CN104230323B - M type calcium lanthanum cobalt permanent-magnet ferrite and preparation method thereof - Google Patents
M type calcium lanthanum cobalt permanent-magnet ferrite and preparation method thereof Download PDFInfo
- Publication number
- CN104230323B CN104230323B CN201310254242.9A CN201310254242A CN104230323B CN 104230323 B CN104230323 B CN 104230323B CN 201310254242 A CN201310254242 A CN 201310254242A CN 104230323 B CN104230323 B CN 104230323B
- Authority
- CN
- China
- Prior art keywords
- ferrite
- permanent magnetic
- equal
- sintering
- cobalt permanent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 103
- ROYOLNQPXVHWNE-UHFFFAOYSA-N [Co].[Ca].[La] Chemical compound [Co].[Ca].[La] ROYOLNQPXVHWNE-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 61
- 239000011575 calcium Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 12
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 61
- 239000002245 particle Substances 0.000 claims description 51
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 239000000843 powder Substances 0.000 claims description 39
- 239000000654 additive Substances 0.000 claims description 28
- 230000000996 additive effect Effects 0.000 claims description 27
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 25
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 24
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 23
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 22
- 229910052681 coesite Inorganic materials 0.000 claims description 21
- 229910052906 cristobalite Inorganic materials 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 229910052682 stishovite Inorganic materials 0.000 claims description 21
- 229910052905 tridymite Inorganic materials 0.000 claims description 21
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 13
- 229910000831 Steel Inorganic materials 0.000 claims description 12
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 12
- 239000010959 steel Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical group OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 5
- 239000004227 calcium gluconate Substances 0.000 claims description 4
- 229960004494 calcium gluconate Drugs 0.000 claims description 4
- 235000013927 calcium gluconate Nutrition 0.000 claims description 4
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 239000012071 phase Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000006698 induction Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 3
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229960005069 calcium Drugs 0.000 description 3
- 230000005347 demagnetization Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WETINTNJFLGREW-UHFFFAOYSA-N calcium;iron;tetrahydrate Chemical compound O.O.O.O.[Ca].[Fe].[Fe] WETINTNJFLGREW-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
Landscapes
- Hard Magnetic Materials (AREA)
- Magnetic Ceramics (AREA)
Abstract
The invention discloses a kind of M type calcium lanthanum cobalt permanent-magnet ferrite, the Hxagonal ferrite principal phase of element such as including A, R, Ca, Fe and M, and there is the molecular formula of following characteristics: A1‑x‑yCaxRyFe2n‑ zMzO19, wherein, A is the combination of Sr or Ba or Sr and Ba, R be La, M be the combination with Co of at least one in Ni and Zn；X, y, z represent the interpolation mole of each main metal element, and the span of x is 0.05 0.19, and y is 0.2 0.29, and z is 0.10 0.24, and n is 5.80 5.90.Also disclosing the preparation method of a kind of M type calcium lanthanum cobalt permanent-magnet ferrite, the method is provided with baking step, a burn in step and secondary burn in step before the sintering step simultaneously.The M type calcium lanthanum cobalt permanent-magnet ferrite that the present invention provides has higher comprehensive magnetic energy, and this preparation method can be when calcined temperature is 1150 DEG C or lower in the case of coercivity reduce, effectively promote the remanent magnetism of sample, thus obtain more excellent comprehensive magnetic energy.
Description
Technical Field
The invention relates to the technical field of permanent magnet materials, in particular to an M-type calcium lanthanum cobalt permanent magnetic ferrite and a preparation method thereof.
Background
Ferrites are generally classified into permanent, soft, rectangular, gyromagnetic, and piezomagnetic ferrites according to their properties and uses.
The final magnetic property of the permanent magnetic ferrite is generally measured by the remanence Br and the intrinsic coercivity HCJ. Among them, the high performance permanent magnetic ferrite generally refers to ferrite having advantages of high residual magnetic induction, strong demagnetization resistance, low manufacturing cost, and the like. Because of these advantages, high-performance permanent magnetic ferrites are widely used in the industries of electronics, information, motorcycles, automobiles, electric tools, and the like.
A widely used conventional ferrite material is Sr ferrite (SrFe) having an M-type magnetoplumbite structure12O19) And Ba ferrite (BaFe)12O19) These ferrites are produced by powder metallurgy using iron oxide and carbonates of Sr or Ba as raw materials. The specific preparation method comprises the following steps: firstly, raw materials such as iron oxide, strontium carbonate or barium carbonate are mixed, and subjected to a complete solid-phase reaction through pre-sintering to obtain pre-sintered blocks (or pellets), the pre-sintered blocks (or pellets) are coarsely crushed, and then the pre-sintered blocks (or pellets) are finely crushed to particles with an average particle size of 0.5 to 0.7 mu m by using water as a medium. In the fine crushing process, an additive capable of controlling the grain growth of the product and improving the density of the product so as to improve the magnetic property of the material is usually added, then, the ground slurry is molded in a magnetic field, and the obtained green body is sintered and ground to prepare the permanent magnetic ferrite.
In recent years, with the development of various motors toward light weight, miniaturization and high efficiency, higher requirements are put on the preparation process and performance of a key material, namely, permanent magnetic ferrite, and the magnet is required to have smaller and smaller volume and higher comprehensive magnetic performance, namely, the permanent magnetic ferrite is required to have higher demagnetization resistance (namely, the intrinsic coercive force Hcj of the material is required to be high) while keeping high residual magnetism Br. Conventional M-type magnetoplumbite Sr and Ba ferrites have not met these requirements.
