CN111196720A - Improved high-performance strontium ferrite for magnetic ring and preparation method thereof - Google Patents

Improved high-performance strontium ferrite for magnetic ring and preparation method thereof Download PDF

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CN111196720A
CN111196720A CN202010020365.6A CN202010020365A CN111196720A CN 111196720 A CN111196720 A CN 111196720A CN 202010020365 A CN202010020365 A CN 202010020365A CN 111196720 A CN111196720 A CN 111196720A
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strontium ferrite
magnetic ring
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ball milling
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周柏祥
沈宏明
吴其万
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Xinghua Huachen Electronic Co Ltd
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Abstract

The invention provides an improved high-performance strontium ferrite for a magnetic ring, and the molecular formula of the strontium ferrite is Sr1‑xCaxFe1‑y‑zNdyMnzWherein x is more than or equal to 0.2 and less than or equal to 0.6; y is more than or equal to 0.2 and less than or equal to 0.6; z is more than or equal to 0.5 and less than or equal to 1.2. According to the invention, Ca ions are used for replacing part of Sr ions, Nd ions and Mn ions are used for replacing part of Fe ions, and a proper molecular formula is obtained by repeatedly adjusting the element proportion, and the improvement and control of the preparation method are matched, so that the residual magnetization intensity and coercive force of the strontium ferrite are improved, the magnetic performance of the magnet is improved, and the production cost can be reduced.

