CN111439995A - High-performance Co-free hexagonal permanent magnetic ferrite material and preparation method thereof - Google Patents

High-performance Co-free hexagonal permanent magnetic ferrite material and preparation method thereof Download PDF

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CN111439995A
CN111439995A CN201910042117.9A CN201910042117A CN111439995A CN 111439995 A CN111439995 A CN 111439995A CN 201910042117 A CN201910042117 A CN 201910042117A CN 111439995 A CN111439995 A CN 111439995A
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ferrite material
caco
permanent magnetic
magnetic ferrite
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CN111439995B (en
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唐明星
余忠
顾闻斌
孙科
赵廷伟
兰中文
李元兴
郭荣迪
邬传健
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Sichuan Magunion Technology Co ltd
University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Abstract

The invention discloses a high-performance Co-free hexagonal permanent magnetic ferrite material and a preparation method thereof, mainly aiming at the problems of relative shortage of strategic cobalt resources and high price and the like in China, and mainly solving the key technical problems in the following two aspects in the field of permanent magnetic ferrite: firstly, the main component completely replaces Co ions, so that the production cost is greatly reduced, and the method has great strategic significance for relieving the relative shortage of the cobalt resources in China; secondly, it has high BrHigh HcjHegao (BH)maxThe performance index of the high-performance Co-free hexagonal permanent magnetic ferrite material prepared by the invention is higher than that of the high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market, and the material is finally usedThe performance indexes are as follows: residual magnetic induction BrMore than or equal to 460 mT; intrinsic coercive force HcjMore than or equal to 370 kA/m; magnetic coercive force HcbNot less than 330 kA/m; maximum magnetic energy product (BH)max≥41kJ/m3。

Description

High-performance Co-free hexagonal permanent magnetic ferrite material and preparation method thereof
Technical Field
The invention belongs to the technical field of ferrite material preparation, and particularly relates to a high-performance Co-free hexagonal permanent magnetic ferrite material and a preparation method thereof.
Background
According to statistics of national prospective industry research institute, market scale of the permanent magnet motor industry in China in 2018 breaks through billions, and along with pace of technical innovation and industrial structure upgrading in the field of permanent magnet motors, permanent magnet ferrite materials at the upstream of an industrial chain are rapidly developed and adjusted.
However, with the rapid development of the economic globalization in recent years, strategic non-renewable resources are gradually exhausted, and the establishment of resource-saving and environment-friendly society becomes an increasingly pursued target. The average content of cobalt used in the field of permanent magnetic ferrite in the earth crust is only 0.001%, while the cobalt resource in China mainly comes from associated minerals of cobalt, the production and utilization cost is high, and at present, Co is high3O4The market price is about 34 ten thousand per ton, mostly depends on foreign import, and forms a potential threat to national economic construction and development. Therefore, the research and preparation of the high-performance Co-free hexagonal permanent magnetic ferrite material are important requirements for the development of the national economic strategy.
Aiming at the research and preparation of the high-performance Co-free hexagonal permanent magnetic ferrite material, the performance index of the Ca-L a substituted hexagonal permanent magnetic ferrite material published by the Korean national transportation university is that the residual magnetic induction strength BrLess than or equal to 340mT and intrinsic coercive force HcjThe residual magnetic induction intensity and intrinsic coercive force of the material are lower and can not meet the performance index (residual magnetic induction intensity B) of the high-performance L a-Co series hexagonal permanent magnetic ferrite material on the marketrNot less than 450mT and intrinsic coercive force HcjNot less than 358kA/m, maximum magnetic energy product (BH)max≥38kJ/m3) And (6) matching. Preparation of SrFe by Germany Siemens Techni GmbH by adopting traditional oxide ceramic method11AlO19The performance indexes of the permanent magnetic ferrite material are as follows: residual magnetic induction BrLess than or equal to 260mT and intrinsic coercive force HcjThe material has intrinsic coercive force reaching the performance index of high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market, but has low residual magnetic induction strength and can not meet the requirements of high efficiency and high air gap magnetic density of a permanent magnet motorrLess than or equal to 430mT and intrinsic coercive force HcjLess than or equal to 250kA/m and maximum magnetic energy product (BH)max≤36kJ/m3The university of Anhui China adopts L a-Cu to replace and prepare the hexagonal permanent magnetic ferrite material, whichThe performance indexes are as follows: residual magnetic induction BrNot more than 420mT, intrinsic coercive force HcjLess than or equal to 235kA/m and maximum magnetic energy product (BH)max≤32kJ/m3Although the residual magnetic induction intensity and the maximum magnetic energy product of the two materials are close to the performance indexes of the high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market, the intrinsic coercive force is low, and the requirements of the overload multiple and high stability of the permanent magnet motor cannot be met.
