CN111704452A - Permanent magnetic ferrite material and preparation method thereof - Google Patents

Permanent magnetic ferrite material and preparation method thereof Download PDF

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CN111704452A
CN111704452A CN202010442968.5A CN202010442968A CN111704452A CN 111704452 A CN111704452 A CN 111704452A CN 202010442968 A CN202010442968 A CN 202010442968A CN 111704452 A CN111704452 A CN 111704452A
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permanent magnetic
primary
magnetic ferrite
slurry
ferrite material
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胡良权
丁伯明
叶华
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Hengdian Group DMEGC Magnetics Co Ltd
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Hengdian Group DMEGC Magnetics Co Ltd
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Abstract

The invention relates to the technical field of permanent magnetic ferrite materials, in particular to a permanent magnetic ferrite material and a preparation method thereof. A permanent magnetic ferrite material is prepared from a main material, a primary additive, a primary dispersant, a secondary dispersant and a secondary additive; the main materials are strontium carbonate and iron powder; the main material is prepared according to the following chemical formula SrO. nFe2O3N is 5.9 to 6.1; based on the total mass of the main materials, the primary additive comprises the following components in percentage by mass: 0.8-1.5% of cobalt oxide and 1.2-2.3% of lanthanum oxide; based on the total mass of the main materials, the secondary additive comprises the following components in percentage by mass: 0.8-1.2% CaCO3，0.3～0.8％SiO2，0.2～0.4％SrCO30.1-0.5% of glucose and 0.1-0.3% of boric acid. The preparation process condition of the invention is easy to control, adopts steel balls of various specifications for fine grinding, has better fine grinding effect, effectively reduces the ball milling time, reduces the production cost and is easy for industrialization.

Description

Permanent magnetic ferrite material and preparation method thereof
Technical Field
The invention relates to the technical field of permanent magnetic ferrite materials, in particular to a permanent magnetic ferrite material and a preparation method thereof.
Background
Since the discovery of permanent magnetic ferrites in the fifties of the last century, the varieties, production methods and production processes thereof have been greatly developed and have undergone a significant technological span from isotropic magnets to anisotropic magnets, from barium ferrites to strontium ferrites, and from dry-press molding to wet-press molding.
At present, the high-performance permanent magnetic ferrite pre-sintering material basically takes iron oxide red as a raw material, and the production cost is relatively high. The production process for producing ferrite materials by using iron powder in the prior art mainly comprises the following steps: the production process has the defects of long ball milling time, high energy consumption and poor consistency of product performance, and is not beneficial to large-scale industrial production.
Disclosure of Invention
The invention provides a permanent magnetic ferrite material with good performance consistency, aiming at overcoming the problems of long ball milling time, high energy consumption and poor product performance consistency of the traditional permanent magnetic ferrite material preparation process.
The invention also provides a preparation method of the permanent magnetic ferrite material, and the method has a good fine grinding effect, effectively reduces the ball milling time, reduces the production cost, and is easy for industrialization.
In order to achieve the purpose, the invention adopts the following technical scheme:
a permanent magnetic ferrite material is prepared from a main material, a primary additive, a primary dispersant, a secondary dispersant and a secondary additive; the main materials are strontium carbonate and iron powder; the main material is prepared according to the following chemical formula SrO. nFe2O3N is 5.9 to 6.1; based on the total mass of the main materials, the primary additive comprises the following components in percentage by mass: 0.8-1.5% of cobalt oxide and 1.2-2.3% of lanthanum oxide; based on the total mass of the main materials, the secondary additive comprises the following components in percentage by mass: 0.8-1.2% CaCO3，0.3～0.8％SiO2，0.2～0.4％SrCO30.1-0.5% of glucose and 0.1-0.3% of boric acid.
