CN107721405B - Preparation of M-type strontium ferrite SrFe through low-temperature calcination12O19Method for pre-firing materials - Google Patents
Preparation of M-type strontium ferrite SrFe through low-temperature calcination12O19Method for pre-firing materials Download PDFInfo
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Abstract
The invention discloses a method for preparing M-type strontium ferrite by low-temperature calcinationBulk SrFe12O19A method of pre-firing a charge. The method is used for analyzing pure SrCO3、Fe2O3Uniformly mixing the raw materials in a ball mill according to the atomic ratio Sr/Fe of 1: 9-1: 10, raising the temperature of the mixed raw materials to 1180-1250 ℃ at the rate of 5 ℃/min, and then carrying out heat preservation and calcination for 2-4 hours to obtain powder, namely M-type strontium ferrite SrFe12O19And (4) pre-firing the material. The pre-sintering material is characterized in that the peak (008) does not generate abnormal growth, and the subsequent SrFe improvement is realized12O19The coercive force of the product is very favorable. And the calcination temperature is far lower than the current calcination temperature of a pre-calcination material factory, so that the method is beneficial to energy conservation and environmental protection.
Description
Technical Field
The invention belongs to the technical field of preparation of hard magnetic ferrite, and particularly relates to preparation of M-type strontium ferrite (SrFe) by low-temperature calcination12O19SrM) pre-firing the material.
Background
Strontium ferrite (SrFe)12O19SrM) has a stable hexagonal magnetoplumbite (M-type) structure, a high coercive force, magnetic energy, and resistivity as a permanent magnetic material, can be used in high-frequency applications, and has been widely used due to its abundant, inexpensive raw materials and good chemical stability. At present, the production technology of high-end SrM ferrite is still mastered in Europe and America and Japan for various reasons. As a big country for producing SrM ferrite, China urgently needs to find a new SrM ferrite production method and technology, so that the performance of the SrM ferrite is expected to exceed that of a high-end product in the world, and the SrM ferrite becomes a strong country for producing the ferrite.
The raw material is one of the important factors for limiting the performance of the SrM ferrite, and particularly the structure and the components of the pre-sintered material have a key influence on the performance of the SrM ferrite. At present, in order to complete phase formation and reduce the shrinkage rate of products in subsequent sintering, the pre-sintering temperature of most pre-sintering material manufacturers is 1300 ℃ or even above. The higher pre-burning temperature consumes a large amount of energy, and is not beneficial to energy conservation and environmental protection.
Through careful study, we found that the powder samples calcined at 1300 ℃ and above had a significant preferential growth at the (008) plane (see fig. 1), which resulted in a decrease in the magnetic properties, especially the coercivity, of the subsequently sintered ferrite. When the pre-sintering temperature is reduced to 1200 ℃, the surprising discovery shows that the reaction not only greatly reduces the sintering temperature, but also improves the structure of the SrM pre-sintering material, and the preferential growth surfaces are (107) and (114) (see figure 2), which is more beneficial to improving the magnetic performance of subsequent sintering products.
Disclosure of Invention
The invention aims to provide an improved method for preparing M-type strontium ferrite SrFe12O19The method for pre-burning the material has simple process and is suitable for industrial production.
In particular, the invention provides a method for preparing M-type strontium ferrite SrFe by low-temperature calcination12O19A method of pre-firing a charge, characterized in that the method comprises the steps of:
1) to analytically pure SrCO3、Fe2O3The raw materials are uniformly mixed in a ball mill according to the atomic ratio Sr/Fe of 1: 9-1: 10;
2) raising the temperature of the mixed raw materials to 1180-1250 ℃ at the speed of 5 ℃/min, and then carrying out heat preservation and calcination for 2-4 hours to obtain powder, namely M-type strontium ferrite SrFe12O19And (4) pre-firing the material.
Preferably, step 1) SrCO3、Fe2O3The materials are charged according to the atomic ratio Sr/Fe of 1: 9.5.
Preferably, the calcination temperature in step 2) is 1200 ℃.
Preferably, the heat-preservation calcining time of the step 2) is 2 hours.