The doping substitution of rare earth elements such as La, La-Co, Ca-La-Co and the like can greatly improve the intrinsic property of the material, so the doping substitution can effectively improve the magnetic property of a sample. However, parameters such as coercive force Hcj sensitive to microstructure are not only related to doping, but also related to the microstructure of grains, and factors having important influence on the grain morphology of the M-type hexaferrite sample include: average particle size and particle size distribution after powder refinement, CaCO3And SiO2The sintering aid has the functions of regulating and controlling crystal grains, optimizing a sintering system and the like. Research finds that the squareness ratio (Hk/Hcj) of a sintered sample is reduced along with the increase of the doping amount of the LaCo, and the reduced squareness ratio is mainly caused by that after doping substitution, incomplete reaction of a pre-sintering material and doping substitution of different degrees exist in crystal grains of the pre-sintering material, so that the crystal grain sizes are different, Hcj is closely related to the crystal grain sizes, and crystal grains with different sizes have different Hcj, so that demagnetization resistance is different, and finally, the Hk/Hcj and comprehensive magnetic performance are reduced. This is difficult to compensate by secondary processes, so how to ensure that the grains are fully ferrite in the pre-sintering stage, and the uniformity and fineness of the grains become the key to obtain high-performance products.
Therefore, in order to obtain a permanent magnetic ferrite with excellent performance to improve the performance of the whole motor, the formula of the permanent magnetic ferrite material and the preparation technology thereof need to be developed vigorously.
Disclosure of Invention
The invention aims to provide an M-type calcium lanthanum cobalt permanent magnetic ferrite and a preparation method thereof, so as to improve the performance of the M-type calcium lanthanum cobalt permanent magnetic ferrite.
In order to solve the above problems, the present invention provides an M-type Ca-la-co permanent magnetic ferrite, which includes a hexagonal ferrite main phase of elements such as a, R, Ca, Fe and M, and has the following characteristic molecular formula: a. the1-x-yCaxRyFe2n-zMzO19Wherein
a is Sr or Ba or the combination of Sr and Ba,
r is La,
m is a combination of Co and at least one of Ni and Zn;
x, y, z, n represent the addition ratio of each main metal element,
the value range of x is 0.05-0.19,
y is 0.2 to 0.29,
z is 0.10 to 0.24,
n is 5.80-5.90.
Preferably, all of the A are Sr.
Preferably, the M is a combination of Ni and Co.
Preferably, the M is a combination of Zn and Co.
Preferably, M is Ni and a combination of Zn and Co.
Preferably, A is removed from the M-type calcium lanthanum cobalt permanent magnetic ferrite1-x-yCaxRyFe2n-zMzO19In addition, the additive also comprises an additive, and the component of the additive is H3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3Each component of which is A1-x-yCaxRyFe2n-zMzO19H is more than or equal to 0 weight percent3BO3≤0.5%，0≤SiO2≤1.0%，0.1%≤CaCO3≤1.2%，0≤La2O3≤1.0%，0≤Co3O4≤1.0%，0≤SrCO3≤0.8%。
Meanwhile, in order to solve the problems, the invention also provides a preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite, which comprises the following steps:
preparing materials: according to the chemical formula A1-x-yCaxRyFe2n-zMzO19Preparing main material powder; adding an additive H according to the weight percentage3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3Each component of which is A1-x-yCaxRyFe2n-zMzO19H is more than or equal to 03BO3≤0.5%，0≤SiO2≤1.0%，0.1%≤CaCO3≤1.2%，0≤La2O3≤1.0%，0≤Co3O4≤1.0%，0≤SrCO3Less than or equal to 0.8 percent; mixing and stirring the main material powder and the additive to form material powder;
primary ball milling: putting the material powder into a ball mill for grinding, adding a steel ball with the diameter of 6mm and water into the ball mill during grinding, wherein the weight ratio of the water to the material powder to the steel ball is as follows: material powder: steel ball = 1: 1: 8; mixing and stirring the mixture in a ball mill for 0.5 to 5 hours to obtain a mixed material with the average particle size of suspended particles being less than 1 mu mm;
drying: drying the slurry ground by the ball mill at the drying temperature of 105-125 ℃;
pre-burning for one time: pre-burning the dried material body for the first time to generate a calcium lanthanum cobalt permanent magnetic ferrite pre-burnt material for the first time; wherein the temperature of one presintering is 1100-1300 ℃, and the presintering time is 1-3 hours;
and (3) secondary pre-burning: performing ball milling and drying on the sample after the primary pre-sintering step again, and performing secondary pre-sintering to ensure complete reaction to generate a secondary pre-sintered material of the calcium-lanthanum-cobalt permanent magnetic ferrite; wherein the temperature of the secondary pre-sintering is 1120-1160 ℃, and the temperature is kept for 20-30 ℃/min;
secondary ball milling: weighing the calcium lanthanum cobalt permanent magnetic ferrite secondary pre-sintered material, adding a secondary additive and a dispersant in a mass ratio mode, and ball-milling the obtained mixture by adopting a wet method until the average particle size of slurry particles is 0.6 um; wherein the secondary additive comprises Al2O3、Cr2O3、H3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3The average particle size of each secondary additive particle is not more than 2.0um, and the addition amount of the secondary additive is more than or equal to 0 and less than or equal to Al2O3≤1.0%，0≤Cr2O3≤1.0%，0≤H3BO3≤0.5%，0≤SiO2≤1.0%，0.1%≤CaCO3≤1.2%，0≤La2O3≤1.0%，0≤Co3O4≤1.0%，0≤SrCO3Less than or equal to 0.8 percent; the dispersing agent is one or more of calcium gluconate, polyvinyl alcohol and sorbitol, and the addition amount of the dispersing agent is 0.2-1.2wt% of the total weight of the components;
pressing a green body: pressing the sample obtained after the secondary ball milling into a green body in a magnetic field, wherein the pressing pressure is 7MPa, and the size of the oriented magnetic field is 5-15 kOe;
and (3) sintering: sintering the green body in an air oxidizing atmosphere at the temperature of 1000-1300 ℃ for 0.5-3 hours at the heating rate of 30-80 ℃/h to obtain a finished product.
