CN111554464A - Ultrahigh magnetic energy product neodymium iron boron permanent magnet material and preparation method thereof - Google Patents
Ultrahigh magnetic energy product neodymium iron boron permanent magnet material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 28
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 50
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 29
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000007704 transition Effects 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 49
- 239000000843 powder Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 25
- 239000013078 crystal Substances 0.000 claims description 20
- 238000010902 jet-milling Methods 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 238000007872 degassing Methods 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000696 magnetic material Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 description 15
- 230000008569 process Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000462 isostatic pressing Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000012217 deletion Methods 0.000 description 2
- 230000037430 deletion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
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- Engineering & Computer Science (AREA)
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to the technical field of rare earth permanent magnet materials, in particular to an ultra-high magnetic energy product neodymium iron boron permanent magnet material and a preparation method thereof, wherein the component is RE1xRE2yRE3 zFqBoMp; wherein RE1 is selected from at least one of rare earth elements Pr/Nd/Ho/Gd/Ce, RE2 is selected from at least one of heavy rare earth elements Dy/Tb, RE3 is an additional rare earth metal or/and a rare earth alloy, and the content of the RE1 is calculated by the total mass of RE1, RE2 and F, B, M, and the content of the RE1 is as follows: x + y + z is more than or equal to 29 wt% and less than or equal to 33.5 wt%, y is more than or equal to 0 wt% and less than or equal to 3 wt%, and z is more than or equal to 0 wt% and less than or equal to 2 wt%; b is selected from at least one of boron and carbon, and the content of B is between 0.85 and 1.2 percent by weight; m is selected from at least one of Al/Cu/Zr/Nb/Ga/Si/Mo/Ti, and the content of the M is more than or equal to 0.01 weight percent and less than or equal to 1.5 weight percent; the balance is F, and F is at least one selected from transition elements Fe/Co/Ni.
Description
Technical Field
The invention relates to the field of permanent magnet materials, in particular to a neodymium iron boron permanent magnet material.
Background
With the development and research of neodymium iron boron, the brittleness problem of neodymium iron boron materials troubles neodymium iron boron manufacturers and processors, and particularly, under the trend of pursuing low cost, the original fine powder has increasingly fine particle size, so that the brittleness problem of permanent magnet materials is more and more obvious, the processing yield is low, and particularly in the aspects of research, development and production of ultrahigh magnetic energy product materials.
In the existing research, the brittleness of the material is improved very little, the brittleness is mainly generated on the principle that the neodymium iron boron flail piece is easy to form crystal-through fracture and crystal-following fracture in the hydrogen breaking process, and meanwhile, as the material is a pore material, air holes, impurities, sharp edges and other defects which influence the brittleness are easily formed on the crystal boundary, so that the final blank is easy to cause the conditions of edge deletion, corner falling and the like in the processing process, and the yield of the product is greatly reduced.
The existing open documents or data provide solutions to the problem of limited processing brittleness, and the main three methods are as follows: one is adding metal rare earth element into the material, such as Chinese publication No. 103177867B; the second kind is that metal Bi, tin and other elements for improving the lubricating effect are added into the permanent magnet; the third category is the use of improved processing methods.
Chinese patent publication No. 103177867A provides a solution to the problem of increased brittleness of permanent magnets by adding rare earth on the basis of the original Nd-Fe-B and filling up pores, wherein the rare earth absorbs hydrogen and then is subjected to heat preservation and dehydrogenation at 830-860 ℃ to below 50ppm, and the rare earth-Fe-B composition absorbs hydrogen and is crushed and then is subjected to dehydrogenation at 400-420 ℃; the invention needs new equipment investment, the hydrogen content is less than 50ppm, the waiting time required by dehydrogenation is long compared with the existing level of 1000ppm, and oxygen in the subsequent production process is easy to contact and react with powder due to the large reduction of the hydrogen content, so that the production of high-coercivity products is very unfavorable.
The Chinese patent publication No. CN107910154A provides a metal Bi with low melting point, which can refine crystal grains and make the crystal grains uniform, and simultaneously, the metal Bi is melted and realizes grain boundary precipitation in the processing process, thereby playing a role of lubricating a grinding surface and further realizing the improvement of the processing qualification rate. Firstly, the Bi element is a non-magnetic phase, the addition of the Bi element can cause little attenuation of remanence, and the larger the addition proportion is, the larger the attenuation amplitude of remanence is. Especially for products or special-shaped products with the orientation size of less than 1mm in the VCM motor, a multi-line cutting, wire cutting or slicing processing method needs to be adopted firstly, the method cannot effectively solve the problem of low processing yield, and Bi is added to improve the brittleness of the neodymium iron boron material very limitedly.