In addition, in the published patent CN1664964, an unsubstituted hexagonal permanent magnetic ferrite material is disclosed, and the performance indexes thereof are as follows: residual magnetic induction Br378mT or less and intrinsic coercive force HcjLess than or equal to 222kA/m and maximum magnetic energy product (BH)max≤26kJ/m3The residual magnetic induction intensity, intrinsic coercive force and maximum magnetic energy product of the product have larger difference with the performance index of the high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market, and the patent CN105060870A discloses a high-coercive force hexagonal permanent magnetic ferrite material (SrFe)12-xAlxO19And x is more than or equal to 0.3 and less than or equal to 0.5) are as follows: residual magnetic induction BrNot more than 370mT, intrinsic coercive force HcjLess than or equal to 400kA/m and maximum magnetic energy product (BH)max≤25kJ/m3The intrinsic coercivity of the product reaches the performance index of a high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market, but the residual magnetic induction intensity and the maximum energy product are low, so that the requirements of small size, high efficiency and high air gap magnetic density of a permanent magnet motor cannot be met12-xCexO19X is more than or equal to 0.3 and less than or equal to 0.5), and the performance indexes are as follows: specific saturation magnetization σsLess than or equal to 60.7emu/g and intrinsic coercive force HcjThe intrinsic coercive force of the product is close to the performance index of the high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market, but the specific saturation magnetization intensity is equal to the specific saturation magnetization intensity (sigma)sNot less than 72 emu/g).
Based on the above, the Co-free hexagonal permanent magnetic ferrite material for the current motor cannot have both high B and performancerHigh HcjHegao (BH)maxTo a problem of (a).
Disclosure of Invention
The invention aims to provide a high-performance Co-free hexagonal permanent magnetic ferrite material with performance indexes superior to those of a high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market and a preparation method thereof.
The technical scheme of the invention is realized as follows: a high-performance Co-free hexagonal permanent magnetic ferrite material comprises the following components of main components and additives, and is characterized in that:
according to the mole percentage of the main components, the main components comprise: 1.38 to 4.46 mol% CaCO3、2.15～6.15mol％La2O3、1.38～5.38mol％SrCO3、73.5～82.2mol％Fe2O3、1.15～5.77mol％Al2O3、1.92～6.54mol％ZnO、1.69～7.31mol％CuO；
The additive comprises 0.01-0.08 wt% of L a calculated by oxide according to the weight percentage of the main component2O3、0.03～0.09wt％Al2O3、0.08～0.18wt％H3BO3、0.08～0.38wt％CaCO3、0.18～0.38wt％SiO2、0.12～0.72wt％Ca(C6H11O7)2、0.12～0.72wt％HO(CH2CH2O)nH。
The high-performance Co-free hexagonal permanent magnetic ferrite material comprises the following main components in percentage by mole: 2.18 to 3.46 mol% CaCO3、2.55～4.15mol％La2O3、2.18～4.23mol％SrCO3、78.5～81.2mol％Fe2O3、2.15～4.77mol％Al2O3、3.04～5.54mol％ZnO、2.69～5.31mol％CuO；
The additive comprises 0.03-0.06 wt% L a calculated by oxide according to the weight percentage of the main component2O3、0.05～0.07wt％Al2O3、0.10～0.16wt％H3BO3、0.18～0.28wt％CaCO3、0.24～0.34wt％SiO2、0.22～0.62wt％Ca(C6H11O7)2、0.22～0.62wt％HO(CH2CH2O)nH。
The high-performance Co-free hexagonal permanent magnetic ferrite material comprises the following main components in percentage by mole: 2.54 mol% CaCO3、2.92mol％La2O3、2.23mol％SrCO3、80.54mol％Fe2O3、4.08mol％Al2O3、4.54mol％ZnO、3.15mol％CuO；