Preferably, the main material powder comprises the following raw materials:
Fe2O3powder with purity more than or equal to 99.3wt% and original average particle size of 0.75 um;
SrCO3powder with purity more than or equal to 99 percent and original average particle size of 1.0 um;
La2O3the purity of the powder is more than or equal to 99 percent, and the original average particle size of the particles is 2.0 um;
Co3O4the purity of the powder is more than or equal to 99.3 percent, and the original average particle size of the particles is 0.8 um;
CaCO3the purity of the powder is more than or equal to 99.9 percent, and the original average particle size of the particles is 2 um;
NiO powder, the purity of which is more than or equal to 99.9 percent, and the original average particle size of the particles is 1.0 um.
Preferably, the one-time burn-in is microwave burn-in.
Preferably, the secondary pre-burning is microwave pre-burning.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages and positive effects:
1) according to the preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite, the primary pre-sintering and/or the secondary pre-sintering are/is microwave pre-sintering, and compared with the traditional muffle furnace pre-sintering, the microwave pre-sintering provided by the invention can obviously improve the final magnetic performance of the calcium lanthanum cobalt permanent magnetic ferrite, particularly the coercive force, the rectangular ratio and the like; the reason is that the traditional muffle furnace pre-sintering method is difficult to improve in the aspect of reducing the grain size, so that the secondary ball milling time is longer, and the grain size distribution after the secondary ball milling is wider, thereby influencing the final magnetic property of the prepared calcium lanthanum cobalt permanent magnetic ferrite.
2) The M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the invention adopts the formula, so that compared with the traditional permanent magnetic ferrite, the M-type calcium lanthanum cobalt permanent magnetic ferrite only contains a small amount of Sr and/or Ba, the value of remanence reaches 450mT-460mT at the sintering temperature of 1150 ℃ or lower, and the value of Hcj reaches 400-; therefore, the invention can effectively improve the remanence of the sample on the basis of not reducing the coercive force, thereby obtaining more excellent comprehensive magnetic performance;
3) the preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the invention comprises the steps of setting a primary pre-sintering step to generate a primary pre-sintered material of the calcium lanthanum cobalt permanent magnetic ferrite; the method comprises the steps of setting a secondary pre-sintering step to enable all components in a material body to react completely to generate a calcium-lanthanum-cobalt permanent magnetic ferrite secondary pre-sintered material; the arrangement of the steps can ensure that the pre-sintering material with complete reaction is obtained after pre-sintering, and is beneficial to improving the magnetic performance.
Drawings
Fig. 1 is a flowchart of a method for preparing an M-type calcium lanthanum cobalt permanent magnetic ferrite according to an embodiment of the present invention.
Detailed Description
The M-type calcium lanthanum cobalt permanent magnetic ferrite and the preparation method thereof proposed by the present invention will be further described in detail with reference to the accompanying drawings and specific examples. Advantages and features of the present invention will become apparent from the following description and from the claims. It is noted that the drawings are in greatly simplified form and that non-precision ratios are used for convenience and clarity only to aid in the description of the embodiments of the invention.
The M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the embodiment of the invention comprises a hexagonal ferrite main phase of elements such as A, R, Ca, Fe, M and the like, and has the following characteristic molecular formula: a. the1-x-yCaxRyFe2n-zMzO19Wherein
a is Sr or Ba or the combination of Sr and Ba,
r is La,
m is a combination of Co and at least one of Ni and Zn;
x, y, z, n represent the addition ratio of each main metal element,
the value range of x is 0.05-0.19, y is 0.2-0.29, z is 0.10-0.24, and n is 5.80-5.90.
In some embodiments, all of a is Sr.
In some embodiments, the M is a combination of Ni and Co.
In some embodiments, the M is a combination of Zn and Co.
In some embodiments, the M is Ni and a combination of Zn and Co.
Preferably, A is removed from the M-type calcium lanthanum cobalt permanent magnetic ferrite1-x-yCaxRyFe2n-zMzO19In addition, the additive also comprises an additive, and the component of the additive is H3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3Each component of which is A1-x-yCaxRyFe2n-zMzO19H is more than or equal to 0 weight percent3BO3≤0.5%，0≤SiO2≤1.0%，0.1%≤CaCO3≤1.2%，0≤La2O3≤1.0%，0≤Co3O4≤1.0%，0≤SrCO3≤0.8%。
Referring to fig. 1, fig. 1 is a flowchart of a method for preparing an M-type calcium lanthanum cobalt permanent magnetic ferrite according to an embodiment of the present invention, and as shown in fig. 1, the method for preparing an M-type calcium lanthanum cobalt permanent magnetic ferrite according to the present invention includes the following steps:
s1, batching: according to the chemical formula A1-x-yCaxRyFe2n-zMzO19Preparing main material powder; adding an additive H according to the weight percentage3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3Each component of which is A1-x-yCaxRyFe2n-zMzO19H is more than or equal to 03BO3≤0.5%，0≤SiO2≤1.0%，0.1%≤CaCO3≤1.2%，0≤La2O3≤1.0%，0≤Co3O4≤1.0%，0≤SrCO3Less than or equal to 0.8 percent; and mixing the main material powder with the additive;
s2, primary ball milling: putting the material powder into a ball mill for grinding, adding a steel ball with the diameter of 6mm and water into the ball mill during grinding, wherein the weight ratio of the water to the material powder to the steel ball is as follows: material powder: steel ball = 1: 1: 8; mixing and stirring the mixture in a ball mill for 0.5 to 5 hours;
s3, drying: drying the slurry ground by the ball mill at 115 ℃;
s4, primary burn-in: pre-burning the dried material body for the first time to generate a primary pre-burnt material of the calcium permanent magnetic ferrite; wherein the temperature of one presintering is 1100-1300 ℃, and the presintering time is 1-3 hours;
s5, secondary pre-burning: performing ball milling and drying on the sample subjected to the primary pre-sintering step again, and performing secondary pre-sintering to ensure complete reaction to generate a secondary calcium permanent magnetic ferrite pre-sintered material; wherein the temperature of the secondary pre-sintering is 1120-1160 ℃, and the temperature is kept for 20-30 ℃/min;
s6, secondary ball milling: weighing the calcium lanthanum cobalt permanent magnetic ferrite secondary pre-sintered material, adding a secondary additive and a dispersant in a mass ratio mode, and ball-milling the obtained mixture by adopting a wet method until the average particle size of slurry particles is 0.6 um; wherein the secondary additive comprises Al2O3、Cr2O3、H3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3The average particle size of each secondary additive particle is not more than 2.0um, and the addition amount of the secondary additive is more than or equal to 0 and less than or equal to Al2O3≤1.0%，0≤Cr2O3≤1.0%，0≤H3BO3≤0.5%，0≤SiO2≤1.0%，0.1%≤CaCO3≤1.2%，0≤La2O3≤1.0%，0≤Co3O4≤1.0%，0≤SrCO3Less than or equal to 0.8 percent; the dispersing agent is one or more of calcium gluconate, polyvinyl alcohol and sorbitol, and the addition amount of the dispersing agent is 0.2-1.2wt% of the total weight of the components;
s7, pressing green bodies: pressing the sample obtained after the secondary ball milling into a green body in a magnetic field, wherein the pressing pressure is 7MPa, and the size of the oriented magnetic field is 5-15 kOe;
s8, sintering: sintering the green body in an air oxidizing atmosphere at the temperature of 1000-1300 ℃ for 0.5-3 hours at the heating rate of 30-80 ℃/h to obtain a finished product.
