Patent Application
20220415549
The present disclosure belongs to the technical field of rare earth-based permanent magnet materials and relates to a grain boundary diffusion cerium-based magnet containing a REFe2 phase and a preparation method thereof.
Rare earth-based permanent magnet materials are widely used in electromechanical, information, robotics and intelligent manufacturing fields. With the continuous development of applications such as wind power generation, new energy vehicles, rail transit, robotics, and information, PrNd rare earth as a main raw material are consumed in large quantities, while co-associated and high-abundance rare earths La and Ce are backlogged in large quantities. In recent years, a high-abundance rare earth-based permanent magnet material, cerium magnet, has successfully achieved industrialization with the development of a double main phase preparation technology. The cerium magnet realizes the balanced utilization of rare earth resources, while significantly reducing a raw material cost of the magnet. With the expansion of application range, the cerium magnet is required to have high coercivity and desirable temperature stability. Grain boundary diffusion technology conducts diffusion heavy rare earths such as Dy and Tb or heavy rare earth compounds into a Nd—Fe—B magnet along a grain boundary, to significantly increase the coercivity and improve a temperature coefficient of the magnet. Meanwhile, the technology has been widely used in mass production of high-coercivity Nd—Fe—B magnets due to a simple process, low cost and great coercivity improvement. The cerium magnet prepared by grain boundary diffusion technology has significantly improved coercivity and stability, with desirable market prospects.
The cerium magnet usually includes more than 20 wt % of a rare earth element Ce. Since a CeFe2 phase replaces a Nd phase of a Nd—Fe—B ternary system in a ternary phase diagram of Ce—Fe—B, the cerium magnet has a grain boundary phase including the CeFe2 phase and a rare earth-enriched phase. Moreover, with an increase of the Ce content, the CeFe2 phase has a further increased content in the magnet, which may even completely replace the rare earth-enriched phase. The CeFe2 phase leads to a grain boundary diffusion process and a diffusion behavior of rare earth elements in the cerium magnet different from those of the Nd—Fe—B magnet. In addition, all rare earth elements except La, Nd, Eu and Yb can form the REFe2 phase; since the REFe2 phase has a melting point higher than that of the rare earth-enriched phase, conventional grain boundary diffusion processes have a low diffusion efficiency and a limited increase in coercivity of the cerium magnet. Therefore, there is an urgent need for a grain boundary diffusion technology of a cerium magnet containing a REFe2 phase, represented by the CeFe2 phase, which has a high diffusion efficiency and can greatly improve the coercivity of cerium magnet. The technology can be widely used in batch preparation and industrial production of high-coercivity cerium magnets.
In view of the above technical problems, an objective of the present disclosure is to provide a grain boundary diffusion cerium-based magnet containing a REFe2 phase. By conducting the grain boundary diffusion near a melting point of the REFe2 phase, a rare earth element in a diffusion source has an improved diffusion efficiency to greatly enhance coercivity of the magnet.
Another objective of the present disclosure is to provide a preparation method of the grain boundary diffusion cerium-based magnet containing a REFe2 phase.
To achieve the above objectives, the present disclosure provides the following technical solutions.
The present disclosure provides a grain boundary diffusion cerium-based magnet containing a REFe2 phase, where an original cerium magnet has a chemical composition of (Cex,RE′1-x)aFe99-a-bB0.9-1.2TMb, x is greater than or equal to 20 wt. % and less than or equal to 85 wt. %, a is greater than or equal to 28 and less than or equal to 35, and b is greater than or equal to 0 and less than or equal to 10; TM is one or more selected from the group consisting of Co, Al, Cu, Ga, Nb, Mo, Ti, Zr, and V; the original cerium magnet is prepared by sintering or hot pressing, and includes a 2-14-1 main phase, the REFe2 phase, and a rare earth-enriched phase; the REFe2 phase is selected from the group consisting of a CeFe2 phase or a (Ce,RE′)Fe2 phase, and RE′ is one or more selected from the group consisting of La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y; and
an RE″ element of a rare earth diffusion source is diffused into the original cerium magnet through the grain boundary diffusion at a melting point of the REFe2 phase as a diffusion temperature; a treated original cerium magnet is directly cooled to room temperature or cooled to room temperature after tempering to obtain a final cerium magnet; and the final cerium magnet includes a new 2-14-1 main phase, a new enhanced REFe2 phase, and a new rare earth-enriched phase; the new 2-14-1 main phase is selected from the group consisting of a (Ce,RE″)2Fe14B main phase and a (Ce,RE′,RE″)2Fe14B main phase, the new enhanced REFe2 phase is selected from the group consisting of a (CeRE″)Fe2 phase and a (Ce,RE′,RE″)Fe2 phase; and RE″ is one or more selected from the group consisting of La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.