The additive comprises 0.04 wt% L a calculated by oxide according to the weight percentage of the main component2O3、0.06wt％Al2O3、0.14wt％H3BO3、0.21wt％CaCO3、0.29wt％SiO2、0.52wt％Ca(C6H11O7)2、0.48wt％HO(CH2CH2O)nH。
The high-performance Co-free hexagonal permanent magnetic ferrite material has the following performance indexes:
residual magnetic induction Br≥460mT；
Intrinsic coercive force Hcj≥370kA/m；
Magnetic coercive force Hcb≥330kA/m；
Maximum magnetic energy product (BH)max≥41kJ/m3。
A high-performance Co-free hexagonal permanent magnetic ferrite material has the performance indexes as follows:
residual magnetic induction Br≥460mT；
Intrinsic coercive force Hcj≥370kA/m；
Magnetic coercive force Hcb≥330kA/m；
Maximum magnetic energy product (BH)max≥41kJ/m3。
The high-performance Co-free hexagonal permanent magnetic ferrite material comprises the following components in percentage by weight: CaCO3、La2O3、SrCO3、Fe2O3、Al2O3ZnO and CuO, wherein the additive comprises L a2O3、Al2O3、H3BO3、CaCO3、SiO2、Ca(C6H11O7)2、HO(CH2CH2O)nH。
A preparation method of a high-performance Co-free hexagonal permanent magnetic ferrite material is characterized by comprising the following steps: the method comprises the following steps:
a) material formulation selection
According to the mole percentage of the main component, 1.38-4.46 mol percent of CaCO is adopted3、2.15～6.15mol％La2O3、1.38～5.38mol％SrCO3、73.5～82.2mol％Fe2O3、1.15～5.77mol％Al2O3、1.92～6.54mol％ZnO、1.69～7.31mol％CuO；
b) One-step ball milling
Uniformly mixing the above material powder in a ball mill, wherein the particle size of the powder is controlled to be 0.7-0.9 μm;
c) pre-firing
Drying the ball-milled material obtained in the step b), and pre-burning in a furnace at 1050-1150 ℃ for 2-4 hours;
d) additive
Adding the additive of 0.01-0.08 wt% L a into the powder obtained in the step c)2O3、0.03～0.09wt％Al2O3、0.08～0.18wt％H3BO3、0.08～0.38wt％CaCO3、0.18～0.38wt％SiO2、0.12～0.72wt％Ca(C6H11O7)2、0.12～0.72wt％HO(CH2CH2O)nH；
e) Secondary ball milling
Ball-milling the powder obtained in the step d) in a ball mill, wherein the particle size of the powder is controlled to be 0.5-0.7 mu m;
f) shaping of
Dehydrating the ball-milling slurry obtained in the step e) to ensure that the water content of the slurry is 35-50%, and performing compression molding under a wet-pressing magnetic field forming machine, wherein the magnetic field intensity of the formed slurry is 7.5-14.5 kOe, and the pressure maintaining time is 6-12 s;
g) sintering
And f), placing the blank obtained in the step f) in a sintering furnace for sintering, applying 100-500N pressure on the upper part of the blank, and preserving heat for 2.5-5.5 hours at the temperature of 1080-1180 ℃.
The invention mainly aims at the problems of relative shortage of strategic cobalt resources and high price and the like in China, provides a high-performance Co-free hexagonal permanent magnetic ferrite material and a preparation method thereof, and mainly solves the following key technical problems in the field of permanent magnetic ferrites in two aspects: firstly, the main component completely replaces Co ions, so that the production cost is greatly reduced, and the method has great strategic significance for relieving the relative shortage of the cobalt resources in China; secondly, it has high BrHigh HcjHegao (BH)maxThe air gap flux density and the overload multiple of the permanent magnet motor can be improved, the number of magnetic shoes required by the motor is reduced, and the small-size high-efficiency and high-stability of the permanent magnet motor are realized.