In some embodiments, the one burn-in is a microwave burn-in.
In some embodiments, the secondary burn-in is a microwave burn-in.
Several specific examples are given below to illustrate the formulation of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the present invention.
Example 1
The M-type Ca-la-co permanent ferrite provided by this embodiment includes a hexagonal ferrite main phase of a, R, Ca, Fe, M, etc., and has the following characteristic molecular formula: a. the1-x-yCaxRyFe2n-zMzO19Wherein A is Sr, R is La, M is the combination of Ni and Co, x takes a value of 0.05, y takes a value of 0.25, z takes a value of 0.13, and n takes a value of 5.80. That is, the characteristic molecular formula of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided in this embodiment is Sr0.7Ca0.05La0.25Fe11.47(Ni0.03Co0.10)O19。
Example 2
The M-type Ca-La-Co permanent magnetic ferrite provided by the embodiment comprises a hexagonal ferrite main phase of A, R, Ca, Fe, M and the like, and hasThe molecular formula characterized below: a. the1-x-yCaxRyFe2n-zMzO19Wherein A is Ba, R is La, M is the combination of Ni and Co, x is 0.05, y is 0.25, z is 0.13, and n is 5.80. That is, the characteristic molecular formula of the M-type ca-la-co permanent magnetic ferrite provided in this embodiment is Ba0.7Ca0.05La0.25Fe11.47(Ni0.03Co0.10)O19。
Example 3
The M-type Ca-la-co permanent ferrite provided by this embodiment includes a hexagonal ferrite main phase of a, R, Ca, Fe, M, etc., and has the following characteristic molecular formula: a. the1-x-yCaxRyFe2n-zMzO19Wherein A is the combination of Sr and Ba, R is La, M is the combination of Zn and Co, x takes a value of 0.10, y takes a value of 0.29, z takes a value of 0.11, and n takes a value of 5.85. That is, the characteristic molecular formula of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided in this embodiment is (Sr)0.50Ba0.11)Ca0.10La0.29Fe11.59(Zn0.01Co0.10)O19。
Example 4
The M-type Ca-la-co permanent ferrite provided by this embodiment includes a hexagonal ferrite main phase of a, R, Ca, Fe, M, etc., and has the following characteristic molecular formula: a. the1-x-yCaxRyFe2n-zMzO19Wherein A is Sr, R is La, M is Ni and the combination of Zn and Co, x is 0.19, y is 0.25, z is 0.20, and n is 5.90. That is, the characteristic molecular formula of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided in this embodiment is Sr0.56Ca0.19La0.25Fe11.60(Ni0.03Zn0.02Co0.15)O19。
M-type calcium lanthanum cobalt permanent magnetic ferrite obtained in each embodimentResidual magnetic induction strength (Br), coercive force (Hcb), intrinsic coercive force (Hcj), maximum magnetic energy product (BH) max, squareness ratio (H)kSee table 1 for the values of/Hcj):
table 1: properties of M-type Ca-La-Co permanent magnetic ferrite obtained in examples 1 to 4
As shown in Table 1, the Br value of the M-type Ca-La-Co permanent magnetic ferrite provided by the invention can reach 450mT-463mT, the Hcj value reaches 390-420kA/M, and the squareness ratio is more than 0.92. Therefore, the invention can effectively improve the remanence of the sample on the basis of not reducing the coercive force, thereby obtaining more excellent comprehensive magnetic performance.
However, the invention is not limited thereto, and the M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the invention can also take other formulas as long as the formula satisfying the characteristics is: a. the1-x-yCaxRyFe2n-zMzO19Wherein A is Sr or Ba or the combination of Sr and Ba, R is La, and M is the combination of Co and at least one of Ni and Zn; x, y, z and n represent the addition ratio of each main metal element, wherein the value range of x is 0.05-0.19, y is 0.2-0.29, z is 0.10-0.24 and n is 5.80-5.90.
Several specific examples are given below to illustrate the preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the present invention. For the sake of easy comparison, the following examples are all prepared by using the characteristic molecular formula Sr0.7Ca0.05La0.25Fe11.47(Ni0.03Co0.10)O19The M-type calcium lanthanum cobalt permanent magnetic ferrite of (1) is illustrated.