The permanent magnetic ferrite material takes the iron powder which is processed by the ball milling ball of the cheap iron scale as the raw material, thereby avoiding the problem that the traditional process takes the iron oxide red as the raw material and has relatively higher production cost; the coercive force of the permanent magnetic ferrite material can be improved by adding the primary additive into the main material in a synergistic way, the synergistic action principle of all the components is that lanthanum and cobalt ions in lanthanum oxide and cobalt oxide replace strontium and iron ions to improve the microstructure of a sintered body, and more stable hexagonal ferrite crystals and larger magnetocrystalline anisotropy constant K are obtained1And a saturation magnetization Ms value, thereby improving the magnetic performance of the product. The secondary additive is used for improving the magnetic property by cooperating with the main material, and the principle of the cooperation of all the components is that the electrostatic repulsion force among ferrite particles can be increased by combining glucose and boric acid, so that the agglomeration of wet grinding slurry is effectively reduced, the melting effect is facilitated, the growth of crystal grains is controlled, the pre-sintering and sintering temperature is reduced, and all the components cooperate to increase the effect.
Preferably, the primary dispersant is calcium gluconate.
Preferably, the secondary dispersant is boric acid.
A preparation method of a permanent magnetic ferrite material comprises the following steps:
(1) according to the proportion, after the main material and the primary additive are uniformly mixed, adding steel balls and water, and carrying out primary wet ball milling to obtain first slurry;
(2) drying the first slurry, prepressing to obtain a green body, and presintering at the low temperature of 800-1000 ℃ for 1-1.5 hours to obtain a primary presintering material; the drying temperature is 110-120 ℃, and preferably 120 ℃; the green body is preferably of a cylindrical structure, having a compacting effect; prepressing to form green body, then presintering at low temperature to increase contact surface between particles, and the main component Fe of raw material iron scale3O4Conversion to Fe2O3The ferrite phase is generated by the chemical reaction with strontium carbonate;
(3) adding a primary dispersing agent into the primary pre-sintered material for vibration grinding treatment to obtain coarse powder; the primary dispersing agent is preferably calcium gluconate, so that powder is not easy to stick to the wall during vibration milling and is convenient to clean, and slurry particles are dispersed during subsequent ball milling;
(4) adding a secondary dispersing agent into the coarse powder, then adding steel balls and water, and carrying out secondary wet ball milling to obtain second slurry; the secondary dispersing agent is preferably boric acid, and the boric acid can increase the electrostatic repulsive force among ferrite particles, effectively reduce the agglomeration of wet grinding slurry, contribute to the melting effect and control the growth of crystal grains, thereby reducing the pre-sintering temperature in the step (5), saving energy and reducing consumption; in the prior art, a reaction system of boric acid is not added, the pre-sintering temperature needs to be higher than 1300 ℃, the energy consumption is high, and the production cost of enterprises is high;
(5) drying the second slurry, prepressing to obtain a green body, and presintering at 1280-1300 ℃ for 1-3 h to obtain a secondary presintering material; the drying temperature is 110-120 ℃, and preferably 120 ℃; the green body is preferably of a cylindrical structure, having a compacting effect; pre-pressing to form a green body and then pre-sintering at high temperature have the effects of increasing the contact surface among particles, facilitating chemical reaction and generating ferrite;
(6) adding a secondary additive into the secondary pre-sintering material, then adding steel balls and water, and carrying out fine grinding for 10-20 hours to obtain third slurry;
(7) and (3) performing wet pressing molding on the third slurry, and performing single-layer rapid sintering in a strong oxidizing atmosphere at the temperature of 1220-1250 ℃ to obtain the permanent magnetic ferrite material. The strong oxidizing atmosphere is formed by adding a blower in a high-temperature area and inflating; acting as complete ferrite.
The invention processes cheap iron scale into iron powder through ball milling, and then directly presintering with strontium carbonate and additive at low temperature and high temperature for two times, so that the solid phase reaction is fully performed to generate hexagonal ferrite presintering material.
Preferably, in the step (1), the time of one-time wet ball milling is 3.5-5 h; the average particle size of the first slurry is 0.9-1.0 μm.