The Chinese patent application No. 200810116020.X provides a method for adding 0.05 wt% -1.2 wt% of tin, reducing the edges and corners of alloy crystal grains, improving the lubricity of a rare earth-rich phase and a matrix, reducing the occurrence probability of transgranular fracture and improving the processing characteristics of a permanent magnet. The tin element is a non-magnetic phase, the remanence is slightly attenuated when the tin element is added, and the larger the adding proportion is, the larger the remanence attenuation amplitude is. Similarly, when the special-shaped product or the product with the thickness of less than 1mm is used, the same situation as that of the special-shaped product or the product with the thickness of less than 1mm still exists, the problem of low processing yield cannot be effectively solved, and the improvement of the brittleness of the neodymium iron boron material by adding tin is very limited.
Chinese patent publication No. 104607634a provides a method for processing a ring magnet, which is a method for improving the brittleness of a ring product to some extent, but does not improve the brittleness of the magnet from the material viewpoint. If the brittleness of the matrix is reduced, the processing yield is higher for the same processing method, meanwhile, the method is complex to process, a plurality of matched tool fixtures are provided, and the matching problem caused by directly pressing the annular product to deform is very troublesome.
In conclusion, the existing three methods have the problems of low cost or insufficient improvement and the like for improving the brittleness.
Disclosure of Invention
The invention aims to provide an ultra-high magnetic energy product neodymium iron boron permanent magnet material and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
an ultra-high magnetic energy product neodymium iron boron permanent magnet material comprises RE1xRE2yRE3 zFqBoMp;
wherein RE1 is selected from at least one of rare earth elements Pr/Nd/Ho/Gd/Ce, RE2 is selected from at least one of heavy rare earth elements Dy/Tb, RE3 is an additional rare earth metal or/and a rare earth alloy, and the content of the RE1 is calculated by the total mass of RE1, RE2 and F, B, M, and the content of the RE1 is as follows: x + y + z is more than or equal to 29 wt% and less than or equal to 33.5 wt%, y is more than or equal to 0 wt% and less than or equal to 3 wt%, and z is more than or equal to 0 wt% and less than or equal to 2 wt%;
b is selected from at least one of boron and carbon, and the content of B is between 0.85 and 1.2 percent by weight;
m is selected from at least one of Al/Cu/Zr/Nb/Ga/Si/Mo/Ti, and the content of the M is more than or equal to 0.01 weight percent and less than or equal to 1.5 weight percent;
the balance of F, wherein F is at least one of transition elements Fe/Co/Ni;
the permanent magnet material has the characteristics that BHmax is more than or equal to 42 MGOe; compared with RE3 rare earth, the Hcj of the matrix is increased by more than 0.2 kOe; the proportion of crystal grains with the size more than 7 mu m in the permanent magnet material is more than 50 percent; the permanent magnet material is processed by slicing and is made into a square sheet with the minimum side of 1mm, and the collision side proportion of the square sheet is less than 6%.
Furthermore, the proportion of crystal grains with the size more than 7.5 mu m in the permanent magnet material is more than 50 percent.
Furthermore, the addition amount of the RE3 is 0.3 wt% -1.2 wt%, and the RE3 is Pr or/and Nd or/and PrNd alloy.
Or the RE3 accounts for 0.3-1.2 wt% of the alloy, and is Dy or/and DyFe alloy.