Further, as a preferred embodiment, the invention provides a method for preparing M-type strontium ferrite SrFe by low-temperature calcination12O19A method of pre-firing a charge, characterized in that the method comprises the steps of:
1) to analytically pure SrCO3、Fe2O3The raw materials are uniformly mixed in a ball mill according to the atomic ratio Sr/Fe of 1: 9.5;
2) the mixed raw materials are heated to the calcination temperature of 1200 ℃ at the speed of 5 ℃/minute, and then the mixed raw materials are calcined for 2 hours in a heat preservation way, and the obtained powder is M-type strontium ferrite SrFe12O19And (4) pre-firing the material.
The invention provides M-type strontium ferrite SrFe prepared by any one of the preparation methods12O19And (4) pre-firing the material.
Preferably, the M-type strontium ferrite SrFe12O19The pre-sinter (008) peak did not produce abnormal growth.
Further, the M-type strontium ferrite SrFe12O19The pre-fired material had an XRD pattern as shown in figure 2.
The key point of the invention is that the Sr/Fe atomic ratio in the raw material is increased to 1: 9-1: 10, preferably 1:9.5, and the powder obtained by calcination can preferentially grow along the crystal faces of (107) and (114) by calcination at a temperature far lower than 1300 ℃ commonly used by pre-calcination material manufacturers, thereby effectively improving the performance of subsequent sintered ferrite. The physical principle is that if the material is calcined at 1300 ℃, the (008) crystal face preferentially grows, more flat crystal grains are generated, and the tiny flat crystal grains are not beneficial to the permanent magnet material to exert the magnetic performance of the permanent magnet material.
In addition, compared with the prior art, the invention has the following technical advantages:
1) the minimum pre-sintering temperature can reach 1180-1250 ℃, preferably 1200 ℃, which is greatly lower than about 1300 ℃ used by the conventional commonly used pre-sintering powder manufacturer, can greatly reduce energy consumption, is beneficial to energy conservation and environmental protection, and is more suitable for industrial production.
2) The crystal face of the (008) crystal face of the pre-sintered powder at the temperature of 1300 ℃ is distinguished, and the (107) and (114) faces of the ferrite pre-sintered powder obtained by low-temperature calcination are used as the preferential growth faces, so that the subsequent improvement of the magnetic property of the ferrite, particularly the coercive force, is facilitated.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 XRD pattern of strontium ferrite pre-sintered material obtained in example 1(1300 deg.C)
FIG. 2 XRD pattern of strontium ferrite pre-sintered material obtained in example 2(1200 deg.C)
FIG. 3 XRD pattern of strontium ferrite pre-sintered material obtained in example 3(1250 deg.C)
FIG. 4 is a hysteresis loop diagram of the strontium ferrite pre-sintered material obtained in example 1(1300 deg.C)
FIG. 5 is a hysteresis loop diagram of the strontium ferrite pre-sintered material obtained in example 2(1200 deg.C)
FIG. 6 is a hysteresis loop diagram of the strontium ferrite pre-sintered material obtained in example 3(1250 ℃)
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Firstly, according to the atomic ratio Sr/Fe of 1:9.5, 3mmol of analytically pure SrCO is used3And 14.25mmol of analytically pure Fe2O3Uniformly mixing the raw materials in a ball mill, raising the temperature of the mixed raw materials to 1300 ℃ at the speed of 5 ℃/min, and then carrying out heat preservation and calcination for 2 hours to obtain the SrFe12O19The pre-firing material of (1).
The XRD pattern of the obtained pre-sintered material is shown in figure 1, and the hysteresis loop is shown in figure 4.
Example 2
The difference from example 1 is that the calcination temperature was 1200 ℃ and the other conditions were the same. The XRD pattern of the obtained pre-sintered material is shown in figure 2, and the hysteresis loop is shown in figure 5.
Example 3
The difference compared to example 1 is that the calcination temperature was 1250 deg.C, and the other conditions were the same. The XRD pattern of the obtained pre-sintered material is shown in figure 3, and the hysteresis loop is shown in figure 6.
