CN112479179A - Preparation method of composite wave absorbing agent based on biomass material - Google Patents
Preparation method of composite wave absorbing agent based on biomass material Download PDFInfo
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- CN112479179A CN112479179A CN202011456219.4A CN202011456219A CN112479179A CN 112479179 A CN112479179 A CN 112479179A CN 202011456219 A CN202011456219 A CN 202011456219A CN 112479179 A CN112479179 A CN 112479179A
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Abstract
The invention discloses a preparation method of a composite wave absorbing agent based on a biomass material, and provides a method for preparing a magnetic particle/biological porous carbon composite wave absorbing material by using a biomass material/Prussian blue as a template, aiming at solving the problems of complex preparation method, high cost, severe preparation conditions, large material density and the like of the existing composite wave absorbing material. The microwave absorbing material prepared by the invention has the advantages of small density, light weight, high absorption strength, wide effective absorption bandwidth, simple preparation process and low cost, is suitable for large-scale batch production, can fully utilize biomass resources, and reduces waste and pollution.
Description
Technical Field
The invention relates to a preparation method of a composite wave absorbing agent based on a biomass material, and particularly relates to the technical field of microwave absorbing materials.
Background
The progress of wireless communication technology has greatly promoted the development of human society, and also has brought about various problems. The electromagnetic wave pollution generated by the method not only causes adverse effects on the health of human bodies but also interferes with the normal work of electronic equipment, and meanwhile, in the military field, the electromagnetic stealth capability of weaponry can greatly improve the fighting capability of the weaponry, so that the weaponry becomes the development trend of the weaponry. Therefore, the microwave absorbing material has wide application prospect, and the existing wave absorbing material is developing towards the direction of thin coating thickness, light weight, wide absorbing bandwidth and high absorbing strength. The carbon-based material has excellent physicochemical properties such as light weight, good stability, high strength and the like, and is expected to become an excellent wave-absorbing material. The carbon materials such as graphene and carbon nano tube have excellent performance, but the preparation conditions are harsh, the cost is high, and the large-scale production, popularization and application are not facilitated. The biomass material is an effective way to obtain cheap green carbon material, and simultaneously, the waste and the pollution can be reduced.
The publication (announcement) No. CN111592050A is named as nano Fe grown in situ by biomass-based porous carbon3O4The microwave absorbing material is prepared through condensation reaction between polyglycol grafted chitosan and aldehyde sodium alginate and Fe-containing reaction solution3+In the system of (1), Fe3+With Na+Exchange to generate polyethylene glycol-chitosan cross-linked ferric alginate composite gel, and pyrolyze the composite gel to obtain porous carbon/Fe3O4A composite wave-absorbing material. The wave-absorbing material prepared by the method has the characteristics of light weight and stability, but the preparation method is more complicated, the reaction device is complex, the cost is high, and the popularization and the application are not facilitated. The publication (publication) No. CN109666451A is named as a method for preparing a wave-absorbing material by utilizing a biomass carbon source, and the carbon-based wave-absorbing material is obtained by cleaning rice hulls with water, ethanol, acetone and the like for a plurality of times, drying and then pyrolyzing. The wave absorbing agent prepared by the method has low density, good stability and simple preparation process, but a large amount of organic solvent is used in the preparation process, so that the cost is increased, the overall wave absorbing performance is general, the effective absorption bandwidth is not more than 4GHz, and the wave absorbing performance in the 15-18GHz frequency band is poor. Therefore, the method for developing the biomass material-based carbon wave-absorbing material with low density, low cost, no toxicity and high performance has wide application prospect.
Disclosure of Invention
The invention aims to solve the problems that: the preparation method of the composite wave absorbing agent based on the biomass material is simple in process, low in cost, light in weight, strong in absorption capacity and wide in effective absorption frequency band.
The technical scheme provided by the invention for solving the problems is as follows: a preparation method of a composite wave absorbing agent based on a biomass material comprises the following steps:
step 1: preparation of Biomass/Prussian blue composite material
Mixing Fe (NO)3)3·9H2O、K3[Fe(CN)6]Dissolving polyvinylpyrrolidone (PVP) and sodium citrate in water to obtain a dark solution, adding 0.4-1g of dried biomass material powder into the solution respectively, stirring uniformly, standing, filtering and separating to obtain a product, washing with water once, and drying to obtain the biomass/Prussian blue composite material;
step 2: preparation of Fe/C composite material
Respectively placing the biomass/Prussian blue composite materials in quartz boats at N2And (3) carrying out medium pyrolysis and cooling to obtain a series of Fe/C composite materials with porous structures.
Preferably, said Fe (NO)3)3·9H2O、K3[Fe(CN)6]And the mass ratio of the sodium citrate to the PVP is 1-2: 0.6-1.2: 0.5-1: 1.
preferably, the biomass material in step 1 is one of corncob, shaddock peel, sea grape and lotus seedpod.
