CN110835447A - Ku waveband composite wave-absorbing material and preparation method thereof - Google Patents
Ku waveband composite wave-absorbing material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
A Ku waveband composite wave-absorbing material and a preparation method thereof comprise the following steps: synthesizing silicon modified graphene oxide by utilizing a silicon-oxygen coupling reaction principle; slowly adding a mixture of hydrated iron salt, the silicon-modified graphene oxide, a surfactant and ethylene glycol into an ethylene glycol mixed solution of acetate, and generating a silicon-modified magnetic graphene composite wave absorbing agent by a hydrothermal synthesis method; dissolving a certain amount of polyvinylidene fluoride in an organic solution, adding a certain amount of the silicon modified graphene magnetic composite wave absorbing agent, uniformly mixing, and then putting the mixture into an oven to heat so as to completely volatilize the solvent, thereby obtaining the silicon modified magnetic graphene composite wave absorbing material. The electromagnetic parameters and impedance matching of the material are optimized by utilizing the influence of different silicon-based functional groups on the wave-absorbing performance of the modified graphene, so that the effect of strong absorption of the composite wave-absorbing material in a high-frequency wave band is realized.
Description
Technical Field
The invention belongs to the technical field of wave-absorbing composite materials, and particularly relates to a Ku waveband composite wave-absorbing material and a preparation method thereof.
Background
The stealth technology is a combat mode capable of improving self survival rate. On the battlefield, the weapon equipment with stealthy property can have the initiative of attack, and the attack abruptness is strengthened. The wave-absorbing material is used as a material basis of the stealth technology and becomes one of the main targets of the modern stealth technology research.
The wave-absorbing material is a novel material which absorbs or weakens the surface electromagnetic wave energy so as to reduce the electromagnetic wave interference. At present, the structural design and preparation of the graphene-based composite wave-absorbing material and the research on the electromagnetic wave absorption performance are gradually carried out internationally. The characteristics of high specific surface area, excellent electrical property, special two-dimensional structure and the like endow graphene with excellent potential as an ideal construction unit of the novel composite wave-absorbing material. However, the graphene-based composite material also has certain disadvantages in the application aspect of the wave-absorbing material, for example, the single graphene has a high dielectric constant, which results in that impedance matching of the wave-absorbing material cannot be satisfied, the graphene has poor compatibility in a resin matrix, and the dispersibility and uniformity of the material are not easy to control.
Disclosure of Invention
The invention aims to provide a Ku waveband composite wave-absorbing material and a preparation method thereof, and aims to solve the problems.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Ku waveband composite wave-absorbing material and a preparation method thereof comprise the following steps:
and 3, dissolving a certain amount of polyvinylidene fluoride in an organic solution, adding a certain amount of the silicon modified graphene magnetic composite wave absorbing agent, uniformly mixing, and then putting the mixture into an oven to heat so as to completely volatilize the solvent, thereby obtaining the silicon modified magnetic graphene composite wave absorbing material.
Further, step 1 specifically comprises: and dispersing graphene oxide in an ethanol solution, controlling the concentration of a dispersion solution to be 1.0g/L, adjusting the pH value to 3-4 by using 0.1M dilute hydrochloric acid, then slowly dropwise adding an organic silicon modifier, controlling the reaction temperature to be 60 ℃, reacting for 24 hours, after the reaction is finished, centrifugally precipitating, washing for 3-5 times by using absolute ethyl alcohol, drying at 40 ℃ in a vacuum drying oven, and drying for 24 hours to obtain black-brown modified graphene oxide powder.
Further, the centrifugal speed is controlled at 8000-9000r/min for 5 min.
Further, step 2 specifically comprises: dissolving hydrated iron salt in an ethylene glycol solution to obtain a clear solution, adding a surfactant and the silicon-modified graphene oxide, performing ultrasonic treatment at room temperature and ultrasonic frequency of 70-80KHz for 30-40min, wherein the hydrated iron salt is ferric trichloride hexahydrate, and the surfactant is polyethylene glycol 200.
