CN113816620A - Dielectric fiber composite wave-absorbing material with surface coated with molybdenum disulfide/iron-cobalt alloy/carbon and preparation method thereof - Google Patents
Dielectric fiber composite wave-absorbing material with surface coated with molybdenum disulfide/iron-cobalt alloy/carbon and preparation method thereof Download PDFInfo
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
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Abstract
A dielectric fiber composite wave-absorbing material with a surface coated with molybdenum disulfide/iron-cobalt alloy/carbon and a preparation method thereof are disclosed. The invention has low production cost, simple process, high yield and good dispersibility in various matrixes, and is suitable for large-scale production and application.
Description
Technical Field
The invention belongs to the field of electromagnetic wave absorbing materials, and particularly relates to a dielectric fiber composite wave absorbing material with a surface coated with molybdenum disulfide/iron-cobalt alloy/carbon and a preparation method thereof.
Background
The ideal wave-absorbing material has the advantages of low density, thin thickness, strong absorption, wide wave-absorbing frequency band and the like. According to a microwave loss mechanism, the wave-absorbing material can be divided into a conductive loss type, a dielectric loss type and a magnetic loss type, the magnetic wave-absorbing material mainly comprises a magnetic metal alloy compound and a magnetic metal oxide, and the saturated magnetic polarization strength of the iron compound and the cobalt compound is high and is a main research object of the magnetic loss type material. The dielectric loss material mainly depends on the modes of electronic polarization, atomic polarization, electric dipole orientation polarization, interface polarization and the like in the material to complete the loss of incident electromagnetic waves, and the current application is mainly based on carbon nano materials such as graphene, carbon nano tubes, carbon fibers and the like. However, the loss form of a single material is single, and the requirement of broadband absorption is difficult to meet.
Molybdenum disulfide is a two-dimensional material which is researched more in recent years, has a laminated structure, and has wide application in the fields of energy storage, catalysis, semiconductors and the like. Meanwhile, molybdenum sulfide is a microwave absorbing material with dielectric loss, has a certain electromagnetic wave absorption capacity, and has poor impedance matching performance due to the huge difference between the dielectric constant and the magnetic conductivity, and the wave absorbing performance needs to be further researched and improved.
Patent CN107768622A discloses a method for preparing a nitrogen-doped carbon nanofiber/molybdenum disulfide composite material, which comprises subjecting a polypyrrole/polymethyl methacrylate nanofiber membrane to hydrothermal reaction to obtain a nitrogen-doped carbon nanofiber/molybdenum disulfide nanofiber membrane, and then sintering in a nitrogen atmosphere to obtain the nitrogen-doped carbon nanofiber/molybdenum disulfide composite material. For the surface modification of conductive fibers such as carbon fibers, silicon carbide fibers and the like, although the wave-absorbing performance can be improved to a certain extent by adjusting the electromagnetic properties of the material, compared with dielectric fibers, the conductivity of the material is difficult to regulate and control due to the characteristic of strong conductivity of the conductive fibers, so that the material has strong electromagnetic wave reflection effect in practical application and the wave-absorbing effect is influenced.
At present, no research is reported on the development of the wave-absorbing composite fiber with adjustable electromagnetic property based on the electromagnetic modification of the surface of the dielectric fiber.
Disclosure of Invention
The invention aims to provide a dielectric fiber composite wave-absorbing material with a surface coated with molybdenum disulfide/iron-cobalt alloy/carbon and a preparation method thereof.
The technical scheme adopted by the invention is as follows: and taking the dielectric fiber as a carrier, growing molybdenum disulfide nanosheets on the surface of the dielectric fiber in situ, and further coating iron-cobalt alloy and nano carbon particles on the molybdenum disulfide nanosheets.
The dielectric fiber is any one of glass fiber, basalt fiber, alumina fiber and mineral wool fiber, and the dielectric constant of the dielectric fiber is not more than 3.