Example 5
The main materials selected in the burdening process are as follows:
Fe2O3powder (wherein Fe2O3The purity of the powder is more than or equal to 99.3wt%, and the original average particle size of the particles is as follows: 0.75 um) 81.46 wt%;
SrCO310.06wt% of powder (the purity is more than or equal to 99%, and the original average particle size of the particles is 1.0 um);
La2O33.55wt% of powder (the purity is more than or equal to 99%, and the original average particle size of the particles is 2.0 um);
Co3O41.44wt% of powder (the purity is more than or equal to 99.3%, and the original average particle size of the particles is 0.8 um);
CaCO30.47wt% of powder (purity is more than or equal to 99.9%, original average particle size of particles: 2 um);
NiO powder (the purity is more than or equal to 99.9 percent, and the original average particle size of the particles is 1.0 um) 3.02wt percent;
the additives selected in the burdening process are as follows:
H3BO3、SiO2、CaCO3、La2O3、Co3O4and SrCO3Each component of which is A1-x-yCaxRyFe2n-zMzO19H is more than or equal to 03BO3≤0.5%，0≤SiO2≤1.0%，0.1%≤CaCO3≤1.2%，0≤La2O3≤1.0%，0≤Co3O4≤1.0%，0≤SrCO3≤0.8%。
Respectively weighing the raw materials, mixing and grinding the raw materials in a planetary wet ball mill, adding a steel ball with the diameter of 6mm and water into the ball mill during grinding, wherein the weight ratio of the water to the material powder to the steel ball is water: material powder: steel ball = 1: 1: 8; mixing and stirring the mixture in a ball mill for 0.5 to 5 hours;
then drying at 105-125 deg.C; presintering in air at 1150 deg.C for 30min to obtain granular presintering material. The one-time burn-in is specifically a microwave burn-in.
Then, carrying out ball milling and drying on the primary pre-sintering material again, and then carrying out secondary pre-sintering, wherein the secondary pre-sintering temperature is 1120 ℃, and the heat preservation time is 20 min; the material body is fully reacted by setting secondary pre-sintering, so that the performance of the finally prepared M-type calcium lanthanum cobalt permanent magnetic ferrite is improved. The secondary burn-in is specifically a microwave burn-in.
And coarsely crushing the obtained secondary pre-sintered material in a crusher for 30 seconds, wherein the average particle size after coarse crushing is less than 3 um.
Then, 100g of the coarsely pulverized material produced by the above method was weighed, and 0.4wt% of organic dispersant calcium gluconate and 0.3wt% of SiO were added2And 0.4% CaCO3(ii) a And adding 250 ml of deionized water as a ball milling medium, and performing wet micro-grinding for 3 hours in a planetary ball mill, wherein the average particle size of slurry particles subjected to wet micro-grinding is 0.6 um.
After the wet micro-pulverization, the water content of the slurry for molding was adjusted to 70% and then magnetic field molding was performed, and a molding magnetic field of 12KOe was applied in the pressing direction at the same time as the pressing. The resulting molded body was a cylinder having a diameter of 22mm and a height of 8mm, and the molding pressure was 7 MPa.
And (3) carrying out heat treatment on the formed body at the temperature of 200-400 ℃, completely removing the organic dispersing agent, then sintering in an air atmosphere at the temperature rise speed of 3 ℃/min, and keeping the temperature at 1150 ℃ for 1.5 hours to obtain the sintered permanent magnetic ferrite.
Three of the multiple sintered permanent magnetic ferrites obtained in example 5 were randomly sampled and subjected to top and bottom surface grinding, and their residual magnetic induction strength (Br), coercive force (Hcb), intrinsic coercive force (Hcj), maximum magnetic energy product (BH) max, squareness ratio (H) were measuredkHcj) as shown in table 2:
table 2: performance of M-type Ca-La-Co permanent magnetic ferrite obtained in example 5
As can be seen from Table 2, when the pre-sintering temperature of the calcium permanent magnetic ferrite material prepared by the method provided by the invention is 1150 ℃ or lower, the Br value reaches 446mT-450mT, the Hcj value reaches 390.5-400.1kA/m, and the rectangle ratios are all above 0.92. The invention can effectively improve the remanence of the sample on the basis of not reducing the coercive force, thereby obtaining more excellent comprehensive magnetic performance.
Comparative example 5-1
The raw material selection is the same as that in example 5, but the standard primary pre-sintering process is carried out by adopting a microwave oven, and the secondary pre-sintering is not carried out. Through a standard one-time presintering process, the presintering temperature is 1150 ℃, the heat preservation time is 90min, and the main phase formula of the obtained presintering material with ferrite detected can be represented as follows: sr0.7Ca0.05La0.25Fe11.47(Ni0.03Co0.10)O19。
The subsequent process is basically the same as in example 5;
three of the samples of the plurality of sintered permanent magnetic ferrites obtained in comparative example 5-1 were randomly sampled and subjected to top and bottom surface grinding, and the residual magnetic induction strength (Br), coercive force (Hcb), intrinsic coercive force (Hcj), maximum magnetic energy product (BH) max, squareness ratio (H) were measuredkHcj) as shown in table 3:
table 3: performance of M-type Ca-La-Co permanent magnetic ferrite obtained in comparative example 5-1
Comparing table 3 with table 2, it is seen from the comparison results of table 3 and table 2 that the permanent magnetic calcium ferrite material prepared by the secondary pre-sintering method can significantly improve Br at the pre-sintering temperature of 1150 ℃ or lower than the permanent magnetic calcium ferrite material prepared by the standard primary pre-sintering method without reducing the coercive force. The invention adds the secondary pre-sintering to ensure that the sample can react completely, thereby being beneficial to improving the comprehensive magnetic property of the finally obtained product.
Comparative example 5-2
The raw material selection is the same as that of the example 5, only the primary pre-sintering process and the secondary pre-sintering process adopt the traditional muffle furnace for pre-sintering, and the microwave pre-sintering is not carried out.
