(19)
(11)EP 3 438 997 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
04.11.2020 Bulletin 2020/45

(21)Application number: 17852382.5

(22)Date of filing:  21.09.2017
(51)International Patent Classification (IPC): 
H01F 41/02(2006.01)
H01F 1/057(2006.01)
(86)International application number:
PCT/CN2017/102605
(87)International publication number:
WO 2018/054314 (29.03.2018 Gazette  2018/13)

(54)

METHOD FOR GRAIN BOUNDARY DIFFUSION OF R-FE-B RARE EARTH SINTERED MAGNETS, HRE DIFFUSION SOURCE AND PREPARATION METHOD THEREFOR

VERFAHREN ZUR KORNGRENZENDIFFUSION VON R-FE-B-SELTENERDSINTERMAGNETEN, HRE-DIFFUSIONSQUELLE UND HERSTELLUNGSVERFAHREN DAFÜR

PROCÉDÉ DE DIFFUSION DE LIMITE DE GRAIN D'AIMANTS FRITTÉS DE TERRES RARES R-FE-B, SOURCE DE DIFFUSION HRE ET SON PROCÉDÉ DE PRÉPARATION


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 26.09.2016 CN 201610850051

(43)Date of publication of application:
06.02.2019 Bulletin 2019/06

(73)Proprietors:
  • Xiamen Tungsten Co., Ltd.
    Huli District Xiamen Fujian 361009 (CN)
  • Fujian Changting Golden Dragon Rare-Earth Co., Ltd.
    Changting Fujian (CN)

(72)Inventors:
  • LIN, Yulin
    Xiamen Fujian 361015 (CN)
  • NAGATA, Hiroshi
    Akiruno Tokyo 81-197-0825 (JP)
  • LIAO, Zongbo
    Xiamen Fujian 361015 (CN)
  • XIE, Juhua
    Xiamen Fujian 361015 (CN)
  • YE, Hanshen
    Xiamen Fujian 361015 (CN)

(74)Representative: Keenway Patentanwälte Neumann Heine Taruttis 
PartG mbB Postfach 10 33 63
40024 Düsseldorf
40024 Düsseldorf (DE)


(56)References cited: : 
CN-A- 1 806 299
CN-A- 103 985 535
JP-A- 2012 169 436
CN-A- 103 985 534
CN-A- 104 299 744
US-A1- 2011 189 498
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    TECHNICAL FIELD



    [0001] The present invention relates to the technical field of magnet manufacturing, in particular to a grain boundary diffusion method of R-Fe-B series rare earth sintered magnet, an HRE diffusion source, and a preparation method thereof.

    BACKGROUND



    [0002] Coercivity (Hcj), which improves the demagnetization resistance of magnets, is the most important technical parameter of rare earth sintered magnets (such as Nd-Fe-B sintered magnets). In traditional methods, the coercivity of Nd-Fe-B sintered magnets is improved mainly through the following methods: 1) adding heavy rare earth elements (hereafter referred to as HRE, HREE, Heavy Rare Earth, or Heavy Rare Earth Elements) in the manufacturing process of Nd-Fe-B sintered magnets; 2) adding trace elements to optimize the grain boundary structure and refine particles, but this method increases the non-magnetic phase content in the magnets and decreases Br; and 3) performing HRE grain boundary diffusion treatment on Nd-Fe-B sintered magnets. In both method 1) and method 3), HRE is used to partially replace or fully replace Nd in Nd2Fe14B grains to increase the coercivity. Of the two methods, method 3) is better for efficiency and economy.

    [0003] In method 1), during sintering, HRE (including Tb, Dy, or the like) diffuses into grain boundaries and enters Nd2Fe14B grains to a depth of about 1-2 µm, and the coercivity increases. Because the anisotropic fields of Dy2Fe14B, Tb2Fe14B, and the like are smaller than the anisotropic field of Nd2Fe14B, the residual magnetism of the sintered magnets drops to a greater extent.

    [0004] In method 3), a machined magnet is heated so that the Nd-rich phase of the grain boundary forms a liquid phase; heavy rare earth elements such as Dy and Tb seep from the surface of the magnet to perform grain boundary diffusion; the grains in the surface area of the magnet form a core-shell structure, and the coercivity increases. As HRE (including Dy, Tb, or the like) only enters the grains to a depth of about 5 nm, the drop of the residual magnetism of the magnet can be controlled to a certain limit (around 0.3 kGs). Conversion of CGS to SI: 1kGs = 0.1T, IkOe = 79.6kA/m, 1MGOe = 7.96kJ/m3.

    [0005] However, because both method 1) and method 3) use HRE to replace Nd in Nd2Fe14B grains, the saturated magnetic polarization intensity of the compound is reduced. As long as the method described above is used to increase the coercivity, the loss of the residual magnetism is inevitable. Methods for treating R-Fe-B magnets are known from JP 2012 169 436 A and CN 104 299 704 A.

    SUMMARY



    [0006] The purpose of the present invention is to overcome the deficiency in the prior art and provide a grain boundary diffusion method of a rare earth sintered magnet. The method can reduce the consumption of heavy rare earth elements and control the loss of the residual magnetism Br when the coercivity is increased.

    [0007] The technical solution adopted by the present invention to solve the technical problem in the field is as follows:
    According to a 1st main aspect specified in claim 1, a grain boundary diffusion method of an R-Fe-B series rare earth sintered magnet is provided, comprising the following steps: method step A of forming a dry layer on a high-temperature-resistant carrier, the dry layer being adhered with HRE compound powder and a film-forming agent, the HRE being at least one selected from a group consisting of Dy, Tb, Gd, or Ho; and method step B of performing heat treatment on the R-Fe-B series rare earth sintered magnet and the high-temperature-resistant carrier treated with the method step A in a vacuum or inert atmosphere and supplying HRE to a surface of the R-Fe-B series rare earth sintered magnet.

    [0008] In the present invention, the dry layer adhered with the HRE compound is formed on the high-temperature-resistant carrier to prepare the HRE diffusion source, which is then diffused toward the rare-earth sintered magnet. This method can reduce the surface area of HRE compound and adjust its diffusion mode and speed, thereby improving the diffusion efficiency and quality. Further, by changing the shape of the high-temperature-resistant carrier, the present invention can obtain any arbitrary-shape of HRE diffusion source corresponding to the shape of a non-planar magnet such as an arch magnet or an annular magnet such that the diffusion distance from the HRE diffusion source to the non-planar magnet also becomes controllable. A magnet with increased Hcj (coercivity) and SQ (squareness) that does not decrease sharply is then obtained.

    [0009] Another purpose of the present invention is to provide an HRE diffusion source.

    [0010] According to a second main aspect specified in claim 16, an HRE diffusion source comprises the following structure: a dry layer formed on a high-temperature-resistant carrier, the dry layer being adhered with HRE compound powder and a film-forming agent, and the HRE being at least one selected from a group consisting of Dy, Tb, Gd, or Ho.

    [0011] In the recommended implementation, the HRE diffusion source is a primary diffusion source. After configuring the HRE diffusion source to be a primary diffusion source, the control of the diffusion temperature and diffusion time can be adjusted to be less strict; Even when the diffusion temperature increases and diffusion time is prolonged, the consistency of the performance of magnets in different batches will not be affected.

    [0012] The diffusion mode of the HRE diffusion source provided by the present invention is different from the existing mode where the rare earth sintered magnet is embedded into the HRE compound. In the process of embedding the rare earth sintered magnet into the HRE compound, the six sides of the magnet contact the HRE diffusion source, resulting in a rapid decrease in Br. The HRE diffusion source provided by the present invention can provide a uniform evaporative supply surface, stably providing atoms to the corresponding receiving surface (e.g., an orientation surface of the magnet). Such a design can control the amount of the diffused HRE compound and the diffusion position and speed to a great extent for accurate and efficient diffusion.

    [0013] The diffusion mode of the HRE diffusion source provided by the present invention is also different from the mode of spraying the HRE diffusion source solution directly onto the rare earth sintered magnet. During the process of spraying the HRE diffusion source solution onto the rare earth sintered magnet, the magnet needs to be flipped. All six sides of the magnet contacting the HRE diffusion source results in a rapid decrease in Br in the diffusion process, which, at the same time, leads to the additional consumption of the HRE diffusion source on non-orientation sides. After the diffusion is done, an additional grinding process needs to be performed on the six sides. However, the HRE diffusion source provided by the present invention does not require the above process because the diffusion process is controllable and efficient.

    [0014] Another purpose of the present invention is to provide a method for preparing an HRE diffusion source.

    [0015] According to a 3rd main aspect specified in claim 17, a method for preparing an HRE diffusion source comprises the following steps:
    1. 1) taking HRE compound powder, adding therein a first organic solvent until the powder is immersed, and fully grinding to obtain ground powder or ground fluid;
    2. 2) adding a film-forming agent into a second organic solvent and preparing second organic solvent solution of the film-forming agent;
    3. 3) adding the ground powder or the ground fluid into the second organic solvent solution according to a weight ratio (0.01-0.1):0.9 of the film-forming agent to the HRE compound powder, and performing uniform mixing to obtain mixed liquid; and
    4. 4) selecting a high-temperature-resistant carrier, spraying the mixed liquid onto a surface of the high-temperature-resistant carrier and performing drying.