The performance index of the high-performance Co-free hexagonal permanent magnetic ferrite material prepared by the invention is higher than that of the high-performance L a-Co series hexagonal permanent magnetic ferrite material on the market, and the final performance index is as follows:
residual magnetic induction Br≥460mT；
Intrinsic coercive force Hcj≥370kA/m；
Magnetic coercive force Hcb≥330kA/m；
Maximum magnetic energy product (BH)max≥41kJ/m3。
Drawings
Fig. 1 shows a scanning electron micrograph of the hexagonal ferrite material in example 1 of the present invention.
Fig. 2 shows a scanning electron micrograph of the hexagonal ferrite material in example 2 of the present invention.
Fig. 3 shows a scanning electron micrograph of the hexagonal ferrite material according to example 3 of the present invention.
Fig. 4 shows a scanning electron micrograph of the hexagonal ferrite material according to example 4 of the present invention.
Fig. 5 shows a scanning electron micrograph of the hexagonal ferrite material in example 5 of the present invention.
FIG. 6 is a scanning electron micrograph of the hexagonal ferrite material of comparative example 1 of the present invention.
FIG. 7 is a scanning electron micrograph of the hexagonal ferrite material of comparative example 2 of the present invention.
FIG. 8 is a scanning electron micrograph of the hexagonal ferrite material of comparative example 3 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems of relative scarcity and high price of strategic cobalt resources in China and the like, the invention provides a cobalt-rich cobaltrHigh HcjHegao (BH)maxA Co-free hexagonal permanent magnetic ferrite material and a preparation method thereof. The guiding idea is as follows: magnetic domain theory, ion space occupying mechanism, crystal inhibition-crystal promotion competitive sintering mechanism, electrostatic steric hindrance mechanism and magnetic stress theory. First, by preference of highly pure CaCO3、La2O3、SrCO3、Fe2O3、Al2O3ZnO and CuO are used as raw materials, the ion occupying situation and the single domain critical dimension of the hexagonal permanent magnetic ferrite material are deeply analyzed, a plurality of metal ions are combined to regulate and control the hexagonal permanent magnetic ferrite material, the high coercive force and the high magnetic induction intensity are taken as guiding ideas, the optimal formula range is formulated, and secondly, the action mechanism of different additives on the microstructure and the magnetic slurry dispersion characteristic of the hexagonal permanent magnetic ferrite material is combined, L a is researched2O3、Al2O3、H3BO3、CaCO3And SiO2The influence on the grain boundary characteristics of the magnetic slurry and the influence on the dispersion characteristics of the magnetic slurry by the calcium gluconate and the polyethylene glycol are used for formulating an optimal additive formula; finally, the above-mentioned formula, additive andunder the premise of optimizing the powder preparation process, the magnetic stress theory sintering technology is used to realize uniform, fine and flaky growth of crystal grains, and finally the high-B-content silicon-based composite material is preparedrHigh HcjHegao (BH)maxAnd the hexagonal permanent magnetic ferrite material is Co-free.
The high-performance Co-free hexagonal permanent magnetic ferrite material comprises the following components in percentage by mole: 1.38 to 4.46 mol% CaCO3、2.15～6.15mol％La2O3、1.38～5.38mol％SrCO3、73.5～82.2mol％Fe2O3、1.15～5.77mol％Al2O3、1.92～6.54mol％ZnO、1.69～7.31mol％CuO。
The additive comprises 0.01-0.08 wt% of L a calculated by oxide according to the weight percentage of the main component2O3、0.03～0.09wt％Al2O3、0.08～0.18wt％H3BO3、0.08～0.38wt％CaCO3、0.18～0.38wt％SiO2、0.12～0.72wt％Ca(C6H11O7)2(calcium gluconate) 0.12-0.72 wt% HO (CH)2CH2O)nH (polyethylene glycol).
In the main component aspect of the invention, one aspect is L a3++Al3+The substitution can increase the critical dimension of a single domain, enhance the magnetocrystalline anisotropy and obviously improve the coercive force of a sintered sample; on the other hand Cu2+Happy Fe3+Middle 2a (≈ 4 f) and 4f2(↓) crystal position with occupying ratio of about 1:2, Zn2+Preferentially occupying Fe3+Middle 4f1And the crystal site of ↓isfavorable for regulating and controlling the saturation magnetic induction intensity of a sintered sample, and simultaneously, the proper amount of CuO with low melting point is introduced into the main formula, so that the pre-sintering temperature can be reduced, the energy consumption can be reduced, and the density of the sintered body can be improved.