Further, slowly adding the dispersed mixed solution into an ethylene glycol solution of acetate, wherein the acetate is anhydrous sodium acetate, magnetically stirring, controlling the rotating speed at 700r/min for 30min and the temperature at 40 ℃, finally transferring the mixed solution into polytetrafluoroethylene, heating to 200 ℃, and reacting for 10 hours; and after the reaction is finished, washing and precipitating, controlling the centrifugal rotating speed at 8000-8500r/min for 5min, or washing the magnetic nanoparticles adsorbed by a magnet for 3-5 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 40 ℃ for 16h to obtain the black silicon modified graphene magnetic composite wave absorbing agent.
Further, heating and dissolving a certain amount of polyvinylidene fluoride in an N, N' -dimethylformamide solution, slowly adding the modified magnetic graphene composite wave absorbing agent obtained in the step 2, carrying out ultrasonic treatment for 1-2 hours, placing the mixture in a vacuum drying oven after the mixed solution is uniformly dispersed, controlling the temperature at 120 ℃, and drying for 2 hours until the solution is completely volatilized to obtain the silicon modified magnetic graphene composite wave absorbing material.
Furthermore, the graphene oxide comprises single-layer graphene oxide and multi-layer graphene oxide, and the mesh number is 500-1000.
Further, the organosilicon modifier is epoxy functional organosilicon reagent trimethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane, 3- (2, 3-glycidoxy) propyl trimethoxysilane, 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane), organosilicon reagent 3-aminopropyltriethoxysilane with amino group, organosilicon reagent 3- (methacryloyloxy) propyl trimethoxysilane with unsaturated ester.
Further, the addition amount of the modified graphene magnetic composite wave absorbing agent is 30 wt%.
Compared with the prior art, the invention has the following technical effects:
the silicon modified magnetic graphene-based wave-absorbing material is characterized in that the influence of the load density, the morphology, the structure, the component content of each component and the synergistic effect among the components on the electromagnetic parameters of the wave-absorbing material is regulated and controlled through the micro structure and the synergistic effect of the composite hybrid particles (ferroferric oxide), and electromagnetic waves are lost through regulating and controlling the lattice defects of graphene and the effects of interface polarization, electronic relaxation polarization, dipole polarization and the like caused by the special properties caused by the compounding of graphene and magnetic nanoparticles by using different silicon-based functional groups, so that a broadband wave-absorbing material structural system which has various electromagnetic wave loss mechanisms and meets the RL < -10dB absorption requirement at 13.2-18GHz is obtained. The composite wave-absorbing material provides scientific theoretical basis for developing the next-generation Ku-band stealth material, and simultaneously has great significance for the development of stealth weapons and military armed technologies in China.
Drawings
Scanning electron micrographs of A1-A2 of the silicon-modified graphene magnetic composite wave absorber in FIG. 1a and FIG. 1b (examples 1 and 2).
FIG. 2 is an infrared spectrum of a silicon-modified graphene magnetic composite wave absorber A1-A2 (example 2).
Fig. 3a and 3B show electromagnetic wave reflection loss spectra of silicon-modified graphene magnetic composite wave-absorbing material B1-B2 (examples 1 and 2).
Detailed Description
The invention is further described below with reference to the accompanying drawings:
referring to fig. 1 to 3, a Ku waveband composite wave-absorbing material and a preparation method thereof include the following steps:
and 3, dissolving a certain amount of polyvinylidene fluoride in an organic solution, adding a certain amount of the silicon modified graphene magnetic composite wave absorbing agent, uniformly mixing, and then putting the mixture into an oven to heat so as to completely volatilize the solvent, thereby obtaining the silicon modified magnetic graphene composite wave absorbing material.
