CN113753958A - Method for preparing high-performance soft and hard magnetic composite material - Google Patents
Method for preparing high-performance soft and hard magnetic composite material Download PDFInfo
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- CN113753958A CN113753958A CN202111065280.0A CN202111065280A CN113753958A CN 113753958 A CN113753958 A CN 113753958A CN 202111065280 A CN202111065280 A CN 202111065280A CN 113753958 A CN113753958 A CN 113753958A
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0054—Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
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- C—CHEMISTRY; METALLURGY
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- C01G51/00—Compounds of cobalt
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- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
Abstract
The invention discloses a method for preparing a high-performance soft and hard magnetic composite material. The chemical composition formula of the soft and hard magnetic composite material is A1‑xLnxFe12O19/CoFe2O4In the compound, the element A is Sr or Ba, Ln is one or two of La and Ca metal elements, and x is more than or equal to 0.0 and less than or equal to 0.3. The invention prepares A by a high-pressure ultrasonic thermal decomposition methodxLn1‑xFe12O19Micron-sized permanent magnetic material and CoFe2O4The preparation method can fully play the coupling advantages of soft and hard magnetic phases, improve the magnetic performance of the material, and simultaneously can effectively reduce the high-temperature sintering temperature and time and save energy consumption.
Description
Technical Field
The invention relates to a method for preparing a high-performance soft and hard magnetic composite material, in particular to a method for preparing a high-performance soft and hard magnetic composite material with low energy consumption.
Background
In recent years, permanent magnetic ferrite materials have been developed rapidly, and particularly, soft and hard magnetic ferrite composite materials have received wide attention due to the advantages of large magnetic energy product, stable chemical properties, no toxicity and the like.
However, the soft and hard magnetic ferrite composite material prepared by the traditional high-temperature solid-phase sintering has complex process flow, and particularly for the soft and hard magnetic ferrite which is sintered for the second time, the sintering time is long, the temperature is high, the energy consumption is very high, and the magnetic performance of the prepared material is low.
In order to improve the magnetic property of the soft and hard magnetic composite material and reduce energy consumption, researchers adopt a sol-gel method to prepare the nano-scale and micron-scale soft and hard magnetic composite material, so that the uniformity of the material is improved, the magnetic property of the material is also improved to a certain extent, but the sol-gel method causes larger pollution and higher cost, so that the method cannot be applied to actual industrial production in a large scale.
The soft and hard magnetic ferrite materials prepared by the high-pressure ultrasonic thermal decomposition method have the advantages that the particle size can be controlled to be 5-10 mu m, the uniformity is good, the magnetic performance is good, the soft and hard magnetic ferrites are compounded by a solid phase sintering method, the advantage of two-phase coupling is exerted, the magnetic performance is improved, the required sintering temperature and time are greatly reduced, and the energy consumption is reduced.
Disclosure of Invention
The invention aims to provide a method for preparing a high-performance soft and hard magnetic composite material by using a high-pressure ultrasonic thermal decomposition method. Compared with the existing preparation of soft and hard magnetic composite materials, the method provided by the invention has the advantages of simple process, high reaction speed and low energy consumption.
The invention provides a method for preparing a high-performance soft and hard magnetic composite material by using a high-pressure ultrasonic thermal decomposition method, which comprises the following preparation steps:
(1) preparing a mixed solution: dissolving barium salt or strontium salt, ferric salt, lanthanum salt and calcium salt in water according to a stoichiometric ratio, and fully stirring to obtain a mixed solution; (2) preparing the permanent magnetic ferrite: in an air pressure type sprayer consisting of a high-pressure bottle and an atomizing nozzle, conveying the mixed solution obtained in the step (1) to a tubular furnace under the action of carrier gas and air pressure by utilizing a high-pressure ultrasonic spraying principle, evaporating and dehydrating under the action of high temperature, carrying out a salt-heat reaction, and finally conveying the mixed solution to a collector at the tail end of the tubular furnace by the carrier gas to obtain permanent magnetic ferrite particles; (3) preparing soft magnetic ferrite: dissolving cobalt salt and ferric salt in water, fully stirring, and repeating the operation step (2) to prepare soft magnetic ferrite particles; (4) and (3) composite sintering: and (3) carrying out high-pressure heat treatment on the permanent magnetic ferrite obtained in the step (2) and the soft magnetic ferrite obtained in the step (3) in a nitrogen or argon atmosphere to obtain the soft and hard magnetic composite material.
Especially, preferably, the salt in the step (1) may be one or more of nitrate, sulfate or chloride.
Particularly, it is preferable that the gas flow rate in the step (2) is 3L/min to 6L/min, the carrier gas to be transported is inert gas such as argon or nitrogen, the length of the tube furnace is 1.5 m, and the permanent magnet is A1-xLnxFe12O19In the compound, the element A is Sr or Ba, Ln is one or two of La and Ca metal elements, and x is more than or equal to 0.0 and less than or equal to 0.3.
