CN113173783A - Ferrite wave-absorbing material with perovskite structure and preparation method thereof - Google Patents

Ferrite wave-absorbing material with perovskite structure and preparation method thereof Download PDF

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CN113173783A
CN113173783A CN202110470289.3A CN202110470289A CN113173783A CN 113173783 A CN113173783 A CN 113173783A CN 202110470289 A CN202110470289 A CN 202110470289A CN 113173783 A CN113173783 A CN 113173783A
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absorbing material
preparation
ferrite wave
perovskite structure
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姚青荣
梁琪华
童兆飞
成丽春
卢照
王江
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Guilin University of Electronic Technology
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Abstract

The invention provides a perovskite structured ferrite wave-absorbing material and a preparation method thereof, wherein the molecular formula of the perovskite structured ferrite wave-absorbing material is NdFe1‑xNixO3(x is 0,0.1,0.2, 0.3). The preparation method comprises the steps of dissolving neodymium nitrate hexahydrate, ferric nitrate nonahydrate and nickel nitrate hexahydrate which serve as raw materials in deionized water according to the stoichiometric amount, adding a proper amount of citric acid monohydrate, dropwise adding ammonia water to adjust the PH to be in an alkaline environment, placing the mixture in a water bath kettle, heating and stirring to obtain uniform wet gel; and putting the prepared wet gel into a forced air drying box for drying, pre-burning to obtain a precursor, adding PVA (polyvinyl alcohol) into the obtained precursor powder for granulation, uniformly grinding, and molding to obtain the cylindrical block. The perovskite structure ferrite wave-absorbing material has good microwave absorption effect in the microwave band of 2-18 GHz,wide absorption frequency band, simple preparation process, easy regulation and control of the preparation process and the like.

Description

Ferrite wave-absorbing material with perovskite structure and preparation method thereof
Technical Field
The invention belongs to the field of wave-absorbing materials, and particularly relates to a perovskite structured ferrite wave-absorbing material and a preparation method thereof.
Background
In modern life where electronic information is dominant, people's life and work are becoming more convenient and efficient because of the use of more and more electronic products. Microwaves are also used in various aspects of life as an information carrier. For example, high frequency electromagnetic waves are increasingly used in high and new technologies such as communication systems, intelligent transportation systems, electronic toll collection systems, medical systems, local area network systems, and the like. The use of a large number of novel digital, informationized and intelligent electronic devices makes the space electromagnetic environment more and more complex, the electromagnetic energy density also continuously increases, and the electromagnetic pollution problem therewith becomes more and more serious. On the one hand, the electromagnetic wave radiated by the electronic equipment during operation can interfere with the normal operation of the surrounding electronic equipment, resulting in the performance degradation and even failure thereof. On the other hand, severe electromagnetic radiation can also be harmful to human health, especially electromagnetic radiation generated by communication equipment. Research shows that electromagnetic radiation has different degrees of influence on the nervous system, the cardiovascular system, the immune system and the like of a human body and has cumulative effect on damage to the human body. Therefore, it is important to realize electromagnetic radiation protection by absorbing or shielding electromagnetic waves generated by electronic and electrical equipment.
In order to effectively reduce the pollution of electromagnetic radiation, people begin to turn the research direction to efficient electromagnetic wave absorbing materials. The electromagnetic wave absorbing material can generally lead incident electromagnetic waves to be absorbed by converting energy into other energy such as heat energy and the like through medium loss on the premise of not changing the appearance of an electronic product, thereby achieving the purpose of reducing the radiation pollution of the electromagnetic waves.
Perovskite (ABO)3) The perovskite-structured compound is very goodIs stable in thermodynamics and has great tolerance to the constituent elements. Ions on A site and B site in the structure of the compound can be singly or compositely substituted by various ions with different electrovalence and radius in a quite wide concentration range to form a solid solution doped by one element or a plurality of elements together, so that the performance of the material can be adjusted in a large range to meet various application requirements. Alkali metals, alkaline earth metals, rare earth elements, transition metals and some main group metals, almost all of which can form stable perovskites (ABO) under certain conditions3) A compound of structure (la). Due to the performances of the material in the aspects of dielectric, magnetism, multiferroic, magneto-optical, catalysis, gas sensitivity and the like, the material becomes an important material in the wide application at present.