The step 1 specifically comprises the following steps: and dispersing graphene oxide in an ethanol solution, controlling the concentration of a dispersion solution to be 1.0g/L, adjusting the pH value to 3-4 by using 0.1M dilute hydrochloric acid, then slowly dropwise adding an organic silicon modifier, controlling the reaction temperature to be 60 ℃, reacting for 24 hours, after the reaction is finished, centrifugally precipitating, washing for 3-5 times by using absolute ethyl alcohol, drying at 40 ℃ in a vacuum drying oven, and drying for 24 hours to obtain black-brown modified graphene oxide powder.
The centrifugal speed is controlled at 8000-9000r/min for 5 min.
The step 2 specifically comprises the following steps: dissolving hydrated iron salt in an ethylene glycol solution to obtain a clear solution, adding a surfactant and the silicon-modified graphene oxide, performing ultrasonic treatment at room temperature and ultrasonic frequency of 70-80KHz for 30-40min, wherein the hydrated iron salt is ferric trichloride hexahydrate, and the surfactant is polyethylene glycol 200.
Slowly adding the dispersed mixed solution into an ethylene glycol solution of acetate, wherein the acetate is anhydrous sodium acetate, magnetically stirring, controlling the rotating speed at 700r/min for 30min and the temperature at 40 ℃, finally transferring the mixed solution into polytetrafluoroethylene, heating to 200 ℃, and reacting for 10 hours; and after the reaction is finished, washing and precipitating, controlling the centrifugal rotating speed at 8000-8500r/min for 5min, or washing the magnetic nanoparticles adsorbed by a magnet for 3-5 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 40 ℃ for 16h to obtain the black silicon modified graphene magnetic composite wave absorbing agent.
Heating and dissolving a certain amount of polyvinylidene fluoride in an N, N' -dimethylformamide solution, slowly adding the modified magnetic graphene composite wave absorbing agent obtained in the step 2, performing ultrasonic treatment for 1-2 hours, after the mixed solution is uniformly dispersed, placing the mixture in a vacuum drying oven, controlling the temperature at 120 ℃, and drying for 2 hours until the solution is completely volatilized to obtain the silicon modified magnetic graphene composite wave absorbing material.
The graphene oxide comprises single-layer graphene oxide and multi-layer graphene oxide, and the mesh number is 500-1000.
The organosilicon modifier is epoxy functional organosilicon reagent trimethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane, 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- [ (2,3) -epoxypropoxy ] propyl methyl dimethoxy silane), organosilicon reagent with amino group (3-aminopropyl triethoxy silane), organosilicon reagent with unsaturated ester (3- (methacryloyloxy) propyl trimethoxy silane).
The addition amount of the modified graphene magnetic composite wave absorbing agent is 30 wt%.
Example 1
(1) Taking a quantitative graphene oxide dispersion liquid, adjusting the pH value to 3-4, adding a certain amount of epoxycyclohexane organic silicon reagent, reacting for 24 hours in a water bath at 60 ℃, then carrying out centrifugal separation, controlling the rotating speed at 7000r/min, washing for multiple times by using absolute ethyl alcohol and deionized water until the pH value is 7, completely removing unreacted coupling agent, drying for 24 hours at 40 ℃, and grinding and storing for later use.
(2) Mixing the silicon-modified graphene oxide dispersion liquid, hydrated iron salt, glycol and polyethylene glycol, performing ultrasonic dispersion for 30min, then slowly dropwise adding the mixture into an ethylene glycol solution of acetate, stirring for 30min at 40 ℃, transferring the mixed solution into a hydrothermal kettle, and reacting for 10h at 200 ℃; after the reaction is finished, the magnetic nanoparticles adsorbed by the magnet are repeatedly washed by absolute ethyl alcohol and deionized water for 3 times, and then the magnetic nanoparticles are placed in a vacuum drying oven for drying for 16 hours at 40 ℃ to obtain the black silicon-modified graphene magnetic composite wave absorbing agent A1.