    [0016] In the recommended implementation, the first organic solvent and the second organic solvent are water and/or ethanol. Water and ethanol are environmentally friendly materials that do not cause harm to the environment.

    [0017] It needs to be stated that any numerical range disclosed in the present invention includes all points in the range.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0018] 

    FIG. 1 is a structural schematic view of a film covered W plate of Embodiment 1;

    FIG. 2 is a schematic view of a diffusion process in Embodiment 1;

    FIG. 3 is a structural schematic view of a film covered zirconia plate of Embodiment 2;

    FIG. 4.1 is a schematic view of a diffusion process in Embodiment 2;

    FIG. 4.2 is a schematic view of a diffusion process in comparative example 2.1 and comparative example 2.2;

    FIG. 4.3 is a schematic view of a diffusion process in comparative example 2.3 and comparative example 2.4;

    FIG. 5 is a structural schematic view of a film covered Mo plate of Embodiment 3;

    FIG. 6 is a schematic view of a diffusion process in Embodiment 3;

    FIG. 7 is a structural schematic view of a film covered W plate of embodiment 4;

    FIG. 8 is a schematic view of a diffusion process in Embodiment 4;

    FIG. 9 is a structural schematic view of a film covered W round ball of Embodiment 5;

    FIG. 10 is a schematic view of a diffusion process in Embodiment 5;

    FIG. 11 is a structural schematic view of a film covered Mo plate of Embodiment 6; and

    FIG. 12 is a schematic view of a diffusion process in Embodiment 6.


    DETAILED DESCRIPTION OF THE EMBODIMENTS



    [0019] In the recommended implementation, the R-Fe-B series rare earth sintered magnet and the dry layer on the high-temperature-resistant carrier treated with the method step A and formed as a film are placed in a treatment chamber; and method step B: heat treatment is performed on the R-Fe-B series rare earth sintered magnet and the dry layer on the high-temperature-resistant carrier in a vacuum or inert atmosphere and HRE is supplied from the dry layer on the high-temperature-resistant carrier to a surface of the R-Fe-B series rare earth sintered magnet.

    [0020] In the recommended implementation, the atmospheric pressure of the treatment chamber is below 0.05 MPa. In the case where the diffusion atmosphere is controlled to be a vacuum environment, two diffusion modes exist: one is direct contact diffusion and the other is steam diffusion, so as to improve the diffusion efficiency.

    [0021] In the recommended implementation, in the method step B, the dry layer adhered with the HRE compound formed on the high-temperature-resistant carrier and the R-Fe-B series rare earth sintered magnet are placed in a contact manner or in a non-contact manner, and when the dry layer and the R-Fe-B series rare earth sintered magnet are placed in a non-contact manner, an average spacing therebetween is set to be below 1 cm. When placed in a contact manner, the speed that the HRE compound enters the rare earth sintered magnet is fast; but surface treatment is needed. When placed in a non-contact manner, the HRE compound is diffused in a steaming process; the speed of entering the rare earth sintered magnet is decreased and the surface treatment process can be skipped; at the same time, a steam concentration gradient is formed and high-efficiency diffusion is achieved.

    [0022] In the recommended implementation, in the method step B, when the dry layer adhered with the HRE compound and R-Fe-B series rare earth sintered magnet are placed in a non-contact manner, the atmospheric pressure of the treatment chamber is below 1000 Pa. When placed in a non-contact manner, the pressure of the treatment chamber can be reduced with the diffusion efficiency being improved. The vacuum atmosphere facilitates the formation of the stream concentration gradient and the diffusion efficiency is therefore improved.

    [0023] In the recommended implementation, in the method step B, when the dry layer adhered with the HRE compound powder and R-Fe-B series rare earth sintered magnet are placed in a non-contact manner, the atmospheric pressure of the treatment chamber is preferably below 100 Pa.

    [0024] In the recommended implementation, the dry layer is a film. The film adhered with the HRE compound powder according to the present invention refers to a film in which the HRE compound powder is fixed; the film refers not simply to a continuous film but it may also be a discontinuous film. Therefore, it needs to be stated that both the continuous film and the discontinuous film should be within the scope of the present invention.

    [0025] In the recommended implementation, a heat treatment temperature of the method step B is a temperature below a sintering temperature of the R-Fe-B series rare earth sintered magnet.

    [0026] In the recommended implementation, in the method step B, the R-Fe-B series rare earth sintered magnet and high-temperature-resistant carrier treated with the method step A are heated for 5-100h in an environment of 800 °C-1020 °C. In the above-mentioned method step, higher diffusion temperatures can be used to reduce diffusion time, thereby reducing energy consumption.

    [0027] In the recommended implementation, the dry layer is a uniformly distributed film and a thickness thereof is below 1 mm. Controlling the thickness of the dry layer prevents chapping or rupture from happening, even in the case where the film-forming agent and the HRE compound powder are poorly selected.

    [0028] In the recommended implementation, at least two dry layers are formed on the high-temperature-resistant carrier, and every two adjacent dry layers are uniformly distributed on the high-temperature-resistant carrier at a spacing of below 1.5 cm.

    [0029] In the recommended implementation, a binding force between the dry layer and the high-temperature-resistant carrier is level 1, level 2, level 3, or level 4. When the binding force between the high-temperature-resistant carrier and the dry layer is too low, the adhesive force of the dry layer to the high-temperature-resistant carrier is not strong, which may lead to the dry layer being slightly detached or slightly agglomerated during the heating process.

    [0030] A binding force test method adopted in the present invention is as follows: eleven cutting lines at a spacing of 5 mm are cut in a direction parallel with the length-width direction of the same length-width surface of the high-temperature-resistant carrier formed with the dry layer by adopting a single-edge cutting tool with a cutting edge angle of 30° and a cutting edge thickness of 50-100 µm. During cutting, the angle between the cutter and the high-temperature-resistant carrier needs to be consistent; the force is uniformly applied. The cutting edge exactly passes through the dry layer and touches the substrate during cutting. Inspection results are as shown in Table 1.
    Table 1 Inspection result grading table
    GradingDescription
    0 The cutting edges are completely smooth without any detached
    1 A small flaking of the dry layer at a plating layer is seen at the cutting intersections, but the cross-cut area is affected significantly not greater than 5%.
    2 The dry layer is detached at the cutting edge or cutting intersection, and the percentage of the affected area is significantly greater than 5% but is significantly not greater than 15%.
    3 The dry layer is partially or completely detached along the cutting edge in the form of large debris, or partially or completely detached at different positions of grids, and the percentage of the affected area is significantly greater than 15% but is significantly not greater than 35%.
    4 The dry layer is completely detached along the cutting edge in the form of large debris, or some grids are partially or completely detached; and the percentage of the affected area is significantly greater than 35% but is significantly not greater than 65%.
    5 Severe detachment higher than level 4


    [0031] In the recommended implementation, the dry layer adhered with the HRE compound powder further comprises a film-forming agent capable of being removed for at least 95wt% in step B, and the film-forming agent is at least one selected from a group consisting of resins, cellulose, fluorosilicone polymers, dry oil, or water glass.

    [0032] In the invention, the dry layer adhered with the HRE compound powder consists of a film-forming agent and HRE compound powder.

    [0033] In an implementation not belonging to the invention, the dry layer adhered with the HRE compound powder is electrostatically adsorbed HRE compound powder. In the process of electrostatic adsorption, no film forming agent and other impurities are added, so that the HRE compound can be recovered directly and reused after the diffusion is complete.

    [0034] In the recommended implementation, the high-temperature-resistant carrier is at least one selected from a group consisting of high-temperature-resistant particle, high-temperature-resistant net, high-temperature-resistant plate, high-temperature-resistant strip, or high-temperature-resistant bodies in other shapes.

    [0035] In the recommended implementation, the high-temperature-resistant carrier is made of a material selected from a group consisting of zirconia, alumina, yttrium oxide, boron nitride, silicon nitride and silicon carbide, or a metal selected from a group consisting of Mo, W, Nb, Ta, Ti, Hf, Zr, Ti, V, Re of group IVB, VB, VIB, or VIIB in Periodic Table or made of alloy of the above materials. The high-temperature-resistant carrier made from the above-mentioned material is not deformed at high temperature, can maintain the same diffusion distance and prevent the deformation of the rare earth sintered magnet when the above-mentioned high-temperature-resistant carrier and the rare earth sintered magnet are stacked.

    [0036] In the recommended implementation, the HRE compound powder is powder of at least one selected from a group consisting of HRE oxide, HRE fluoride, HRE chloride, HRE nitrate, or HRE oxyfluoride, and a particle size of the power is below 200 micrometers.

    [0037] In the recommended implementation, in the dry layer adhered with the HRE compound, the amount of HRE oxide, HRE fluoride, HRE chloride, HRE nitrate, and HRE oxyfluoride is more than 90 wt%. Increasing the amount of HRE oxides, HRE fluoride, HRE chloride, HRE nitrate and HRE oxyfluoride can appropriately increase the diffusion efficiency.

    [0038] In the recommended implementation, a thickness of the R-Fe-B series rare earth sintered magnet along a magnetic orientation direction thereof is below 30 mm. The grain boundary diffusion method provided in the present invention can greatly enhance the properties of the rare earth sintered magnet with the maximum thickness of 30 mm.

