CN114956192A - Lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and preparation method thereof - Google Patents

Lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and preparation method thereof Download PDF

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CN114956192A
CN114956192A CN202210650609.8A CN202210650609A CN114956192A CN 114956192 A CN114956192 A CN 114956192A CN 202210650609 A CN202210650609 A CN 202210650609A CN 114956192 A CN114956192 A CN 114956192A
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lanthanum
cobalt
barium ferrite
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吴玉程
杨智慧
崔接武
刘家琴
张勇
吴运飞
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Hefei University of Technology
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Abstract

The invention discloses a lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and a preparation method thereof, wherein the wave-absorbing powder material is Ba 1‑x La x Co x Fe 12‑x O 19 Wherein x is 0.1 to 0.4. The preparation method comprises doping rare earth element lanthanum and metal element cobalt into barium ferrite to respectively replace Ba in the barium ferrite 2+ And Fe 3+ The synchronous substitution of different element sites is realized, and the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material is obtained. The lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material is low in price and simple in production process, can be used for a wave-absorbing coating, and can be applied to a decimetric waveband (300 MHz-3 GHz), a centimeter waveband (3 GHz-30 GHz) and a millimeter waveband (30 GHz-300 GHz) to a certain extent.

Description

Lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and preparation method thereof
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and a preparation method thereof.
Background
With the continuous progress of scientific technology, electromagnetic waves are increasingly widely used in human life, such as radio waves for communication, microwaves for microwave oven and satellite communication, and the like. However, the electromagnetic wave inevitably causes problems of electromagnetic radiation, electromagnetic wave interference and the like, and has certain harm to human bodies, and meanwhile, the stealth aircraft technology in military also puts higher requirements on the wave absorbing material, so that the research on the novel multifunctional wave absorbing material with light weight, thin thickness, wide absorption frequency band and strong absorption capacity is urgent.
Rare earth is an important resource, is an element with an electronic structure similar to chemical properties, and shows distinctive optical, electrical, magnetic and chemical properties due to the unique electronic layer structure and the incomplete filling of the outermost layer 4f electron orbit, so that the rare earth element has wide application in various fields. In recent years, a plurality of researchers apply rare earth to wave-absorbing materials, and ideal wave-absorbing effect is obtained by utilizing the unique performance of rare earth elements.
The M-type ferrite becomes a permanent magnet material with wide application because of the advantages of high uniaxial magnetocrystalline anisotropy, high coercive force, low price, high stability and the like. Researches show that the magnetic properties of the ferrite can be improved to a certain extent by simply improving the preparation process conditions of the ferrite.
Ion doping in barium ferrites is an effective method of tuning performance, typically using non/weakly magnetic ions or combinations of ions such as Al 3+ 、Cr 3+ 、Co 2+ -Ti 4+ 、Co 2+ -Ru 4+ Isosubstituted for Fe in doped barium ferrite 3+ Ions to increase the dielectric constant of barium ferrite, or rare earth ions to replace Ba in barium ferrite 2+ The ion can effectively adjust the magnetic property of the barium ferrite by controlling the content of the doped ion. However, the research on the wave absorption performance of the lanthanum-cobalt co-doped barium ferrite in the dual-frequency bands of 1-18 GHz and 26.5-40 GHz is only reported at present. The preparation of materials with dual-band wave-absorbing properties requires a material costThe body resonance frequency is close to a certain frequency band. Secondly, the interaction among the elements of the material can generate a plurality of resonance peaks under the combined action of a plurality of resonances, thereby widening the wave-absorbing frequency band.
Disclosure of Invention
The invention aims to provide a lanthanum-cobalt co-doped barium ferrite dual-band wave-absorbing powder material and a preparation method thereof, which can improve the electromagnetic constant of barium ferrite and obtain a high-efficiency wave-absorbing material capable of being applied to dual bands.
In one aspect of the invention, the invention provides a lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material. According to the embodiment of the invention, the wave-absorbing powder material is Ba 1-x La x Co x Fe 12-x O 19 Wherein x is 0.1 to 0.4.
In another aspect of the invention, the invention provides a preparation method of a lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material. According to the embodiment of the invention, the rare earth element lanthanum and the metal element cobalt are doped into the barium ferrite together to respectively replace Ba in the barium ferrite 2+ And Fe 3+ The synchronous substitution of different element sites is realized, and the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material is obtained.