In particular, it is preferable that the central temperature of the tube furnace in the step (2) is 800-.
Especially, preferably, the salt in the step (3) can be one or more of nitrate, sulfate or chloride, and the soft magnetic oxide is CoFe2O4。
Especially, preferably, CoFe in the step (4)2O4The mass fraction of the micron particles is about 3-5% of the total mass of the composite material, the heat treatment temperature is 300-600 ℃, the pressure is 5-15 Mpa, and the time is 30 min-6 h.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) nitrate or sulfate is used as a raw material, so that organic salt is avoided, the raw material cost is low, and the experiment is nontoxic;
(2) compared with the traditional solid phase sintering method, the high pressure ultrasonic thermal decomposition method has short reaction time and reduced energy consumption;
(3) the obtained product has uniform particle size, the size is not micron-sized, the soft and hard magnetic coupling is good, and the magnetic performance of the material can be improved in a limited way.
Drawings
FIG. 1 is a schematic diagram of a high-pressure ultrasonic thermal decomposition device for preparing ferrite materials, 1, an air compressor 2, an air filter 3, a liquid storage tank 4, a pump 5, a flow meter 6, an ultrasonic atomizer 7, a temperature control furnace 8, a quartz tube 9, a powder catcher 10 and a gas washing device.
FIG. 2 Sr0.7La0.3Fe12O19SEM electron micrograph of ferrite.
Detailed Description
Preparation A is illustrated below with reference to specific examples1-xLnxFe12O19/CoFe2O4A method for preparing soft and hard magnetic composite material.
Example 1
(1) Preparation of A by high pressure ultrasonic thermal decomposition1-xLnxFe12O19Precursor, A is strontium, Ln is lanthanum, wherein x =0.3, and Sr is prepared0.7La0.3Fe12O19The precursor, the high-pressure ultrasonic thermal decomposition device is shown in figure 1.
Sr (NO)3)2、La(NO3)3、Fe(NO3)3According to a molar ratio of 0.7: 0.3: 12 is prepared into 500mL of metal salt solution with the proportion of 1mol/L, the metal salt solution is poured into a high-pressure bottle, the tube furnace is heated to 800 ℃ at the speed of 10 ℃/min, an atomizer is opened, the internal pressure of high pressure is 10MPa, and N is2The gas flow rate of (2) was set to 5L/min, and the atomized water mist was transported to a tube furnace by a carrier gas, and the product was collected in a collector at the end of the tube. Putting the collected product into a mortar, grinding until no granular sensation exists, putting a magnet at the bottom of the mortar, pouring the washing liquid by utilizing the magnetic separation principle, and washing for 3 times by using absolute ethyl alcohol. Drying the cleaned product in a vacuum drying oven at 60 deg.C for 12 hr to obtain pure Sr0.7La0.3Fe12O19Ferrite as shown in fig. 2.
(2) Preparation of CoFe by high-pressure ultrasonic thermal decomposition2O4The precursor, the high-pressure ultrasonic thermal decomposition device is shown in figure 1.
Mixing Co (NO)3)2、Fe(NO3)3500mL of gold is prepared according to the molar ratio of 1:2, wherein the gold is 1mol/LBelongs to salt solution, and pure CoFe is prepared according to the operation step (1)2O4And (3) precursor.
(3) Preparation of Sr by sintering process0.7La0.3Fe12O19/CoFe2O4Soft and hard magnetic composite material prepared by mixing Sr0.7La0.3Fe12O19Precursor and CoFe2O4The precursor is put into a sintering furnace, nitrogen is introduced, and the temperature is increased to 400 ℃ at the temperature rising speed of 15 ℃/min under the pressure of 8MPaoC, preserving the heat for 30min, and slowly cooling to room temperature to obtain Sr0.7La0.3Fe12O19/CoFe2O4The soft and hard magnetic composite material measures a magnetic hysteresis loop by using VSM to obtain the magnetic energy product of the soft and hard magnetic composite material: (BH)max=3.95 MGOe, Sr with less magnetic energy product0.7La0.3Fe12O19The improvement is 12 percent.
Example 2
(1) Preparation of A by high pressure ultrasonic thermal decomposition1-xLnxFe12O19Precursor, A is barium, Ln is calcium, wherein x =0.3, Ba is prepared0.7Ca0.3Fe12O19The precursor, the high-pressure ultrasonic thermal decomposition device is shown in figure 1.