A preparation method of an ultra-high magnetic energy product neodymium iron boron permanent magnet material comprises the following steps:
(1) selecting the corresponding raw materials of the permanent magnet material for smelting, and preparing a throwing sheet with the thickness of 0.2-0.4 mm;
(2) the throwing sheet is subjected to hydrogen breaking treatment, the hydrogen content of the material after hydrogen breaking is controlled to be 600 ppm-1500 ppm, and RE3 is added according to any one of the following modes:
firstly, carrying out hydrogen breaking treatment on rare earth metal or/and rare earth alloy;
secondly, the rare earth metal or/and the rare earth alloy are independently hydrogen-broken and added according to the proportion of RE3 before the jet milling;
thirdly, breaking the rare earth metal or/and the rare earth alloy by independent hydrogen and independent jet milling, and then mixing and adding the rare earth metal or/and the rare earth alloy in the fine powder stage according to the proportion of RE 3;
(3) carrying out jet milling on the coarse powder after hydrogen breaking, and grinding the powder until the granularity of 50% volume fraction is more than or equal to 4.5 mu m, namely the granularity corresponding to X50 is more than or equal to 4.5 mu m, and the oxygen content in a milling chamber is controlled to be 25-40 ppm;
(4) uniformly mixing the powder after the jet milling, and performing compression molding in an orientation field with the magnetic field intensity being more than 1.6T to prepare a molding blank;
(5) sintering the formed blank, sintering, degassing and dehydrogenating at 750-1000 ℃ until the vacuum degree is lower than 100Pa, sintering and aging;
(6) the sintered permanent magnet has the microscopic characteristics that the grain size of the crystal with the proportion of more than 50 percent is more than 7 mu m;
(7) the permanent magnet is processed with length multiplied by width multiplied by orientation, the corresponding dimension is less than 20mm in length, less than 2mm in width and less than 1mm in orientation, and the edge-breaking rate of the final product is lower than 6% by adopting a slicing processing method.
Furthermore, the addition amount of the RE3 is 0.3 wt% -1.2 wt%, and the RE3 is Pr or/and Nd or/and PrNd alloy.
Furthermore, the proportion of crystal grains with the size more than 7.5 mu m in the prepared permanent magnet material is more than 50 percent.
Further, in the step (2), the hydrogen content is controlled to be 800ppm to 1300 ppm.
Furthermore, in the step (3), the particle size X50 of the jet milling powder is controlled within the range of 4.7-5.4 μm.
Further, in the step (7), the permanent magnet is processed in length × width × orientation, the corresponding dimensions are less than 10mm in length, less than 1.7mm in width and less than 0.7mm in orientation, and the edge-broken rate of the final product is lower than 3.5% by adopting a slicing processing method.
Furthermore, the addition amount of RE3 is 0.3 wt% -1.2 wt%, and is Dy or/and DyFe alloy.
The technical scheme has the following mechanism analysis:
(1) the rare earth or the rare earth alloy with the weight percent of 0.1 percent or more is added to supplement the rare earth liquid phase deletion phenomenon caused in the production process, and simultaneously, the rare earth is added in the process of forming a liquid phase or filling gaps among large and small crystal grains, so that the proportion of pores is reduced. Because the neodymium iron boron permanent magnet contains about 30 wt% of rare earth which is very active metal, and micron-sized fine powder is prepared by airflow grinding, the neodymium iron boron permanent magnet is easy to react with oxygen in the storage and pressing processes, so that the liquid phase at the crystal boundary is in short supply, pores are formed finally, the brittleness of materials is increased, and the processing yield is reduced. In addition, the neodymium iron boron can not completely remove hydrogen at the temperature of below 1000 ℃, so that hydrogen can come out of the base body inevitably or cause in the sintering process, a plurality of channels exist microscopically, the filled rare earth can form liquid phase filling in the sintering process, and the brittleness of the base body is further improved.
(2) The grain size of 50 percent of the final magnet is more than 7 mu m, the grain size of the jet mill is controlled mainly by controlling the grain size, namely X50 is more than 4.5 mu m, the finer the powder is, although the coercive force is obviously improved, the problems exist that the porosity is increased, the collision frequency of the fine powder is greatly increased when the powder is ground, the proportion of the ultrafine powder is greatly increased, rare earth phase loss is inevitably caused, and finally the infiltration characteristic and the porosity of the rare earth phase are influenced. The rare earth content of the superfine powder basically exceeds 60 percent, and the more the superfine powder is ground, the more the superfine powder is, the more the rare earth loss is serious. In addition, the larger the size of the matrix, the smaller the number of crystallites, while the less brittle the same impact.
(2) Hydrogen breaking content is controlled to be 600-1500 ppm, the higher the hydrogen content is, the more unfavorable the sintering vacuum dehydrogenation is, a large amount of hydrogen is easy to generate, the pores of a matrix are increased, and the brittleness is increased; the lower the hydrogen content is, the more easily oxygen reacts with the powder, and the material characteristics deteriorate.
Compared with the prior art, the invention has the beneficial effects that:
(1) on the basis of the existing equipment, the invention can realize the increase of the rare earth phase at the crystal boundary without increasing the equipment investment, fill the air gap and improve the processing characteristics.