Preferably, in the step (3), the duration of the vibromilling treatment is 2-4 min; the average particle size of the coarse powder is 3.5-5.5 mu m; preferably, in the step (3), the addition amount of the primary dispersant is 0.1-0.3 wt% based on the total mass of the primary pre-sintered material. The addition amount of the primary dispersant is too low, which can cause poor fluxing effect; too high an amount of addition results in easy brightening at the time of pre-firing and a decrease in magnetic properties.
Preferably, in the steps (1) and (4), the diameter of the steel ball is 6mm, and the ratio of the material: ball: the mass ratio of water is 1:1.5: 13.
Preferably, in the step (6), the steel balls are combined according to the following specifications by mass ratio: diameter 4 steel ball: diameter 6 steel ball: diameter 8mm steel ball is 5:3: 2; material preparation: ball: the mass ratio of water is 1: 1.6: 15; in the step, steel balls with different specifications are selected for fine grinding, so that more powder materials are in contact with the steel balls during fine grinding, the fine grinding effect is improved, the ball milling time is shortened, the production efficiency is improved, the production cost is reduced, and the industrialization is easy.
Preferably, in the step (6), the average particle size of the third slurry is 0.7 to 0.9 μm. The granularity of the third slurry is too fine, so that the forming is difficult and the product is easy to crack; the particle size of the third slurry is too coarse, which may result in a decrease in the magnetic properties of the product.
Preferably, in the step (4), the average particle size of the second slurry is 0.7-0.8 μm; the granularity of the second slurry is too fine, so that the second slurry can shine during pre-sintering and reduce the magnetic performance; the particle size of the second slurry is too coarse, which may result in poor reaction performance.
Preferably, in the step (4), the secondary dispersant is added in an amount of 0.1 to 0.3 wt% based on the total mass of the coarse powder. The addition amount of the secondary dispersing agent is too low, so that the slurry particles cannot be dispersed, and the magnetic property is difficult to improve; too high an amount of addition results in difficult molding, difficult water absorption and easy cracking of the product during sintering.
Preferably, in the step (7), the forming magnetic field of the wet pressing forming is 8000-8500 Gs; the single-layer rapid sintering is carried out by adopting a roller way type electric kiln, and the glue is easy to discharge.
Therefore, the invention has the following beneficial effects:
(1) the permanent magnetic ferrite material has excellent magnetic property due to synergistic effect of all component formulas;
(2) the preparation process conditions are easy to control, the fine grinding effect is good due to the adoption of the fine grinding of steel balls with various specifications, the ball milling time is effectively shortened, the production cost is reduced, and the industrialization is easy.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) SrO. nFe is mixed according to the following chemical formula2O3And n is 5.95: weighing 77.1 g of main materials strontium carbonate and 500g of iron powder; adding 8.7 g of lanthanum oxide and 5.8 g of silicon dioxide, and uniformly mixing; according to the reference: ball: the water mass ratio is 1:1.5:13 adding phi 6mm steel balls and water, and carrying out primary wet ball milling for 4.5h to obtain first slurry with the average particle size of 0.98 mu m;
(2) drying the first slurry at 120 ℃, prepressing to obtain a cylinder green body, and presintering at 950 ℃ for 1h to obtain a primary presintering material;
(3) adding calcium gluconate into the pre-sintered material, and performing vibration milling for 2min to obtain coarse powder with average particle size of 5.1 μm; the addition amount of the calcium gluconate is 0.3 wt% based on the total mass of the primary pre-sintering material;
(4) adding boric acid into the coarse powder, and mixing the following materials: ball: the water mass ratio is 1:1.5:13 adding phi 6mm steel balls and water, and carrying out secondary wet ball milling to obtain second slurry with the average particle size of 0.78 mu m; the addition amount of boric acid is 0.2 wt% based on the total mass of the coarse powder;
(5) drying the second slurry at 120 ℃, prepressing to obtain a green body, and presintering at 1290 ℃ for 2 hours to obtain a secondary presintering material;
(6) 500g of secondary pre-sintered material is taken and 5 g of CaCO is added32 g of SiO21.5 g SrCO31 g of glucose and 1 g of boric acid, and combining steel balls according to the following specifications by mass ratio: diameter 4 steel ball: diameter 6 steel ball: diameter 8mm steel ball is 5:3: 2; according to the reference: ball: the mass ratio of water is 1: 1.6: 15 adding steel balls and water, and finely grinding the mixture 15h, obtaining a third slurry with the granularity of 0.83 mu m;
(7) and (3) wet-pressing and molding the third slurry in a molding magnetic field of 8000Gs, and carrying out single-layer rapid sintering in a roller way type electric kiln at the temperature of 1230 ℃ in a strong oxidation atmosphere to obtain the permanent magnetic ferrite material.