    [0039] In the recommended implementation, the R-Fe-B series rare earth sintered magnet takes R2Fe14B crystallized grains as a main phase, wherein R is at least one selected from a group consisting of rare earth elements including Y and Sc, wherein an amount of Nd and/or Pr is above 50 wt% of an amount of R.

    [0040] In the recommended implementation, components of the R-Fe-B series rare earth sintered magnet comprise M, and M is at least one selected from a group consisting of Co, Bi, Al, Cu, Zn, In, Si, S, P, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, Ta, or W.

    [0041] In the recommended implementation, a heat treatment process is further performed on the R-Fe-B series rare earth sintered magnet after the method step B. After the heat treatment process, the magnetic performance and consistency of the rare earth sintered magnet can be improved.

    [0042] The present disclosure is further described in detail in conjunction with examples hereinafter.

    Example 1



    [0043] 

    Step a: TbF3 powder with an average grain size of 10 micrometers was taken; water was added therein until the TbF3 powder was immersed; and the mixture was placed in a ball mill for grinding for 5 hours to obtain ground powder.

    Step b: cellulose was added into water to prepare an aqueous solution of cellulose with a concentration of 1 wt%.

    Step c: the ground powder obtained in step a was added into the aqueous solution obtained in step b according to a weight ratio 1:9 of cellulose to TbF3 powder. And performing uniform mixing to obtain mixed liquid.

    Step d: a W plate 11 with a length and width of 10 cm x 10 cm and a thickness of 0.5 mm was taken and placed into an oven for heating until the temperature reached 80 °C and then was removed from the oven; the above-mentioned mixed liquid was uniformly sprayed onto the surface of the above-mentioned W plate; and then the W plate was placed into the oven again for drying to obtain a film covered W plate, wherein the film was adhered with TbF3 powder.



    [0044] The operation of step d was repeated on the other side surface of the film covered W plate to obtain a film covered W plate 1 with the same film thickness on each side, as illustrated in FIG 1.

    [0045] The above-mentioned operation was repeated to obtain W plates with different film thickness (film thickness is as shown in Table 2).

    [0046] After the binding force test, as shown in Table 2, in Embodiment 1.1, Embodiment 1.2, Embodiment 1.3 and Embodiment 1.4, the binding force between the film 12 and the W plate 11 is below Grade 4; and in Embodiment 1.5 and Embodiment 1.6, the binding force between the film 12 and the W plate 11 is Grade 5.

    Embodiment 1.1 -Embodiment 1.6:



    [0047] A rare earth magnet sintered body was prepared. The sintered body had the following atomic components: 14.7 of Nd, 1 of Co, 6.5 of B, 0.4 of Cu, 0.1 of Mn, 0.1 of Ga, 0.1 of Zr, 0.3 of Ti and balance of Fe. Preparation was performed according to the existing processes of smelting, casting, hydrogen decrepitation, jet milling, pressing, sintering, and heat treatment of rare earth magnets.

    [0048] The sintered body obtained after the heat treatment was processed into a magnet with a size of 15 mm×15 mm×30 mm, with the direction of 30 mm being the orientation direction of the magnetic field; and the processed magnet was subjected to sand blasting, purging, and surface cleaning. The magnet was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China.

    [0049] The determination temperature was 20 °C, and the determination results are as follows: Br: 13.45 kGs, Hcj: 19.00 kOe, (BH)max: 42.41 MGOe, SQ: 98.8%, and Hcj standard deviation value: 0.1.

    [0050] As illustrated in FIG. 2, the magnet 6 and the film covered W plate 1 were stacked in the magnet orientation direction, and diffusion heat treatment was performed for 30 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.

    Comparative Example 1.1-Comparative Example 1.5:



    [0051] 

    Step a: TbF3 powder with an average grain size of 10 micrometers was taken; water was added therein until the TbF3 powder was immersed; and the mixture was placed in a ball mill for grinding for 5 hours to obtain ground powder.

    Step b: cellulose was added into water to prepare an aqueous solution of cellulose with a concentration of 1 wt%.

    Step c: the ground powder obtained in step a was added into the aqueous solution obtained in step b according to a weight ratio 1:9 of cellulose to TbF3 powder. And performing uniform mixing to obtain mixed solution.

    Step d: mixed solution obtained in step c in an amount equivalent to that of Embodiment 1.1, Embodiment 1.2, Embodiment 1.3, Embodiment 1.4, and Embodiment 1.5 was taken; the above-mentioned mixed solution was uniformly and comprehensively spray-coated onto the above-mentioned magnet; the coated magnet was dried in an 80 °C environment; and diffusion heat treatment was performed for 30 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.



    [0052] The magnet after diffusion was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C.

    Comparative Example 2:



    [0053] Cellulose and TbF3 powder (with average grain size of 10 micrometers) were taken according to a weight ratio of 1:9 and were pressed to obtain a pressed block with a thickness of 0.6 mm. The magnet and the pressed block were stacked in the magnet orientation direction, and diffusion heat treatment was performed for 30 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.

    [0054] The performance evaluation for magnets in Embodiments and Comparative Examples is shown in Table 2.
    Table 2 Performance Evaluation for Magnets in Embodiments and Comparative Examples
    No.Film thickness (mm)Br (kGs)Hcj (kOe)(BH)max (MGOe)SQ (%)Hcj Standard Deviation
    Embodiment 1.1 0.2 13.30 21.24 43.00 92.3 0.42
    Embodiment 1.2 0.4 13.31 23.29 42.98 91.9 0.35
    Embodiment 1.3 0.6 13.29 24.68 42.78 93.4 0.32
    Embodiment 1.4 0.8 13.20 25.50 42.26 92.3 0.28
    Embodiment 1.5 1 13.13 27.29 41.93 93.5 0.25
    Embodiment 1.6 1.2 13.06 27.68 41.38 94.4 0.34
    Comparative Example 1.1 0.2 13.29 20.73 42.75 92.8 1.12
    Comparative Example 1.2 0.4 13.04 21.30 41.33 93.1 1.03
    Comparative Example 1.3 0.6 12.87 22.42 40.65 89.5 0.84
    Comparative Example 1.4 0.8 12.78 23.83 39.82 90.7 0.78
    Comparative Example 1.5 1 12.56 24.29 38.36 81.2 0.62
    Comparative Example 2: 0.6 12.84 20.11 40.11 93.9 1.33


    [0055] In the implementations of Embodiment 1.1, Embodiment 1.2, Embodiment 1.3, Embodiment 1.4, Embodiment 1.5, and Embodiment 1.6, spraying and drying of the mixed solution were performed on the W plate. Therefore, in Embodiment 1.1, Embodiment 1.2, Embodiment 1.3, Embodiment 1.4, Embodiment 1.5, and Embodiment 1.6, oxidization and rusting on the surface of the magnet were not observed. In Comparative Example 1.1, Comparative Example 1.2, Comparative Example 1.3, Comparative Example 1.4, and Comparative Example 1.5, on the other hand, oxidization and rusting on the surface of the magnet were observed.

    [0056] From Comparative Example 1.1 to Comparative Example 1.5 and Embodiment 1.1 to Embodiment 1.6, it can be seen that directly coating the mixed solution onto the surface of the magnet leads to a decrease of residual magnetism (Br) and a lower increasing trend of the coercivity of the magnet. This is because, when the mixed solution on the magnet surface is dried, the surface nature of the magnet changes, which greatly affects the diffusion effect. The change of the surface nature of the magnet may be due to the grainboundary corrosion caused by the wet heat environment during drying, or it may also be due to the decrease in diffusion efficiency because a film-forming agent fills a diffusion path of the magnet surface when the film-forming agent forms a film thereon.

    [0057] In addition, in the implementations of Comparative Example 1.1 to Comparative Example 1.5, during the process of spraying the HRE diffusion source solution onto the rare earth sintered magnet, the magnet needs to be flipped. All six sides of the magnet contacting the HRE diffusion source results in a rapid decrease in Br in the diffusion process, which, at the same time, leads to the additional consumption of the HRE diffusion source on non-orientation sides. After the diffusion is done, an additional grinding process needs to be performed on the six sides.

    [0058] In Comparative Example 2, the pressed block is constricted during the diffusion process. Thus, the diffusion effect of each magnet is very different.

    Embodiment 2



    [0059] 

    Step a: Dy2O3 powder with an average grain size of 20 micrometers was taken; absolute ethyl alcohol was added therein until the Dy2O3 powder was immersed; and the mixture was placed in a ball mill for grinding for 25h to obtain ground powder.

    Step b: resin was added into the absolute ethyl alcohol to prepare an absolute ethyl alcohol solution of resin with a concentration of 20 wt%.

    Step c: the ground powder obtained in step a was added into the absolute ethyl alcohol solution obtained in step b according to a weight ratio 0.07:1 of resin to Dy2O3 powder. And performing uniform mixing to obtain mixed liquid.

    Step d: a zirconia plate 21 with a length and width of 10 cm × 10 cm and a thickness of 0.5 mm was taken and placed into an oven for heating until the temperature reached 120 °C and then was removed from the oven; the above-mentioned mixed liquid was uniformly sprayed onto the surface of the above-mentioned zirconia plate; and then the zirconia plate was placed into the oven again for drying to obtain a film covered zirconia plate, wherein the film 22 was adhered with Dy2O3 powder.