In addition, the preparation method of the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material according to the embodiment of the invention can also have the following additional technical characteristics:
in some embodiments of the invention, the method comprises the steps of:
(1) mixing barium nitrate, lanthanum nitrate, cobalt nitrate, ferric nitrate and citric acid monohydrate, adding deionized water, stirring for 30-60 min, and dissolving to obtain sol;
(2) adding a proper amount of ammonia water into the sol obtained in the step (1) to adjust the pH value to 7, and then placing the sol in an oil bath kettle at the temperature of 120 ℃ to continuously stir and heat for 3-5 h to obtain dark brown wet gel;
(3) drying the wet gel obtained in the step (2) to form dry gel;
(4) grinding the xerogel obtained in the step (3) to obtain brown precursor powder;
(5) and (4) calcining the precursor powder obtained in the step (4), cooling to room temperature, and grinding to finally obtain the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material.
In some embodiments of the invention, in the step (1), the molar ratio of barium nitrate, lanthanum nitrate, cobalt nitrate, ferric nitrate and citric acid monohydrate is 0.6-0.9: 0.1-0.4: 11.6-11.9: 13.
In some embodiments of the present invention, in the step (3), the drying temperature is 150 ℃ and the drying time is 12 hours.
In some embodiments of the invention, in the step (5), the calcination process comprises heating to 250 ℃ and maintaining the temperature for 1.5 hours, heating to 450 ℃ and maintaining the temperature for 2 hours, and finally heating to 1100-1400 ℃ and maintaining the temperature for 3 hours.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention utilizes a sol-gel method to mix rare earth element lanthanum and metal element cobalt into barium ferrite, and rare earth ion La 3+ Substituted for Ba in barium ferrite 2+ ,Co 2+ Substituted for Fe in barium ferrite 3+ And synchronous substitution of different element sites of the barium ferrite is realized. The rare earth element is introduced, so that the crystal boundary magnetic domain activity can be improved, and the domain wall resonance and the natural resonance are increased, wherein the natural resonance is a main mechanism of the barium ferrite as a wave-absorbing material for magnetic loss at 26.5-40 GHz. By using Co 2+ Substituted Fe 3+ And the magnetocrystalline anisotropy is reduced, thereby improving the dielectric constant of barium ferrite. In addition, the rare earth element lanthanum and the transition group metal element cobalt generate interaction, so that the material is more favorable for widening an effective absorption frequency band under the action of natural resonance and exchange resonance, and has certain loss capacity on electromagnetic waves in two frequency bands of 1-18 GHz and 26.5-40 GHz, so that the material can be applied to three frequency bands of decimetric waves (300 MHz-3 GHz), centimeter waves (3 GHz-30 GHz) and millimeter waves (30 GHz-300 GHz) at the same time.
2) The thickness of the material can be reduced and the wave-absorbing frequency band of the barium ferrite can be changed by adjusting the amount of lanthanum ions and cobalt ions doped into the barium ferrite, so that the light and efficient wave-absorbing material can be obtained. When x is less than or equal to 0.4, the more doping content, the lower the matching thickness of the material. When the doping amount x is 0.1 and 0.2, the increase of the doping content brings the reduction of the matching thickness, and simultaneously the maximum reflection loss value is also reduced, namely the wave-absorbing performance is improved; when x is 0.3 and 0.4, the matching thickness is reduced along with the increase of the doping content, the maximum reflection loss value is increased to about-19 dB, and the wave absorbing material still has good wave absorbing performance (the reflection loss is less than-10 dB, namely the electromagnetic wave with 90% of attenuation loss, and the reflection loss is less than-20 dB, namely the electromagnetic wave with 99% of attenuation loss). When X is 0.1, 0.2 and 0.3, the wave-absorbing frequency band of the maximum reflection loss is reduced to be near 27GHz from 40 GHz; when x is 0.4, the wave-absorbing frequency band of the maximum reflection loss is increased to be around 38 GHz.
3) The wave-absorbing material has the characteristic of strong reflection loss. The sample doped with a certain amount has good reflection loss in two frequency bands, and when the doping amount x is 0.2, the optimal reflection loss value under a specific frequency can reach-52.69 dB.
4) The preparation method is simple and easy to operate, safe, pollution-free and low in cost, provides possibility for industrial production, and provides a new way for research of wave-absorbing materials and magnetic materials.
Drawings
FIG. 1 shows a wave-absorbing material Ba obtained in example 1 of the present invention 0.8 La 0.2 Co 0.2 Fe 11.8 O 19 A wave-absorbing performance variation relation curve graph along with frequency in a frequency range of 1-18 GHz;
FIG. 2 shows a wave-absorbing material Ba obtained in example 1 of the present invention 0.8 La 0.2 Co 0.2 Fe 11.8 O 19 A curve graph of the variation relation of the wave absorbing performance with the frequency in the frequency range of 26.5-40 GHz;
FIG. 3 shows a Ba wave-absorbing material obtained in example 2 of the present invention 0.6 La 0.4 Co 0.4 Fe 11.6 O 19 A wave-absorbing performance variation relation curve graph along with frequency in a frequency range of 1-18 GHz;