NdFeO3As an important perovskite type rare earth ferrite, the rare earth ferrite has excellent chemical, thermodynamic and mechanical stability. Because the shape and chemical components of the material can influence the final performance of the material, how to control the growth of the material and realize the regulation and control of the shape, composition and physical properties of the material is of great significance for deeply researching the association between the structure and the performance and finally designing and combining the material with ideal performance. Thus passing through Ni3+Doped NdFeO3The morphology is changed so as to achieve the regulation and control of the wave absorption performance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a perovskite structure ferrite wave-absorbing material and a preparation method thereof, and the material has a wider microwave absorption frequency band and high microwave absorption efficiency in a 2-18 GHz microwave frequency band.
The invention adopts the following technical scheme:
the ferrite wave-absorbing material with the perovskite structure has the structure of NdFe1-xNixO3Wherein x is 0,0.1, 0.3.
The preparation method of the ferrite wave-absorbing material with the perovskite structure comprises the following specific steps:
(1) analytically pure grade neodymium nitrate hexahydrate (Nd (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and Nickel nitrate hexahydrate (Ni (NO)3)3·6H2O) is taken as an ion source of Nd, Fe and Ni, samples are weighed according to the stoichiometric ratio of experimental components, ultrasonic dispersion is utilized, and the weighed samples are dissolved into deionized water with a certain volume to obtain a solution.
(2) Adding citric acid monohydrate with the molar ratio of the citric acid monohydrate to the metal ions being 1: 1-2: 1 into the solution, and dropping ammonia water to adjust the pH value of the weak alkaline water environment to be 7.3-9.0;
(3) putting the prepared solution into a water bath kettle at the temperature of 60-90 ℃, adding a clean and pollution-free magnetic rotor into the solution, and stirring the solution for 2.5-4 hours by using a magnetic stirrer until the solution is uniform and is transparent and gel-like;
(4) placing the wet gel in a drying oven at 90-120 ℃ for drying for 24-36 hours to obtain dry gel;
(5) putting the obtained xerogel into a crucible, putting the crucible into a resistance furnace for presintering at 200-350 ℃, removing organic matters to obtain a precursor, and grinding the precursor into uniform powder by using a mortar;
(6) granulating the prepared precursor powder by using 8-10% by mass of polyvinyl alcohol (PVA) glue, drying in a drying oven, sieving by using a screen with no meshes to obtain uniform powder particles, putting the uniform powder particles into a mold, and pressing the powder into a wafer block with the thickness of 1.5-2.5 mm and the diameter of 12.0mm under the pressure of 5.0-20.0 Mpa;
(7) and placing the prepared wafer block in a muffle furnace, raising the temperature to 400-700 ℃ at a heating rate of 1 ℃/min, preserving the heat for 0.5 hour, removing the glue, then annealing at a heating rate of 0.5 ℃/min to 600-900 ℃ for 4-7 hours, finally reducing the temperature to room temperature at a cooling rate of 3 ℃/min, and finally preparing the sample.
And (3) detecting the structure and the performance of the sample:
and (3) detecting a crystal structure:
to ensure purity of the prepared sample and Ni-doped p-NdFeO3Influence of Crystal Structure on the study, measured by X-ray powder diffractometer (PANalytical X' pert)With Cu target (Ka, wavelength)
Figure BDA0003045099790000033
Figure BDA0003045099790000034
) Diffraction analysis detection is carried out on the prepared powder sample.
Analyzing the surface topography and structure of the sample:
in order to analyze the surface morphology of the prepared sample and the Ni-doped p-NdFeO3Influence of morphology study, morphological structure analysis was performed on the prepared powder sample by transmission electron microscopy (FEI Talos F200X) using a thermal field emission electron gun.
And (3) detecting the wave absorbing performance:
according to NdFe1-xNixO3Powder: and (3) mixing paraffin wax in a ratio of 3:1 (mass ratio), preparing coaxial samples with the inner diameter and the outer diameter of 3mm and 7mm respectively and the thickness of 3.0-3.6 mm, and measuring the complex dielectric constant and the complex permeability of the samples in a 2-18 GHz frequency band respectively by using an HP8722ES microwave vector network analyzer. And calculating the reflectivity RL of the single-layer wave-absorbing material by adopting the following formula.