    [0060] The operation of step d was repeated on the other side surface of the film covered zirconia plate to obtain a film covered zirconia plate 2 with the same film thickness at each side as illustrated in FIG 3. The film thickness was 35 µm,.

    [0061] After the binding force test, the binding force between the film 22 and the zirconia plate 21 is found to be below Grade 4.

    Embodiment 2.1-Embodiment 2.5:



    [0062] A rare earth magnet sintered body was prepared. The sintered body had the following atomic components: 13.6 of Nd, 1 of Co, 6.0 of B, 0.4 of Cu, 0.1 of Mn, 0.2 of Al, 0.1 of Bi, 0.3 of Ti, and balance of Fe. Preparation was performed according to the existing processes of smelting, casting, hydrogen decrepitation, jet milling, pressing, sintering, and heat treatment of rare earth magnets.

    [0063] The sintered body obtained after the heat treatment was processed into a magnet with a size of 15 mm×15 mm×5mm, with the direction of 5mm being the orientation direction of the magnetic field; and the processed magnet was subjected to sand blasting, purging, and surface cleaning. The magnet was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C, and the determination results are as follows: Br: 14.43 kGs, Hcj: 16.27 kOe, (BH)max: 49.86 MGOe, SQ: 91.2%, and Hcj standard deviation value: 0.11.

    [0064] As illustrated in FIG. 4.1, the magnet 7 and the film covered zirconia plate 2 were placed with different distances therebetween in the magnet orientation direction (for the distances, see Table 3); and diffusion heat treatment was performed for 12 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.

    Comparative Example 2.1-Comparative Example 2.4:



    [0065] 

    Comparative Example 2.1: as illustrated in FIG. 4.2, the magnet and the Dy plate 71 with a thickness of 1 mm were placed at a distance of 0.1 cm therebetween in the magnet orientation direction of the magnet 7; and diffusion heat treatment was performed for 24 hours at the temperature of 850 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.

    Comparative Example 2.2: as illustrated in FIG. 4.2, the magnet and the Dy plate 71 with a thickness of 1 mm were placed at a distance of 0.1 cm therebetween in the magnet orientation direction of the magnet 7; and diffusion heat treatment was performed for 12 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.

    Comparative Example 2.3: as illustrated in FIG. 4.3, resin and Dy2O3 powder (with an average grain size of 20 micrometers) were taken according to a weight ratio of 0.07:1, and were pressed to obtain a pressed block with a thickness of 1 mm. The magnet 7 and the pressed block 72 were placed with a distance of 0.1 cm therebetween in the magnet orientation direction; and diffusion heat treatment was performed for 24 hours at the temperature of 850 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.

    Comparative Example 2.4: as illustrated in FIG. 4.3, resin and Dy2O3 powder (with an average grain size of 20 micrometers) were taken according to a weight ratio of 0.07:1, and were pressed to obtain a pressed block with a thickness of 1 mm. The magnet 7 and the pressed block 72 were placed with a distance of 0.1 cm therebetween in the magnet orientation direction; and diffusion heat treatment was performed for 12 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 800 Pa-1000 Pa.



    [0066] The magnet after diffusion was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C.

    [0067] The performance evaluation for magnets in Embodiments and Comparative Examples is shown in Table 3.
    Table 3 Performance Evaluation for Magnets in Embodiments and Comparative Examples
    No.Distance (cm)Br (kGs)Hcj (kOe)(BH)max (MGOe)SQ (%)Hcj Standard Deviation
    Embodiment 2.1 0.1 14.02 24.81 47.78 92.7 0.36
    Embodiment 2.2 0.5 14.11 23.58 48.30 93.3 0.52
    Embodiment 2.3 0.7 14.13 22.56 48.43 92.2 0.82
    Embodiment 2.4 1 14.26 21.45 49.35 92.1 1.13
    Embodiment 2.5 1.5 14.39 20.29 49.98 93.0 1.45
    Comparative Example 2.1 0.1 14.37 19.08 50.10 93.6 0.84
    Comparative Example 2.2 0.1 14.33 20.24 49.92 93.6 0.76
    Comparative Example 2.3 0.1 14.23 18.69 48.85 94.2 1.24
    Comparative Example 2.4 0.1 14.18 19.71 48.65 93.7 1.23


    [0068] In the implementations of Embodiment 2.1, Embodiment 2.2, Embodiment 2.3, Embodiment 2.4, and Embodiment 2.5, spraying and drying of the mixed solution were performed on the zirconia plate. Therefore, in Embodiment 2.1, Embodiment 2.2, Embodiment 2.3, Embodiment 2.4, and Embodiment 2.5, oxidization and rusting on the surface of the magnet were not observed.

    [0069] From the Comparative Examples and the Embodiments, it can be seen that the diffusion efficiency in Embodiment 2.1, Embodiment 2.2, Embodiment 2.3, Embodiment 2.4, and Embodiment 2.5 decreases with the increases of the distance. When the distance is below 1 cm, the influence on the diffusion efficiency is small. In Comparative Example 2.3 and Comparative Example 2.4, the pressed block 72 is constricted in the diffusion process; thus, the diffusion effect of each magnet is very different.

    [0070] Different from the known method of diffusion through direct contact with HRE compound powder, the diffusion is done by using the HRE vapor process (not in direct contact) in Embodiment 2, and good diffusion effects are also achieved.

    Embodiment 3



    [0071] 

    Step a: groups of TbF3 powder with different average grain sizes were taken (as illustrated in FIG. 4); absolute ethyl alcohol was added therein until the TbF3 powder was immersed; and the mixture was placed in a ball mill for grinding for 5 hours to obtain ground powder.

    Step b: dry oil was added into the absolute ethyl alcohol to prepare an absolute ethyl alcohol solution of dry oil with a concentration of 1 wt%.

    Step c: the ground powder obtained in step a was added into the absolute ethyl alcohol solution obtained in step b according to a weight ratio 0.05:1 of dry oil to TbF3 powder. And performing uniform mixing to obtain mixed liquid.

    Step d: a Mo plate 31 with a length and width of 10 cm x 10 cm and a thickness of 0.5 mm was taken and placed into an oven until the temperature reached 100 °C and then was removed from the oven; the above-mentioned mixed liquid was uniformly sprayed onto the surface of one side of the above-mentioned Mo plate; and then the Mo plate was put into the oven again for drying to obtain a film covered Mo plate, wherein the film 32 was adhered with TbF3 powder.



    [0072] The operation of step d was repeated on the other side surface of the film covered Mo plate to obtain a film covered Mo plate 3 with the same film thickness at each side as illustrated in FIG 5. The film thickness was 100 µm,.

    [0073] After the binding force test, the binding force between the film (the average grain size of the TbF3 powder is as shown in Table 4) and the Mo plate is found to be below Grade 4.

    Embodiment 3.1-Embodiment 3.5:



    [0074] A rare earth magnet sintered body was prepared. The sintered body had the following atomic components: 0.1 of Ho, 13.8 of Nd, 1 of Co, 6.0 of B, 0.4 of Cu, 0.1 of Al, 0.2 of Ga, and balance of Fe. Preparation was performed according to the existing processes of smelting, casting, hydrogen decrepitation, jet milling, pressing, sintering, and heat treatment of rare earth magnets.

    [0075] The sintered body obtained after the heat treatment was processed into a magnet with a size of 15 mm×15 mm×10 mm, with the direction of 10 mm being the orientation direction of the magnetic field; and the processed magnet was subjected to sand blasting, purging, and surface cleaning. The magnet was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C, and the determination results are as follows: Br: 14.39 kGs, Hcj: 18.36 kOe, (BH)max: 50.00 MGOe, SQ: 92.9%, and Hcj standard deviation value: 0.13.

    [0076] As illustrated in FIG. 6, the magnet 8 and the film covered Mo plate 3 (the average grain size of TbF3 powder is as shown in Table 4) were stacked in the magnet orientation direction; and diffusion heat treatment was performed for 12 hours at the temperature of 1000 °C in a high-purity Ar gas atmosphere at 1800 Pa-2000 Pa.

    Comparative Example 3.1-Comparative Example 3.4:



    [0077] 

    Comparative Example 3.1: a magnet was embedded in TbF3 powder (with average grain size of 50 micrometers), and diffusion heat treatment was performed for 24 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 1800 Pa-2000 Pa.

    Comparative Example 3.2: a magnet was embedded in TbF3 powder (with average grain size of 50 micrometers), and diffusion heat treatment was performed for 12 hours at the temperature of 1000 °C in a high-purity Ar gas atmosphere at 1800 Pa-2000 Pa.

    Comparative Example 3.3: a Tb film was electro-deposited on the above-mentioned magnet (the thickness of Tb electroplating layer: 100 µm); and diffusion heat treatment was performed for 24 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 1800 Pa-2000 Pa.

    Comparative Example 3.4: a Tb film was electro-deposited on the above-mentioned magnet (the thickness of Tb electroplating layer: 100 µm); and diffusion heat treatment was performed for 12 hours at the temperature of 1000°C in a high-purity Ar gas atmosphere at 1800 Pa-2000 Pa.



    [0078] The magnet after diffusion was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C.

