rapid cooling of the magnet and avoid the metastable main phase SmCo in the magnet7During cooling, the magnetic material decomposes to produce a heterogeneous phase, so that the magnetic material maintains high remanence.
In the present invention, the aging may be performed by a method conventional in the art. The aging can be one-stage aging or multi-stage aging. The preferred operation of aging includes: carrying out primary heat preservation at 810-860 ℃; and (5) cooling to 400 ℃, and then carrying out secondary heat preservation.
Wherein the temperature of the first heat preservation is 850 ℃; the first heat preservation time can be 15-30 h, and preferably 20-25 h. The time of the second heat preservation can be 5-15 hours, and preferably 8-12 hours. The cooling rate may be less than 1.2 ℃/min, preferably less than 0.8 ℃/min, for example 0.7 ℃/min.
The invention also provides a 2-17 type samarium cobalt permanent magnet material which is prepared according to the preparation method of the 2-17 type samarium cobalt permanent magnet material.
The invention also provides a 2-17 type samarium cobalt permanent magnet material, and the tissue structure of the 2-17 type samarium cobalt permanent magnet material comprises crystal grains and grain boundaries, wherein the crystal grains comprise a cellular structure, and the main phase Sm of the cellular structure2(Co,Fe)17Wall-mixing Sm (Co, Cu)5The cell wall surrounding the main phase; and flaky M-rich phases are distributed at the crystal boundary and are distributed perpendicular to the c axis.
The size of the cell structure can be 50-100 nm, the thickness of the cell wall can be 1-20 nm, and the volume ratio of the cell wall to the cell structure can be 5-10%.
Wherein the flaky M-rich phase is preferably a Zr-rich phase. The flaky rich M phase can be Cu element to cell wall phase Sm (Co, Cu)5Provide a fast channel. The width of the flaky M-rich phase can be 2-20 nm.
In the invention, optionally, the structure of the 2-17 type samarium cobalt permanent magnetic material further comprises a rare earth oxide phase. Wherein the rare earth oxide phase is generally Sm2O3. The rare earth oxideThe phase content may be 1.45 wt% to 2.18 wt%, corresponding to an oxidation amount of 0.2 to 0.3 wt%. Due to the characteristics of the powder metallurgy manufacturing process and the activity of rare earth, the rare earth magnetic material can generate partial rare earth oxide phases which are inevitable in the manufacturing process, belong to impurities in the magnet, and are uniformly and randomly distributed in the magnet.
In the invention, the magnetic performance of the 2-17 type samarium cobalt permanent magnet material meets the following requirements: br is more than or equal to 11.95kGs, Hcj is more than or equal to 20.5kOe, Hcb is more than or equal to 11.0kOe, Hk is more than or equal to 16.25kOe, BHmax is more than or equal to 33.0MGOe, and SQ is more than or equal to 66.0%.
Preferably, the magnetic performance of the 2-17 type samarium cobalt permanent magnet material meets the following requirements: br is 11.95-12.35 kGs; hcj is 20.5-26.32 kOe; hcb is 11.04 to 11.23kOe, Hk is 16.25 to 19.65kOe, BHmax is 33.04 to 34.24MGOe, and SQ is 66.31 to 79.59%.
The invention also provides application of the 2-17 type samarium cobalt permanent magnet material in electronic communication equipment, aerospace equipment or rail transit equipment.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: according to the invention, the samarium cobalt sintered body is subjected to metal Cu diffusion treatment before aging, so that the Cu content in the magnet grain boundary is effectively increased, and Sm (Co, Cu) is promoted5The formation of the (1: 5H) phase effectively restores the incomplete cell structure of the grain boundary region and eliminates the small steps of the demagnetization curve of the magnet.
The 2-17 type samarium cobalt permanent magnet material has high remanence Br, high coercive force (Hcj, Hk and Hcb) and high magnetic energy product BH, and improves the squareness SQ of a magnet.
Drawings
FIG. 1 is a view showing the microscopic distribution EPMA of Cu element in the magnet before and after Cu diffusion treatment in the example;
wherein, 1-main phase, 2-grain boundary; 3-rare earth oxide phase.