Description

Improved high-performance strontium ferrite for magnetic ring and preparation method thereof
Technical Field
The invention relates to ferrite, in particular to improved high-performance strontium ferrite for a magnetic ring and a preparation method thereof.
Background
The permanent magnetic material is an important component in the magnetic functional material, and is generally applied to the fields of electric motors, electric motors and medical equipment driving motors, the demand and the attention degree of the permanent magnetic material are continuously improved, and the magnetic ring is a product which is widely applied in the permanent magnetic material. After the 21 st century, China has the first place of permanent magnetic ferrite in the world with the production of half of permanent magnetic ferrite worldwide, and is a major country for producing permanent magnetic ferrites. The M-type strontium ferrite is a basic functional material with large coercive force, good chemical stability, high cost performance and larger saturation magnetization. The M-type strontium ferrite belongs to a hexagonal crystal system, and the remanence (Br) and the coercive force (Hc) of the M-type strontium ferrite are generally tested to measure the performance of the material.
In order to improve the magnetic performance of the material, an ion substitution technology is generally adopted, wherein La-Co jointly replaces Sr-Fe, and La is used on the basis of M-type strontium ferrite+Replacement of Sr2+,Co2+Substitution of Fe3+Thereby increasing the upward spin Fe3+The magnetic moment quantity of the magnetic powder improves the saturation magnetization intensity of the M-shaped strontium iron oxide, can effectively improve the remanence and the coercive force of the M-shaped strontium iron oxide, and is also a common production method for preparing high-performance M-shaped ferrite at present. However, La and Co are expensive, so that the production cost is greatly increased, and therefore, a strontium ferrite for a magnetic ring and a preparation process thereof are needed, wherein the strontium ferrite can maintain high performance and reduce the production cost.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides an improved high-performance strontium ferrite for a magnetic ring and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
an improved high-performance strontium ferrite for magnetic ring, whose molecular formula is Sr1-xCaxFe1-y-zNdyMnzWherein x is more than or equal to 0.2 and less than or equal to 0.6; y is more than or equal to 0.2 and less than or equal to 0.6; z is more than or equal to 0.5 and less than or equal to 1.2.
Preferably, it has the formula Sr1-xCaxFe1-y-zNdyMnzWherein x is more than or equal to 0.3 and less than or equal to 0.55; y is more than or equal to 0.3 and less than or equal to 0.55; z is more than or equal to 0.8 and less than or equal to 1.2.
A method for preparing the high-performance strontium ferrite for the improved magnetic ring, comprising the following steps:
step 1, proportioning, namely, according to the chemical formula Sr of the strontium ferrite1-xCaxFe1-y-zNdyMnzComputingWeighing the raw materials including calcium carbonate, strontium carbonate, ferric oxide, neodymium oxide and manganese oxide;
step 2, carrying out primary ball milling, namely placing the prepared raw materials into a ceramic ball milling tank, carrying out wet milling on the mixed materials for 1h, wherein the mass ratio of the grinding balls to the raw materials to absolute ethyl alcohol is 9:1:0.5, the rotating speed of a planetary ball mill is 450r/min, and then drying powder obtained by ball milling and placing the powder into a die for tabletting and molding;
step 3, pre-burning, namely drying the mixture, pre-burning at 1100-1200 ℃, keeping the temperature for 1-3h, cooling the mixture to room temperature along with a furnace, crushing the mixture, and sieving the crushed mixture to obtain a ferrite pre-burning material;
step 4, performing secondary ball milling, namely adding a dispersing agent and an additive into the pre-sintered material, performing ball milling together, wherein the material-water ratio of the secondary ball milling is 1:1.4, the time of the secondary ball milling is 16-20 hours, drying, placing the mixed material into a tabletting mold, and pressing into a flaky sample;
step 5, sintering, namely placing the flaky sample in a high-temperature box type resistance furnace, heating to 1160-1-xCaxFe1-y-zNdyMnzThe high-performance strontium ferrite.
Preferably, the dispersant in step 4 is calcium gluconate.
Preferably, the calcium gluconate is 0.6 wt%.
Preferably, the additive in step 4 is one or two of calcium carbonate, silica and alumina.
Preferably, the additive is 1.4 wt%.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, Ca ions are used for replacing part of Sr ions, Nd ions and Mn ions are used for replacing part of Fe ions, and a proper molecular formula is obtained by repeatedly adjusting the element proportion, and the improvement and control of the preparation method are matched, so that the residual magnetization intensity and coercive force of the strontium ferrite are improved, and the production cost can be reduced.
Detailed Description
In order to further understand the objects, structures, features and functions of the present invention, the following embodiments are described in detail.
Example 1
An improved high-performance strontium ferrite for magnetic ring, whose molecular formula is Sr1-xCaxFe1-y-zNdyMnzWherein x is 0.2; y is 0.3; and z is 1.0.
Example 2
An improved high-performance strontium ferrite for magnetic ring, whose molecular formula is Sr1-xCaxFe1-y-zNdyMnzWherein x is 0.3; y is 0.2; z is 1.2.
Example 3
An improved high-performance strontium ferrite for magnetic ring, whose molecular formula is Sr1-xCaxFe1-y-zNdyMnzWherein x is 0.4; y is 0.4; and z is 0.8.
Example 4
An improved high-performance strontium ferrite for magnetic ring, whose molecular formula is Sr1-xCaxFe1-y-zNdyMnzWherein x is 0.6; y is 0.6; and z is 0.5.
A method for preparing the high-performance strontium ferrite for the improved magnetic ring, comprising the following steps:
step 1, proportioning, namely, according to the chemical formula Sr of the strontium ferrite1-xCaxFe1-y-zNdyMnzCalculating the content of the main components and weighing the raw materials including calcium carbonate, strontium carbonate, ferric oxide, neodymium oxide and manganese oxide;
step 2, carrying out primary ball milling, namely placing the prepared raw materials into a ceramic ball milling tank, carrying out wet milling on the mixed materials for 1h, wherein the mass ratio of the grinding balls to the raw materials to absolute ethyl alcohol is 9:1:0.5, the rotating speed of a planetary ball mill is 450r/min, and then drying powder obtained by ball milling and placing the powder into a die for tabletting and molding;
step 3, pre-burning, namely drying the mixture, pre-burning at 1100-1200 ℃, keeping the temperature for 1-3h, cooling the mixture to room temperature along with a furnace, crushing the mixture, and sieving the crushed mixture to obtain a ferrite pre-burning material;
step 4, performing secondary ball milling, namely adding a dispersing agent and an additive into the pre-sintered material, performing ball milling together, wherein the material-water ratio of the secondary ball milling is 1:1.4, the time of the secondary ball milling is 16-20 hours, drying, placing the mixed material into a tabletting mold, and pressing into a flaky sample;
step 5, sintering, namely placing the flaky sample in a high-temperature box type resistance furnace, heating to 1160-1-xCaxFe1-y-zNdyMnzThe high-performance strontium ferrite.
Preferably, the dispersant in step 4 is calcium gluconate. Furthermore, the calcium gluconate accounts for 0.6wt%, which is beneficial to improving the density of the magnet, so that the residual magnetism Br is larger, and when the residual magnetism Br exceeds 0.6wt%, CO generated by decomposition of the calcium gluconate2And water vapor venting will increase the porosity of the sample, reducing the sample density.
Preferably, the additive in step 4 is one or two of calcium carbonate, silica and alumina.
Preferably, the additive is 1.4 wt%.
In the step 4, the ratio of material to water is 1:1.4, the ratio of material to water is large, the average particle size of slurry particles is small, the particle size dispersion degree is small, the orientation degree and the green density of a sample under the action of a magnetic field can be improved, and the residual magnetism of the sample can be improved. Meanwhile, the average particle size of the slurry is smaller, the grain size of the sintered blank is smaller, and the coercive force is improved along with the grain size. Meanwhile, the ball milling time is set to be longer, and the magnetic remanence (Br) and intrinsic coercivity (H) are improvedcj) And magnetically induced coercivity (H)cb).
In step 5, after the pre-firing, the magnetic remanence (Br) can be increased. The sintering temperature is too low, the magnet has impurity phases, the purity is not enough, and various magnetic properties are poor; the sintering temperature is increased, the constant temperature time is prolonged, the average size of crystal grains is increased, and the magnetic moment orientation in the internal magnetic domain of the manger is changed, so that the magnetic performance of the magnet is improved.
The main performance indexes of the high performance strontium ferrite in the above embodiments are shown in table 1:
Br(mT) Hcb(kA/m) Hcj(kA/m) (BH)max(kJ/m)
example 1 423.5 338.3 367.1 36
Example 2 427.2 345.5 378.5 38
Example 3 430.8 342.5 376.9 38
Example 4 424.1 336.2 364.3 37
TABLE 1 Performance index of improved high performance strontium ferrite for magnetic ring
In the performance index of the improved high-new strontium-updating ferrite, the remanence (Br) is improved to a certain extent; coercive force, including intrinsic coercive force (H)cj) And magnetically induced coercivity (H)cb) Respectively represents the hysteresis capacity and the demagnetization resistance of the magnet, and is greatly improved.
According to the invention, Ca ions are used for replacing part of Sr ions, Nd ions and Mn ions are used for replacing part of Fe ions, the molecular formula range of the remanence and the coercive force of the improved high-performance strontium ferrite for the magnetic ring are improved by repeatedly testing the specific gravity of each raw material, and part of test performance data are shown in table 1. Ca and Sr are alkaline earth metal elements, Sr2+Ionic radius of 0.127nm, Ca2+The ionic radius is 0.106nm, compared with La, Ce and other elements, Ca element is convenient to obtain, the cost is low, and the industrial production is facilitated; when Ca is present2+The substitution amount x of (2) is 0.4 and the sintering temperature is 1170 ℃, the sintered sample achieves the best performance. Mn element is adjacent element of Fe element in the same period, is easier to realize in doping means, and the outmost electron arrangement of Mn is 3d according to outmost electron arrangement condition54s2And the outermost electron arrangement of Fe is 3d64s2Therefore, compared with Fe, Mn has higher electron spinning magnetic moment and can not cause obvious changes of lattice constant and volume, the doping of Mn reduces the band gap of a system, improves the conductivity of the strontium ferrite, and is expected to improve the mechanical strength of the strontium ferrite; in addition, China has rich Mn resources, mature preparation process and lower industrial production cost. By substituting Nd ions for a part of the Fe ions, Nd3+Has an ionic radius of 0.0995nm and Fe3+The ion radius of the strontium ferrite is 0.067nm, the magnetic property of the strontium ferrite can be improved by Nd doping, and better remanence and coercive force can be obtained by doping with Mn.
The present invention has been described in relation to the above embodiments, which are only exemplary of the implementation of the present invention. It should be noted that the disclosed embodiments do not limit the scope of the invention. Rather, it is intended that all such modifications and variations be included within the spirit and scope of this invention.