In the aspect of additives, the invention introduces a trace amount of L a2O3And Al2O3Repairing lattice defects generated in the pre-sintering process and improving the purity of a sintered sample; by means of H3BO3As a combustion aid, at high temperaturesSolution generation B2O3The glass phase is enriched at the crystal boundary to inhibit the growth of crystal grains and improve the coercivity; doped CaCO3And SiO2The crystal grains are refined, the particle distribution is narrowed, and the remanence orientation is improved; calcium gluconate is added to form a double electric layer structure on the surface of the ferrite, polyethylene glycol is introduced to be adsorbed on the surfaces of the particles to hinder agglomeration among the particles, and the effect of dispersing magnetic particles is achieved.
The magnetostriction coefficient lambda of the hexagonal permanent magnetic ferrite materials< 0, in the course of sintering, adding a certain weight of sintering-supporting plate on the ferrite magnetic sheet to raise c-axis orientation of crystal grain, i.e. L a is introduced by means of main formula3+、Al3+Metal ions are subjected to plasma treatment, the critical dimension of a single domain is increased, the occupied distribution of the ions is regulated and controlled, and high coercivity and high saturation magnetic induction intensity are realized; by doping the crystal-inhibiting crystal-promoting crystal double-property composite additive, the crystal grain boundary characteristic of crystal grains is optimized, and the maximization of the single-domain particle size and the densification growth are realized; combining ionic and steric type dispersing agents, constructing a double electric layer structure and a steric effect, controlling the viscosity of the slurry and realizing the dispersion among magnetic particles; based on a magnetic stress theoretical model, the c-axis orientation of the crystal grain magnetic moment is regulated and controlled, and uniform and fine flaky growth is realized.
The preparation method of the high-performance Co-free hexagonal permanent magnetic ferrite material comprises the following steps:
a) material formulation selection
According to the mole percentage of the main component, 1.38-4.46 mol percent of CaCO is adopted3、2.15～6.15mol％La2O3、1.38～5.38mol％SrCO3、73.5～82.2mol％Fe2O3、1.15～5.77mol％Al2O3、1.92～6.54mol％ZnO、1.69～7.31mol％CuO。
b) One-step ball milling
The above materials are mixed uniformly in a ball mill, and the particle size of the powder is controlled between 0.7 and 0.9 mu m.
c) Pre-firing
Drying the ball milling material obtained in the step b), and pre-sintering in a furnace at 1050-1150 ℃ for 2-4 hours.
d) Additive
Adding the additive of 0.01-0.08 wt% L a into the powder obtained in the step c)2O3、0.03～0.09wt％Al2O3、0.08～0.18wt％H3BO3、0.08～0.38wt％CaCO3、0.18～0.38wt％SiO2、0.12～0.72wt％Ca(C6H11O7)2(calcium gluconate) 0.12-0.72 wt% HO (CH)2CH2O)nH (polyethylene glycol).
e) Secondary ball milling
Ball-milling the powder obtained in the step d) in a ball mill, wherein the particle size of the powder is controlled to be 0.5-0.7 mu m.
f) Shaping of
Dehydrating the ball-milling slurry obtained in the step e) to enable the water content of the slurry to be 35-50%, and performing compression molding under a wet-pressing magnetic field forming machine, wherein the magnetic field intensity of the forming machine is 7.5-14.5 kOe, and the pressure maintaining time is 6-12 s.
g) Sintering
And f), placing the blank obtained in the step f) in a sintering furnace for sintering, applying 100-500N pressure on the upper part of the blank, and preserving heat for 2.5-5.5 hours at the temperature of 1080-1180 ℃.
h) Testing
Testing the permanent magnetic property of the sample obtained in the step g) to obtain the residual magnetic induction strength B of the materialrIntrinsic coercive force HcjMagnetic coercive force HcbAnd maximum magnetic energy product (BH)maxAnd an AMT-4A permanent magnet characteristic automatic measuring instrument is adopted for testing.