Figure 2 is a demagnetization curve for a type 2-17 samarium cobalt permanent magnet material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Examples 1 to 9
The 2-17 type samarium cobalt permanent magnet material is prepared according to the following steps:
(1) preparing materials: the ingredients were mixed according to the ingredient ratios in table 1.
(2) Smelting: melting the metal material by adopting an induction melting mode, vacuumizing the interior of a furnace body before melting, filling 70kPa argon for atmosphere protection, simultaneously inhibiting the volatilization of metal components in the melting process, and melting the metal material to form uniformly mixed molten alloy liquid at the highest melting temperature of 1520 ℃.
(3) Casting: the molten alloy was refined and then cast by casting on a rotating cooling ring wall (centrifugal casting), and the molten alloy was cast into an alloy ingot 5mm thick.
(4) Coarse crushing: and (3) performing coarse crushing by using a disc grinder under the protection of inert gas to obtain coarse powder, wherein the granularity of the coarse powder is 80 meshes.
(5) And (3) jet milling: and (3) carrying out jet milling on the coarse powder, wherein high-purity nitrogen is used as a carrier gas in the jet milling, and the sorting rotating speed of the jet milling is controlled to 3300 rpm, so that fine powder is obtained, and the average particle size of the fine powder is 6.5 mu m.
(6) Pressing: placing the fine powder in a magnetic field press for magnetic field orientation pressing, wherein the magnetizing magnetic field of the magnetic field orientation pressing is 1.2T, and the pressure of the magnetic field orientation pressing is 10T; and then carrying out cold isostatic pressing on the green body obtained by the magnetic field orientation pressing under 200MPa to obtain the green body.
(7) Sintering, solid solution and cooling: sintering the green body at 1210 ℃ for 3 h; slowly cooling to 1180 ℃ after sintering, preserving heat for 5 hours, and carrying out solid solution treatment; and then rapidly cooling the magnet at the solid solution temperature at the cooling speed of 150 ℃/min to obtain the samarium cobalt sintered body.
(8) Diffusion: a metal Cu layer is applied to the surface of a samarium cobalt sintered body with the thickness of 2mm in an electroplating mode, the thickness of the metal Cu layer is 20 mu m, the mass percent of the metal Cu layer in the samarium cobalt sintered body is 2.1%, and diffusion treatment is carried out at 950 ℃ for 10 h.
(9) Aging: preserving the heat of the diffused magnet for the first time for 20h at 850 ℃; cooling to 400 ℃, and then preserving heat for 5 hours for the second time; wherein the cooling speed is 0.7 ℃/min; thereby obtaining the 2-17 type samarium cobalt permanent magnet material.
TABLE 1
Note: in Table 1, "-" indicates that the element is not contained.
Comparative example 1
Comparative example 1 the same amount of Cu was added directly to the batch without diffusion treatment and the other preparation process was the same as in example 1.
Comparative example 2
The samarium cobalt sintered body of comparative example 2 had too low a Zr content and the other preparation processes were the same as in example 1.
Comparative example 3
The samarium cobalt sintered body of comparative example 3 had too high a Zr content and the other preparation processes were the same as in example 1.
Effect example 1
Magnetic performance tests were performed on the samarium cobalt sintered bodies (before diffusion) and the samarium cobalt permanent magnet materials (after diffusion) in examples 1 to 9 and the magnets prepared in comparative examples 1 to 3, wherein the magnetic performance tests of Br, Hcj, Hcb, BHmax, Hk and SQ were performed by using a pfm14.cn type pulsed magnetic field magnetometer and a Φ 10 × 10mm cylindrical sample at 20 ℃. The magnetic properties were measured and the results are shown in Table 2.
As can be seen from table 2, for example 1: compared with the samarium cobalt sintered body before diffusion, the samarium cobalt permanent magnet material obtained after diffusion has high remanence, greatly improves the coercive force (from 11.53kOe to 25.43kOe and from 120.5 percent), improves the magnetic energy product (from 29.02MGOe to 33.50MGOe), and improves the demagnetization curve squareness of the magnet (from 46.7 percent to 75.4 percent).