Example 2
(1) SrO. nFe is mixed according to the following chemical formula2O3And n is 5.9: weighing 77.1 g of main materials strontium carbonate and 500g of iron powder; taking the total mass of the main materials as a reference, adding 0.8 wt% of cobalt oxide and 2.3 wt% of lanthanum oxide, and uniformly mixing; according to the reference: ball: the water mass ratio is 1:1.5:13 adding phi 6mm steel balls and water, and carrying out wet ball milling for 3.5h to obtain first slurry with the particle size of 0.9 mu m;
(2) drying the first slurry at 110 ℃, prepressing to obtain a cylinder green body, and presintering at 800 ℃ for 1.5 hours to obtain a primary presintering material;
(3) adding calcium gluconate into the pre-sintered material, and performing vibration milling for 2min to obtain coarse powder with particle size of 5.5 μm; the addition amount of the calcium gluconate is 0.2 wt% based on the total mass of the primary pre-sintering material;
(4) adding boric acid into the coarse powder, and mixing the following materials: ball: the water mass ratio is 1:1.5:13 adding phi 6mm steel balls and water, and carrying out secondary wet ball milling to obtain second slurry with the average particle size of 0.7 mu m; the addition amount of boric acid is 0.1 wt% based on the total mass of the coarse powder;
(5) drying the second slurry at 110 ℃, prepressing to obtain a green body, and presintering at 1280 ℃ for 3 hours to obtain a secondary presintering material;
(6) adding a secondary additive into the secondary pre-sintering material, and combining the steel balls according to the following specifications by mass ratio: diameter 4 steel ball: diameter 6 steel ball: diameter 8mm steel ball is 5:3: 2; according to the reference: ball: the mass ratio of water is 1: 1.6: adding steel balls and water into the mixture 15, and finely grinding the mixture for 10 hours to obtain third slurry with the granularity of 0.9 mu m; based on the total mass of the main materials, the secondary additive comprises the following components in percentage by mass: 0.8% CaCO3，0.3％SiO2，0.4％SrCO30.5% glucose and 0.1% boric acid;
(7) and (3) wet-pressing and molding the third slurry under a molding magnetic field of 8300Gs, and performing single-layer rapid sintering by adopting a roller-way type electric kiln at a temperature higher than 1220 ℃ in an oxidizing atmosphere to obtain the permanent magnetic ferrite material.