Further, the RE″ element may form a (Ce,RE″)2Fe14B main phase or a (Ce,RE′,RE″)2Fe14B main phase with a core-shell structure at an edge of main phase grains.
Further, an anisotropy field of the RE″2Fe14B phase may be larger than that of the Ce2Fe14B phase or the (Ce,RE′)2Fe14B phase.
Further, the grain boundary diffusion may be conducted at 850° C. to 1,000° C. for 0.1 h to 48 h.
Further, the tempering may be conducted at an eutectic temperature of a Ce-RE′-RE″-Fe phase of 400° C. to 700° C. for 0.5 h to 12 h.
Further, the rare earth diffusion source containing the RE″ element may be selected from the group consisting of a rare earth metal, a rare earth hydride, a rare earth fluoride, a rare earth oxide, and a rare earth alloy.
The present disclosure further provides a preparation method of the grain boundary diffusion cerium-based magnet containing a REFe2 phase, including the following steps:
a, preparing a blocky original cerium magnet with a chemical composition of (Cex,RE′1-x)aFe100-a-b-cTMbBc by sintering or hot pressing, where x is greater than or equal to 20 wt. % and less than or equal to 85 wt. %, a is greater than or equal to 28 and less than or equal to 35, b is greater than or equal to 0 and less than or equal to 10, and c is greater than or equal to 0.9 and less than or equal to 1.5; TM is one or more selected from the group consisting of Co, Al, Cu, Ga, Nb, Mo, Ti, Zr, and V; the original cerium magnet includes the 2-14-1 main phase, the REFe2 phase, and the rare earth-enriched phase; the REFe2 phase is selected from the group consisting of the CeFe2 phase or the (Ce,RE′)Fe2 phase, and RE′ is one or more selected from the group consisting of La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y;
b, attaching the rare earth diffusion source containing the RE″ element to a surface of the original cerium magnet by grain boundary diffusion at a melting point of the REFe2 phase for 0.1 h to 48 h, where RE″ is one or more selected from the group consisting of La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y; and
c, cooling directly to room temperature, or tempering at an eutectic temperature of a Ce-RE′-RE″-Fe phase for 0.5 h to 12 h and cooling to room temperature to obtain the final cerium magnet.
Further, the rare earth diffusion source containing the RE″ element may be selected from the group consisting of a rare earth metal, a rare earth hydride, a rare earth fluoride, a rare earth oxide, and a rare earth alloy.
Further, when the grain boundary diffusion reaches a melting point of the CeFe2 phase or the (Ce,RE′)Fe2 phase, the CeFe2 phase or the (Ce,RE′)Fe2 phase may become a liquid phase; alternatively, the CeFe2 phase or the (Ce,RE′)Fe2 phase may be reacted with a RE′-enriched phase to form a Ce-RE′-Fe multiphase liquid phase; heat preservation may be conducted at the melting point for 0.1 h to 48 h, such that the RE″ element is diffused into the magnet along a channel of the CeFe2 phase, the (Ce,RE′)Fe2 phase, or the Ce-RE′-Fe multiphase liquid phase, to form the (CeRE″)Fe2 phase, the (Ce,RE′,RE″)Fe2 phase, or the Ce-RE′-RE″-Fe phase.
Further, the grain boundary diffusion may be conducted at 850° C. to 1,000° C.; and the tempering may be conducted at 400° C. to 700° C.
Further, the final cerium magnet may include the (CeRE″)Fe2 phase and a Ce-RE″-enriched phase, or the (Ce,RE′,RE″)Fe2 phase and a Ce-RE′-RE″-enriched phase.
Further, the rare earth diffusion source may be attached by coating, evaporation, electrophoretic deposition, and magnetron sputtering.
