CN114315360B - Broadband-absorption high-entropy carbide wave-absorbing ceramic material, and preparation method and application thereof - Google Patents
Broadband-absorption high-entropy carbide wave-absorbing ceramic material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a broadband absorption high-entropy carbide wave-absorbing ceramic material, a preparation method and application thereof, wherein the broadband absorption high-entropy carbide wave-absorbing ceramic material is prepared from the following raw materials in molar ratio: 0.98-1.02 parts of chromium oxide; 1.96-2.04 parts of zirconium dioxide; 1.96-2.04 parts of hafnium oxide; 0.98-1.02 parts of niobium pentoxide; 0.98-1.02 parts of tantalum pentoxide; and 23 parts of graphite. The preparation method comprises the following steps: mixing the raw material powder with absolute ethyl alcohol in a ball milling tank to obtain uniformly mixed slurry; drying and sieving the slurry to obtain mixed powder, and calcining the mixed powder at 1850-2000 ℃ for 1-2 h under the condition of the calcining vacuum degree of 8-15 Pa to obtain the high-entropy carbide wave-absorbing ceramic material powder. Analysis shows that the high-entropy ceramic has the characteristics of high temperature resistance, good wave-absorbing performance and wide absorption frequency band, and the preparation method is simple, is suitable for industrial production and has good application prospect in the field of electromagnetic wave absorption materials.
Description
Technical Field
The invention relates to a broadband absorbing high-entropy carbide wave-absorbing ceramic material, in particular to a high-entropy carbide wave-absorbing ceramic material with high temperature resistance, good wave-absorbing performance and wide absorption frequency band, belongs to the field of microwave absorbing materials, and can be applied to scenes such as electromagnetic wave pollution prevention and control, microwave darkrooms and the like.
Background
With the development of modern science and technology, various electronic and electrical equipment provide great help for people's daily life. However, at the same time, the problems of electromagnetic radiation and interference generated by these devices create new problems for people's production and life, and worsen the human living space, so it is necessary to develop wave-absorbing materials to absorb electromagnetic wave signals. The ideal wave-absorbing material has the characteristics of thinness, lightness, width and strength, but the traditional wave-absorbing material has larger proportion of ferromagnetic material, not only has large mass, but also has the problem that the magnetism is weakened or even disappears along with the temperature rise, thus seriously affecting the wave-absorbing performance; the composite wave-absorbing material mainly made of carbon materials has the problems of low absorption strength and narrow absorption frequency band. Meanwhile, in order to improve the wave absorbing capability as much as possible, the microstructure needs to be finely designed or regulated, such as the preparation of nano materials, core-shell structures and yolk structures, and the introduction of micro wave absorbing mechanisms such as interface polarization, and the like, so that the material preparation process is complex and difficult, and the stability of the micro fine structure in the use process is also very difficult, and the material is not beneficial to large-scale industrial production and popularization and application.
The metal carbide not only has the characteristics of low density, good high-temperature stability and the like, but also has large adjustability of the size of the metal atoms contained in the crystal lattice, has good performance regulation and control space, and is beneficial to large-scale control of the performance of the metal carbide through the addition of different metals. Chinese patent with application publication No. CN112341199A discloses a high-entropy wave-absorbing carbide ceramic powder material, which takes titanium dioxide, zirconium dioxide, hafnium dioxide, niobium pentoxide, tantalum pentoxide, vanadium pentoxide and carbon black as raw materials, has the maximum wave-absorbing loss of not less than 38.5dB and the maximum absorption frequency bandwidth of not less than 2.3GHz, and can be applied to the field of wave-absorbing materials. However, the formula and the material disclosed in the patent have narrow electromagnetic wave absorption band, can only realize the absorption of electromagnetic waves in a small part of frequency bands, cannot realize broadband absorption, and have limited practical application range and scenes. However, no relevant formula and technical report is found on how to realize the wide-frequency-band absorption of electromagnetic waves in metal carbides.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor of the invention carries out intensive research, provides a broadband absorption high-entropy carbide wave-absorbing ceramic material, a preparation method and application, can effectively improve the absorption frequency bandwidth of the carbide electromagnetic waves, has high temperature resistance, good wave-absorbing performance and wide absorption frequency bandwidth, and can be used as a wave-absorbing coating to be applied to the aspects of electromagnetic wave pollution prevention, microwave darkroom and the like, thereby completing the invention.