Figure BDA0003045099790000031
Figure BDA0003045099790000032
Figure BDA0003045099790000041
Wherein Z is the wave impedance, wherein Z is0Wave impedance of vacuum, ZinIs the normalized input impedance, mur、εrRelative permittivity and permeability, f is frequency, c is speed of light, μ0、ε0And d is the vacuum magnetic conductivity, the vacuum dielectric constant and the wave-absorbing coating thickness respectively, and j is a constant.
The invention has the beneficial effects that:
NdFeO3the perovskite-type material has an excellent perovskite-type structure, the structure has strong controllability, and meanwhile, the material of the perovskite structure has attractive multifunctionality.
The invention dopes NdFeO by transition element Ni3The wave-absorbing material with the perovskite structure has excellent microwave absorption characteristic in a 2-18 GHz microwave band, wide absorption frequency band and low reflection loss rate. By studying doping of Ni3+Ion pair NdFeO3The crystal structure and the surface morphology have important significance for the interaction of wave absorption performance, basic research and potential application.
At the same time, to prepare pure phase NdFeO3Provides a new idea, and the preparation technology of the material by adopting sol-gel has many advantages, such as: high product uniformity and purity, easy regulation and control of reaction process parameters, simple process, less required energy and the like.
Drawings
FIG. 1 is a process flow diagram of a sample preparation method of the present invention;
FIG. 2 shows NdFe1-xNixO3(x is 0,0.1,0.2,0.3) an XRD refined spectrum of the ferrite wave-absorbing material with the perovskite structure;
FIG. 3(a) shows NdFe1-xNixO3(x ═ 0) a unit cell model of a perovskite structured ferrite wave-absorbing material;
FIG. 3(b) shows NdFe1-xNixO3(x ═ 0.1) a unit cell model of a perovskite structured ferrite wave-absorbing material;
FIG. 3(c) shows NdFe1-xNixO3(x ═ 0.2) unit cell model of perovskite structured ferrite wave-absorbing material;
FIG. 3(d) shows NdFe1-xNixO3(x ═ 0.3) unit cell model of perovskite structured ferrite wave-absorbing material;
FIG. 4(a) shows NdFe1-xNixO3(x is 0) transmission electron microscopy spectrogram of the ferrite wave-absorbing material with the perovskite structure;
FIG. 4(b) shows NdFe1-xNixO3(x is 0.3) a transmission electron microscope spectrogram of the ferrite wave-absorbing material with the perovskite structure;
FIG. 5 shows NdFe1-xNixO3(x is 0,0.1,0.2,0.3) reflectance of the perovskite-structured ferrite wave-absorbing material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, the preparation method of the ferrite wave-absorbing material with the perovskite structure comprises the following specific steps:
(1) analytically pure grade neodymium nitrate hexahydrate (Nd (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and Nickel nitrate hexahydrate (Ni (NO)3)3·6H2O) is taken as an ion source of Nd, Fe and Ni, samples are weighed according to the stoichiometric ratio of experimental components, ultrasonic dispersion is utilized, and the weighed samples are dissolved into deionized water with a certain volume to obtain a solution.
(2) Adding citric acid monohydrate with the molar ratio of the citric acid monohydrate to the metal ions being 1: 1-2: 1 into the solution, and dropping ammonia water to adjust the pH value of the solution to be in a weakly alkaline water environment of 7.3-9.0.
(3) Putting the prepared solution into a water bath kettle at the temperature of 60-90 ℃, adding a clean and pollution-free magnetic rotor into the solution, and stirring for 2.5-4 hours by using a magnetic stirrer until the solution is uniform and is transparent and gel-like.
(4) And (3) drying the wet gel in a drying oven at the temperature of 90-120 ℃ for 24-36 hours to obtain dry gel.
(5) And putting the obtained xerogel into a crucible, putting the crucible into a resistance furnace for presintering at 200-350 ℃, removing organic matters to obtain a precursor, and grinding the precursor into uniform powder by using a mortar.
(6) Granulating the prepared precursor powder by using 8-10% of polyvinyl alcohol (PVA) glue by mass, placing the granules in a drying box for drying, then sieving the granules by using a sieve with no meshes to obtain uniform powder particles, putting the powder particles into a mould, and pressing the powder into a wafer block with the thickness of 1.5-2.5 mm and the diameter of 12.0mm under the pressure of 5.0-20.0 MPa.