Preferably, the standing time in the step 1 is 20-48h, the drying time is 6-12h, and the drying temperature is 60-80 ℃.
Preferably, the pyrolysis temperature in the step 2 is 700-.
Preferably, the mass ratio of the biomass material to the Prussian blue in the precursor of the Fe/C composite microwave absorbing material is 1 (0.4-0.8).
Compared with the prior art, the invention has the advantages that: according to the invention, Prussian blue grown in situ by a biomass material is used as a precursor, and the iron/porous carbon composite wave-absorbing material is prepared by pyrolysis in a nitrogen atmosphere. The biomass materials selected by the invention are shaddock peel, corncob and the like, which have a large number of pores, and the biomass materials contain a large number of groups such as-OH, -COOH and-NH2Etc. the Prussian blue can grow in situ inside and on the surface of the biomass material and is obtained after pyrolysisIron/porous carbon composite wave-absorbing material. Impedance matching is optimized through compounding of magnetic iron and porous carbon with dielectric property, a porous carbon skeleton can generate conduction loss, nano iron particles can generate magnetic loss, biomass contains a large amount of N, S, P and other elements, heteroatom-doped porous carbon such as N, S, P is obtained after pyrolysis, dipole polarization is enhanced, and excellent wave-absorbing property is obtained through combined action of multiple attenuation mechanisms.
Compared with the granted patent, the method has the advantages of simple process, high repeatability and reliability, low cost and light weight, and obviously improves the absorption strength and the absorption bandwidth. Electromagnetic parameters can be effectively regulated and controlled by adjusting conditions such as the ratio of the Prussian blue to the biomass material, the pyrolysis temperature and the like, and excellent wave-absorbing performance is obtained. When the thickness of the Fe/C composite wave-absorbing material prepared by taking the shaddock peel/Prussian blue as a precursor is 2.1mm, the maximum reflection loss reaches-50.1 dB. The Fe/C composite wave-absorbing material prepared by taking corncobs/Prussian blue as a precursor has the maximum reflection loss of-48.2 dB when the thickness is 1.83mm, has the effective bandwidth of 6.4GHz (11.6-18.0GHz) when the thickness is 2.04mm, and covers the whole Ku waveband.
According to the invention, Prussian blue grown in situ by a biomass material is used as a precursor, and the iron/porous carbon composite wave-absorbing material is prepared by pyrolysis in a nitrogen atmosphere. No toxic and harmful substances are generated in the whole preparation process, expensive raw materials are not used, the technical advantages of high-efficiency wave-absorbing performance, low manufacturing cost and no pollution are obtained, and the industrial large-scale production and the commercial application of the microwave absorbing material are promoted.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a powder X-ray diffraction pattern of samples prepared in examples 1 and 2, and it can be seen from the pattern that the purity of the sample is high in both examples, and diffraction peaks of iron and graphitized carbon can be seen in both examples.
Fig. 2 is an optical microscopic image of the shaddock peel in the sample of example 1, from which it can be seen that the material appears as a fluffy porous sheet, wrinkled.
Fig. 3 is a transmission electron microscope image of the Fe/C composite wave-absorbing material prepared in example 1, from which it can be seen that iron particles are coated inside the porous carbon, and the flaky and wrinkled carbon material is clearly visible.
FIG. 4 is a reflection loss spectrum of the Fe/C composite wave-absorbing material coating in example 1, which is calculated by simulation, and different reflection losses of the simulated thickness from 1.0 mm to 5.0mm are calculated. The figure shows that the material has certain wave absorbing capacity under a plurality of thicknesses, wherein when the thickness is 1.4mm, the effective absorption bandwidth reaches 4.3 GHz; at a thickness of 2.1mm, the maximum reflection loss reaches-51.21 dB.
FIG. 5 is a reflection loss spectrum of the Fe/C composite wave-absorbing material coating prepared in example 2, which is calculated by simulation, and different reflection losses of the simulated thickness from 1.0 mm to 5.0mm are calculated. It can be seen from the figure that under different thicknesses, the maximum reflection loss is less than-30 dB, and the material has excellent wave-absorbing capability. Wherein, the thickness is 1.83mm, the maximum reflection loss is-48.2 dB, when the thickness is 2.04mm, the effective absorption bandwidth can reach 6.4GHz, and when the thickness is 4.0mm, the maximum reflection loss reaches-51.77 dB.
Detailed Description
The embodiments of the present invention will be described in detail with reference to the accompanying drawings and examples, so that how to implement the technical means for solving the technical problems and achieving the technical effects of the present invention can be fully understood and implemented.
Example 1
Step 1: preparation of shaddock peel/Prussian blue composite material
Mixing 1gFe (NO)3)3·9H2O、0.6gK3[Fe(CN)6]Dissolving 1g of PVP and 0.5g of sodium citrate in 100mL of water to obtain a dark solution, adding 0.4g of shaddock peel into the solution, uniformly stirring, standing for 24 hours, filtering and separating to obtain a product, washing with water once, and drying at 60 ℃ for 10 hours to obtain the shaddock peel/Prussian blue composite material.