The technical scheme provided by the invention is as follows:
in a first aspect, the broadband absorbing high-entropy carbide wave-absorbing ceramic material is prepared from the following raw materials in molar ratio:
in a second aspect, a preparation method of the broadband absorption high-entropy carbide wave-absorbing ceramic material comprises the following steps:
step 1, mixing raw material powder with absolute ethyl alcohol in a ball milling tank to obtain uniformly mixed slurry;
and 2, drying the slurry obtained in the step 1, sieving to obtain mixed powder, calcining the mixed powder at 1850-2000 ℃ for 1-2 h, and controlling the calcination vacuum degree at 8-15 Pa to obtain the high-entropy carbide wave-absorbing ceramic material powder.
In a third aspect, the broadband absorbing high-entropy carbide wave-absorbing ceramic material of the first aspect is applied as a wave-absorbing coating.
According to the broadband absorption high-entropy carbide wave-absorbing ceramic material, the preparation method and the application, the broadband absorption high-entropy carbide wave-absorbing ceramic material has the following beneficial effects:
(1) According to the broadband absorption high-entropy carbide wave-absorbing ceramic material and the preparation method thereof, the high-entropy carbide ceramic is obtained by taking chromium sesquioxide, zirconium dioxide, hafnium dioxide, niobium pentoxide, tantalum pentoxide and graphite as raw materials; the high-entropy carbide ceramic with high purity, strong wave absorption performance and wide absorption frequency band is obtained by high-temperature calcination under the vacuum condition, and analysis shows that the prepared high-entropy carbide ceramic has the lowest wave absorption loss of-21.6 dB and the maximum absorption frequency band width of 10.5GHz;
(2) The broadband-absorption high-entropy carbide wave-absorbing ceramic material and the preparation method thereof have the advantages of simple and rapid preparation process, strong practicability, no need of microstructure control, high temperature resistance, strong wave-absorbing performance, wide absorption frequency band and the like.
Drawings
FIG. 1 shows an X-ray diffraction spectrum of a broadband absorption high-entropy carbide wave-absorbing ceramic material prepared in example 1 of the present invention;
FIG. 2 shows a dielectric loss and magnetic loss spectrogram of the broadband absorbing high-entropy carbide wave-absorbing ceramic material prepared in embodiment 1 of the present invention;
FIG. 3 shows a wave-absorbing loss spectrogram of the broadband absorbing high-entropy carbide wave-absorbing ceramic material prepared in embodiment 1 of the invention at a frequency of 2-18 GHz.
FIG. 4 shows a comparison graph of room-temperature micro-morphology (a) of the broadband absorbing high-entropy carbide wave-absorbing ceramic material prepared in example 1 of the present invention and micro-morphology (b) of the ceramic material after being processed at 1850 ℃.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
The invention provides a broadband absorption high-entropy carbide wave-absorbing ceramic material which is prepared from the following raw materials in molar ratio:
in a preferred embodiment, the chromium sesquioxide, zirconium dioxide, hafnium dioxide, niobium pentoxide, tantalum pentoxide and graphite are all powder materials.