For comparative example 1: due to the non-magnetic characteristic of Cu atoms, when the Cu atoms are distributed in the main phase of the magnet 2-17, the Cu atoms play a role in diluting the remanence of the magnet, so when the same amount of Cu element is added into the formula, the remanence of the magnet is reduced, and the magnet with high remanence and high magnetic energy product cannot be obtained. As can be seen from table 2, although the intrinsic coercive force Hcj of comparative example 1 increases, the remanence Br of comparative example 1 decreases (from 11.98 to 11.57), the magnetic induction coercive force Hcb decreases (from 11.15 to 10.53), the knee point coercive force Hk decreases (from 19.17 to 15.87), the magnetic energy product BHmax decreases (from 33.39 to 30.46), and the squareness SQ decreases (from 75.4% to 52.69%) compared to example 1. The main advantages of example 1 over comparative example 1 are high remanence, good Hcb and high magnetic energy product. The remanence of 11.98 and 11.57 in the field of samarium-cobalt magnets is large in remanence difference, and the magnetic energy products of 33.39 and 30.12 are different by two national standard marks and are large in difference. The higher coercive force can be easily obtained by directly adding a sufficient amount of Cu element and melting, but the remanence and Hcb values are low, so the magnetic energy product of the magnet is inferior to that of example 1.
For comparative examples 2 and 3: the Zr element has the function of forming flaky Zr-rich phase in the magnet during the aging process, and the Zr-rich phase is formed by Cu element oriented to cell wall phase Sm (Co, Cu)5Diffusion enrichment in phase provides a fast migration path. Too low Zr element, low proportion of flaky Zr-rich phase, insufficient diffusion channel of Cu, uneven distribution of Cu element Sm (Co, Cu)5The formation is insufficient, and the coercive force and squareness of the magnet are reduced. The Zr element is too high, the effect is similar to the Cu element excess, and the magnet generates excessive non-magnetic flaky Zr-rich phase, thereby causing the reduction of the remanence of the magnet.
TABLE 2
In addition, the demagnetization curves of the samarium cobalt sintered body (before diffusion) and the samarium cobalt permanent magnet material (after diffusion) in example 1 are shown in fig. 2, and it can be seen that the invention eliminates the small steps in the demagnetization curves.
Effect example 2
The vertically oriented surfaces of the samarium cobalt sintered body (before diffusion) and the samarium cobalt permanent magnet material (after diffusion) in example 1 were polished by FE-EPMA detection, and the Cu element distribution in the main phase and the grain boundary was detected by field emission electron probe microanalyzer (FE-EPMA) (JEOL, 8530F), and the results are shown in fig. 1.
In FIG. 1, 1 is the main phase, 2 is the grain boundary, and 3 is the rare earth oxide (Sm)2O3). Cu diffusion enables the crystal boundary of the samarium cobalt magnet to be changed into a copper-rich state from a copper-poor state (the Cu concentration in the crystal boundary after diffusion is 2-5 times of the Cu concentration in the magnet before diffusion), the cell structure of the magnet in the crystal grain boundary area is effectively repaired, the generation of a Cu-rich cell wall (1:5H phase) is promoted, the coercive force of the magnet is greatly improved, and the squareness of the magnet is improved.
In samarium cobalt permanent magnet materials, a plurality of cell structures are often contained in a crystal grain, and the cell wall phase of the cell structures has copper-poor and incomplete and discontinuous phenomena at the position close to the edge of the grain boundary in the crystal grain due to the deficiency of Cu element at the grain boundary at the edge of the crystal grain. In the process of increasing the content of Cu at the grain boundary and promoting the diffusion of Cu into the crystal grains, firstly, the cellular structure, especially the cell wall phase, of the crystal grain boundary part is repaired, and secondly, when the Cu is diffused into the deeper crystal grains, the cell wall phase in the crystal grains is strengthened. The coercive force of the samarium cobalt permanent magnet material is derived from the domain wall energy difference between the cell wall phase and the main phase in the cell structure, and the domain wall energy difference of the two phases is larger, and the coercive force is higher.
Claims (10)
1. A preparation method of a 2-17 type samarium cobalt permanent magnet material comprises the following steps: applying a metal Cu layer on the surface of the samarium cobalt sintered body, performing diffusion treatment, and performing aging treatment to obtain the samarium cobalt sintered body;
wherein the samarium cobalt sintered body has a composition of RxFeyCo1-x-y-p-qCupMqWherein R is Sm, or R comprises Sm and one or more elements selected from La, Pr, Nd, Gd,One or more rare earth elements of Ho, Er, Dy and Tb; m is selected from one or more of Zr, Ti and Hf; 0.11<x<0.12，0.25<y<0.45，0.03<p<0.065，0.015<q<0.035, and satisfies 0.05<p+q<0.08，1.5<p/q<4.5，7.5<(1-x)/x<8.0; wherein x, y, p and q represent atomic ratios, and the total number of atoms of R, Fe, Co, Cu and M is represented as 1.