The presintering temperature of the primary presintering is 1180 ℃, and the heat preservation time is 2 hours. The temperature of the secondary presintering is 1000 ℃, and the heat preservation time is 30 min; the main phase equation for detecting that it has ferrite can be expressed as: sr0.7Ca0.05La0.25Fe11.47(Ni0.03Co0.10)O19。
The subsequent process is basically the same as in example 5;
three of the samples of the plurality of sintered permanent magnetic ferrites obtained in comparative example 5-2 were randomly sampled and subjected to top and bottom surface grinding, and the residual magnetic induction strength (Br), coercive force (Hcb), intrinsic coercive force (Hcj), maximum magnetic energy product (BH) max, squareness ratio (H) were measuredkHcj) as shown in table 4:
table 4: performance of M-type Ca-La-Co permanent magnetic ferrite obtained in comparative example 5-2
Comparing table 4 with table 2, it can be seen from the comparison results of table 2 and table 4 that the calcium lanthanum cobalt permanent magnetic ferrite material prepared by the primary microwave pre-sintering and the secondary microwave pre-sintering can be obviously improved in various indexes, especially the squareness ratio, when the pre-sintering temperature is 1130 ℃ or lower, compared with the calcium lanthanum cobalt permanent magnetic ferrite material prepared by the primary microwave pre-sintering and the secondary microwave pre-sintering in the conventional muffle furnace.
The invention is characterized in that microwave preburning method is adopted in preburning stage, so that completely reacted, uniform and fine crystal grains are hopefully obtained in preburning stage. Therefore, the obtained material body after pre-sintering has good performance on one hand, and on the other hand, the difficulty of secondary ball milling can be reduced, and the phenomena of doping caused by secondary ball milling and widening of particle size distribution caused by long-time ball milling are reduced, which is very helpful for improving the coercive force of the product, so that the comprehensive magnetic performance of the finally obtained product can be improved. The microwave method is adopted in the pre-burning stage and not adopted in the sintering stage by the applicant, because the microwave method causes the product to be easy to crack. And the microwave method is arranged in the pre-burning stage, so that the comprehensive magnetic property of the product can be improved, and the defect that the product is easy to crack is avoided.
Above only to prepare Sr0.7Ca0.05La0.25Fe11.47(Ni0.03Co0.10)O19The ferrite is taken as an example to explain the preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the present invention, however, the present invention is not limited thereto, and the preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the present invention can also be used for preparing other specific ferrites, such as, but not limited to, the ferrites in examples 2 to 4, and at this time, only the raw materials of the main material selected in the batching process need to be adjusted.
In summary, the invention provides an M-type calcium lanthanum cobalt permanent magnetic ferrite, which includes a hexagonal ferrite main phase of elements such as a, R, Ca, Fe and M, and has the following characteristic molecular formula: a. the1-x-yCaxRyFe2n-zMzO19Wherein A is Sr or Ba or the combination of Sr and Ba, R is La, and M is the combination of Co and at least one of Ni and Zn; x, y, z and n represent the addition proportion of each main metal element, and the value range of x0.05-0.19, y 0.2-0.29, z 0.10-0.24, and n 5.80-5.90. And simultaneously, a preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite is also provided, and the method adopts a microwave pre-sintering process to perform primary pre-sintering and secondary pre-sintering. The M-type calcium lanthanum cobalt permanent magnetic ferrite provided by the invention has higher comprehensive magnetic performance, and the preparation method can improve Br performance under the condition that the coercive force is not reduced when the pre-sintering temperature is 1130 ℃ or lower.
It will be apparent to those skilled in the art that various changes and modifications may be made in the invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (7)
1. The M-type calcium lanthanum cobalt permanent magnetic ferrite is characterized by comprising a hexagonal ferrite main phase containing A, R, Ca, Fe and M elements, wherein the hexagonal ferrite main phase has the following characteristic molecular formula: a. the1-x-yCaxRyFe2n-zMzO19Wherein
a is Sr or Ba or the combination of Sr and Ba,
r is La,
m is a combination of Co and at least one of Ni and Zn;
x, y, z, n represent the addition ratio of each main metal element,
the value range of x is 0.1-0.19,
y is 0.25 to 0.29,
z is 0.11 to 0.24,
n is 5.85-5.90;
and removing A from the M-type calcium lanthanum cobalt permanent magnetic ferrite1-x-yCaxRyFe2n-zMzO19In addition, the additive also comprises an additive, and the component of the additive is H3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3Each component of which is A1-x-yCaxRyFe2n-zMzO19H is more than or equal to 0 weight percent3BO3≤0.5％，0≤SiO2≤1.0％，0.1％≤CaCO3≤1.2％，0≤La2O3≤1.0％，0≤Co3O4≤1.0％，0≤SrCO3≤0.8％。