A preparation method of a dielectric fiber composite wave-absorbing material with a surface coated with molybdenum disulfide/iron-cobalt alloy/carbon comprises the following steps:
step 3, mixing the molybdenum disulfide reaction solution prepared in the step 2 with the dielectric fiber after pretreatment, so that the dielectric fiber is uniformly dispersed in the molybdenum dioxide reaction solution;
and 7, calcining the composite fiber material prepared in the step 6 in a reducing atmosphere to obtain the dielectric fiber composite wave-absorbing material with the surface uniformly coated with the molybdenum disulfide/iron-cobalt alloy/carbon.
In the step 1, the method comprises the following steps of,
and (2) soaking the surface of the dielectric fiber by using a strong oxidizing chemical reagent, wherein the strong oxidizing chemical reagent is any one of 60% concentrated nitric acid, 30% hydrogen peroxide solution and 20% sodium hypochlorite solution, and the soaking time is 1-4 hours.
And 2, preparing a molybdenum disulfide reaction solution, wherein the raw materials comprise sodium molybdate dihydrate, thiourea, water and hydrochloric acid or sulfuric acid, the mass ratio of the sodium molybdate dihydrate to the thiourea is 1: 2-3, 140ml of water is used, and the dosage of the hydrochloric acid or sulfuric acid is determined according to the pH value, so that the pH value of the molybdenum disulfide reaction solution is guaranteed to be 3.
In the step 3, the dielectric fiber is uniformly dispersed in the molybdenum disulfide reaction solution by ultrasonic dispersion, and the energy density of the ultrasonic dispersion is not lower than 2000J/ml; and (3) continuously stirring after ultrasonic dispersion, wherein the stirring speed is 300-600 rpm, the stirring time is 2-5 hours, and the mass ratio of the fiber to the molybdenum disulfide reaction solution is 1: 28.
and after the hydrothermal reaction is finished, naturally cooling, soaking and cleaning the product in deionized water for 3-5 times, soaking and cleaning in absolute ethyl alcohol for 1-2 times, and drying.
And 5, dissolving the iron source and the cobalt source in a molar mass ratio of 2:1 in 140ml of water, adding 0.2-0.8 g of glucose and 0.25-0.75 g of polyvinyl alcohol, uniformly mixing, dropwise adding 1-2 ml of hydrogen peroxide with the concentration of 10%, and dropwise adding ammonia water until the pH value of the solution is not less than 10.
In the step 6, dispersing the composite fiber product prepared in the step 4 in the reaction solution prepared in the step 5, and stirring for 5-8 hours at a stirring speed of 100-200 rpm;
and after the reaction is finished, filtering the composite fiber material, washing the composite fiber material for 3-5 times by using deionized water, soaking and washing the composite fiber material for 1-2 times by using absolute ethyl alcohol, and drying the composite fiber material.
In the step 7, the calcining temperature is 650-750 ℃, the heating rate is 5-10 ℃/min, the calcining time is 3-6 hours, the atmosphere is a nitrogen-hydrogen or argon-hydrogen mixed atmosphere, and the volume of hydrogen accounts for 5-7%.
In the working process, the dielectric fiber is used as a carrier, molybdenum disulfide grows in situ on the surface of the dielectric fiber, an iron source, a cobalt source, glucose, polyvinyl alcohol and the like are attached to the surface of the dielectric fiber, and the composite fiber material is obtained after calcination in a reducing atmosphere, wherein the material attached to the surface of the fiber is in a sandwich structure and is uniformly distributed.
Compared with the prior art, the invention has the following beneficial effects:
1) compared with other methods, the method has the advantages of simple equipment and manufacturing process and the like;
2) the composite wave-absorbing material with the sandwich coating structure on the surface of the dielectric fiber can be obtained only by three steps of reactions, and has good wave-absorbing performance in the microwave frequency range.