    [0079] The performance evaluation for magnets in Embodiments and Comparative Examples is shown in Table 4.
    Table 4 Performance Evaluation for Magnets in Embodiments and Comparative Examples
    No.TbF3 powder average grain size (µm)Br (kGs)Hcj (kOe)(BH)max (MGOe)SQ (%)Hcj Standard Deviation
    Embodiment 3.1 20 14.37 30.12 49.96 92.4 0.28
    Embodiment 3.2 50 14.34 27.97 50.30 94.4 0.55
    Embodiment 3.3 100 14.37 25.38 50.09 93.8 0.72
    Embodiment 3.4 200 14.34 23.13 50.04 93.1 0.84
    Embodiment 3.5 300 14.37 19.90 50.12 90.5 1.33
    Comparative Example 3.1 50 14.16 23.50 48.80 91.7 1.12
    Comparative Example 3.2 50 14.02 24.32 46.80 88.9 1.06
    Comparative Example 3.3 / 14.04 23.42 47.35 88.7 0.82
    Comparative Example 3.4 / 14.03 24.10 47.29 87.5 0.74


    [0080] In the implementations of Embodiment 3.1, Embodiment 3.2, Embodiment 3.3, Embodiment 3.4, and Embodiment 3.5, spraying and drying of the mixed solution were performed on the Mo plate; and therefore, in Embodiment 3.1, Embodiment 3.2, Embodiment 3.3, Embodiment 3.4, and Embodiment 3.5, oxidization and rusting on the surface of the magnet were not observed.

    [0081] From the Comparative Examples and Embodiments, it can be seen that the diffusion effects in Embodiment 3.1, Embodiment 3.2, Embodiment 3.3, Embodiment 3.4, and Embodiment 3.5 are better; Br of the magnet is almostly not decreased; the coercivity is improved significantly and the diffusion effect of each magnet is uniform. In Comparative Example 3.1 and Comparative Example 3.2, the TbF3 powder is not uniformly aggregated in the diffusion process; thus, the diffusion effect of each magnet is very different.

    Embodiment 4



    [0082] 

    Step a: TbCl3 powder with an average grain size of 50 micrometers was taken and added therein with absolute ethyl alcohol to prepare TbCl3 solution.

    Step b: fluorosilicone was added into water to prepare an aqueous solution of fluorosilicone with a concentration of 10 wt%.

    Step c: the solution obtained in step a was added into the aqueous solution obtained in step b according to a weight ratio 0.02:1 of fluorosilicone to TbCl3. And performing uniform mixing to obtain mixed liquid.

    Step d: a W plate 41 with a length and width of 9 cm × 9 cm and a thickness of 0.5 mm was taken and placed into an oven for heating until the temperature reached 80 °C and then was removed from the oven; the W plate 41 was respectively covered with an equally wide obstacle at a distance of 2 cm; the width of the obstacle was as shown in Table 5; the above-mentioned mixed liquid was uniformly sprayed onto the surface of the above-mentioned W plate; and then the W plate was placed into the oven again for drying to strip the obstacle to obtain a film covered W plate with a film 42, wherein the film thickness was 0.5 mm. The film was adhered with TbCl3 powder.



    [0083] The operation of step d was repeated on the other side surface of the film covered W plate to obtain a film covered W plate 4 with the same film thickness on each side, as illustrated in FIG 7.

    Embodiment 4.1-Embodiment 4.5:



    [0084] A rare earth magnet sintered body was prepared. The sintered body had the following atomic components: 0.1 of Pr, 13.7 of Nd, 1 of Co, 6.5 of B, 0.4 of Cu, 0.1 of Al, 0.1 of Ga, 0.3 of Ti, and balance of Fe. Preparation was performed according to the existing processes of smelting, casting, hydrogen decrepitation, jet milling, pressing, sintering, and heat treatment of rare earth magnets.

    [0085] The sintered body obtained after the heat treatment was processed into a magnet with a size of 10 mm×10 mm×20 mm, with the direction of 20 mm being the orientation direction of the magnetic field; and the processed magnet was subjected to sand blasting, purging, and surface cleaning. The magnet was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C, and the determination results are as follows: Br: 14.30 kGs, Hcj: 17.07 kOe, (BH)max: 49.20 MGOe, SQ: 92.2%, and Hcj standard deviation value: 0.22.

    [0086] As illustrated in FIG. 8, the magnet 9 and the film covered W plate 4 were stacked in the magnet orientation direction, and diffusion heat treatment was performed for 6 hours at the temperature of 1020 °C in a high-purity Ar gas atmosphere at 0.05 MPa.

    [0087] The magnet after diffusion was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C.

    [0088] The performance evaluation for magnets in Embodiments is shown in Table 5.
    Table 5 Performance Evaluation for Magnets in Embodiments
    No.Obstacle width (cm)Br (kGs)Hcj (kOe)(BH)max (MGOe)SQ (%)Hcj Standard Deviation
    Embodiment 4.1 0.1 14.27 28.07 49.62 94.0 0.32
    Embodiment 4.2 0.5 14.30 26.16 49.26 93.9 0.43
    Embodiment 4.3 1 14.30 24.07 49.75 94.4 0.54
    Embodiment 4.4 1.5 14.34 22.71 49.75 95.4 0.72
    Embodiment 4.5 2 14.32 19.90 49.82 93.9 1.13


    [0089] It can be seen from the examples that in a step-by-step film forming diffusion mode, when the distance between the films at the two ends is below 1.5 cm, the uniformity of the diffusion effect is not affected, which is possibly because the diffusion speed is not greatly influenced when the diffusion distance fluctuates within the range of about 1.5 cm.

    Embodiment 5



    [0090] 

    Step a: Tb(NO3)3 powder with an average grain size of 80 micrometers was taken and added therein with water to prepare Tb(NO3)3 solution.

    Step b: water glass was added into water to prepare an aqueous solution of water glass with a concentration of 1 wt%.

    Step c: the solution obtained in step a was added into the aqueous solution obtained in step b according to a weight ratio 0.01:0.9 of water glass to Tb(NO3)3 powder. And performing uniform mixing to obtain mixed liquid.

    Step d: a W round ball 51 with a diameter of 0.1 mm-3 mm (with the diameter of the W round ball shown in Table 6) was taken and placed in an oven for heating until the temperature reached 80 °C, and then was removed from the oven; the above-mentioned mixed liquid was uniformly sprayed onto the surface of the above-mentioned W round ball; and the W round ball was placed in the oven again to obtain a film covered W round ball 5, as illustrated in FIG. 9. The thickness of the film 52 is 0.15 mm and the film is adhered with Tb(NO3)3.


    Embodiment 5.1-Embodiment 5.5:



    [0091] A rare earth magnet sintered body was prepared. The sintered body had the following atomic components: 0.1 of Ho, 13.8 of Nd, 1 of Co, 6.0 of B, 0.4 of Cu, 0.1 of Mn, 0.2 of Ga, and balance of Fe. Preparation was performed according to the existing processes of smelting, casting, hydrogen decrepitation, jet milling, pressing, sintering, and heat treatment of rare earth magnets.

    [0092] The sintered body obtained after the heat treatment was processed into a magnet with a size of 10 mm×10 mm×12 mm, with the direction of 12 mm being the orientation direction of the magnetic field; and the processed magnet was subjected to sand blasting, purging, and surface cleaning. The magnet 10 was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C, and the determination results are as follows: Br: 14.39 kGs, Hcj: 18.36 kOe, (BH)max: 50.00 MGOe, SQ: 92.9%, and Hcj standard deviation value: 0.13.

    [0093] As illustrated in FIG. 10, the film covered W round balls 5 are densely arranged and placed on the surface of the magnet 10 in the orientation direction; and diffusion heat treatment was performed for 100 hours at the temperature of 800 °C in a high-purity Ar gas atmosphere at 2800 Pa-3000 Pa.

    [0094] The performance evaluation for magnets in Embodiments is shown in Table 6.
    Table 6 Performance Evaluation for Magnets in Embodiments
    No.W round ball diameter (mm)Br (kGs)Hcj (kOe)(BH)max (MGOe)SQ (%)Hcj Standard Deviation
    Embodiment 5.1 0.1 14.29 28.29 49.46 92.9 0.25
    Embodiment 5.2 0.5 14.32 27.74 49.59 94.2 0.46
    Embodiment 5.3 1 14.32 25.47 49.77 93.7 0.62
    Embodiment 5.4 2 14.31 24.72 49.69 93.4 0.74
    Embodiment 5.5 3 14.34 23.13 50.04 93.1 1.09

    Embodiment 6



    [0095] 

    Step a: different powder with an average grain size of 10 µm was taken (with powder types shown in Table 7); absolute ethyl alcohol was added therein until the TbF3 powder was immersed; and the mixture was placed in a ball mill for grinding for 5h to obtain ground powder.

    Step b: cellulose was added into absolute ethyl alcohol to prepare an absolute ethyl alcohol solution of cellulose with a concentration of 1 wt%.

    Step c: the ground powder obtained in step a was added into the absolute ethyl alcohol solution obtained in step b according to a weight ratio 0.05:1 of cellulose to TbF3 powder. And performing uniform mixing to obtain mixed liquid.

    Step d: a Mo plate 61 with a length and width of 10 cm × 10 cm and a thickness of 0.5 mm was taken and placed into an oven for heating until the temperature reached 100 °C and then was removed from the oven; the above-mentioned mixed liquid was uniformly sprayed onto the surface of one side of the above-mentioned Mo plate; and then the Mo plate was put into the oven again for drying to obtain a film covered Mo plate, wherein the film 62 was adhered with TbF3 powder.