(7) And placing the prepared wafer block in a muffle furnace, raising the temperature to 400-700 ℃ at a heating rate of 1 ℃/min, preserving the heat for 0.5 hour, removing the glue, then annealing at a heating rate of 0.5 ℃/min to 600-900 ℃ for 4-7 hours, finally reducing the temperature to room temperature at a cooling rate of 3 ℃/min, and finally preparing the sample.
Example 1
1) The analytically pure grade of neodymium hexa-ammonium nitrate (Nd (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) is taken as an ion source of Nd and Fe, samples are weighed according to the stoichiometric ratio of 1:1, ultrasonic dispersion is utilized, and the weighed samples are dissolved into deionized water with a certain volume to obtain a solution;
2) adding citric acid monohydrate with the molar ratio of the citric acid monohydrate to the metal ions being 1:2 into the solution, and dropping ammonia water to adjust the pH value to 7.5;
3) putting the prepared solution into a water bath kettle at 60 ℃, and stirring for 5 hours by using a magnetic stirrer until the solution is uniform and is transparent, gel-like;
4) the wet gel is placed in a drying oven at the temperature of 90 ℃ for drying for 36 hours to obtain dry gel;
5) putting the obtained xerogel into a crucible, presintering the xerogel in a resistance furnace at 200 ℃ for 2 hours, and removing organic matters to obtain precursor powder;
6) granulating the prepared precursor powder by using polyvinyl alcohol glue (PVA) with the mass fraction of 8%, then fully and uniformly grinding the precursor powder in an agate mortar, putting the mixture into a mold, and pressing the powder into a wafer block with the thickness of 1.0-2.0 mm and the diameter of 12.0mm under the pressure of 5.0 Mpa;
7) and (3) placing the prepared wafer block in an annealing furnace at the temperature of 400 ℃ for heat preservation for 0.5 hour, removing the glue, annealing at the temperature of 600 ℃ for 4 hours, and finally preparing a sample.
Product detection: the obtained NdFeO3Ferrite wave-absorbing material powder samples were prepared using a Cu target (Ka, wavelength) by an X-ray powder diffractometer (PANalytical X' pert)
Figure BDA0003045099790000061
) Detecting and structurally analyzing the prepared powder sample; the prepared powder samples were subjected to morphological structure analysis by transmission electron microscopy (FEI Talos F200X) using an electron gun for thermal field emission; according to NdFeO3Powder: and (3) mixing paraffin wax in a ratio of 3:1 (mass ratio), preparing coaxial samples with the inner diameter and the outer diameter of 3mm and the outer diameter of 7mm respectively and the thickness of 3.0mm respectively, measuring the complex permeability and the complex dielectric constant of the sample in a 2-18 GHz frequency band respectively by using an HP8722ES microwave vector network analyzer, and calculating the reflectivity RL of the single-layer wave-absorbing material.
And (3) performance test results:
as shown in FIG. 2, the analysis showed that NdFeO was produced3The sample is pure single phase, and the spatial structure is pnma type.
As shown in FIGS. 3(a) to 3(d), NdFeO was shown3The bond length and bond angle of the chemical bond at room temperature;
as shown in FIG. 4(a), the transmission electron microscope showed NdFeO3It is a pure single phase at room temperature, further illustrating that its spatial structure is pnma.
The reflectivity R is shown in fig. 5, and it can be seen from the graph that in the microwave band of 3 to 18GHz with a thickness d of 3.0mm, the effective bandwidth is 1.1GHz (the absorption rate is greater than 90%), which has a better broadband effect; the minimum reflectance value reaches around-32.9 dB at a frequency of 16.64 GHz.