Drawings
FIG. 1 is a scanning electron microscope image of the composite wave-absorbing material coated with molybdenum disulfide/iron cobalt alloy/carbon dielectric fiber prepared in example 1,
FIG. 2 is an X-ray diffraction pattern of the fiber composite wave-absorbing material prepared in example 1,
FIG. 3 shows the wave-absorbing properties of the fiber composite wave-absorbing material prepared in example 1,
FIG. 4 is a scanning electron microscope image and an element distribution image of the surface-coated molybdenum disulfide/iron cobalt alloy/carbon dielectric fiber composite wave-absorbing material prepared in example 2,
FIG. 5 shows the wave-absorbing properties of the fiber composite wave-absorbing material prepared in example 2,
FIG. 6 is a scanning electron microscope image and an element distribution image of the surface-coated molybdenum disulfide/iron cobalt alloy/carbon dielectric fiber composite wave-absorbing material prepared in example 3,
FIG. 7 shows the wave-absorbing properties of the fiber composite wave-absorbing material prepared in example 3,
FIG. 8 is a SEM image and an element distribution image of the molybdenum disulfide/iron cobalt alloy/carbon powder composite wave-absorbing material in comparison,
FIG. 9 shows the wave-absorbing properties of the molybdenum disulfide/iron cobalt alloy/carbon powder composite wave-absorbing material.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
According to the invention, dielectric fiber is used as a carrier, molybdenum disulfide nanosheets grow in situ on the surface of the dielectric fiber, and iron-cobalt alloy and nano carbon particles are further coated on the molybdenum disulfide nanosheets.
The invention utilizes the combination of the magnetic material and the electric material, not only can improve impedance matching, but also can synergistically promote the electric loss and the magnetic loss of the material, and effectively improve the wave-absorbing performance. In addition, by utilizing the microstructure characteristics of the material, a surface microstructure or a hollow structure with three-dimensional structure characteristics is constructed, loss mechanisms such as electromagnetic wave scattering and multiple reflection caused by the microstructure effect are introduced, and the wave absorbing performance of the material can be effectively improved.
The dielectric fiber (mineral fiber or glass fiber and the like) does not have conductivity and electromagnetic loss capability, and after the surface of the dielectric fiber is subjected to electromagnetic modification, a linear cavity microstructure beneficial to electromagnetic wave absorption can be formed, and the material cost is low.
The electromagnetic modified dielectric fiber can realize the integration of the functions of the wave absorber and the reinforced fiber, can improve the electromagnetic absorption performance when being applied to the composite material on the premise of ensuring the mechanical property of the composite material, and simultaneously effectively solves the problem that the powder wave absorber reduces the mechanical property of the composite material.
The dielectric fiber can realize the adjustment of the surface conductivity through the surface electromagnetic modification, the conductivity of the fiber can be adjusted according to the actual requirement, meanwhile, the low dielectric and high magnetic composite material formed by compounding the low dielectric constant dielectric fiber and the modified material has excellent impedance matching characteristics, and the wave absorbing performance can be further improved by the formed flower-shaped three-dimensional microstructure and the hollow structure.
The dielectric fiber is any one of glass fiber, basalt fiber, alumina fiber and mineral wool fiber, and the dielectric constant of the dielectric fiber is not more than 3.
A preparation method of a dielectric fiber composite wave-absorbing material with a surface coated with molybdenum disulfide/iron-cobalt alloy/carbon comprises the following steps:
step 3, mixing the molybdenum disulfide reaction solution prepared in the step 2 with the dielectric fiber after pretreatment, so that the dielectric fiber is uniformly dispersed in the molybdenum dioxide reaction solution; the coating amount of the reaction product on the surface of the dielectric fiber is improved.
And 7, calcining the composite fiber material prepared in the step 6 in a reducing atmosphere to obtain the dielectric fiber composite wave-absorbing material with the surface uniformly coated with the molybdenum disulfide/iron-cobalt alloy/carbon.
In the step 1, the method comprises the following steps of,
and (2) soaking the surface of the dielectric fiber by using a strong oxidizing chemical reagent, wherein the strong oxidizing chemical reagent is any one of 60% concentrated nitric acid, 30% hydrogen peroxide solution and 20% sodium hypochlorite solution, and the soaking time is 1-4 hours.