Example 3
(1) SrO. nFe is mixed according to the following chemical formula2O3N is 6.1: weighing 77.1 g of main materials strontium carbonate and 500g of iron powder; taking the total mass of the main materials as a reference, adding 1.5 wt% of cobalt oxide and 1.2 wt% of lanthanum oxide, and uniformly mixing; according to the reference: ball: the water mass ratio is 1:1.5:13 adding phi 6mm steel balls and water, and carrying out wet ball milling for 5h to obtain first slurry with the particle size of 1.0 mu m;
(2) drying the first slurry at 115 ℃, prepressing to obtain a cylinder green body, and presintering at 1000 ℃ for 1h to obtain a primary presintering material;
(3) adding calcium gluconate into the primary pre-sintered material, and performing vibration grinding for 2-4 min to obtain coarse powder with the particle size of 3.5 microns; the addition amount of the calcium gluconate is 0.4 wt% based on the total mass of the primary pre-sintering material;
(4) adding boric acid into the coarse powder, and mixing the following materials: ball: the water mass ratio is 1:1.5:13 adding phi 6mm steel balls and water, and carrying out secondary wet ball milling to obtain second slurry with the average particle size of 0.8 mu m; the addition amount of boric acid is 0.3 wt% based on the total mass of the coarse powder;
(5) drying the second slurry at 115 ℃, prepressing to obtain a green body, and presintering at 1300 ℃ for 1h to obtain a secondary presintering material;
(6) adding a secondary additive into the secondary pre-sintering material, and combining the steel balls according to the following specifications by mass ratio: diameter 4 steel ball: diameter 6 steel ball: diameter 8mm steel ball is 5:3: 2; according to the reference: ball: the mass ratio of water is 1: 1.6: adding a steel ball and water into the slurry 15, and carrying out fine grinding for 20 hours to obtain a third slurry with the particle size of 0.7 mu m; based on the total mass of the main materials, the secondary additive comprises the following components in percentage by mass: 1.2% CaCO3，0.8％SiO2，0.2％SrCO30.1% glucose and 0.3% boric acid;
(7) and (3) wet-pressing and molding the third slurry under a molding magnetic field of 8500Gs, and performing single-layer rapid sintering at 1250 ℃ in a strong oxidation atmosphere of a roller-way type electric kiln to obtain the permanent magnetic ferrite material.
Comparative example 1 (without addition of secondary dispersant)
Comparative example 1 differs from example 1 in that: in the step (4), boric acid is not added into the coarse powder, and the rest processes are completely the same.
COMPARATIVE EXAMPLE 2 (glucose-free Secondary additive component)
Comparative example 2 differs from example 1 in that: in the step (6), the secondary additives have different formulas: 5 g of CaCO32 g of SiO21.5 g SrCO31 g of boric acid, and the rest of the process is completely the same.
COMPARATIVE EXAMPLE 3 (different Fine grinding process)
Comparative example 3 differs from example 1 in that: in the step (6), only steel balls with the uniform specification phi 6mm are adopted for fine grinding, and the other processes are completely the same.
Comparative example 4 (no primary dispersant added)
Comparative example 4 differs from example 1 in that: in the step (3), calcium gluconate is not added in the vibration grinding process, and the other processes are completely the same.
Comparative example 5 (different primary dispersants)
Comparative example 5 differs from example 1 in that: in the step (3), calcium gluconate added in the vibration grinding process is replaced by sorbitol, and other processes are completely the same.
The performance indexes of the permanent magnetic ferrite materials prepared in examples 1 to 3 and comparative examples 1 to 5 are detected, and the results are shown in table 1:
TABLE 1 test results
Numbering Br(Gs) Hcb(Oe) Hcj(Oe) (BH)max(MGOe)
Example 1 4197 3869 4325 4.293
Example 2 4312 3987 4622 4.542
Example 2 4250 3950 4700 4.389
Comparative example 1 4166 3725 4193 4.207
Comparative example 2 4171 3826 4305 4.233
Comparative example 3 4167 3692 4120 4.192
Comparative example 4 4153 3712 4201 4.179
Comparative example 5 4125 3652 4157 4.126
As can be seen from Table 1, the formulation and preparation process of the permanent magnetic ferrite material of the present invention are an integral, and any change in the composition or process conditions leads to defects in the product properties. The data of the embodiment 1 and the comparative example 1 are compared, the reaction system without the boric acid needs higher presintering temperature, and the relatively lower presintering temperature directly adopted by the invention can cause the Hcj performance of the product to be greatly reduced; comparing the data of example 1 and comparative example 2 can result in no small amount of glucose added in the second time, which results in a decrease in Br value of the product; according to the data of the comparative example 1 and the comparative example 3, the ball milling effect of the steel ball with a single specification is poorer than that of the shot balls with multiple specifications according to different proportions, and the influence on the magnetic performance is larger; according to the data of the comparative example 1 and the comparative example 4, the magnetic performance of the product can be greatly reduced due to no addition of calcium gluconate during vibration grinding; it is important to select a primary dispersant by comparing the data of example 1 and comparative example 5, and the addition of the remaining conventional dispersant results in a great decrease in the magnetic properties of the product.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (10)

1. A permanent magnetic ferrite material is characterized by being prepared from a main material, a primary additive, a primary dispersant, a secondary dispersant and a secondary additive; the main materials are strontium carbonate and iron powder; the main material is prepared according to the following chemical formula SrO. nFe2O3N is 5.9 to 6.1; based on the total mass of the main materials, the primary additive comprises the following components in percentage by mass: 0.8-1.5% of cobalt oxide and 1.2-2.3% of lanthanum oxide; based on the total mass of the main materials, the secondary additive comprises the following components in percentage by mass: 0.8-1.2% CaCO3，0.3～0.8％SiO2，0.2～0.4％SrCO30.1-0.5% of glucose and 0.1-0.3% of boric acid.