Example 2
1) An analytically pure grade of neodymium nitrate hexahydrate (Nd (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and hexahydrate and nickel nitrate (Ni (NO)3)3·6H2O) as a source of ions of Nd, Fe, Ni in a 9:1 stoichiometryWeighing NdFe according to the weight ratio0.9Ni0.1O3Dispersing a sample by using ultrasonic waves, and dissolving the weighed sample into deionized water with a certain volume to obtain a solution;
2) adding citric acid monohydrate with the molar ratio of the citric acid monohydrate to the sum of the metal ions being 1:1.25 into the solution, and dropping ammonia water to adjust the pH value to 8;
3) putting the prepared solution into a water bath kettle at 70 ℃, and stirring for 4 hours by using a magnetic stirrer until the solution is uniform and is transparent, gel-like;
4) the wet gel is placed in a drying oven at 100 ℃ for drying for 32 hours to obtain dry gel;
5) putting the obtained xerogel into a crucible, presintering the xerogel in a resistance furnace at 250 ℃ for 2 hours, and removing organic matters to obtain precursor powder;
6) granulating the prepared precursor powder by using polyvinyl alcohol glue (PVA) with the mass fraction of 8%, then fully and uniformly grinding the precursor powder in an agate mortar, putting the mixture into a mold, and pressing the powder into a wafer block with the thickness of 1.0-2.0 mm and the diameter of 12.0mm under the pressure of 10.0 Mpa;
7) and (3) placing the prepared wafer block in an annealing furnace at the temperature of 600 ℃ for heat preservation for 0.5 hour, removing the glue, annealing at the temperature of 800 ℃ for 4 hours, and finally preparing a sample.
Product detection:
the obtained NdNi0.9Fe0.1O3Ferrite wave-absorbing material powder samples were prepared using a Cu target (Ka, wavelength) by an X-ray powder diffractometer (PANalytical X' pert)
Figure BDA0003045099790000071
) Detecting and structurally analyzing the prepared powder sample; the prepared powder samples were subjected to morphological structure analysis by transmission electron microscopy (FEI Talos F200X) using an electron gun for thermal field emission; according to NdNi0.9Fe0.1O3Powder: mixing paraffin wax in a ratio of 3:1 (mass ratio), preparing coaxial samples with the inner diameter and the outer diameter of 3mm and 7mm respectively and the thickness of 3.0mm respectively, and measuring the complex frequency band of the samples at 2-18 GHz respectively by using an HP8722ES microwave vector network analyzerMagnetic conductivity and complex dielectric constant, and calculating the reflectivity RL of the single-layer wave-absorbing material.
And (3) performance test results:
as shown in FIG. 2, the analysis showed NdFeO as the main component of the prepared sample3And a small fraction of NdFe0.5Ni0.5O3Phase, spatial structure is pbnm type.
As shown in FIGS. 3(a) to 3(d), NdNi is shown0.9Fe0.1O3The bond length of a chemical bond is related to the magnitude of the bond angle at room temperature.
Wherein the reflectance R is shown in fig. 5; it can be seen from the figure that, in the microwave band of 2-18 GHz with the thickness d of 3.0mm, the effective bandwidth is 1.3GHz (the absorption rate is greater than 90%), and a better broadband effect is achieved; the minimum reflectance value reaches around-18.78 dB at a frequency of 5.44 GHz.
Example 3
1) An analytically pure grade of neodymium nitrate hexahydrate (Nd (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and Nickel nitrate hexahydrate (Ni (NO)3)3·6H2O) is taken as an ion source of Nd, Fe and Ni, and NdFe is weighed according to the stoichiometric ratio of 8:10.8Ni0.2O3Dispersing a sample by using ultrasonic waves, and dissolving the weighed sample into deionized water with a certain volume to obtain a solution;
2) adding citric acid monohydrate with the molar ratio of the citric acid monohydrate to the sum of the metal ions being 1:1.5 into the solution, and dropping ammonia water to adjust the pH value to 8.5;
3) placing the prepared solution in a water bath kettle at 80 ℃, and stirring for 3 hours by using a magnetic stirrer until the solution is uniform and is transparent gel;
4) the wet gel is placed in a drying oven at 110 ℃ for drying for 28 hours to obtain dry gel;
5) putting the obtained xerogel into a crucible, presintering in a resistance furnace at 300 ℃ for 2 hours, and removing organic matters to obtain precursor powder;
6) granulating the prepared precursor powder by using polyvinyl alcohol glue (PVA) with the mass fraction of 8%, then fully and uniformly grinding the precursor powder in an agate mortar, putting the mixture into a mold, and pressing the powder into a wafer block with the thickness of 1.0-2.0 mm and the diameter of 12.0mm under the pressure of 15.0 Mpa;
7) and (3) placing the prepared wafer block in an annealing furnace at the temperature of 600 ℃ for heat preservation for 0.5 hour, removing the glue, annealing at the temperature of 800 ℃ for 4 hours, and finally preparing a sample.