The surface of the dielectric fiber is soaked and pretreated by a chemical reagent with strong oxidizing property, so that resin, impurities and other water-insoluble materials on the surface of the dielectric fiber are removed, and functional groups (such as hydroxyl groups of-OH, -H-and the like) on the surface of the dielectric fiber are increased, thereby forming a surface form suitable for the growth of a coating layer in the next step.
And 2, preparing a molybdenum disulfide reaction solution, wherein the raw materials comprise sodium molybdate dihydrate, thiourea, water and hydrochloric acid or sulfuric acid, the mass ratio of the sodium molybdate dihydrate to the thiourea is 1: 2-3, 140ml of water is used, and the dosage of the hydrochloric acid or sulfuric acid is determined according to the pH value, so that the pH value of the molybdenum disulfide reaction solution is guaranteed to be 3.
The proportion is determined according to the proportion of S and Mo elements in the product, the proportion of sodium molybdate and thiourea cannot be too large, and impurities or other substances may remain due to incomplete reaction, so that the purity of the product is influenced.
In the step 3, the dielectric fiber is uniformly dispersed in the molybdenum disulfide reaction solution by ultrasonic dispersion, and the energy density of the ultrasonic dispersion is not lower than 2000J/ml; and (3) continuously stirring after ultrasonic dispersion, wherein the stirring speed is 300-600 rpm, the stirring time is 2-5 hours, and the mass ratio of the fiber to the molybdenum disulfide reaction solution is 1: 28.
and after the hydrothermal reaction is finished, naturally cooling, soaking and cleaning the product in deionized water for 3-5 times, soaking and cleaning in absolute ethyl alcohol for 1-2 times, and drying.
Thus, the residual reaction solution and other impurities on the surface of the product are removed, and the volume ratio of the hydrothermal reaction kettle to the reaction solution is 10: 7.
And 5, dissolving the iron source and the cobalt source in a molar mass ratio of 2:1 in 140ml of water, adding 0.2-0.8 g of glucose and 0.25-0.75 g of polyvinyl alcohol, uniformly mixing, dropwise adding 1-2 ml of hydrogen peroxide with the concentration of 10%, and dropwise adding ammonia water until the pH value of the solution is not less than 10.
Wherein the glucose is used for providing an energy carbon source, and the polyvinyl alcohol is used for increasing the viscosity of the solution and improving the coating and the cohesiveness of a reaction product on the surface of the fiber; the hydrogen peroxide has the function of oxidizing ferrous ions into iron ions; the pH value of the solution is adjusted by the action of ammonia water.
Wherein the iron source is ferrous chloride tetrahydrate or ferrous sulfate heptahydrate, the cobalt source is cobalt chloride hexahydrate or cobalt sulfate heptahydrate, and acid radical ions of the iron source and the cobalt source need to be consistent with the strong acid used in the step 2.
In the step 6, dispersing the composite fiber product prepared in the step 4 in the reaction solution prepared in the step 5, and stirring for 5-8 hours at a stirring speed of 100-200 rpm;
and after the reaction is finished, filtering the composite fiber material, washing the composite fiber material for 3-5 times by using deionized water, soaking and washing the composite fiber material for 1-2 times by using absolute ethyl alcohol, and drying the composite fiber material.
In the step 7, the calcining temperature is 650-750 ℃, the heating rate is 5-10 ℃/min, the calcining time is 3-6 hours, the atmosphere is a nitrogen-hydrogen or argon-hydrogen mixed atmosphere, and the volume of hydrogen accounts for 5-7%.
The inert gas atmosphere is mainly used for avoiding other gases from reacting with the product to form other substances, so that the purity of the product is influenced; hydrogen mainly functions as a reducing agent.
Calcination is primarily to obtain a FeCo alloy product and to provide a suitable temperature range and time for the reduction of carbon, too low a temperature to complete the reaction, and too high a temperature to form other products.
Example 1:
(1) 5g of basalt fiber was put into a 30% hydrogen peroxide solution and soaked for 4 hours.