The high-performance Co-free hexagonal permanent magnetic ferrite material has residual magnetic induction strength BrNot less than 460mT and intrinsic coercive force HcjNot less than 370kA/m, magnetic coercive force HcbNot less than 330kA/m, maximum magnetic energy product (BH)max≥41kJ/m3。
Specific examples 1 to 5 of the present invention and comparative examples 1 to 3 include the following steps:
a) selecting a formula, wherein CaCO is adopted as a main component in examples 1-53、La2O3、SrCO3、Fe2O3、Al2O3、ZnO、CuO, CaCO as the main component in comparative examples 1 to 33、La2O3、SrCO3、Fe2O3(ii) a The corresponding main component ratios are shown in the following table, calculated as oxides in mol percent.
Figure BDA0001947893020000101
b) And (3) performing primary ball milling, namely uniformly mixing the raw material powder in a ball mill, wherein the particle size of the powder is controlled to be 0.7-0.9 mu m.
c) Pre-sintering, namely drying the ball-milled material obtained in the step b), and pre-sintering in a furnace at 1070 ℃ for 3.5 hours.
d) Adding an additive into the powder obtained in the step c) according to the weight ratio of L a adopted in the embodiments 1-52O3、Al2O3、H3BO3、CaCO3、SiO2、Ca(C6H11O7)2(calcium gluconate), HO (CH)2CH2O)nH (polyethylene glycol) as used in comparative examples 1 to 33BO3、CaCO3、SiO2、Ca(C6H11O7)2(calcium gluconate); the corresponding additive ratio is shown in the following table, and is calculated by the mass percent of the main components and calculated by oxides.
Figure BDA0001947893020000102
Figure BDA0001947893020000111
e) And d) secondary ball milling, wherein the material powder obtained in the step d) is ball milled in a ball mill, and the particle size of the powder is controlled to be 0.5-0.7 mu m.
f) And e) forming, namely dehydrating the ball-milled slurry obtained in the step e) to ensure that the water content of the slurry is 38%, and performing compression forming under a wet-pressing magnetic field forming machine, wherein the forming magnetic field intensity is 8.5kOe, and the pressure maintaining time is 7 s.
g) And f), sintering, namely placing the blank obtained in the step f) in a sintering furnace for sintering, applying 100-500N pressure on the upper part of the blank, and preserving heat for 3.5 hours at 1120 ℃.
h) Testing, the sample obtained in the step g) is subjected to permanent magnet characteristic testing, and the residual magnetic induction strength B of the materialrIntrinsic coercive force HcjMagnetic coercive force HcbAnd maximum magnetic energy product (BH)maxAnd an AMT-4A permanent magnet characteristic automatic measuring instrument is adopted for testing.
The high-performance Co-free hexagonal permanent magnetic ferrite material is prepared by the process, and the performance indexes are as follows:
the test results of examples 1 to 5 and comparative examples 1 to 3 are as follows:
Figure BDA0001947893020000112
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (7)

1. A high-performance Co-free hexagonal permanent magnetic ferrite material comprises the following components of main components and additives, and is characterized in that:
according to the mole percentage of the main components, the main components comprise: 1.38 to 4.46 mol% CaCO3、2.15～6.15mol％La2O3、1.38～5.38mol％SrCO3、73.5～82.2mol％Fe2O3、1.15～5.77mol％Al2O3、1.92～6.54mol％ZnO、1.69～7.31mol％CuO；
The additive comprises 0.01-0.08 wt% of L a calculated by oxide according to the weight percentage of the main component2O3、0.03～0.09wt％Al2O3、0.08～0.18wt％H3BO3、0.08～0.38wt％CaCO3、0.18～0.38wt％SiO2、0.12～0.72wt％Ca(C6H11O7)2、0.12～0.72wt％HO(CH2CH2O)nH。