Claims (7)

1. An improved high-performance strontium ferrite for magnetic ring is characterized in that the molecular formula is Sr1-xCaxFe1-y-zNdyMnzWherein x is more than or equal to 0.2 and less than or equal to 0.6; y is more than or equal to 0.2 and less than or equal to 0.6; z is more than or equal to 0.5 and less than or equal to 1.2.
2. The improved high performance strontium ferrite for magnetic ring as claimed in claim 1, wherein the molecular formula is Sr1- xCaxFe1-y-zNdyMnzWherein x is more than or equal to 0.3 and less than or equal to 0.55; y is more than or equal to 0.3 and less than or equal to 0.55; z is more than or equal to 0.8 and less than or equal to 1.2.
3. A method for preparing high performance strontium ferrite for improved magnetic ring as claimed in any of claims 1-2, comprising the following steps:
step 1, proportioning, namely, according to the chemical formula Sr of the strontium ferrite1-xCaxFe1-y-zNdyMnzCalculating the content of the main components and weighing the raw materials including calcium carbonate, strontium carbonate, ferric oxide, neodymium oxide and manganese oxide;
step 2, carrying out primary ball milling, namely placing the prepared raw materials into a ceramic ball milling tank, carrying out wet milling on the mixed materials for 1h, wherein the mass ratio of the grinding balls to the raw materials to absolute ethyl alcohol is 9:1:0.5, the rotating speed of a planetary ball mill is 450r/min, and then drying powder obtained by ball milling and placing the powder into a die for tabletting and molding;
step 3, pre-burning, namely drying the mixture, pre-burning at 1100-1200 ℃, keeping the temperature for 1-3h, cooling the mixture to room temperature along with a furnace, crushing the mixture, and sieving the crushed mixture to obtain a ferrite pre-burning material;
step 4, performing secondary ball milling, namely adding a dispersing agent and an additive into the pre-sintered material, performing ball milling together, wherein the material-water ratio of the secondary ball milling is 1:1.4, the time of the secondary ball milling is 16-20 hours, drying, placing the mixed material into a tabletting mold, and pressing into a flaky sample;
step 5, sintering, namely placing the flaky sample in a high-temperature box type resistance furnace, heating to 1160-1-xCaxFe1-y-zNdyMnzThe high-performance strontium ferrite.
4. The preparation method of the improved high-performance strontium ferrite for the magnetic ring as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 4, the dispersant is calcium gluconate.
5. The preparation method of the improved high-performance strontium ferrite for the magnetic ring as claimed in claim 4, wherein the preparation method comprises the following steps: the weight percentage of the calcium gluconate is 0.6 percent.
6. The preparation method of the improved high-performance strontium ferrite for the magnetic ring as claimed in claim 3, wherein the preparation method comprises the following steps: in the step 4, the additive is one or two of calcium carbonate, silicon dioxide and aluminum oxide.
7. The method of claim 6, wherein: the additive was 1.4 wt%.
CN202010020365.6A 2020-01-09 2020-01-09 Improved high-performance strontium ferrite for magnetic ring and preparation method thereof Pending CN111196720A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116120049A (en) * 2023-02-17 2023-05-16 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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116120049A (en) * 2023-02-17 2023-05-16 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
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

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