(2) Dissolving 2.0g of thiourea and 1.0g of sodium molybdate dihydrate in 140mL of deionized water, dropwise adding hydrochloric acid until the pH value is 3, adding the pretreated dielectric fiber, carrying out ultrasonic treatment, and carrying out energy density of 2500J/mL, stirring at 300rpm for 2 hours, transferring the reaction solution into a hydrothermal kettle with the volume of 200mL, carrying out reaction at the temperature of 150 ℃ for 15 hours, naturally cooling to room temperature, filtering the product, sequentially washing with deionized water for 4 times, washing with absolute ethyl alcohol for 2 times, and then drying the product in a vacuum drying oven for 24 hours.
(3) Dissolving 0.489g of ferrous chloride tetrahydrate and 0.238g of cobalt chloride hexahydrate in 140mL of water, adding 0.25g of polyvinyl alcohol and 0.468g of glucose, dropwise adding 2mL of hydrogen peroxide, dropwise adding ammonia water until the pH value of the solution is 12, adding the composite fiber obtained in the step (2) into the solution, stirring for 5 hours in the whole process, and stirring at the rotation speed of 150 rpm. After 5 hours of reaction, the product was filtered off, washed 5 times with deionized water, 3 times with absolute ethanol and dried.
(4) And (4) calcining the composite fiber obtained in the step (3) in a tubular furnace in a nitrogen-hydrogen mixed atmosphere, wherein the hydrogen ratio is 5%, the heating rate is 5 ℃/min, the temperature is 700 ℃, and the dielectric fiber wave-absorbing material with the surface coated with molybdenum disulfide/iron-cobalt alloy/carbon is obtained after calcining for 5 hours.
Fig. 1 is a scanning electron microscope image of the composite wave-absorbing material coated with molybdenum disulfide/iron-cobalt alloy/carbon dielectric fiber prepared in example 1, and it can be found that a continuous and uniform coating layer is formed on the surface of the basalt dielectric fiber, the coating layer is in a three-dimensional flower-like shape in a microscopic view, and iron-cobalt alloy particles are clearly visible. Fig. 2 is an X-ray diffraction pattern of the fiber composite wave-absorbing material prepared in example 1, from which the corresponding components of molybdenum disulfide, iron-cobalt alloy and carbon contained in the synthesized product can be seen, which proves that the dielectric fiber wave-absorbing composite material with the surface coated with molybdenum disulfide/iron-cobalt alloy/carbon is successfully prepared. FIG. 3 shows the wave-absorbing properties of the fiber composite wave-absorbing material prepared in example 1, when the matching thickness is 3.5mm, the wave-absorbing properties of the material are better than-5 dB in the frequency range of 7.9-17 GHz, and the optimal wave-absorbing properties of-18.63 dB are obtained at 11.8 GHz.
Example 2:
(1) 5g of glass fiber was immersed in a 60% concentrated nitric acid solution for 1 hour.
(2) Dissolving 2.0g of thiourea and 1.0g of sodium molybdate dihydrate in 140mL of deionized water, dropwise adding sulfuric acid until the pH value is 3, adding pretreated glass fiber, carrying out ultrasonic treatment, carrying out energy density of 2000J/mL, stirring at 400rpm for 4 hours, transferring the reaction solution into a hydrothermal kettle with the volume of 200mL, carrying out reaction at the temperature of 120 ℃ for 20 hours, naturally cooling to room temperature, filtering the product, sequentially washing with deionized water for 5 times, washing with absolute ethyl alcohol for 2 times, and then drying the product in a vacuum drying oven for 24 hours.
(3) Dissolving 0.556g of ferrous sulfate heptahydrate and 0.281g of cobalt sulfate heptahydrate in 140mL of water, adding 0.5g of polyvinyl alcohol and 0.6g of glucose, dropwise adding 2mL of hydrogen peroxide, dropwise adding ammonia water until the pH value of the solution is 12, adding the composite fiber obtained in the step (2) into the solution, stirring for 6 hours in the whole process, and stirring at the rotating speed of 100 rpm. After 6 hours of reaction, the product was filtered off, washed 4 times with deionized water, 2 times with absolute ethanol and dried.