Product detection: the obtained NdNi0.8Fe0.2O3Ferrite wave-absorbing material powder samples were prepared using a Cu target (Ka, wavelength) by an X-ray powder diffractometer (PANalytical X' pert)
Figure BDA0003045099790000091
Figure BDA0003045099790000092
) Detecting and structurally analyzing the prepared powder sample; the prepared powder samples were subjected to morphological structure analysis by transmission electron microscopy (FEI Talos F200X) using an electron gun for thermal field emission; according to NdNi0.8Fe0.2O3Powder: and (3) mixing paraffin wax in a ratio of 3:1 (mass ratio), preparing coaxial samples with the inner diameter and the outer diameter of 3mm and the outer diameter of 7mm respectively and the thickness of 3.0mm respectively, measuring the complex permeability and the complex dielectric constant of the samples in a 2-18 GHz frequency band respectively by using an HP8722ES microwave vector network analyzer, and calculating the reflectivity RL of the single-layer wave-absorbing material.
And (3) performance test results:
as shown in FIG. 2, the analysis showed that the prepared sample was mainly NdFeO3And a small fraction of NdFe0.5Ni0.5O3Phase, spatial structure is pbnm type.
As shown in FIGS. 3(a) to 3(d), NdNi0.8Fe0.2O3The bond length of a chemical bond is related to the magnitude of the bond angle at room temperature.
Wherein the reflectance R is shown in fig. 5; it can be seen from the figure that, in the microwave band of 2-18 GHz with the thickness d of 3.0mm, the effective bandwidth is 2.5GHz (the absorption rate is greater than 90%), and a better broadband effect is achieved; the minimum reflectance value reaches around-48.78 dB at a frequency of 4.78 GHz.
Example 4
1) An analytically pure grade of neodymium nitrate hexahydrate (Nd (NO)3)3·6H2O), iron nitrate nonahydrate (Fe (NO)3)3·9H2O) and Nickel nitrate hexahydrate (Ni (NO)3)3·6H2O) is taken as an Nd, Fe and Ni ion source, and NdFe is weighed according to the stoichiometric ratio of 7:10.7Ni0.3Dispersing a sample by using ultrasonic waves, and dissolving the weighed sample into deionized water with a certain volume to obtain a solution;
2) adding citric acid monohydrate with the molar ratio of the citric acid monohydrate to the sum of the metal ions being 1:2 into the solution, and dropping ammonia water to adjust the pH value to 9;
3) putting the prepared solution into a water bath kettle at 90 ℃, and stirring for 2 hours by using a magnetic stirrer until the solution is uniform and is transparent, gel-like;
4) the wet gel is placed in a drying oven at 120 ℃ for drying for 24 hours to obtain dry gel;
5) putting the obtained xerogel into a crucible, presintering the xerogel in a resistance furnace at 350 ℃ for 2 hours, and removing organic matters to obtain precursor powder;
6) granulating the prepared precursor powder by using polyvinyl alcohol glue (PVA) with the mass fraction of 8%, then fully and uniformly grinding the precursor powder in an agate mortar, putting the mixture into a mold, and pressing the powder into a wafer block with the thickness of 1.0-2.0 mm and the diameter of 12.0mm under the pressure of 20.0 Mpa;
7) and (3) placing the prepared wafer block in an annealing furnace at the temperature of 700 ℃ for heat preservation for 0.5 hour, removing the glue, annealing at the temperature of 900 ℃ for 4 hours, and finally preparing a sample.
Product detection:
the obtained NdNi0.7Fe0.3O3Iron positive body wave absorbing material powder sample, using Cu target (Ka, wavelength) by X-ray powder diffractometer (PANALYTICAL X' pert)
Figure BDA0003045099790000101
) Detecting and structurally analyzing the prepared powder sample; by transmission electron microscopy (FEI Talos F200X)) Carrying out morphological structure analysis on the prepared powder sample by using an electron gun for thermal field emission; according to NdNi0.7Fe0.3O3Powder: and (2) mixing paraffin wax in a ratio of 3:1 (mass ratio), preparing coaxial samples with the inner diameter and the outer diameter of 3mm and the outer diameter of 7mm respectively and the thickness of 3.0mm respectively, and measuring the complex permeability and the complex dielectric constant of the samples in a 2-18 GHz frequency band respectively by using an HP8722ES microwave vector network analyzer and calculating the reflectivity RL of the single-layer wave-absorbing material.