(2) The invention supplements rare earth, improves the wettability among crystals and is beneficial to improving the coercive force of the material.
(3) The large proportion of crystal grains with the size larger than 7 mu m can better improve the grinding time and the loss of ultrafine powder in the jet milling process, reduce the loss of rare earth and be beneficial to reducing the number of air gaps in the magnet.
(4) The large proportion of crystal grains is larger than 7 μm, the number of small crystals is reduced, the characteristics such as impact resistance and the like are enhanced, and the processing resistance of the magnet is improved.
(5) The hydrogen content in the hydrogen breaking process is proper, so that the number of pores caused by sintering degassing is reduced.
(6) The added rare earth can fill a channel generated by hydrogen in the sintering dehydrogenation process, reduce pores and improve the processing characteristics.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Smelting the raw materials according to a nominal composition Pr7.1 Nd21.3 Tb1.76B 0.9 Cu0.12 Co1.38 Zr0.2 Ga0.24Fe67, preparing a0.2 mm-0.4 mm flail, carrying out hydrogen breaking on the flail, controlling the hydrogen content of coarse powder after hydrogen breaking to be 1000-1200 ppm, carrying out air flow grinding on the obtained hydrogen crushed powder, controlling the X50 to be 4.5-4.7 mu m, controlling the oxygen content of a grinding chamber to be 25-40 ppm, pressing the powder under the action of a 1.6T magnetizing field, carrying out isostatic pressing on the pressed forming blank, then sintering, degassing at 880 ℃, keeping 5H to ensure that the vacuum degree is less than 20Pa, heating at 1095 ℃/5H, carrying out first aging treatment at 900 ℃ and second aging treatment at 490 ℃, and testing the magnetic property and observing and testing the grain size.
Example 2
The jet mill particle size X50 in example 1 was controlled to 4.9 μm to 5.1. mu.m, and the parameters were the same for the other steps.
Example 3
The throwing plate in the example 1 is added with 0.3 wt% of small pieces of PrNd alloy, and the jet milling granularity X50 is controlled to be 4.9-5.1 μm, and the parameters of other steps are the same.
Example 4
The throwing plate in the example 1 is added with 0.7 wt% of small pieces of PrNd alloy, and the jet milling granularity X50 is controlled to be 4.9-5.1 μm, and the parameters of other steps are the same.
Example 5
The throwing plate in the example 1 is added with 1.2 wt% of small pieces of PrNd alloy, and the jet milling granularity X50 is controlled to be 5.2-5.4 μm, and the parameters of other steps are the same.
Example 6
0.3 wt% of small DyFe alloy is added into the flaked piece in the example 1, and the jet milling granularity X50 is controlled to be 4.8-5.0 μm, and the parameters of other steps are the same.
Example 7
0.7 wt% of small DyFe alloy is added into the flaked piece in the example 1, and the jet milling granularity X50 is controlled to be 4.8-5.0 μm, and the parameters of other steps are the same.
Example 8
Smelting raw materials according to a nominal composition Pr6.8 Nd22.7B 0.9 Cu0.15 Co1.2 Zr0.2 Ga0.25 Fe67.8, preparing a0.2 mm-0.4 mm flail, breaking the flail by hydrogen, wherein the hydrogen content of coarse powder after hydrogen breaking is 1000-1200 ppm, performing jet milling on the obtained hydrogen crushed powder, controlling the X50 to be 4.8-5.0 mu m, controlling the oxygen content of a milling chamber to be 25-40 ppm, pressing powder under the action of a 1.6T magnetizing field, performing isostatic pressing on the pressed forming blank, sintering, degassing at 880 ℃, keeping 5H to ensure that the vacuum degree is less than 20Pa, heating at 1085 ℃/5H, performing first aging treatment at 900 ℃, second aging treatment at 490 ℃, testing the magnetic performance, observing the microstructure and testing the grain size.
Example 9
The throwing plate of example 8 was added with 1 wt% of a small piece of PrNd alloy, and the jet milling grain size X50 was controlled to 4.8 to 5.0. mu.m, and the rest were the same.