(4) And (4) calcining the composite fiber obtained in the step (3) in a tubular furnace in a nitrogen-hydrogen mixed atmosphere, wherein the hydrogen ratio is 7%, the heating rate is 10 ℃/min, the temperature is 650 ℃, and the dielectric fiber wave-absorbing material with the surface coated with molybdenum disulfide/iron-cobalt alloy/carbon is obtained after calcining for 6 hours.
Fig. 4 is a scanning electron microscope image and an element distribution image of the composite wave-absorbing material coated with the molybdenum disulfide/iron-cobalt alloy/carbon dielectric fiber prepared in example 2, and it can be seen that a continuous and uniform coating layer is formed on the surface of the glass dielectric fiber, the coating layer is microscopically in a three-dimensional flower-like shape, and iron-cobalt alloy particles are clearly visible. The element distribution diagram proves that the glass fiber surface coating layer contains corresponding components of molybdenum disulfide, iron-cobalt alloy and carbon. FIG. 5 shows the wave-absorbing properties of the fiber composite wave-absorbing material prepared in example 2, when the matching thickness is 3mm, the wave-absorbing properties of the material are better than-5 dB in the frequency range of 8-18 GHz, and the optimal wave-absorbing properties of-17.5 dB are obtained at 12.2 GHz.
Example 3:
(1) 5g of mineral wool fibres are immersed in a 20% sodium hypochlorite solution for 5 hours.
(2) Dissolving 3.0g of thiourea and 1.0g of sodium molybdate dihydrate in 140mL of deionized water, dropwise adding hydrochloric acid until the pH value is 3, adding the pretreated mineral wool fiber, carrying out ultrasonic treatment, wherein the energy density is 2200J/mL, stirring at 500rpm for 5 hours, transferring the reaction solution into a 200mL hydrothermal kettle, reacting at the temperature of 180 ℃ for 15 hours, naturally cooling to room temperature, filtering the product, sequentially washing with deionized water for 5 times, washing with absolute ethyl alcohol for 2 times, and then drying the product in a vacuum drying oven for 24 hours.
(3) Dissolving 0.489g of ferrous chloride tetrahydrate and 0.238g of cobalt chloride hexahydrate in 140mL of water, adding 0.3g of polyvinyl alcohol and 0.5g of glucose, dropwise adding 2mL of hydrogen peroxide, dropwise adding ammonia water until the pH value of the solution is 12, adding the composite fiber obtained in the step (2) into the solution, stirring for 8 hours in the whole process, and stirring at the rotating speed of 150 rpm. After 8 hours of reaction, the product was filtered off, washed 4 times with deionized water, 2 times with absolute ethanol and dried.
(4) And (4) calcining the composite fiber obtained in the step (3) in a tubular furnace in a nitrogen-hydrogen mixed atmosphere, wherein the hydrogen ratio is 5%, the heating rate is 10 ℃/min, the temperature is 500 ℃, and the dielectric fiber wave-absorbing material with the surface coated with molybdenum disulfide/iron-cobalt alloy/carbon is obtained after calcining for 4 hours.
Fig. 6 is a scanning electron microscope image and an element distribution image of the composite wave-absorbing material coated with molybdenum disulfide/iron-cobalt alloy/carbon dielectric fiber prepared in example 3, and it can be seen that a continuous and uniform coating layer is formed on the surface of the mineral wool dielectric fiber, the coating layer is microscopically in a three-dimensional flower-like shape, and iron-cobalt alloy particles are clearly visible. The element distribution diagram proves that the glass fiber surface coating layer contains corresponding components of molybdenum disulfide, iron-cobalt alloy and carbon. FIG. 7 shows the wave-absorbing properties of the fiber composite wave-absorbing material prepared in example 3, when the matching thickness is 3.5mm, the wave-absorbing properties of the material are better than-5 dB in the frequency range of 7.6-17.2 GHz, and the optimal wave-absorbing properties of-14.76 dB are obtained at 10.9 GHz.