2. The high-performance Co-free hexagonal permanent magnetic ferrite material according to claim 1, wherein: according to the mole percentage of the main components, the main components comprise: 2.18 to 3.46 mol% CaCO3、2.55～4.15mol％La2O3、2.18～4.23mol％SrCO3、78.5～81.2mol％Fe2O3、2.15～4.77mol％Al2O3、3.04～5.54mol％ZnO、2.69～5.31mol％CuO；
The additive comprises 0.03-0.06 wt% L a calculated by oxide according to the weight percentage of the main component2O3、0.05～0.07wt％Al2O3、0.10～0.16wt％H3BO3、0.18～0.28wt％CaCO3、0.24～0.34wt％SiO2、0.22～0.62wt％Ca(C6H11O7)2、0.22～0.62wt％HO(CH2CH2O)nH。
3. The high-performance Co-free hexagonal permanent magnetic ferrite material according to claim 2, wherein: according to the mole percentage of the main components, the main components comprise: 2.54 mol% CaCO3、2.92mol％La2O3、2.23mol％SrCO3、80.54mol％Fe2O3、4.08mol％Al2O3、4.54mol％ZnO、3.15mol％CuO；
The additive comprises 0.04 wt% L a calculated by oxide according to the weight percentage of the main component2O3、0.06wt％Al2O3、0.14wt％H3BO3、0.21wt％CaCO3、0.29wt％SiO2、0.52wt％Ca(C6H11O7)2、0.48wt％HO(CH2CH2O)nH。
4. The high performance Co-free hexagonal permanent ferrite material of claim 1, 2 or 3, wherein: the performance indexes of the material are as follows:
residual magnetic induction Br≥460mT；
Intrinsic coercive force Hcj≥370kA/m；
Magnetic coercive force Hcb≥330kA/m；
Maximum magnetic energy product (BH)max≥41kJ/m3。
5. A high-performance Co-free hexagonal permanent magnetic ferrite material is characterized in that: the performance indexes of the material are as follows:
residual magnetic induction Br≥460mT；
Intrinsic coercive force Hcj≥370kA/m；
Magnetic coercive force Hcb≥330kA/m；
Maximum magnetic energy product (BH)max≥41kJ/m3。
6. The high-performance Co-free hexagonal permanent magnetic ferrite material according to claim 5, wherein: the components of the composition are composed of main components and additives, wherein the main components comprise: CaCO3、La2O3、SrCO3、Fe2O3、Al2O3ZnO and CuO, wherein the additive comprises L a2O3、Al2O3、H3BO3、CaCO3、SiO2、Ca(C6H11O7)2、HO(CH2CH2O)nH。
7. A preparation method of a high-performance Co-free hexagonal permanent magnetic ferrite material is characterized by comprising the following steps: the method comprises the following steps:
a) material formulation selection
According to the mole percentage of the main component, 1.38-4.46 mol percent of CaCO is adopted3、2.15～6.15mol％La2O3、1.38～5.38mol％SrCO3、73.5～82.2mol％Fe2O3、1.15～5.77mol％Al2O3、1.92～6.54mol％ZnO、1.69～7.31mol％CuO；
b) One-step ball milling
Uniformly mixing the above material powder in a ball mill, wherein the particle size of the powder is controlled to be 0.7-0.9 μm;
c) pre-firing
Drying the ball-milled material obtained in the step b), and pre-burning in a furnace at 1050-1150 ℃ for 2-4 hours;
d) additive
Adding the additive of 0.01-0.08 wt% L a into the powder obtained in the step c)2O3、0.03～0.09wt％Al2O3、0.08～0.18wt％H3BO3、0.08～0.38wt％CaCO3、0.18～0.38wt％SiO2、0.12～0.72wt％Ca(C6H11O7)2、0.12～0.72wt％HO(CH2CH2O)nH；
e) Secondary ball milling
Ball-milling the powder obtained in the step d) in a ball mill, wherein the particle size of the powder is controlled to be 0.5-0.7 mu m;
f) shaping of
Dehydrating the ball-milling slurry obtained in the step e) to ensure that the water content of the slurry is 35-50%, and performing compression molding under a wet-pressing magnetic field forming machine, wherein the magnetic field intensity of the formed slurry is 7.5-14.5 kOe, and the pressure maintaining time is 6-12 s;
g) sintering
And f), placing the blank obtained in the step f) in a sintering furnace for sintering, applying 100-500N pressure on the upper part of the blank, and preserving heat for 2.5-5.5 hours at the temperature of 1080-1180 ℃.
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