2. A method of making a 2-17 type samarium cobalt permanent magnet material as claimed in claim 1 wherein x is in the range 0.114< x <0.118, such as 0.1132, 0.1145, 0.115, 0.1155 or 0.12;
and/or, y ranges from 0.285< y <0.365, e.g., 0.305, 0.32, or 0.325;
and/or, p is in the range 0.04< p <0.055, e.g., 0.042, 0.05, or 0.055;
and/or, q ranges from 0.015< q <0.025, e.g., 0.017, 0.0185, 0.0215, or 0.0245;
and/or, p + q ranges from 0.06< p + q <0.078, e.g. 0.0665 or 0.068;
and/or, p/q ranges from 1.6< p/q <3.0, e.g., 1.7 or 2.0;
and/or the range of (1-x)/x is 7.65< (1-x)/x <7.85, for example 7.73.
3. The method of making a 2-17 type samarium cobalt permanent magnet material of claim 1, wherein R satisfies one of the following conditions:
the conditions are as follows: the R is Sm and Nd; wherein, preferably, the atomic ratio of Sm is 0.1, and the atomic ratio of Nd is 0.0145; or the atomic ratio of Sm is 0.115 and the atomic ratio of Nd is 0.005;
condition two: r is Sm and Dy; wherein, preferably, the atomic ratio of Sm is 0.1045, and the atomic ratio of Nd is 0.01;
condition (c): r is Sm, La and Nd; wherein preferably, the atomic ratio of Sm is 0.1045, the atomic ratio of La is 0.005, and the atomic ratio of Nd is 0.005.
4. The method of making a 2-17 type samarium cobalt permanent magnet material of claim 1 wherein the samarium cobalt sintered body comprises Sm0.1145Fe0.285Co0.537Cu0.042M0.0215；
Or the samarium cobalt sintered body has Sm as a component0.1Nd0.1045Fe0.285Co0.537Cu0.042Zr0.0215；
Or the samarium cobalt sintered body has Sm as a component0.1045Dy0.01Fe0.285Co0.537Cu0.042Zr0.0215；
Or the samarium cobalt sintered body has Sm as a component0.1045La0.005Nd0.005Fe0.285Co0.537Cu0.042Zr0.0215；
Or the samarium cobalt sintered body has Sm as a component0.1145Fe0.285Co0.537Cu0.042Ti0.0215；
Or the samarium cobalt sintered body has Sm as a component0.1145Fe0.285Co0.537Cu0.042Hf0.0215；
Or the samarium cobalt sintered body has Sm as a component0.1155Fe0.305Co0.511Cu0.05Zr0.0185；
Or the samarium cobalt sintered body has Sm as a component0.1132Fe0.32Co0.4948Cu0.055Zr0.017；
Or the samarium cobalt sintered body has Sm as a component0.115Nd0.005Fe0.365Co0.4385Cu0.055Zr0.0215。
5. The method of making a 2-17 type samarium cobalt permanent magnetic material of claim 1 wherein the method of applying the metallic Cu layer is electroplating, PVD coating, evaporation or coating;
and/or the thickness of the metal Cu layer is 5-50 μm, such as 10 μm;
and/or the metal Cu layer accounts for 0-3.0% of the samarium cobalt sintered body by mass and is not 0, such as 2.1%;
and/or the temperature of the diffusion treatment is 880-1000 ℃, such as 950 ℃;
and/or the diffusion treatment time is 2-20 h, such as 10 h;
and/or the samarium cobalt sintered body has a thickness of 1 to 20mm, for example 2 mm.