2. The permanent magnetic ferrite material according to claim 1, wherein the primary dispersant is calcium gluconate.
3. The permanent magnetic ferrite material according to claim 1, wherein the secondary dispersant is boric acid.
4. A method for preparing a permanent magnetic ferrite material according to any one of claims 1 to 3, comprising the steps of:
(1) according to the proportion, after the main material and the primary additive are uniformly mixed, adding steel balls and water, and carrying out primary wet ball milling to obtain first slurry;
(2) drying the first slurry, prepressing to obtain a green body, and presintering at the low temperature of 800-1000 ℃ for 1-1.5 hours to obtain a primary presintering material;
(3) adding a primary dispersing agent into the primary pre-sintered material for vibration grinding treatment to obtain coarse powder;
(4) adding a secondary dispersing agent into the coarse powder, then adding steel balls and water, and carrying out secondary wet ball milling to obtain second slurry;
(5) drying the second slurry, prepressing to obtain a green body, and presintering at 1280-1300 ℃ for 1-3 h to obtain a secondary presintering material;
(6) adding a secondary additive into the secondary pre-sintering material, then adding steel balls and water, and carrying out fine grinding to obtain third slurry;
(7) and (3) performing wet pressing molding on the third slurry, and performing single-layer rapid sintering in a strong oxidizing atmosphere at the temperature of 1220-1250 ℃ to obtain the permanent magnetic ferrite material.
5. The preparation method of the permanent magnetic ferrite material according to claim 4, characterized in that in the step (1), the time of one-time wet ball milling is 3.5-5 h; the average particle size of the first slurry is 0.9-1.0 μm.
6. The preparation method of the permanent magnetic ferrite material according to claim 4, characterized in that in the step (3), the duration of the vibromilling treatment is 2-4 min; the average particle size of the coarse powder is 3.5-5.5 mu m; the addition amount of the primary dispersant is 0.2-0.4 wt% based on the total mass of the primary pre-sintered material.
7. The method for preparing a permanent magnetic ferrite material according to claim 4, wherein in steps (1) and (4), the diameter of the steel ball is 6mm, and the ratio of the material: ball: the mass ratio of water is 1:1.5: 13.
8. The method for preparing a permanent magnetic ferrite material according to claim 4, wherein in the step (6), the steel balls are combined according to the following specification by mass ratio: diameter 4 steel ball: diameter 6 steel ball: diameter 8mm steel ball is 5:3: 2; material preparation: ball: the mass ratio of water is 1: 1.6: 15; the average particle size of the third slurry is 0.7-0.9 μm.
9. The method for preparing a permanent magnetic ferrite material according to claim 4, wherein in the step (4), the average particle size of the second slurry is 0.7 to 0.8 μm; the addition amount of the secondary dispersant is 0.1-0.3 wt% based on the total mass of the coarse powder.
10. The method for preparing a permanent magnetic ferrite material according to claim 4, wherein in the step (7), the forming magnetic field of the wet pressing forming is 8000-8500 Gs; the single-layer rapid sintering is carried out by adopting a roller way type electric kiln.
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