And (3) performance test results:
as shown in FIG. 2, the analysis showed that the prepared sample was mainly NdFeO3And part of NdFe0.5Ni0.5O3Phase, spatial structure is pbnm type.
As shown in FIGS. 3(a) to 3(d), NdNi is shown0.7Fe0.3O3The bond length of a chemical bond is related to the magnitude of the bond angle at room temperature.
Shown in FIG. 4(b) is NdNi0.7Fe0.3O3The transmission electron micrograph at room temperature shows that a two-phase structure exists in the lens, and the unit cell spacing is 0.224nm and 0.225 nm. The comparison shows that the (011) crystal face corresponds to the NdFeO crystal face and the (101) crystal face3Phase, and the (101) plane corresponds to NdNi0.5Fe0.5O3And (4) phase(s).
Wherein the reflectance R is shown in fig. 5; it can be seen from the figure that, in the microwave band of 2 to 18GHz with the thickness d of 3.0mm, the effective bandwidth is 1.5GHz (the absorption rate is greater than 90%), and a better broadband effect is achieved; the minimum reflectance value reaches around-30.25 dB at a frequency of 5.39 GHz.
The principle of the invention is as follows: citric acid monohydrate is an organic acid, and when the citric acid monohydrate is under alkaline conditions, certain foaming effect is generated, so that the complexation reaction is more sufficient, and the hydroxyl groups can inhibit the reducibility of elements under the alkaline conditions, so that the valence change in the valence is reduced.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (6)

1. The ferrite wave-absorbing material with the perovskite structure is characterized in that the molecular structural formula of the material is NdFe1-xNixO3Wherein x is 0,0.1,0.2, 0.3.
2. The preparation method of the ferrite wave-absorbing material with the perovskite structure is characterized by comprising the following steps:
step 1, taking analytical pure grade neodymium nitrate hexahydrate, ferric nitrate nonahydrate and nickel nitrate hexahydrate as ion sources of Nd, Fe and Ni according to Nd1-xNixFeO3X is 0.0-0.3, the sample ingredients are weighed according to the stoichiometric ratio, ultrasonic dispersion is utilized, and the weighed sample is dissolved into deionized water with a certain volume to obtain a solution;
step 2, adding a certain amount of citric acid into the solution, and dropping ammonia water to adjust the pH value to be alkaline;
step 3, putting the solution into a water bath kettle at the temperature of 60-90 ℃ and stirring for 2-5 hours until the solution is uniform and is transparent and wet colloid;
step 4, placing the wet gel in a drying box for drying, then placing the wet gel in a resistance furnace for presintering, and discharging organic matters to obtain precursor powder;
step 5, granulating the precursor powder by using polyvinyl alcohol glue, drying, grinding, sieving, uniformly filling into a mold, and pressing into a block;
and 6, placing the prepared block in an annealing furnace at the temperature of 400-700 ℃ for presintering, and then placing the block in a annealing furnace at the temperature of 600-900 ℃ for heat treatment to finally prepare a sample.
3. The preparation method of the perovskite structure ferrite wave-absorbing material according to claim 2, wherein in the step 2, citric acid monohydrate with a molar ratio of 2:1 to the sum of metal ions is added into the solution, and ammonia is dropped to adjust the pH value to 7.3-9.0.
4. The preparation method of the perovskite structure ferrite wave-absorbing material as claimed in claim 2, wherein in the step 4, the wet gel is placed in a drying oven at 80-120 ℃ for drying for 24-36 hours, and presintered at 200-350 ℃ for 2-3 hours to obtain precursor powder.
5. The preparation method of the perovskite structure ferrite wave-absorbing material according to claim 2, wherein in the step 5, precursor powder is granulated by using 8-10% by mass of polyvinyl alcohol glue, then the granulated precursor powder is uniformly ground in an agate mortar and is filled in a mold, and the powder is pressed into a wafer block with the thickness of 1.0-2.0 mm and the diameter of 12.0mm under the pressure of 5.0-20.0 MPa.
6. The preparation method of the perovskite structure ferrite wave-absorbing material as claimed in claim 2, wherein in the step 6, the prepared wafer block is subjected to heat preservation at 400-700 ℃ for 0.5-1 hour for glue removal, and then is subjected to heat preservation at 600-900 ℃ for 4-7 hours, and finally a sample is prepared.
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