Preferably, the RE″ element may be one or two selected from the group consisting of Tb and Dy.
Preferably, the grain boundary diffusion may be conducted at 940° C. to 960° C.
Compared with the prior art, the present disclosure has the following beneficial effects:
1. Due to the presence of REFe2 phase-forming elements such as cerium, the grain boundary phase of magnet includes the REFe2 phase and a small amount of the rare earth-enriched phase, or includes completely the REFe2 phase; since a melting point of the REFe2 phase is higher than that of the rare-earth-enriched phase, common grain boundary diffusion processes have a low diffusion efficiency and a limited increase in the coercivity. In the present disclosure, the grain boundary diffusion is conducted near the melting point of the REFe2 phase, such that all the grain boundary phases are transformed into liquid phases, to improve a diffusion efficiency of rare earth elements in the grain boundary.
2. The magnet after diffusion is directly cooled, or tempered near an eutectic temperature of a Ce-RE′-RE″-Fe phase; a new enhanced REFe2 phase is formed in the cerium magnet, and subjected to interdiffusion with the main phase to a new main phase with a core-shell structure, thus improving coercivity of the grain boundary diffusion cerium-based magnet. A grain boundary diffusion cerium-based magnet with a squareness of not less than 95% can be obtained by optimized diffusion process and tempering process.
3. Rare earth elements capable of grain boundary diffusion are not limited to heavy rare earth elements such as Dy and Tb. The grain boundary diffusion of rare earth elements such as Pr and Nd can improve the coercivity and temperature stability of cerium magnet, thereby preparing SH and UH grades of grain boundary diffusion cerium-based magnets.
4. In the present disclosure, the grain boundary diffusion technology has desirable compatibility with the existing production processes, to rapidly realize batch preparation and production in the existing production lines.
The present disclosure will be further described below in conjunction with the accompanying drawings and examples.
The present disclosure provides a grain boundary diffusion cerium-based magnet containing a REFe2 phase, where an original cerium magnet has a chemical composition of (Cex,RE′1-x)aFe100-a-b-cTMbBc, x is greater than or equal to 20 wt. % and less than or equal to 85 wt. %, a is greater than or equal to 28 and less than or equal to 35, b is greater than or equal to 0 and less than or equal to 10, and c is greater than or equal to 0.9 and less than or equal to 1.5; TM is one or more selected from the group consisting of Co, Al, Cu, Ga, Nb, Mo, Ti, Zr, and V; the original cerium magnet is prepared by sintering or hot pressing, and includes a 2-14-1 main phase, the REFe2 phase, and a rare earth-enriched phase; the REFe2 phase is selected from the group consisting of a CeFe2 phase or a (Ce,RE′)Fe2 phase, and RE′ is one or more selected from the group consisting of La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y. An RE″ element of a rare earth diffusion source is diffused into the original cerium magnet through the grain boundary diffusion at a melting point of the REFe2 phase as a diffusion temperature; a treated original cerium magnet is directly cooled to room temperature or cooled to room temperature after tempering to obtain a final cerium magnet; and the final cerium magnet includes a new 2-14-1 main phase, a new enhanced REFe2 phase, and a new rare earth-enriched phase; the new 2-14-1 main phase is selected from the group consisting of a (Ce,RE″)2Fe14B main phase and a (Ce,RE′, RE″)2Fe14B main phase, the new enhanced REFe2 phase is selected from the group consisting of a (CeRE″)Fe2 phase and a (Ce,RE′,RE″)Fe2 phase; and RE″ is one or more selected from the group consisting of La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.