Example 10
Smelting raw materials according to a nominal composition Pr7.3 Nd21.7 Dy 2B 0.9 Al0.05 Cu0.15 Co1.2 Zr0.2Ga0.3 Fe66.2, preparing a 0.2-0.4 mm flail, carrying out hydrogen crushing on the flail, controlling the hydrogen content of coarse powder after hydrogen crushing to be 1000-1200 ppm, carrying out air flow grinding on the obtained hydrogen crushed powder, controlling the X50 to be 4.8-5.0 mu m, controlling the oxygen content of a grinding chamber to be 25-40 ppm, pressing the powder under the action of a 1.6T magnetizing field, carrying out isostatic pressing on the pressed formed blank, then sintering, degassing at 880 ℃, keeping 5H until the vacuum degree is less than 20Pa, heating, sintering at 1090 ℃ for 5H, carrying out first-step aging treatment at 900 ℃, second-step aging treatment at 490 ℃, and testing magnetic performance and microstructure observation and grain size test.
Example 11
The throwing plate of example 10 was added with 1 wt% of a small piece of PrNd alloy, and the jet milling grain size X50 was controlled to 4.8 to 5.0. mu.m, and the other parts were the same.
To highlight the advantageous effects of the present invention, the following comparative example experiments are exemplified.
Comparative example 1
Smelting the raw materials according to a nominal composition Pr7.1 Nd21.3 Tb1.76B 0.9 Cu0.12 Co1.38 Zr0.2 Ga0.24Fe67, preparing a 0.2-0.4 mm flail, carrying out hydrogen breaking on the flail, controlling the hydrogen content of coarse powder after hydrogen breaking to be 1000-1200 ppm, carrying out air flow grinding on the obtained hydrogen crushed powder, controlling the X50 to be 4.2-4.4 mu m, controlling the oxygen content of a grinding chamber to be 25-40 ppm, pressing the powder under the action of a 1.6T magnetizing field, carrying out isostatic pressing on the pressed forming blank, then sintering, degassing at 880 ℃, keeping 5H to ensure that the vacuum degree is less than 20Pa, heating at 1095 ℃/5H, carrying out first aging treatment at 900 ℃ and second aging treatment at 490 ℃, and testing the magnetic property and observing and testing the grain size.
Comparative example 2
And (3) carrying out hydrogen breaking on the throwing piece in the example 1, controlling the hydrogen content of the powder after the hydrogen breaking to be 500-600 ppm, controlling the airflow grinding granularity X50 to be 4.9-5.1 mu m, and keeping the other steps with the same parameters.
Comparative example 3
And (3) carrying out hydrogen breaking on the flail piece in the embodiment 1, controlling the hydrogen content of the powder after the hydrogen breaking to be 1500-1600 ppm, controlling the airflow grinding granularity X50 to be 4.9-5.1 μm, and keeping the other steps with the same parameters.
Magnetic performance tests are carried out on the blanks obtained in the examples and the comparative examples, the sizes and the proportions of crystal grains are observed, small square pieces of 10mm x 1.7mm x 0.7mm are processed at the same time, and the broken edge or incomplete proportion is counted. The results are shown in the following table.
The data show that the technical scheme of the invention can obviously improve the processing characteristics of the neodymium iron boron by controlling the hydrogen-breaking content, coarsening the granularity and adding a small amount of rare earth under the condition of meeting the requirement of magnetic performance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The utility model provides an ultra-high magnetic energy product neodymium iron boron permanent magnet material which characterized in that: the component is RE1xRE2yRE3 zFqBoMp;
wherein RE1 is selected from at least one of rare earth elements Pr/Nd/Ho/Gd/Ce, RE2 is selected from at least one of heavy rare earth elements Dy/Tb, RE3 is an additional rare earth metal or/and a rare earth alloy, and the content of the RE1 is calculated by the total mass of RE1, RE2 and F, B, M, and the content of the RE1 is as follows: x + y + z is more than or equal to 29 wt% and less than or equal to 33.5 wt%, y is more than or equal to 0 wt% and less than or equal to 3 wt%, and z is more than or equal to 0 wt% and less than or equal to 2 wt%;
b is selected from at least one of boron and carbon, and the content of B is between 0.85 and 1.2 percent by weight;
m is selected from at least one of Al/Cu/Zr/Nb/Ga/Si/Mo/Ti, and the content of the M is more than or equal to 0.01 weight percent and less than or equal to 1.5 weight percent;
the balance of F, wherein F is at least one of transition elements Fe/Co/Ni;
the permanent magnet material has the characteristics that BHmax is more than or equal to 42 MGOe; compared with RE3 rare earth, the Hcj of the matrix is increased by more than 0.2 kOe; the proportion of crystal grains with the size more than 7 mu m in the permanent magnet material is more than 50 percent; the permanent magnet material is processed by slicing and is made into a square sheet with the minimum side of 1mm, and the collision side proportion of the square sheet is less than 6%.