Mixing Ba (NO)3)2、Ca(NO3)2、Fe(NO3)3According to a molar ratio of 0.7: 0.3: 12 is prepared into 500mL of metal salt solution with the proportion of 1mol/L, the metal salt solution is poured into a high-pressure bottle, the tube furnace is heated to 800 ℃ at the speed of 10 ℃/min, an atomizer is opened, the internal pressure of high pressure is 10MPa, and N is2The gas flow rate of (2) was set to 5L/min, and the atomized water mist was transported to a tube furnace by a carrier gas, and the product was collected in a collector at the end of the tube. Putting the collected product into a mortar, grinding until no granular sensation exists, putting a magnet at the bottom of the mortar, pouring the washing liquid by utilizing the magnetic separation principle, and washing for 3 times by using absolute ethyl alcohol. Drying the cleaned product in a vacuum drying oven at 60 deg.C for 12 hr to obtain pure Ba0.7Ca0.3Fe12O19And (3) precursor.
(2) By high pressure ultrasonic heat separationPreparation of CoFe by decomposition2O4The precursor, the high-pressure ultrasonic thermal decomposition device is shown in figure 1.
Mixing Co (NO)3)2、Fe(NO3)3500mL of metal salt solution is prepared according to the molar ratio of 1:2, and pure CoFe is prepared according to the operation step (1)2O4And (3) precursor.
(3) Preparation of Ba by sintering process0.7Ca0.3Fe12O19/CoFe2O4A soft and hard magnetic composite material prepared by mixing Ba0.7Ca0.3Fe12O19Putting the precursor and Ni nano-particles into a sintering furnace, introducing argon, and heating to 600 ℃ at the temperature rise speed of 20 ℃/min under the pressure of 15MPaoC, sintering for 2h, and slowly cooling to room temperature to obtain Ba0.7Ca0.3Fe12O19/CoFe2O4The soft and hard magnetic composite material measures a magnetic hysteresis loop by using VSM to obtain the magnetic energy product of the soft and hard magnetic composite material: (BH)max=4.03MGOe, Ba with less magnetic energy product than that of the un-compounded Ba0.7Ca0.3Fe12O19The improvement is 21 percent.
Claims (6)
1. A method for preparing a high-performance soft and hard magnetic composite material is characterized by comprising the following steps:
(1) preparing a mixed solution: dissolving barium salt or strontium salt, ferric salt, lanthanum salt and calcium salt in water according to a stoichiometric ratio, and fully stirring to obtain a mixed solution;
(2) preparing the permanent magnetic ferrite: atomizing the mixed solution obtained in the step (1) in an air pressure type atomizer consisting of a high-pressure bottle and an atomizing nozzle by utilizing a high-pressure ultrasonic atomizing principle, conveying the atomized mixed solution into a tube furnace under the action of carrier gas and air pressure, evaporating, dehydrating and carrying out a salt-heat reaction under the action of high temperature, and finally conveying the atomized mixed solution onto a collector at the tail end of the tube furnace by the carrier gas to obtain permanent magnetic ferrite particles;
(3) preparing soft magnetic ferrite: dissolving cobalt salt and ferric salt in water, fully stirring, and repeating the operation step (2) to prepare soft magnetic ferrite particles;
(4) and (3) composite sintering: and (3) carrying out high-pressure heat treatment on the permanent magnetic ferrite obtained in the step (2) and the soft magnetic ferrite obtained in the step (3) in a nitrogen or argon atmosphere to obtain the soft and hard magnetic composite material.
2. The method of claim 1, wherein the salt in step (1) is one or more of nitrate, sulfate or chloride.
3. The method of claim 1, wherein the gas flow rate in step (2) is 3L/min to 6L/min, the carrier gas is inert gas such as argon or nitrogen, the length of the tube furnace is 1.5 m, and the permanent magnet is A1- xLnxFe12O19In the compound, the element A is Sr or Ba, Ln is one or two of La and Ca metal elements, and x is more than or equal to 0.0 and less than or equal to 0.3.
4. The method of claim 1, wherein the core temperature of the tube furnace in step (2) is 800 ℃oC-900 oCA centrosymmetric temperature gradient is formed along the length direction.
5. The method according to claim 1, wherein the salt in step (3) can be one or more of nitrate, sulfate or chloride, and the soft magnetic oxide is CoFe2O4。
6. The method of claim 1, wherein the CoFe in step (4)2O4The mass fraction of the micron particles is about 3-5% of the total mass of the composite material, and the heat treatment temperature is 300% oC -600 oCThe pressure is 5-15 Mpa, and the time is 30 min-6 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116947475A (en) * | 2023-08-15 | 2023-10-27 | 中国计量大学 | Preparation method of high-performance composite ferrite for self-bias circulator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116947475A (en) * | 2023-08-15 | 2023-10-27 | 中国计量大学 | Preparation method of high-performance composite ferrite for self-bias circulator |
| CN116947475B (en) * | 2023-08-15 | 2024-02-23 | 中国计量大学 | Preparation method of high-performance composite ferrite for self-bias circulator |
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