FIG. 4 is a graph obtained in example 2 of the present inventionWave-absorbing material Ba 0.6 La 0.4 Co 0.4 Fe 11.6 O 19 And a curve chart of the change relation of the wave absorbing performance along with the frequency in the frequency range of 26.5-40 GHz.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A preparation method of a lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material comprises the following steps:
(1) mixing barium nitrate, lanthanum nitrate, cobalt nitrate, ferric nitrate and citric acid monohydrate according to a molar ratio of 0.8:0.2:0.2:11.8:13, adding deionized water, and stirring for 40min to obtain sol;
(2) adding a proper amount of ammonia water into the sol obtained in the step (1) to adjust the pH value to 7, and then placing the sol in an oil bath kettle at the temperature of 120 ℃ to continuously stir and heat for 4 hours to obtain brown wet gel;
(3) putting the wet gel obtained in the step (2) into a 150 ℃ forced air drying oven to be dried for 12 hours to form dry gel;
(4) grinding the xerogel obtained in the step (3) in an agate mortar to obtain tan precursor powder;
(5) putting the precursor powder obtained in the step (4) in a muffle furnace, heating to 250 ℃, preserving heat for 1.5h, heating to 450 ℃, preserving heat for 2h, heating to 1400 ℃, preserving heat for 3h, cooling to room temperature along with the furnace, grinding in a mortar for 10min, and finally obtaining the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material Ba 0.8 La 0.2 Co 0.2 Fe 11.8 O 19
The wave-absorbing performance of the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material prepared by the embodiment is tested by using a vector network analyzer. During testing, the wave-absorbing material powder is mixed with solid paraffin according to the mass ratio of 8:2 to prepare a block paraffin sample for testing.
FIG. 1 and FIG. 2 show the absorbing material Ba obtained in example 1 0.8 La 0.2 Co 0.2 Fe 11.8 O 19 The change relation curve of the wave absorption performance along with the frequency in 1-18 GHz and 26.5-40 GHz. FIG. 1 shows data obtained at a matching thickness of 5.4mm, and it can be seen from the graph that an absorption peak appears at frequencies of 5.04GHz and 16.26GHz respectively, forming a dual-resonance loss mechanism, and the effective wave-absorbing bandwidth in this band is 4.38GHz (i.e. RL<Frequency range of-10 dB), the reflection loss is strongest at 16.26GHz, reaching-18.36 dB. Figure 2 is the data obtained at a matching thickness of 3.2mm and it can be seen that the reflection loss is strongest at 27.72GHz, reaching-52.69 dB, and the effective bandwidth at this band is 3.17 GHz.
Example 2
A preparation method of a lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material comprises the following steps:
(1) mixing barium nitrate, lanthanum nitrate, cobalt nitrate, ferric nitrate and citric acid monohydrate according to a molar ratio of 0.6:0.4:0.4:11.6:13, adding deionized water, and stirring for 40min to obtain sol;
(2) adding a proper amount of ammonia water into the sol obtained in the step (1) to adjust the pH value to 7, and then placing the sol in an oil bath kettle at 120 ℃ to continuously stir and heat for 4 hours to obtain brown wet gel;
(3) putting the wet gel obtained in the step (2) into a 150-degree air-blast drying oven to be dried for 12 hours to form dry gel;
(4) grinding the xerogel obtained in the step (3) in an agate mortar to obtain tan precursor powder;
(5) putting the precursor powder obtained in the step (4) into a muffle furnace, heating to 250 ℃, preserving heat for 1.5h, heating to 450 ℃, preserving heat for 2h, heating to 1400 ℃, preserving heat for 3h, cooling to room temperature along with the furnace, grinding in a mortar for 10min, and finally obtaining the lanthanum-cobalt co-doped barium ferrite wave-absorbing powder material Ba 0.6 La 0.4 Co 0.4 Fe 11.6 O 19
The wave-absorbing performance of the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material prepared by the embodiment is tested by using a vector network analyzer. During testing, the wave-absorbing material powder is mixed with solid paraffin according to the mass ratio of 8:2 to prepare a block paraffin sample for testing.
FIGS. 3 and 4 show the Ba wave-absorbing material obtained in example 1 0.6 La 0.4 Co 0.4 Fe 11.6 O 19 The change relation curve of the wave absorption performance along with the frequency in 1-18 GHz and 26.5-40 GHz. FIG. 3 is the data obtained under the matching thickness of 5.2mm, and it can be seen from the figure that an absorption peak appears at the frequency of 5.25GHz and 16.47GHz respectively, a double resonance loss mechanism is formed, the effective wave-absorbing bandwidth at the waveband is 3.44GHz, and the reflection loss is strongest at 16.47GHz, reaching-23.38 dB. Figure 4 is the data obtained at a matching thickness of 2.4mm and it can be seen that the reflection loss is strongest at 37.27GHz, reaching-19.55 dB, and the effective bandwidth at this band is 5.84 GHz.
The above examples are typical examples of the present invention, and are not intended to limit the present invention, and for example, the stirring time, the oil bath temperature, and the drying temperature can be further adjusted. Therefore, it is within the scope of the present invention to modify and modify the process parameters described by those skilled in the art without departing from the spirit of the invention or exceeding the scope defined by the claims.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.