Further, the purity of the chromium sesquioxide, the zirconium dioxide, the hafnium dioxide, the niobium pentoxide and the tantalum pentoxide is not less than 99.9%, and the particle size is not more than 1 micron; the purity of the graphite is not lower than 99%, and the particle size is not larger than 2 microns. The particle size of the powder directly influences the synthesis purity and temperature of the carbide, and the smaller the particle size is, the higher the synthesis purity at the same temperature is; the inventor finds through a large number of experiments that when the particle size of the metal oxide is not more than 1 micron and the particle size of the graphite is not more than 2 microns, pure high-entropy carbide can be obtained by keeping the temperature at 1850-2000 ℃ for 1-2 hours; when the particle size of the metal oxide and the particle size of the graphite become larger, pure high-entropy carbide cannot be obtained under the same synthesis condition, the synthesis temperature needs to be increased and the synthesis time needs to be prolonged, and in order to synthesize the pure high-entropy carbide and save energy, the particle size of the raw material powder needs to be controlled to be not more than 1 micron in the particle size of the metal oxide, and the particle size of the graphite is not more than 2 microns.
In a preferred embodiment, the purity of the broadband absorption high-entropy carbide wave-absorbing ceramic material is not less than 99wt%.
In a preferred embodiment, the broadband absorption high-entropy carbide wave-absorbing ceramic material has the lowest wave-absorbing loss of-21.6 dB; the maximum absorption bandwidth is 10.5GHz.
The invention also provides a preparation method of the broadband absorption high-entropy carbide wave-absorbing ceramic material, which comprises the following steps:
step 1, mixing raw material powder with absolute ethyl alcohol in a ball milling tank to obtain uniformly mixed slurry;
and 2, drying the slurry obtained in the step 1, sieving to obtain mixed powder, and calcining the mixed powder in a high-temperature electric furnace at 1850-2000 ℃ for 1-2 h under the condition that the calcining vacuum degree is controlled at 8-15 Pa to obtain the high-entropy carbide wave-absorbing ceramic material powder.
The invention also provides application of the broadband absorbing high-entropy carbide wave-absorbing ceramic material as a wave-absorbing coating.
Examples
The raw material sources of the examples and the comparative examples in the invention are as follows: cr (chromium) component 2 O 3 (Beijing Huaweiruike chemical Co., ltd., purity 99.9%, particle size less than or equal to 1 μm); zrO (zirconium oxide) 2 (Beijing Waverrucke chemical Co., ltd., purity 99.9%, particle size not more than 1 μm); hfO 2 (Beijing Waverrucke chemical Co., ltd., purity 99.9%, particle size not more than 1 μm); nb 2 O 5 (Beijing Huawei)Ruiko chemical Co., ltd, purity 99.9%, particle size less than or equal to 1 μm); ta 2 O 5 (Beijing Waverrucke chemical Co., ltd., purity 99.9%, particle size not more than 1 μm); graphite (Beijing Waverrucke chemical Co., ltd., purity 99%, particle size 2 μm or less).
Example 1
Mixing Cr 2 O 3 、ZrO 2 、HfO 2 、Nb 2 O 5 、Ta 2 O 5 And graphite as Cr 2 O 3 :ZrO 2 :HfO 2 :Nb 2 O 5 :Ta 2 O 5 Graphite = 1; and filtering and drying the obtained slurry, sieving the slurry by a 120-mesh sieve to obtain mixture powder, and calcining the dried powder in a high-temperature furnace at 1950 ℃ for 1 hour under the vacuum degree of 8Pa to obtain broadband absorption high-entropy carbide wave-absorbing ceramic material powder with the ceramic purity of 100wt%.