    [0096] The operation of step d was repeated on the other side surface of the film covered Mo plate to obtain a film covered Mo plate 5' with the same film thickness at each side as illustrated in FIG 11. The film thickness was 30 µm,.

    [0097] After the binding force test, the binding force between the film and the Mo plate is found to be below 4.

    Embodiment 6.1-Embodiment 6.4:



    [0098] A rare earth magnet sintered body was prepared. The sintered body had the following atomic components: 0.1 of Ho, 13.8 of Nd, 1 of Co, 6.0 of B, 0.4 of Cu, 0.1 of Al, 0.2 of Ga, and balance of Fe. Preparation was performed according to the existing processes of smelting, casting, hydrogen decrepitation, jet milling, pressing, sintering, and heat treatment of rare earth magnets.

    [0099] The sintered body obtained after the heat treatment was processed into a magnet with a size of 15 mm×15 mm×5 mm, with the direction of 5 mm being the orientation direction of the magnetic field; and the processed magnet was subjected to sand blasting, purging, and surface cleaning. The magnet was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C, and the determination results are as follows: Br: 14.39 kGs, Hcj: 18.36 kOe, (BH)max: 50.00 MGOe, SQ: 92.9%, and Hcj standard deviation value: 0.13.

    [0100] As illustrated in FIG. 12, the magnet 101 and the film covered Mo plate 5' were stacked in the magnet orientation direction, and diffusion heat treatment was performed for 12 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 1800 Pa-2000 Pa.

    [0101] The magnet after diffusion was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C.

    [0102] The performance evaluation for magnets in Embodiments is shown in Table 7.
    Table 7 Performance Evaluation for Magnets in Embodiments
    No.Powder typeBr (kGs)Hcj (kOe)(BH)max (MGOe)SQ (%)Hcj Standard Deviation
    Embodiment 6.1 TbF3 powder 14.24 29.97 49.43 92.3 0.24
    Embodiment 6.2 TbF3:Tb2O3=1:1 14.29 21.47 49.31 89.5 0.84
    Embodiment 6.3 TbF3:TbCu=1:1 14.26 26.57 49.40 91.0 0.62
    Embodiment 6.4 TbF3:Al2O3=1:1 14.27 22.61 49.01 92.9 0.78


    [0103] As can be seen from the Embodiments, different types of powder are used in Embodiment 6.1, Embodiment 6.2, Embodiment6.3, and Embodiment 6.4. The mixed powder easily lead to other reactions and the diffusion effects are relatively poor.

    Embodiment 7



    [0104] 

    Step a: TbF3 powder with an average grain size of 20 micrometers was taken; absolute ethyl alcohol was added therein until the TbF3 powder was immersed; and grinding was performed for 20h to obtain ground powder.

    Step b: resin was added into the absolute ethyl alcohol to prepare an absolute ethyl alcohol solution of resin with a concentration of 20 wt%.

    Step c: the ground powder obtained in step a was added into the absolute ethyl alcohol solution obtained in step b according to a weight ratio 0.07:1 of resin to TbF3 powder. And performing uniform mixing to obtain mixed liquid.

    Step d: a zirconia plate 21 with a length and width of 10 cm x 10 cm and a thickness of 0.5 mm was taken and placed into an oven for heating until the temperature reached 120 °C and then was removed from the oven; the above-mentioned mixed liquid was uniformly sprayed onto the surface of the above-mentioned zirconia plate; and then the zirconia plate was placed into the oven again for drying to obtain a film covered zirconia plate, wherein the film 22 was adhered with TbF3 powder.



    [0105] The operation of step d was repeated on the other side surface of the film covered zirconia plate to obtain a film covered zirconia plate with the same film thickness at each side, and the film thickness was 30 µm.

    [0106] After the binding force test, the binding force between the film and the zirconia plate is found to be below Grade 4.

    Embodiment 7.1-Embodiment 7.5:



    [0107] A rare earth magnet sintered body was prepared. The sintered body had the following atomic components: 13.6 of Nd, 1 of Co, 6.0 of B, 0.4 of Cu, 0.05 of Mn, 0.3 of Al, 0.1 of Bi, 0.3 of Ti, and balance of Fe. Preparation was performed according to the existing processes of smelting, casting, hydrogen decrepitation, jet milling, pressing, sintering, and heat treatment of rare earth magnets.

    [0108] The sintered body obtained after the heat treatment was processed into a magnet with a size of 15 mm× 15 mm×5 mm, with the direction of 5 mm being the orientation direction of the magnetic field; and the processed magnet was subjected to sand blasting, purging, and surface cleaning. The magnet was subjected to magnet performance testing by using the NIM-10000H large rare earth permanent magnet nondestructive testing system of the National Institute of Metrology, China. The determination temperature was 20 °C, and the determination results are as follows: Br: 14.33 kGs, Hcj: 15.64 kOe, (BH)max: 49.25 MGOe, SQ: 89.8%, and Hcj standard deviation value: 0.11.

    [0109] The film covered zirconia plate, a molybdenum net with a thickness of 0.5 mm, the magnet, and a molybdenum net with a thickness of 0.5 mm were sequentially stacked in the magnet orientation direction (atmospheric pressure therebetween are shown in Table 8); and diffusion heat treatment was performed for 12 hours at the temperature of 950 °C in a high-purity Ar gas atmosphere at 10-3 Pa-1000 Pa.
    Table 8 Performance Evaluation for Magnets in Embodiments
    No.Atmospheric pressure (Pa)Br (kGs)Hcj (kOe)(BH)max (MGOe)SQ (%)Hcj Standard Deviation
    Embodiment 7.1 10-3 14.35 28.35 49.47 84.1 0.36
    Embodiment 7.2 10-1 14.28 27.62 49.16 87.3 0.52
    Embodiment 7.3 10 14.32 26.23 49.65 86.7 0.82
    Embodiment 7.4 100 14.33 25.20 49.37 86.7 1.13
    Comparative Example 7.1 1000 14.36 24.08 49.88 89.0 1.52


    [0110] The embodiments described above only serve to further illustrate some particular implementations of the present disclosure; however, the present invention is not limited to these embodiments.


    Claims

    1. A grain boundary diffusion method of an R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101), wherein the method comprises:

    method step A of forming a dry layer (12,22,32,42,52,62) on a high-temperature-resistant carrier (11,21,31,41,51,61), the dry layer (12,22,32,42,52,62) being adhered with HRE compound powder, the HRE being at least one of Dy, Tb, Gd, or Ho, wherein the dry layer (12,22,32,42,52,62) adhered with the HRE compound powder consists of a film-forming agent and HRE compound powder; and

    method step B of performing heat treatment on the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) and the high-temperature-resistant carrier (11,21,31,41,51,61) treated with the method step A in a vacuum or inert atmosphere and supplying HRE to a surface of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101).


     
    2. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein atmospheric pressure of a treatment chamber in which the heat treatment is performed is below 0.05 MPa.
     
    3. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1 or claim 2, wherein in the method step B, the dry layer (12,22,32,42,52,62) adhered with the HRE compound powder formed on the high-temperature-resistant carrier (11,21,31,41,51,61) and the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) are placed in a contact manner or in a non-contact manner, and when the dry layer (12,22,32,42,52,62) and the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) are placed in a non-contact manner, an average spacing therebetween is set to be below 1 cm.
     
    4. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 3, wherein in the method step B, when the dry layer (12,22,32,42,52,62) adhered with the HRE compound powder and R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) are placed in a non-contact manner, atmospheric pressure of a treatment chamber in which the heat treatment is performed is below 1000 Pa.
     
    5. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein the dry layer (12,22,32,42,52,62) is a film.
     
    6. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein in the method step B, the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) and the high-temperature-resistant carrier (11,21,31,41,51,61) treated with the method step A are heated for 5-100h in an environment of 800 °C-1020 °C.
     
    7. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein the dry layer (12,22,32,42,52,62) is a uniformly distributed film and a thickness of the dry layer is below 1 mm.
     
    8. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein at least two dry layers (12,22,32,42,52,62) are formed on the high-temperature-resistant carrier (11,21,31,41,51,61), and every two adjacent dry layers (12,22,32,42,52,62) are uniformly distributed on the high-temperature-resistant carrier (11,21,31,41,51,61) at a spacing of below 1.5 cm.
     
    9. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet according to claim 1, wherein the dry layer adhered with the HRE compound powder further comprises a film-forming agent capable of being removed for at least 95wt% in step B, and the film-forming agent is at least one of resins, cellulose, fluorosilicone polymers, dry oil, or water glass.
     
    10. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein the dry layer (12,22,32,42,52,62) adhered with the HRE compound powder is electrostatically adsorbed HRE compound powder.
     
    11. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet according to claim 1, wherein the high-temperature-resistant carrier is a high-temperature-resistant particle, a high-temperature-resistant net, a high-temperature-resistant plate or a high-temperature-resistant strip, and wherein the high-temperature-resistant carrier is made of a material selected from a group consisting of zirconia, alumina, yttrium oxide, boron nitride, silicon nitride and silicon carbide, and a metal selected from a group consisting of Mo, W, Nb, Ta, Ti, Hf, Zr, Ti, V, Re of group IVB, VB, VIB, and VIIB in Periodic Table or made of alloy of the above materials.
     