Comparing fig. 1-fig. 3, the (008) peak intensity of the calcined pre-sintering material at 1300 ℃ is obviously stronger than other peaks, and the calcined pre-sintering material appears very sharp; while the (008) peak intensity of the calcined pre-sinter at 1200 ℃ is much lower than the (107) and (114) peaks, which is consistent with the standard spectrum; the relative intensity of the (008) peak of the 1250 c calcined pre-sinter was still high but was much lower compared to fig. 1.
Comparing fig. 4-6, although the saturation magnetization (68.57emu/g) of the pre-sintered material at 1300 ℃ is slightly higher than that (63.01 emu/g) at 1200 ℃, the coercive force is seriously reduced from 2635.5Oe to 1279.8Oe, and is more than 50%, obviously, the pre-sintered material at 1300 ℃ is not beneficial to improving the coercive force of the raw material, and the abnormal growth of the peak (008) is obviously closely related; the saturation magnetization of the pre-sintered material at 1250 ℃ is 65.3emu/g, the difference between the saturation magnetization and the powder pre-sintered at 1300 ℃ is not large, and the coercive force is 1527.2Oe, so that the saturation magnetization is improved to a greater extent compared with the powder pre-sintered at 1300 ℃.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications and additions may be made thereto by those skilled in the art without departing from the spirit of the invention or exceeding the scope defined by the claims.
Claims (4)
1. M-type strontium ferrite SrFe12O19The pre-sintering material is characterized by being prepared through the following steps:
1) to analytically pure SrCO3、Fe2O3The raw materials are uniformly mixed in a ball mill according to the atomic ratio Sr/Fe =1: 9-1: 10;
2) raising the temperature of the mixed raw materials to 1180-1200 ℃ at 5 ℃/min, and then calcining for 2-4 hours in a heat preservation manner to obtain powder, namely M-type strontium ferrite SrFe12O19Pre-firing the material;
wherein, the peak of the XRD pattern (008) of the obtained pre-sintered material does not generate abnormal growth.
2. The M-type strontium ferrite SrFe of claim 112O19Pre-firing the material, wherein, step 1) SrCO3、Fe2O3The proportion of Sr/Fe =1:9.5 is calculated according to the atomic ratio.
3. The M-type strontium ferrite SrFe of claim 112O19Pre-sintering the material, wherein the calcining temperature in the step 2) is 1200 ℃.
4. The M-type strontium ferrite SrFe of claim 112O19Pre-sintering the material, wherein the heat preservation and calcination time of the step 2) is 2 hours.
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| CN110240476A (en) * | 2019-06-26 | 2019-09-17 | 北京信息科技大学 | A kind of novel ferrite ceramic material and preparation method thereof |
| CN116371408A (en) * | 2023-04-24 | 2023-07-04 | 华中科技大学 | Sr-Fe-based oxygen carrier, preparation method thereof and application thereof in reforming hydrogen production/CO |
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| CN103304230A (en) * | 2013-06-13 | 2013-09-18 | 东阳市金砖磁业有限公司 | Permanent magnetic ferrite low-temperature pre-sintering powder and preparation method thereof |
| CN104507889A (en) * | 2012-10-11 | 2015-04-08 | Tdk株式会社 | Sr ferrite powder, method for manufacturing Sr ferrite sintered magnet, motor, and generator |
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| CN104507889A (en) * | 2012-10-11 | 2015-04-08 | Tdk株式会社 | Sr ferrite powder, method for manufacturing Sr ferrite sintered magnet, motor, and generator |
| CN103304230A (en) * | 2013-06-13 | 2013-09-18 | 东阳市金砖磁业有限公司 | Permanent magnetic ferrite low-temperature pre-sintering powder and preparation method thereof |
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Denomination of invention: A method for preparing M-type strontium ferrite SrFe12O19 Effective date of registration: 20221230 Granted publication date: 20200811 Pledgee: Dangtu Branch of Industrial and Commercial Bank of China Ltd. Pledgor: ANHUI XINCIYUAN MAGNETIC INDUSTRY CO.,LTD. Registration number: Y2022980029936 |