The components of the broadband-absorbing high-entropy carbide wave-absorbing ceramic material obtained in the embodiment are shown in an X-ray diffraction pattern of fig. 1, and the broadband-absorbing high-entropy carbide wave-absorbing ceramic material has diffraction peaks at the following 2 theta angles: 34.1, 39.6, 57.4, 68.5 and 71.9, and the synthesized high-entropy carbide is a pure rock-salt type structure through an X-ray diffraction spectrum; the measured dielectric loss and magnetic loss of the wave-absorbing ceramic material are shown in figure 2, and it can be seen that the synthesized high-entropy carbide has obvious dielectric loss and magnetic loss at the same time, and the dielectric loss and the magnetic loss have similar sizes, which shows that the wave-absorbing ceramic material has good electromagnetic matching performance and is beneficial to the absorption of electromagnetic waves; the wave-absorbing ceramic material has the wave-absorbing loss of-21.6 dB at the frequency of 2-18GHz as shown in a return loss spectrogram in figure 3, and the maximum absorbing frequency bandwidth of 10.5GHz when the reflectivity is below-10 dB by using an Agilent N5244A vector network analyzer. The results show that the ultrahigh-temperature broadband-absorbing high-entropy carbide wave-absorbing ceramic material with the broadband absorption capacity can be prepared when the reaction temperature is 1950 ℃, the microscopic morphology of the wave-absorbing ceramic material after being treated at 1850 ℃ is shown in fig. 4, the particle size and the morphology of the high-entropy carbide material can be seen to be basically unchanged, and meanwhile, the composition characterization shows that the phase composition change does not occur in the process, which shows that the carbide has excellent high-temperature structure and phase stability.
Example 2
This example is identical to example 1, differing only in that: the calcination temperature is 1900 ℃, the calcination time is 2 hours, the vacuum degree is 15Pa, the broadband absorption high-entropy carbide wave-absorbing ceramic material powder is obtained, the ceramic purity is 100wt%, the maximum wave-absorbing loss is-30 dB, and the maximum absorption frequency bandwidth is 8.5GHz when the reflectivity is below-10 dB.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.
Claims (7)
1. The broadband absorption high-entropy carbide wave-absorbing ceramic material is characterized by being prepared from the following raw materials in molar ratio:
0.98 to 1.02 parts of chromic oxide;
1.96 to 2.04 parts of zirconium dioxide;
1.96 to 2.04 parts of hafnium oxide;
0.98 to 1.02 parts of niobium pentoxide;
0.98 to 1.02 parts of tantalum pentoxide;
23 parts of graphite;
the lowest wave-absorbing loss of the broadband absorption high-entropy carbide wave-absorbing ceramic material is-21.6 dB; the maximum absorption bandwidth is 10.5GHz.
2. The broadband absorbing high-entropy carbide wave-absorbing ceramic material of claim 1, wherein the chromium oxide, zirconium dioxide, hafnium dioxide, niobium pentoxide, tantalum pentoxide, and graphite are all powder materials.
3. The broadband absorbing high-entropy carbide wave-absorbing ceramic material of claim 1, wherein the purity of the chromium sesquioxide, zirconium dioxide, hafnium dioxide, niobium pentoxide, and tantalum pentoxide is not less than 99.9%, and the particle size is not greater than 1 μm; the purity of the graphite is not lower than 99%, and the particle size is not larger than 2 microns.
4. The broadband absorbing high-entropy carbide wave-absorbing ceramic material of claim 1, wherein the purity of the broadband absorbing high-entropy carbide wave-absorbing ceramic material is not less than 99wt%.
5. A method for preparing the broadband absorbing high-entropy carbide wave-absorbing ceramic material in claims 1 to 4, which is characterized by comprising the following steps:
step 1, mixing raw material powder with absolute ethyl alcohol in a ball milling tank to obtain uniformly mixed slurry;
and 2, drying the slurry obtained in the step 1, sieving to obtain mixed powder, and calcining the mixed powder in vacuum to obtain the high-entropy carbide wave-absorbing ceramic material powder.
6. The preparation method of the broadband absorption high-entropy carbide wave-absorbing ceramic material as claimed in claim 5, wherein in the step 2, the calcination temperature is 1850 ℃ to 2000 ℃, the calcination time is 1 to 2 hours, and the calcination vacuum degree is controlled to be 8 to 15 Pa.
7. Use of the broadband absorbing high entropy carbide wave absorbing ceramic material of any one of claims 1 to 4 as a wave absorbing coating.
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