(3) Heating and dissolving a certain amount of polyvinylidene fluoride in an N, N' -dimethylformamide solution, slowly adding the black magnetic composite wave absorbing agent obtained in the step (2) after the solution is clarified, carrying out ultrasonic treatment for 1-2h, placing the mixture in a vacuum drying oven after the mixed solution is uniformly dispersed, controlling the temperature at 120 ℃, drying for 2h, and completely volatilizing the solution to obtain the silicon modified graphene magnetic composite wave absorbing material B1.
Example 2
(1) Taking a quantitative graphene oxide dispersion liquid, adjusting the pH value to 3-4, adding a certain amount of epoxypropane organosilicon reagent, reacting for 24 hours in a water bath at 60 ℃, then carrying out centrifugal separation, controlling the rotating speed at 7000r/min, washing for multiple times by using absolute ethyl alcohol and deionized water until the pH value is 7, completely removing unreacted coupling agent, drying for 24 hours at 40 ℃, and grinding and storing for later use.
(2) Mixing the silicon-modified graphene oxide dispersion liquid, hydrated iron salt, glycol and polyethylene glycol, performing ultrasonic dispersion for 30min, then slowly dropwise adding the mixture into an ethylene glycol solution of acetate, stirring for 30min at 40 ℃, transferring the mixed solution into a hydrothermal kettle, and reacting for 10h at 200 ℃; after the reaction is finished, the magnetic nanoparticles adsorbed by the magnet are repeatedly washed by absolute ethyl alcohol and deionized water for 3 times, and then the magnetic nanoparticles are placed in a vacuum drying oven for drying for 16 hours at 40 ℃ to obtain the black silicon-modified graphene magnetic composite wave absorbing agent A2.
(3) Heating and dissolving a certain amount of polyvinylidene fluoride in an N, N' -dimethylformamide solution, slowly adding the black composite nano wave absorbing agent obtained in the step (2), performing ultrasonic treatment for 1-2h, after the mixed solution is uniformly dispersed, placing the mixture in a vacuum drying oven, controlling the temperature at 120 ℃, drying for 2h, and after the solution is completely volatilized, obtaining the silicon modified graphene magnetic composite wave absorbing material B2.
B electromagnetic performance test of silicon modified graphene magnetic composite wave-absorbing material
The silicon modified graphene magnetic composite wave-absorbing material is hot-pressed at the temperature of 200 ℃ to prepare an annular sample with the outer ring diameter of 7.0mm and the inner ring diameter of 3.00 mm. And (3) testing the electromagnetic parameters of the sample in the range of 2-18GHz by using a network analyzer, and calculating the reflection loss of the composite wave-absorbing material by using a formula. As a result: the electromagnetic absorption performance of the composite wave-absorbing material B2 is better than that of the composite wave-absorbing agent B1, when the thickness is 2mm, the reflection loss RL of the composite wave-absorbing material B1 is < -10dB at a frequency band of 17-18GHz, the composite wave-absorbing material B2 has broadband absorption at a frequency band of 13.2-18GHz, and the reflection loss is less than-10 dB. In addition, the reflection intensity of the composite wave-absorbing material B1 can reach-27 dB at a frequency band of 3.3GHz, and the reflection loss of the composite wave-absorbing material B2 can reach-32 dB at a frequency band of 3.7 GHz.
Claims (9)
1. A Ku waveband composite wave-absorbing material and a preparation method thereof are characterized by comprising the following steps:
step 1, synthesizing silicon modified graphene oxide by utilizing a silicon-oxygen coupling reaction principle;
step 2, slowly adding a mixture of hydrated iron salt, the silicon-modified graphene oxide, a surfactant and ethylene glycol into an ethylene glycol mixed solution of acetate, and generating a silicon-modified magnetic graphene composite wave absorbing agent by a hydrothermal synthesis method;
and 3, dissolving a certain amount of polyvinylidene fluoride in an organic solution, adding a certain amount of the silicon modified graphene magnetic composite wave absorbing agent, uniformly mixing, and then putting the mixture into an oven to heat so as to completely volatilize the solvent, thereby obtaining the silicon modified magnetic graphene composite wave absorbing material.