2. The ultra-high magnetic energy product neodymium-iron-boron permanent magnet material of claim 1, characterized in that: the proportion of crystal grains with the size more than 7.5 mu m in the permanent magnet material is more than 50 percent.
3. The ultra-high magnetic energy product neodymium-iron-boron permanent magnet material of claim 1, characterized in that: the addition amount of the RE3 is 0.3 wt% -1.2 wt%, and the RE3 is Pr or/and Nd or/and PrNd alloy.
4. The ultra-high magnetic energy product neodymium-iron-boron permanent magnet material of claim 1, characterized in that: the addition amount of RE3 is 0.3 wt% -1.2 wt%, and is Dy or/and DyFe alloy.
5. The method for preparing the ultra-high magnetic energy product neodymium-iron-boron permanent magnet material according to any one of claims 1 to 4, characterized in that: the method comprises the following steps:
(1) selecting the corresponding raw materials of the permanent magnet material for smelting, and preparing a throwing sheet with the thickness of 0.2-0.4 mm;
(2) the throwing sheet is subjected to hydrogen breaking treatment, the hydrogen content of the material after hydrogen breaking is controlled to be 600 ppm-1500 ppm, and RE3 is added according to any one of the following modes:
firstly, carrying out hydrogen breaking treatment on rare earth metal or/and rare earth alloy;
secondly, the rare earth metal or/and the rare earth alloy are independently hydrogen-broken and added according to the proportion of RE3 before the jet milling;
thirdly, breaking the rare earth metal or/and the rare earth alloy by independent hydrogen and independent jet milling, and then mixing and adding the rare earth metal or/and the rare earth alloy in the fine powder stage according to the proportion of RE 3;
(3) carrying out jet milling on the coarse powder after hydrogen breaking, and grinding the powder until the granularity of 50% volume fraction is more than or equal to 4.5 mu m, namely the granularity corresponding to X50 is more than or equal to 4.5 mu m, and the oxygen content in a milling chamber is controlled to be 25-40 ppm;
(4) uniformly mixing the powder after the jet milling, and performing compression molding in an orientation field with the magnetic field intensity being more than 1.6T to prepare a molding blank;
(5) sintering the formed blank, sintering, degassing and dehydrogenating at 750-1000 ℃ until the vacuum degree is lower than 100Pa, sintering and aging;
(6) the sintered permanent magnet has the microscopic characteristics that the grain size of the crystal with the proportion of more than 50 percent is more than 7 mu m;
(7) the permanent magnet is processed with length multiplied by width multiplied by orientation, the corresponding dimension is less than 20mm in length, less than 2mm in width and less than 1mm in orientation, and the edge-breaking rate of the final product is lower than 6% by adopting a slicing processing method.
6. The method for preparing the ultra-high magnetic energy product neodymium-iron-boron permanent magnet material according to claim 5, characterized in that: the addition amount of the RE3 is 0.3 wt% -1.2 wt%, and the RE3 is Pr or/and Nd or/and PrNd alloy.
7. The method for preparing the ultra-high magnetic energy product neodymium-iron-boron permanent magnet material according to claim 5, characterized in that: the proportion of crystal grains with the size more than 7.5 mu m in the prepared permanent magnetic material is more than 50 percent.
8. The method for preparing the ultra-high magnetic energy product neodymium-iron-boron permanent magnet material according to claim 5, characterized in that: in the step (2), the hydrogen content is controlled to be 800 ppm-1300 ppm;
in the step (3), the control range of the granularity X50 of the airflow milling powder is 4.7-5.4 microns.
9. The method for preparing the ultra-high magnetic energy product neodymium-iron-boron permanent magnet material according to claim 5, characterized in that: in the step (7), the permanent magnet is processed with length multiplied by width multiplied by orientation, the corresponding dimensions are that the length is less than 10mm, the width is less than 1.7mm, the orientation is less than 0.7mm, and the edge-knocking rate of the final product is lower than 3.5% by adopting a slicing processing method.
10. The method for preparing the ultra-high magnetic energy product neodymium-iron-boron permanent magnet material according to claim 5, characterized in that: the addition amount of RE3 is 0.3 wt% -1.2 wt%, and is Dy or/and DyFe alloy.
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