2. The M-type calcium lanthanum cobalt permanent magnetic ferrite of claim 1, wherein all of a is Sr.
3. The M-type ca-la-Co permanent ferrite of claim 1 or 2, wherein M is a combination of Ni and Co.
4. The M-type ca-la-Co permanent ferrite of claim 1 or 2, wherein M is a combination of Zn and Co.
5. The M-type ca-la-Co permanent ferrite of claim 1 or 2 wherein M is Ni and a combination of Zn and Co.
6. The preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite according to claim 1, characterized by comprising the following steps:
preparing materials: according to the chemical formula A1-x-yCaxRyFe2n-zMzO19Preparing main material powder; adding an additive H according to the weight percentage3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3Each component of which is A1-x-yCaxRyFe2n-zMzO19H is more than or equal to 03BO3≤0.5％，0≤SiO2≤1.0％，0.1％≤CaCO3≤1.2％，0≤La2O3≤1.0％，0≤Co3O4≤1.0％，0≤SrCO3≤0.8％；
Primary ball milling: putting the material powder into a ball mill for grinding, wherein a grinding medium adopts a steel ball with the thickness of 6mm, and the weight ratio of water to the material powder to the steel ball is as follows: material powder: steel ball 1: 1: 8; mixing and stirring the mixture in a ball mill for 0.5 to 5 hours;
drying: drying the slurry ground by the ball mill at the drying temperature of 105-125 ℃;
pre-burning for one time: pre-burning the dried material body for the first time to generate a calcium lanthanum cobalt permanent magnetic ferrite pre-burnt material for the first time; wherein the temperature of one presintering is 1100-1300 ℃, and the presintering time is 1-3 hours;
and (3) secondary pre-burning: performing ball milling and drying on the sample after the primary pre-sintering step again, and performing secondary pre-sintering to ensure complete reaction to generate a secondary pre-sintered material of the calcium-lanthanum-cobalt permanent magnetic ferrite; wherein the temperature of the secondary pre-sintering is 1120-1160 ℃, and the temperature is kept for 20-30 min;
secondary ball milling: weighing the calcium lanthanum cobalt permanent magnetic ferrite secondary pre-sintered material, adding a secondary additive and a dispersant in a mass ratio manner, and ball-milling the obtained mixture by adopting a wet method until the average particle size of slurry particles is about 0.6 mu m; wherein the secondary additive comprises Al2O3、Cr2O3、H3BO3、SiO2、CaCO3、La2O3、Co3O4And SrCO3The average particle size of each secondary additive particle is not more than 2.0 mu m, and the addition amount of the secondary additive is more than or equal to 0 and less than or equal to Al2O3≤1.0％，0≤Cr2O3≤1.0％，0≤H3BO3≤0.5％，0≤SiO2≤1.0％，0.1％≤CaCO3≤1.2％，0≤La2O3≤1.0％，0≤Co3O4≤1.0％，0≤SrCO3Less than or equal to 0.8 percent; the dispersing agent is one or more of calcium gluconate, polyvinyl alcohol and sorbitol, and the addition amount of the dispersing agent is 0.2-1.2wt% of the total weight of the components;
pressing a green body: pressing the sample obtained after the secondary ball milling in an oriented magnetic field to obtain a green body, wherein the pressing pressure is 7MPa, and the size of the oriented magnetic field is 5-15 kOe;
and (3) sintering: sintering the green body in an air oxidizing atmosphere at the temperature of 1000-1300 ℃ to obtain a finished product, wherein the sintering time is 0.5-3 hours, and the heating rate is 30-80 ℃/h; wherein,
the primary pre-burning is microwave pre-burning and/or the secondary pre-burning is microwave pre-burning.
7. The preparation method of the M-type calcium lanthanum cobalt permanent magnetic ferrite according to claim 6, wherein the main material powder comprises the following raw materials:
Fe2O3powder with purity more than or equal to 99.3wt% and original average particle size of 0.75 μm;
SrCO3powder with purity more than or equal to 99 percent and original average particle size of 1.0 mu m;
La2O3powder with purity more than or equal to 99 percent and original average particle size of 2.0 mu m;
Co3O4powder with purity more than or equal to 99.3% and original average particle size of 0.8 μm;
CaCO3powder with purity more than or equal to 99.9% and original average particle size of 2 μm;
NiO powder, the purity of which is more than or equal to 99.9 percent, and the original average particle size of the particles is 1.0 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310254242.9A CN104230323B (en) | 2013-06-24 | 2013-06-24 | M type calcium lanthanum cobalt permanent-magnet ferrite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310254242.9A CN104230323B (en) | 2013-06-24 | 2013-06-24 | M type calcium lanthanum cobalt permanent-magnet ferrite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104230323A CN104230323A (en) | 2014-12-24 |
| CN104230323B true CN104230323B (en) | 2016-12-28 |
Family
ID=52219341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310254242.9A Active CN104230323B (en) | 2013-06-24 | 2013-06-24 | M type calcium lanthanum cobalt permanent-magnet ferrite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104230323B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102277414B1 (en) * | 2015-10-16 | 2021-07-14 | 유니온머티리얼 주식회사 | Ferrite magnetic material and ferrite sintered magnet |
| JP7358758B2 (en) * | 2019-03-27 | 2023-10-11 | Tdk株式会社 | Ferrite sintered magnet and rotating electric machine equipped with the same |
| CN110156452B (en) * | 2019-05-28 | 2020-12-22 | 横店集团东磁股份有限公司 | M-type strontium ferrite and preparation method thereof |
| CN111362686A (en) * | 2019-12-05 | 2020-07-03 | 横店集团东磁股份有限公司 | Hexagonal magnetoplumbite permanent magnetic ferrite material and preparation method thereof |
| CN110937888B (en) * | 2019-12-17 | 2021-03-26 | 横店集团东磁股份有限公司 | High-performance permanent magnetic ferrite material with secondary pre-sintering of powder and preparation method thereof |
| CN111423226B (en) * | 2020-03-17 | 2022-05-24 | 江门江益磁材有限公司 | Permanent magnetic ferrite and preparation method and application thereof |
| JP7367581B2 (en) | 2020-03-23 | 2023-10-24 | Tdk株式会社 | ferrite sintered magnet |
| JP2021155317A (en) | 2020-03-30 | 2021-10-07 | Tdk株式会社 | Ferrite sintered magnet and rotating electric machine |