Step 2: preparation of Fe/C composite material
Placing the shaddock peel/Prussian blue composite material in quartz boats respectively, and placing the quartz boats in a reactor with a reactor in a reactor2And (3) pyrolyzing for 2h at the medium temperature of 700 ℃, wherein the temperature rise and reduction rate is 2 ℃/min, and cooling to obtain a series of Fe/C composite materials with porous structures. The prepared composite material and a paraffin base are uniformly mixed, and the mass ratio of the composite material to the paraffin is 1: 1.5.
The electromagnetic parameters of the material are measured by a vector network analyzer, and according to the transmission line theory, the reflection loss of the material to electromagnetic waves is calculated by the complex dielectric constant and the complex permeability under given frequency and the thickness of the wave-absorbing material through the following equation.
(1)Zin＝Z0(μr/εr) 1/2tanh[j(2πfd/c)(μr/εr)1/2],
(2)RL(dB)＝20log|(Zin－1)/(Zin+1)|。
Example 2
The present embodiment differs from embodiment 1 in that:
mixing 1gFe (NO)3)3·9H2O、1g K3[Fe(CN)6]Dissolving 1g of PVP and 1g of sodium citrate in 150mL of water to obtain a dark solution, adding 1g of corncob into the solution, uniformly stirring, standing for 48 hours, filtering, and drying at 80 ℃ for 8 hours to obtain the corncob/Prussian blue composite material.
In the step 2, the corncobs/Prussian blue is placed in a quartz boat, the temperature rising and falling speed of the tube furnace is 3 ℃/min, and the mass ratio of the obtained Fe/C composite material to the paraffin is 1:1. The rest is the same as in embodiment 1.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (6)
1. A preparation method of a composite wave absorbing agent based on a biomass material is characterized by comprising the following steps: the method comprises the following steps:
step 1: preparation of Biomass/Prussian blue composite material
Mixing Fe (NO)3)3·9H2O、K3[Fe(CN)6]Dissolving polyvinylpyrrolidone (PVP) and sodium citrate in water to obtain a dark solution, adding 0.4-1g of dried biomass material powder into the solution respectively, stirring uniformly, standing, filtering and separating to obtain a product, washing with water once, and drying to obtain the biomass/Prussian blue composite material;
step 2: preparation of Fe/C composite material
Respectively placing the biomass/Prussian blue composite materials in quartz boats at N2And (3) carrying out medium pyrolysis and cooling to obtain a series of Fe/C composite materials with porous structures.
2. The preparation method of the composite wave absorbing agent based on the biomass material as claimed in claim 1, wherein the preparation method comprises the following steps: said Fe (NO)3)3·9H2O、K3[Fe(CN)6]And the mass ratio of the sodium citrate to the PVP is 1-2: 0.6-1.2: 0.5-1: 1.
3. the preparation method of the composite wave absorbing agent based on the biomass material as claimed in claim 1, wherein the preparation method comprises the following steps: the biomass material in the step 1 is one of corncobs, shaddock peels, sea grapes and lotus seedpods.
4. The preparation method of the composite wave absorbing agent based on the biomass material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 1, the standing time is 20-48h, the drying time is 6-12h, and the drying temperature is 60-80 ℃.
5. The preparation method of the composite wave absorbing agent based on the biomass material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 2, the pyrolysis temperature is 700-.
6. The preparation method of the composite wave absorbing agent based on the biomass material as claimed in claim 1, wherein the preparation method comprises the following steps: the mass ratio of the biomass material to Prussian blue in the precursor of the Fe/C composite microwave absorbing material is 1 (0.4-0.8).
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Cited By (3)
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| CN114275762A (en) * | 2021-12-24 | 2022-04-05 | 南京林业大学 | Nitrogen-doped hard carbon sodium ion battery negative electrode material and preparation method thereof |
| CN115651606A (en) * | 2022-12-14 | 2023-01-31 | 中南大学 | Three-dimensional metal organic framework derivative/carbon foam composite wave-absorbing material and preparation method thereof |
| CN117840421A (en) * | 2024-03-07 | 2024-04-09 | 朗峰新材料启东有限公司 | Amorphous powder with excellent electromagnetic wave absorption performance and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115651606A (en) * | 2022-12-14 | 2023-01-31 | 中南大学 | Three-dimensional metal organic framework derivative/carbon foam composite wave-absorbing material and preparation method thereof |
| CN115651606B (en) * | 2022-12-14 | 2023-09-19 | 中南大学 | Three-dimensional metal organic framework derivative/carbon foam composite wave-absorbing material and preparation method thereof |
| CN117840421A (en) * | 2024-03-07 | 2024-04-09 | 朗峰新材料启东有限公司 | Amorphous powder with excellent electromagnetic wave absorption performance and preparation method thereof |
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