    12. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein the HRE compound powder is powder of at least one of HRE oxide, HRE fluoride, HRE chloride, HRE nitrate, or HRE oxyfluoride, and an average particle size of the powder is below 200 micrometers.
     
    13. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 12, wherein in the dry layer adhered with the HRE compound powder, the content of HRE oxide, HRE fluoride, HRE chloride, HRE nitrate, and HRE oxyfluoride is above 90 wt%.
     
    14. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein a thickness of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) along a magnetic orientation direction thereof is below 30 mm.
     
    15. The grain boundary diffusion method of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) according to claim 1, wherein the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) takes R2Fe14B crystallized grains as a main phase, wherein R comprises at least one rare earth element, wherein an amount of Nd and/or Pr is above 50 wt% of an amount of R, wherein components of the R-Fe-B series rare earth sintered magnet (6,7,8,9,10,101) comprise M, and M is at least one of Co, Bi, Al, Ca, Mg, O, C, N, Cu, Zn, In, Si, S, P, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta, or W.
     
    16. An HRE diffusion source (1,2,3,4,5,5'), wherein the HRE diffusion source (1,2,3,4,5,5') comprises: a dry layer (12,22,32,42,52,62) formed on a high-temperature-resistant carrier (11,21,31,41,51,61), the dry layer (12,22,32,42,52,62) being adhered with HRE compound powder, and the HRE being at least one of Dy, Tb, Gd, or Ho, wherein the dry layer (12,22,32,42,52,62) adhered with the HRE compound powder consists of a film-forming agent and HRE compound powder.
     
    17. A method for preparing an HRE diffusion source (1,2,3,4,5,5'), wherein the method comprises:

    1) taking HRE compound powder, adding therein a first organic solvent until the HRE compound powder is immersed, and fully grinding to obtain ground powder or ground fluid;

    2) adding a film-forming agent into a second organic solvent and preparing second organic solvent solution of the film-forming agent;

    3) adding the ground powder or the ground fluid into the second organic solvent solution according to a weight ratio (0.01-0.1):0.9 of the film-forming agent to the HRE compound powder, and performing uniform mixing to obtain mixed liquid; and

    4) selecting a high-temperature-resistant carrier (11,21,31,41,51,61), spraying the mixed liquid onto a surface of the high-temperature-resistant carrier (11,21,31,41,51,61) and performing drying.


     


    Ansprüche

    1. Korngrenzendiffusionsverfahren eines Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101), wobei das Verfahren umfasst:

    Verfahrensschritt A zum Ausbilden einer Trockenschicht (12,22,32,42,52,62) auf einem hochtemperaturbeständigen Träger (11,21,31,41,51,61), wobei die Trockenschicht (12,22,32,42,52,62) mit HRE-Verbindungspulver verklebt wird, wobei das HRE Dy, Tb, Gd und/oder Ho ist, wobei die Trockenschicht (12,22,32,42,52,62), die mit dem HRE-Verbindungspulver verklebt ist, aus einem filmausbildenden Mittel und einem HRE-Verbindungspulver besteht; und

    Verfahrensschritt B zum Durchführen einer Wärmebehandlung des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) und dem hochtemperaturbeständigen Träger (11,21,31,41,51,61), der mit dem Verfahrensschritt A in einem Vakuum oder einer inerten Atmosphäre behandelt wird, und des Zuführen von HRE zu einer Oberfläche des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101).


     
    2. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei der Atmosphärendruck einer Behandlungskammer, in der die Wärmebehandlung durchgeführt wird, unter 0,05 MPa liegt.
     
    3. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1 oder 2, wobei in dem Verfahrensschritt B die Trockenschicht (12,22,32,42,52,62), die mit dem HRE-Verbindungspulver verklebt ist, das auf dem hochtemperaturbeständigen Träger (11,21,31,41,51,61) ausgebildet ist, und der Seltenerdmagneten der Serie R-Fe-B (6,7,8,9,10,101) auf berührbare oder berührungslose Art angebracht angeordnet wird, und wenn die Trockenschicht (12,22,32,42,52,62) und der Seltenerd-Sintermagnet der R-Fe-B-Serie (6,7,8,9,10,101) auf berührungslose Art angeordnet werden, ein durchschnittlicher Abstand unter 1 cm dazwischen eingestellt wird.
     
    4. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 3, wobei in dem Verfahrensschritt B, wenn die Trockenschicht (12,22,32,42,52,62), die mit dem HRE-Verbindungspulver verklebt ist, und der Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9, 10,101) auf berührungslose Art angeordnet sind, der atmosphärische Druck einer Behandlungskammer, in der die Wärmebehandlung durchgeführt wird, unter 1000 Pa liegt.
     
    5. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei die Trockenschicht (12,22,32,42,52,62) ein Film ist.
     
    6. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei in dem Verfahrensschritt B der Seltenerd-Sintermagnet der R-Fe-B-Serie (6,7,8,9,10,101) und der hochtemperaturbeständige Träger (11,21,31,41,51,61), der mit dem Verfahrensschritt A behandelt wird, für 5-100 Std in einer Umgebung von 800 °C-1020 °C erhitzt werden.
     
    7. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei die Trockenschicht (12,22,32,42,52,62) ein gleichmäßig verteilter Film ist, und wobei eine Dicke der Trockenschicht unter 1 mm liegt.
     
    8. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei wenigstens zwei Trockenschichten (12,22,32,42,52, 62) auf dem hochtemperaturbeständigen Träger (11,21,31,41,51,61) ausgebildet werden, und jeweils zwei angrenzende Trockenschichten (12,22,32,42,52,62) auf dem hochtemperaturbeständigen Träger (11,21,31,41,51,61) in einem Abstand von unter 1,5 cm gleichmäßig verteilt sind.
     
    9. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie nach Anspruch 1, wobei die Trockenschicht, die mit dem HRE-Verbindungspulver verklebt ist, ferner ein filmausbildendes Mittel umfasst, das schrittweise für wenigstens 95 Gew.-% in Schritt B entfernt werden kann, und wobei das filmausbildende Mittel Harze, Cellulose, Fluorsilikonpolymere, trockenes Öl und/oder Wasserglas ist.
     
    10. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei die Trockenschicht (12, 22, 32, 42, 52, 62), die mit dem HRE-Verbindungspulver verklebt ist, elektrostatisch adsorbiertes HRE-Verbindungspulver ist.
     
    11. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie nach Anspruch 1, wobei der hochtemperaturbeständige Träger ein hochtemperaturbeständiges Teilchen, ein hochtemperaturbeständiges Netz, eine hochtemperaturbeständige Platte oder ein hochtemperaturbeständiges Band ist, und wobei der hochtemperaturbeständige Träger aus einem Material hergestellt ist, das aus einer Gruppe ausgewählt ist, die aus Zirkonoxid, Aluminiumoxid, Yttriumoxid, Bornitrid, Siliciumnitrid und Siliciumcarbid besteht, und einem Metall, das aus einer Gruppe ausgewählt ist, die aus Mo, W, Nb, Ta, Ti, Hf, Zr, Ti, V, Re der Gruppe IVB, VB, VIB und VIIB des Periodensystems besteht, oder aus einer Legierung der obigen Materialien hergestellt ist.
     
    12. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei das HRE-Verbindungspulver Pulver aus einem HRE-Oxid, HRE-Fluorid, HRE-Chlorid, HRE-Nitrat und/oder HRE-Oxyfluorid ist, und wobei eine durchschnittliche Teilchengröße des Pulvers unter 200 Mikrometer liegt.
     
    13. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 12, wobei in der Trockenschicht, die mit dem HRE-Verbindungspulver verklebt ist, der Gehalt an HRE-Oxid, HRE-Fluorid, HRE-Chlorid, HRE-Nitrat und HRE-Oxyfluorid über 90 Gew.-% liegt.
     
    14. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei eine Dicke des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) entlang einer Magnetorientierungsrichtung davon unter 30 mm liegt.
     
    15. Das Korngrenzendiffusionsverfahren des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) nach Anspruch 1, wobei der Seltenerd-Sintermagnet der R-Fe-B-Serie (6,7, 8,9,10,101) kristallisierte Körner R2Fe14B als Hauptphase nimmt, wobei R wenigstens ein Seltenerdelement umfasst, wobei eine Menge von Nd und/oder Pr über 50 Gew.-% einer Menge von R ist, wobei Komponenten des Seltenerd-Sintermagneten der R-Fe-B-Serie (6,7,8,9,10,101) M umfassen, und wobei M Co, Bi, Al, Ca, Mg, O, C, N, Cu, Zn, In, Si, S, P, Ti, V, Cr, Mn, Ni, Ga, Ge, Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, Hf, Ta und/oder W ist.
     
    16. Eine HRE-Diffusionsquelle (1,2,3,4,5,5'), wobei die HRE-Diffusionsquelle (1,2,3,4,5,5') umfasst: eine Trockenschicht (12,22,32,42,52,62), die auf einem hochtemperaturbeständigen Träger (11,21,31,41,51,61) ausgebildet ist, wobei die Trockenschicht (12,22,32,42,52,62) mit HRE-Verbindungspulver verklebt wird, und die HRE Dy, Tb, Gd und/oder Ho ist, wobei die Trockenschicht (12,22,32,42,52,62), die mit dem HRE-Verbindungspulver verklebt ist, aus einem filmausbildenden Mittel und einem HRE-Verbindungspulver besteht.
     