| JP7347296B2 (en) | 2020-03-30 | 2023-09-20 | Tdk株式会社 | Ferrite sintered magnets and rotating electrical machines |
| CN111620684A (en) * | 2020-05-22 | 2020-09-04 | 浙江凯文磁钢有限公司 | Sodium lanthanum permanent magnetic ferrite and preparation method and application thereof |
| CN111960816B (en) * | 2020-08-27 | 2022-04-19 | 安徽万磁电子有限公司 | Preparation process of permanent magnetic ferrite |
| CN113024241A (en) * | 2021-02-08 | 2021-06-25 | 江门江益磁材有限公司 | Lanthanum-cobalt permanent magnetic ferrite and preparation method thereof |
| CN113072369B (en) * | 2021-03-25 | 2022-05-31 | 电子科技大学 | U-shaped hexagonal ferrite material with high remanence ratio and preparation method thereof |
| CN113724953A (en) * | 2021-09-12 | 2021-11-30 | 杨杭福 | Method for preparing high-performance permanent magnet composite material by using high-pressure ultrasonic thermal decomposition method |
| CN114591074A (en) * | 2022-03-28 | 2022-06-07 | 电子科技大学 | Preparation technology of high-remanence M-type barium ferrite for self-biased circulator |
| CN115784733B (en) * | 2022-12-22 | 2023-12-01 | 矿冶科技集团有限公司 | High-performance calcium lanthanum cobalt ferrite material and preparation method thereof |
| CN116120049B (en) * | 2023-02-17 | 2024-01-19 | 矿冶科技集团有限公司 | Preparation method of calcium lanthanum cobalt ferrite magnet, calcium lanthanum cobalt ferrite magnet and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101552069A (en) * | 2009-01-08 | 2009-10-07 | 横店集团东磁股份有限公司 | Magnetoplumbite permanent magnetic ferrite and method of producing the same |
| CN102167576A (en) * | 2011-01-15 | 2011-08-31 | 五邑大学 | High performance permanent magnetic ferrite magnetic powder and method for preparing same |
| CN102945718A (en) * | 2003-09-12 | 2013-02-27 | 日立金属株式会社 | Ferrite sintered magnet |
| CN102964120A (en) * | 2012-08-31 | 2013-03-13 | 横店集团东磁股份有限公司 | Sintered permanent magnetic ferrite and its preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6476943A (en) * | 1987-09-16 | 1989-03-23 | Seiko Epson Corp | Superconducting material |
-
2013
- 2013-06-24 CN CN201310254242.9A patent/CN104230323B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102945718A (en) * | 2003-09-12 | 2013-02-27 | 日立金属株式会社 | Ferrite sintered magnet |
| CN101552069A (en) * | 2009-01-08 | 2009-10-07 | 横店集团东磁股份有限公司 | Magnetoplumbite permanent magnetic ferrite and method of producing the same |
| CN102167576A (en) * | 2011-01-15 | 2011-08-31 | 五邑大学 | High performance permanent magnetic ferrite magnetic powder and method for preparing same |
| CN102964120A (en) * | 2012-08-31 | 2013-03-13 | 横店集团东磁股份有限公司 | Sintered permanent magnetic ferrite and its preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104230323A (en) | 2014-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104230323B (en) | M type calcium lanthanum cobalt permanent-magnet ferrite and preparation method thereof | |
| EP2660830B1 (en) | Ferrite sintered magnet and method for producing same | |
| US8337714B2 (en) | Ferrite powders for bonded magnet, process for the production of the powders, and bonded magnet made by using the same | |
| EP3364426B1 (en) | Ferrite magnetic material and ferrite sintered magnet | |
| CN112679207B (en) | Permanent magnetic ferrite material and preparation method thereof | |
| CN101552069A (en) | Magnetoplumbite permanent magnetic ferrite and method of producing the same | |
| CN104230326B (en) | The preparation method of M type calcium permanent ferrite | |
| WO2011001831A1 (en) | Ferrite sintered magnet producing method and ferrite sintered magnet | |
| CN104230321B (en) | M type calcium permanent ferrites and preparation method thereof | |
| CN103058641B (en) | Method for preparing non-rare-earth high-magnetism permanent magnetic ferrite material | |
| EP3473606B1 (en) | Ferrite sintered magnet | |
| CN104230325A (en) | Preparation method of permanent magnetic ferrite pre-sintering material and preparation method of permanent magnetic ferrite | |
| CN103548101B (en) | Magneto-plumbite type ferrite magnetic material and segment permanent magnet body therefrom | |
| CN103172360A (en) | Plumbite type yttrium permanent magnetic ferrite material and preparation method thereof | |
| JP2000501893A (en) | Ferrite magnets, powders for ferrite magnets, and methods for producing them | |
| CN104230322A (en) | M-type calcium permanent magnetic ferrite and preparation method thereof | |
| CN104496444A (en) | Low-cost sintered permanent magnet ferrite material and preparation method thereof | |
| JP7468009B2 (en) | Ferrite calcined body, sintered ferrite magnet and method for producing same | |
| KR102430475B1 (en) | Method for preparing ferrite sintered magnet and ferrite sintered magnet | |
| JP2008270785A (en) | Method for manufacturing ferrite sintered magnet | |
| JP7287371B2 (en) | Calcined ferrite body, sintered ferrite magnet and method for producing the same | |
| KR102587856B1 (en) | Ferrite calcined body and method for manufacturing sintered ferrite magnet | |
| JP7238917B2 (en) | Method for producing calcined ferrite powder and sintered ferrite magnet | |
| KR102588230B1 (en) | Ferrite magnetic material and ferrite sintered magnet | |
| KR20170142758A (en) | Ferrite magnetic material and ferrite sintered magnet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No. 8 Longwan Road, Jiangmen, Guangdong Patentee after: Guangdong led Limited by Share Ltd Address before: No. 8 Longwan Road, Jiangmen, Guangdong Patentee before: JPMF Guangdong Co., Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200811 Address after: No. 359, Jinou Road, Jianghai District, Jiangmen City, Guangdong Province:282 Nanshan Road, Jianghai District, Jiangmen City; 126 Gaoxin West Road, Jianghai District, Jiangmen City) No. 359, Jinou Road, Jianghai District, Jiangmen City, Guangdong Province (place of business: No. 282, Nanshan Road, Jianghai District, Jiangmen City; No. 126, Gaoxin West Road, Jianghai District, Jiangmen City) Patentee after: Jiangmen Jiangyi magnetic material Co.,Ltd. Address before: 529000 No. 8, Longwan Road, Jiangmen, Guangdong Patentee before: Guangdong led Limited by Share Ltd. |
|
| TR01 | Transfer of patent right |