Claims (6)

1. The utility model provides a lanthanum cobalt codope barium ferrite dual-waveband wave-absorbing powder material which characterized in that: the wave-absorbing powder material is Ba 1-x La x Co x Fe 12-x O 19 Wherein x is 0.1 to 0.4.
2. The preparation method of the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material according to claim 1, which is characterized by comprising the following steps of: doping rare earth element lanthanum and metal element cobalt into barium ferrite to respectively replace the rare earth element lanthanum and the metal element cobalt in the barium ferrite
Figure FDA0003685936010000011
And
Figure FDA0003685936010000012
synchronous substitution of different element sites is realized, and the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material is obtained.
3. The preparation method of the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material according to claim 2, wherein the method comprises the following steps:
(1) mixing barium nitrate, lanthanum nitrate, cobalt nitrate, ferric nitrate and citric acid monohydrate, adding deionized water, stirring for 30-60 min, and dissolving to obtain sol;
(2) adding a proper amount of ammonia water into the sol obtained in the step (1) to adjust the pH value to 7, and then placing the sol in an oil bath kettle at the temperature of 120 ℃ to continuously stir and heat for 3-5 hours to obtain brown wet gel;
(3) drying the wet gel obtained in the step (2) to form dry gel;
(4) grinding the xerogel obtained in the step (3) to obtain brown precursor powder;
(5) and (4) calcining the precursor powder obtained in the step (4), cooling to room temperature, and grinding to finally obtain the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material.
4. The lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and the preparation method thereof according to claim 3, wherein the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material is characterized in that: in the step (1), the molar ratio of barium nitrate, lanthanum nitrate, cobalt nitrate, ferric nitrate and citric acid monohydrate is 0.6-0.9: 0.1-0.4: 11.6-11.9: 13.
5. The lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and the preparation method thereof according to claim 3, wherein the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material is characterized in that: in the step (3), the drying temperature is 150 ℃, and the drying time is 12 h.
6. The lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material and the preparation method thereof according to claim 3, wherein the lanthanum-cobalt co-doped barium ferrite dual-waveband wave-absorbing powder material is characterized in that: in the step (5), the calcining process comprises the steps of heating to 250 ℃ and preserving heat for 1.5h, heating to 450 ℃ and preserving heat for 2h, and finally heating to 1100-1400 ℃ and preserving heat for 3 h.
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