A rare earth diffusion source containing RE″ element is attached on a surface of the original cerium magnet; according to a type of the diffusion source-contained RE″, the grain boundary diffusion is conducted at a melting point 850° C. to 1,000° C. of the REFe2 phase for 0.1 to 48 h, such that the RE″ element is diffused into the original cerium magnet along a channel of the CeFe2 phase and a Ce-RE′-Fe liquid phase generated by a reaction of the CeFe2 phase with a RE′-enriched phase, to form a (CeRE″)Fe2 phase and a Ce-RE′-RE″-Fe phase; and tempering is conducted at an eutectic temperature 400° C. to 700° C. of the Ce-RE′-RE″-Fe phase for 0.5 h to 12 h, followed by cooling to room temperature to form a new enhanced (CeRE″)Fe2 phase+Ce-RE″-enriched phase; alternatively,
the RE″ element is diffused into the original cerium magnet along a channel of a (Ce,RE′)Fe2 phase and the Ce-RE′-Fe liquid phase generated by a reaction of a (Ce,RE′)Fe2 phase with the RE′-enriched phase, to form a (Ce,RE′,RE″)Fe2 phase and the Ce-RE′-RE″-Fe phase; and tempering is conducted at an eutectic temperature 400° C. to 700° C. of the Ce-RE′-RE″-Fe phase for 0.5 h to 12 h, followed by cooling to room temperature to form a new enhanced (Ce,RE′,RE″)Fe2 phase+Ce-RE′-RE″-enriched phase; where
and RE″ is one or more selected from the group consisting of La, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y.
When an anisotropy field of RE″2Fe14B phase is larger than that of Ce2Fe14B or (Ce,RE′)2Fe14B phase, the RE″ element has an enhancing effect on the grain boundary, and is subjected to interdiffusion with the main phase to form a new main phase with a core-shell structure, thereby enhancing the coercivity of grain boundary diffusion cerium-based magnet.
The rare earth diffusion source is attached by, but not limited to coating, evaporation, electrophoretic deposition, and magnetron sputtering.
The rare earth diffusion source is selected from the group consisting of, but not limited to a rare earth metal, a rare earth hydride, a rare earth fluoride, a rare earth oxide, and a rare earth alloy.
An original cerium magnet was a 38M cerium magnet with a Ce content accounting for 20 wt % of a total amount of rare earths, and having an alloy composition of (Ce0.2Nd0.7Ho0.1)31.5Fe66.5B1.0Co0.4Cu0.2Al0.2Nb0.2.
(1) Metal Tb was roughly crushed, and subjected to hydrogen decrepitation to obtain TbH3; and the TbH3 was ball-milled for 12 h under the protection of ethanol to obtain a diffusion source slurry, where the ethanol to the TbH3 had a mass ratio of 1:1.
(2) The original 38M cerium magnet was cut into a Φ10*5 mm3 cylinder, oil stains on a surface of the magnet was washed off, and an oxide layer on the surface was removed use sandpapers.
(3) The diffusion source slurry mixed by TbH3 and ethanol was coated on the surface of the cylindrical magnet to obtain a diffusion source-attached magnet.
(4) The diffusion source-attached cerium magnet was diffused for 10 h near a melting point (940° C.) of a (Ce,Nd,Ho)Fe2 phase.
(5) A diffused magnet was tempered at 500° C. for 2 h to obtain a grain boundary diffusion cerium-based magnet containing a (Ce,Nd,Ho,Tb)Fe2 phase.
A magnet of Comparative Example 1 with a same composition of magnet and a heavy rare earth coating was subjected to grain boundary diffusion at 840° C. for 10 h, and then tempered at 500° C. for 2 h.
The properties of the original cerium magnet and the magnets in Comparative Example 1 and Example 1 were listed in Table 1. The original cerium magnet has coercivity of 14.19 kOe; in Comparative Example 1, the magnet subjected to conventional grain boundary diffusion at 840° C./10 h has coercivity increased by 5.20 kOe; in Example 1, the magnet has coercivity increased by 7.38 kOe after the grain boundary diffusion at 940° C./10 h, reaching 21.57 kOe, and remanence does not decrease, which is comparable to that of the conventionally-diffused magnet, meeting requirements of coercivity and magnetic energy product of a 38SH magnet.
An original cerium magnet had a Ce content accounting for 30 wt % of a total amount of rare earths, and an alloy composition of (Ce0.3Nd0.6Gd0.1)31Fe67B1.0Co0.2Cu0.2Al0.4Nb0.2. The magnet had a remanence of 12.18 kGs, coercivity of 11.86 kOe and a magnetic energy product of 34.96 MGOe.