6. The method of making a 2-17 type samarium cobalt permanent magnet material of claim 1 wherein the method of making the samarium cobalt sintered body comprises the steps of, in order: proportioning, smelting, casting, pulverizing, pressing, sintering, solid dissolving and cooling;
preferably, the smelting is induction smelting; the preferred operation of the induction melting comprises: melting the metal materials, vacuumizing the interior of the furnace body before melting, then filling argon for atmosphere protection, simultaneously inhibiting the volatilization of metal components in the melting process, and heating to melt the metal materials into uniformly mixed molten alloy liquid; wherein the pressure range of the argon gas is preferably 30-80 kPa, such as 70 kPa; the highest temperature of heating is preferably 1450-1600 ℃, for example 1520 ℃;
preferably, the casting is casting by a melt spinning, centrifugal casting or book-type casting; wherein the melt-spun casting is carried out by rotating a cooling roller, the centrifugal casting is carried out by rotating a cooling ring wall, and the book-type casting adopts a water-cooling book-type casting mold; the casting is preferably to cast the molten alloy liquid into an alloy block with the thickness of 5 mm-25 mm;
preferably, the milling comprises coarse crushing and jet milling in sequence; wherein, the coarse crushing is preferably carried out in a common jaw crushing, disc grinding crushing, airflow impact or ball milling crushing mode under the protection of inert gas; the coarse powder obtained by the coarse crushing preferably has a particle size of less than 40 mesh, for example 80 mesh; the jet mill preferably uses high purity nitrogen as a carrier gas; the sorting rotating speed of the jet mill is preferably 3000-3500 revolutions per minute, such as 3300 revolutions per minute; the average particle size of fine powder obtained by the airflow mill is preferably 4-8 μm, such as 6.5 μm;
preferably, the pressing comprises magnetic field orientation pressing and cold isostatic pressing in sequence; wherein the magnetizing magnetic field for the magnetic field orientation pressing is preferably 1-1.5T, such as 1.2T; the pressure of the magnetic field orientation pressing is preferably 8-20T, such as 10T; wherein the pressure of the cold isostatic pressing is preferably 150-300 MPa, such as 200 MPa;
preferably, the sintering temperature is 1195-1230 ℃, preferably 1205-1215 ℃, for example 1210 ℃; the sintering time is 2-8 h, preferably 3-6 h;
preferably, the temperature of the solid solution is 1175-1195 ℃, preferably 1180-1190 ℃; the solid solution time is 5-10 h;
preferably, the rate of cooling is greater than 120 deg.C/min, such as 150 deg.C/min;
preferably, the aging is one-stage aging or multi-stage aging; the preferred operation of said aging comprises: carrying out primary heat preservation at 810-860 ℃; cooling to 400 ℃ and then carrying out secondary heat preservation; wherein the temperature of the first heat preservation is 850 ℃; the first heat preservation time is 15-30 hours, preferably 20-25 hours; the time for the second heat preservation is 5-15 hours, and preferably 8-12 hours; the cooling rate may be less than 1.2 ℃/min, preferably less than 0.8 ℃/min, for example 0.7 ℃/min.
7. A2-17 type samarium cobalt permanent magnet material prepared by the method of any one of claims 1 to 6 of making a 2-17 type samarium cobalt permanent magnet material.
8. 2-17 type samarium cobalt permanent magnet material, characterized in that the structure of the 2-17 type samarium cobalt permanent magnet material comprises crystal grains and grain boundaries, wherein the crystal grains comprise a cellular structure, and the main phase Sm of the cellular structure2(Co,Fe)17Wall-mixing Sm (Co, Cu)5The cell wall surrounding the main phase; the crystal boundary is distributed with flaky M-rich phase which is vertical to the c axisAnd (3) cloth.
9. The 2-17 type samarium cobalt permanent magnet material of claim 8 wherein the cell structures have a size of 50 to 100nm, the cell walls have a thickness of 1 to 20nm, and the cell walls can comprise 5 to 10 percent by volume of the cell structures;
and/or the flaky M-rich phase is a Zr-rich phase;
and/or the width of the flaky M-rich phase is 2-20 nm;
and/or the tissue structure of the 2-17 type samarium cobalt permanent magnetic material also comprises a rare earth oxide phase; wherein the rare earth oxide phase is preferably Sm2O3(ii) a The content of the rare earth oxide phase is preferably 1.45 wt% to 2.18 wt%.
10. Use of a 2-17 type samarium cobalt permanent magnet material according to any of claims 7 to 9 in an electronic communication device, an aerospace device or an orbital transportation device.
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