2. The Ku waveband composite wave-absorbing material and the preparation method thereof according to claim 1, wherein the step 1 specifically comprises the following steps: and dispersing graphene oxide in an ethanol solution, controlling the concentration of a dispersion solution to be 1.0g/L, adjusting the pH value to 3-4 by using 0.1M dilute hydrochloric acid, then slowly dropwise adding an organic silicon modifier, controlling the reaction temperature to be 60 ℃, reacting for 24 hours, after the reaction is finished, centrifugally precipitating, washing for 3-5 times by using absolute ethyl alcohol, drying at 40 ℃ in a vacuum drying oven, and drying for 24 hours to obtain black-brown modified graphene oxide powder.
3. The Ku waveband composite wave-absorbing material and the preparation method thereof as claimed in claim 2, wherein the centrifugal rotation speed is controlled at 8000-.
4. The Ku waveband composite wave-absorbing material and the preparation method thereof according to claim 1, wherein the step 2 specifically comprises the following steps: dissolving hydrated iron salt in an ethylene glycol solution to obtain a clear solution, adding a surfactant and the silicon-modified graphene oxide, performing ultrasonic treatment at room temperature and ultrasonic frequency of 70-80KHz for 30-40min, wherein the hydrated iron salt is ferric trichloride hexahydrate, and the surfactant is polyethylene glycol 200.
5. The Ku waveband composite wave-absorbing material and the preparation method thereof as claimed in claim 3, wherein the dispersed mixed solution is slowly added into an ethylene glycol solution of acetate, the acetate is anhydrous sodium acetate, the magnetic stirring is carried out, the rotating speed is controlled at 700r/min, the time is 30min, the temperature is 40 ℃, finally, the mixed solution is transferred into polytetrafluoroethylene, the heating is carried out to 200 ℃, and the reaction time is 10 hours; and after the reaction is finished, washing and precipitating, controlling the centrifugal rotating speed at 8000-8500r/min for 5min, or washing the magnetic nanoparticles adsorbed by a magnet for 3-5 times by using absolute ethyl alcohol, and finally drying in a vacuum drying oven at 40 ℃ for 16h to obtain the black silicon modified graphene magnetic composite wave absorbing agent.
6. The Ku waveband composite wave-absorbing material and the preparation method thereof as claimed in claim 1, wherein a certain amount of polyvinylidene fluoride is heated and dissolved in N, N' -dimethylformamide solution, then the modified magnetic graphene composite wave-absorbing agent obtained in the step 2 is slowly added, ultrasonic treatment is carried out for 1-2h, after the mixed solution is uniformly dispersed, the mixed solution is placed in a vacuum drying oven, the temperature is controlled at 120 ℃, and drying is carried out for 2h until the solution is completely volatilized, so that the silicon modified magnetic graphene composite wave-absorbing material is obtained.
7. The Ku waveband composite wave-absorbing material and the preparation method thereof as claimed in claim 2, wherein the graphene oxide comprises single-layer graphene oxide and multi-layer graphene oxide, and the mesh number is 500-1000.
8. The Ku waveband composite wave-absorbing material and the preparation method thereof as claimed in claim 2, wherein the organosilicon modifier is epoxy functional group organosilicon reagent trimethoxy [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl ] silane, 3- (2, 3-glycidoxy) propyl trimethoxysilane, 3- [ (2,3) -glycidoxy ] propyl methyl dimethoxysilane), organosilicon reagent 3-aminopropyl triethoxysilane with amino group, organosilicon reagent 3- (methacryloyloxy) propyl trimethoxysilane with unsaturated ester.
9. The Ku waveband composite wave-absorbing material and the preparation method thereof as claimed in claim 2, wherein the addition amount of the modified graphene magnetic composite wave-absorbing agent is 30 wt%.
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