    17. Ein Verfahren zum Herstellen einer HRE-Diffusionsquelle (1,2,3,4,5,5'), wobei das Verfahren umfasst:

    1) Nehmen von HRE-Verbindungspulver, Hinzufügen eines ersten organischen Lösungsmittels darin, bis das HRE-Verbindungspulver eingetaucht ist, und vollständiges Mahlen, um gemahlenes Pulver oder gemahlenes Fluid zu erhalten;

    2) Hinzufügen eines filmausbildenden Mittels zu einem zweiten organischen Lösungsmittel und Herstellen einer zweiten organischen Lösungsmittellösung des filmausbildenden Mittels;

    3) Hinzufügen des gemahlenen Pulvers oder des gemahlenen Fluids zu der zweiten organischen Lösungsmittellösung gemäß einem Gewichtsverhältnis (0,01-0,1):0,9 des filmausbildenden Mittels zu dem HRE-Verbindungspulver und Durchführen eines gleichmäßigen Mischens, um eine gemischte Flüssigkeit zu erhalten, und

    4) Auswählen eines hochtemperaturbeständigen Trägers (11,21,31,41,51,61), Sprühen der gemischten Flüssigkeit auf eine Oberfläche des hochtemperaturbeständigen Trägers (11,21,31,41,51,61) und Durchführen des Trocknens.


     


    Revendications

    1. Procédé de diffusion de limite de grain d'un aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101), dans lequel le procédé comprend :

    l'étape A du procédé de formation d'une couche sèche (12, 22, 32, 42, 52, 62) sur un support résistant aux températures élevées (11, 21, 31, 41, 51, 61), une poudre composite d'ETR étant fixée à la couche sèche (12, 22, 32, 42, 52, 62), les ETR étant Dy, et/ou Tb, et/ou Gd, et/ou Ho, dans lequel la poudre composite d'ETR fixée à la couche sèche (12, 22, 32, 42, 52, 62) est constituée d'un agent filmogène et d'une poudre composite d'ETR ; et

    l'étape B du procédé d'exécution de traitement thermique sur l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) et le support résistant aux températures élevées (11, 21, 31, 41, 51, 61) traité au moyen de l'étape A du procédé dans une atmosphère sous vide ou inerte et la fourniture d'ETR sur une surface de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101).


     
    2. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel la pression atmosphérique d'une chambre de traitement dans laquelle le traitement thermique est exécuté est inférieure à 0,05 MPa.
     
    3. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1 ou la revendication 2, dans lequel au cours de l'étape B du procédé, la poudre composite d'ETR fixée à la couche sèche (12, 22, 32, 42, 52, 62) formée sur le support résistant aux températures élevées (11, 21, 31, 41, 51, 61) et l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) sont placés de manière à être en contact ou de manière à ne pas être en contact, et lorsque la couche sèche (12, 22, 32, 42, 52, 62) et l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) sont placés de manière à être en contact, un espacement moyen entre eux est réglé pour être inférieur à 1 cm.
     
    4. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 3, dans lequel au cours de l'étape B du procédé, lorsque la poudre composite d'ETR fixée à la couche sèche (12, 22, 32, 42, 52, 62) et l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) sont placés de manière à ne pas être en contact, la pression atmosphérique d'une chambre de traitement dans laquelle le traitement thermique est exécuté est inférieure à 1 000 Pa.
     
    5. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel la couche sèche (12, 22, 32, 42, 52, 62) est un film.
     
    6. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel au cours de l'étape B du procédé, l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) et le support résistant aux températures élevées (11, 21, 31, 41, 51, 61) traité au moyen de l'étape A du procédé sont chauffés pendant 5 à 100 h dans un environnement de 800 °C à 1 020 °C.
     
    7. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel la couche sèche (12, 22, 32, 42, 52, 62) est un film uniformément distribué et l'épaisseur de la couche sèche est inférieure à 1 mm.
     
    8. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel au moins deux couches sèches (12, 22, 32, 42, 52, 62) sont formées sur le support résistant aux températures élevées (11, 21, 31, 41, 51, 61), et toutes les couches sèches adjacentes sur deux (12, 22, 32, 42, 52, 62) sont uniformément réparties sur le support résistant aux températures élevées (11, 21, 31, 41, 51, 61) à un espacement inférieur à 1,5 cm.
     
    9. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B selon la revendication 1, dans lequel la poudre composite d'ETR fixée à la couche sèche comprend en outre un agent filmogène capable d'être retiré pour au moins 95 % en poids au cours de l'étape B, et l'agent filmogène est constitué de résines, et/ou de cellulose, et/ou de polymères fluorosilicone, et/ou d'huile sèche et/ou de verre soluble.
     
    10. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel la poudre composite d'ETR fixée à la couche sèche (12, 22, 32, 42, 52, 62) est une poudre composite d'ETR adsorbée électrostatiquement.
     
    11. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B selon la revendication 1, dans lequel le support résistant aux températures élevées est une particule résistante aux températures élevées, un filet résistant aux températures élevées, une plaque résistante aux températures élevées ou une bande résistante aux températures élevées, et dans lequel le support résistant aux températures élevées est composé d'un matériau choisi dans un groupe constitué de zircone, d'alumine, d'oxyde d'yttrium, de nitrure de bore, de nitrure de silicium et de carbure de silicium, et un métal choisi dans un groupe constitué de Mo, W, Nb, Ta, Ti, Hf, Zr, Ti, V, Re du groupe IV B, V B, VI B et VII B dans le tableau périodique ou composé d'un alliage des matériaux ci-dessus.
     
    12. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel la poudre composite d'ETR est une poudre d'oxyde d'ETR, et/ou de fluorure d'ETR, et/ou de chlorure d'ETR, et/ou de nitrate d'ETR, et/ou d'oxyfluorure d'ETR, et la taille moyenne des particules de la poudre est inférieure à 200 micromètres.
     
    13. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 12, dans lequel dans la poudre composite d'ETR fixée à la couche sèche, la teneur en oxyde d'ETR, en fluorure d'ETR, en chlorure d'ETR, en nitrate d'ETR et en oxyfluorure d'ETR est supérieure à 90 % en poids.
     
    14. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel une épaisseur de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) le long d'une direction d'orientation magnétique de celui-ci est inférieure à 30 mm.
     
    15. Procédé de diffusion de limite de grain de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) selon la revendication 1, dans lequel l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) prend des grains cristallisés R2Fe14B comme phase principale, dans lequel R comprend au moins un élément de terre rare, dans lequel une quantité de Nd et/ou de Pr est supérieure à 50 % en poids d'une quantité de R, dans lequel des composants de l'aimant fritté de terres rares de la série R-Fe-B (6, 7, 8, 9, 10, 101) comprennent M, et M est Co, et/ou Bi, et/ou Al, et/ou Ca, et/ou Mg, et/ou O, et/ou C, et/ou N, et/ou Cu, et/ou Zn, et/ou In, et/ou Si, et/ou S, et/ou P, et/ou Ti, et/ou V, et/ou Cr, et/ou Mn, et/ou Ni, et/ou Ga, et/ou Ge, et/ou Zr, et/ou Nb, et/ou Mo, et/ou Pd, et/ou Ag, et/ou Cd, et/ou In, et/ou Sn, et/ou Sb, et/ou Hf, et/ou Ta et/ou W.
     
    16. Source de diffusion d'ETR (1, 2, 3, 4, 5, 5'), dans laquelle la source de diffusion d'ETR (1, 2, 3, 4, 5, 5') comprend : une couche sèche (12, 22, 32, 42, 52, 62) formée sur un support résistant aux températures élevées (11, 21, 31, 41, 51, 61), une poudre composite d'ETR étant fixée à la couche sèche (12, 22, 32, 42, 52, 62), et les ETR étant Dy, et/ou Tb, et/ou Gd, et/ou Ho, dans lequel la poudre composite d'ETR fixée à la couche sèche (12, 22, 32, 42, 52, 62) est constituée d'un agent filmogène et d'une poudre composite d'ETR.
     
    17. Procédé de préparation d'une source de diffusion d'ETR (1, 2, 3, 4, 5, 5'), dans lequel le procédé comprend :

    1) le fait de prendre la poudre composite d'ETR, d'y ajouter un premier solvant organique jusqu'à ce que la poudre composite d'ETR soit immergée et de broyer complètement pour obtenir de la poudre broyée ou du fluide broyé ;

    2) l'ajout d'un agent filmogène dans un second solvant organique et la préparation d'une seconde solution de solvant organique de l'agent filmogène ;

    3) l'ajout de la poudre broyée ou du fluide broyé dans la seconde solution de solvant organique selon un rapport (0,01-0,1):0,9 en poids de l'agent filmogène à la poudre composite d'ETR, et l'exécution d'un mélange uniforme pour obtenir un liquide mélangé, et

    4) la sélection d'un support résistant aux températures élevées (11, 21, 31, 41, 51, 61), la pulvérisation du liquide mélangé sur une surface du support résistant aux températures élevées (11, 21, 31, 41, 51, 61) et l'exécution du séchage.


     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



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    Patent documents cited in the description