Metal Dy was sputtered on a surface of the above magnet by magnetron sputtering for 40 min; under vacuum conditions, grain boundary diffusion was conducted at 850° C./48 h, tempering was conducted near an eutectic temperature 700° C. of Ce-RE′-Gd for 12 h, followed by rapidly cooling to room temperature to obtain a magnet of Example 2.
The magnet of Comparative Example 2 (with a same composition and coating as Example 2) was treated by grain boundary diffusion at 850° C./48 h, and then tempered conventionally at 520° C. for 12 h.
The properties of the three magnets with different states were listed in Table 2. After a reasonable Dy grain boundary diffusion process, followed by conventional (520° C./12 h) tempering, the magnet has coercivity increased by 3.77 kOe; while the grain boundary diffusion cerium-based magnet tempered at the eutectic temperature (700° C./12 h) of CE-RE′-Gd has coercivity of 1.01 kOe higher than that of the magnets using conventional tempering process, reaching 16.64 kOe, and the magnet has an Hk/Hcj value greater than 95, with its demagnetization curve still maintaining a desirable squareness.
An original cerium magnet had a Ce content accounting for 20 wt % of a total amount of rare earths, and an alloy composition of (Ce0.2Nd0.7Dy0.1)31.5Fe66.5B1.0Co0.3Cu0.2Al0.4. The magnet had a remanence of 12.15 kGs, coercivity of 16.06 kOe and a magnetic energy product of 34.60 MGOe.
A metal Tb powder was sputtered on a surface of the above magnet by spraying; under vacuum conditions, grain boundary diffusion was conducted at 1,000° C./0.1 h, followed by rapidly cooling to room temperature to obtain a magnet of Example 3.
The magnet of Comparative Example 3 (with a same composition and coating as Example 3) was treated by grain boundary diffusion at 840° C./0.1 h.
The properties of the three magnets with different states were listed in Table 3. After diffusing Tb at 1,000° C./0.1 h, the magnet has coercivity reaching 18.26 kOe, which is 2.20 kOe higher than that of the original magnet. Although a diffusion time in this example is short, since a diffusion temperature is high, and the rare earth-enriched phase and the REFe2 phase each are liquid, the heavy rare earth Tb can rapidly enter the magnet by grain boundary diffusion at high temperature, thereby enhancing the coercivity. In the magnet of Comparative Example 3, since there is a low diffusion temperature, and only the rare earth-enriched phase is liquid, there is little diffusion of heavy rare earth into the magnet, resulting in coercivity only slightly increased by 0.36 kOe.
A high-cerium magnet with a Ce content of up to 85 wt. % was prepared without PrNd elements, where the magnet had an alloy composition of (Ce0.85Nd0.15)32.3Fe65.5B1.3Co0.2Al0.3Cu0.2Zr0.2, and all grain boundary phases each were a (Ce,Nd)Fe2 phase. Metal Dy was sputtered on a surface of the above magnet by magnetron sputtering for 60 min; under vacuum conditions, grain boundary diffusion was conducted at 940° C. for 10 h (since there was a high Ce content, resulting in a decreased melting point of the (Ce,Nd)Fe2 phase); and tempering was conducted at 400° C./0.5 h to obtain a magnet of Example 4. As shown in Table 4, after grain boundary diffusion at 940° C./10 h and tempering at 400° C./0.5 h, the high-Ce magnet has coercivity increased from 2.37 kOe to 6.53 kOe, with an increasing rate of 175%; and the magnet has a significantly improved magnetic energy product, as well as squareness increased from 84% to about 90%.
The above description of the embodiments is intended to facilitate a person of ordinary skill in the art to understand and use the disclosure. Obviously, a person skilled in the art can easily make various modifications to these examples, and apply a general principle described herein to other examples without creative efforts. Therefore, the present disclosure is not limited to the aforementioned examples. All improvements and modifications made by those skilled in the art according to the principle of the present disclosure without departing from the scope of the present disclosure should fall within the protection scope of the present disclosure.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201910434469.9 | May 2019 | CN | national |
This application is a national stage application, filed under 35 U.S.C. § 371, of International Application No. PCT/CN2020/085835, filed Apr. 21, 2020, which claims priority to Chinese Application No. 201910434469.9, filed May 23, 2019, the contents of both of which as are hereby incorporated by reference in their entirety.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CN2020/085835 | 4/21/2020 | WO |