Comparative example:
the preparation method of the molybdenum disulfide/iron cobalt alloy/carbon powder composite wave-absorbing material is basically the same as that in the embodiment 1, and the difference is that the composite material is not compounded with dielectric fibers.
As shown in fig. 8 and 9, the powder material prepared by the comparative example also forms a three-dimensional flower-like micro-morphology, and the element distribution diagram also proves that corresponding components such as molybdenum disulfide, iron-cobalt alloy, carbon and the like are formed. The shape and the components of the comparative example powder material are basically consistent with those of the coating composite material of the embodiment. However, the wave-absorbing performance of the comparative example powder material is obviously inferior to that of the examples 1-3, the wave-absorbing performance reaches-5 dB only in the range of 10.5-16.6 GHz, and the best wave-absorbing performance can only reach-8.47 dB. According to the comparison of the wave-absorbing properties of the embodiment and the comparative example, the wave-absorbing material formed by coating the molybdenum disulfide/iron-cobalt alloy/carbon composite material on the surface of the dielectric fiber is further demonstrated, and the wave-absorbing property can be remarkably improved.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications to the present invention without departing from the principles of the present invention should be considered within the scope of the present invention by those of ordinary skill in the art.
Claims (10)
1. A dielectric fiber composite wave-absorbing material with a surface coated with molybdenum disulfide/iron cobalt alloy/carbon is characterized in that,
and taking the dielectric fiber as a carrier, growing molybdenum disulfide nanosheets on the surface of the dielectric fiber in situ, and further coating iron-cobalt alloy and nano carbon particles on the molybdenum disulfide nanosheets.
2. The dielectric fiber composite wave-absorbing material with the surface coated with molybdenum disulfide/iron cobalt alloy/carbon as claimed in claim 1, wherein the dielectric fiber is any one of glass fiber, basalt fiber, alumina fiber and mineral wool fiber, and the dielectric constant of the dielectric fiber should not be greater than 3.
3. A preparation method of a dielectric fiber composite wave-absorbing material with a surface coated with molybdenum disulfide/iron-cobalt alloy/carbon is characterized by comprising the following steps:
step 1, dielectric fiber surface pretreatment is carried out, and attachments on the fiber surface are removed;
step 2, preparing a molybdenum disulfide reaction solution;
step 3, mixing the molybdenum disulfide reaction solution prepared in the step 2 with the dielectric fiber after pretreatment, so that the dielectric fiber is uniformly dispersed in the molybdenum dioxide reaction solution;
step 4, growing molybdenum disulfide nanosheets in situ on the surface of the dielectric fiber by adopting a low-temperature hydrothermal method, and cleaning and drying the composite fiber product for the next step;
step 5, preparing a cobalt ferrite and glucose reaction solution;
step 6, mixing the composite fiber product prepared in the step 4 with the reaction solution prepared in the step 5, and preparing the composite material fiber by adopting a normal-temperature coprecipitation method;
and 7, calcining the composite fiber material prepared in the step 6 in a reducing atmosphere to obtain the dielectric fiber composite wave-absorbing material with the surface uniformly coated with the molybdenum disulfide/iron-cobalt alloy/carbon.
4. The method for preparing the dielectric fiber composite wave-absorbing material with the surface coated with the molybdenum disulfide/iron cobalt alloy/carbon as claimed in claim 3, wherein in the step 1,
and (2) soaking the surface of the dielectric fiber by using a strong oxidizing chemical reagent, wherein the strong oxidizing chemical reagent is any one of 60% concentrated nitric acid, 30% hydrogen peroxide solution and 20% sodium hypochlorite solution, and the soaking time is 1-4 hours.
5. The preparation method of the dielectric fiber composite wave-absorbing material with the surface coated with molybdenum disulfide/iron-cobalt alloy/carbon according to claim 3, wherein a molybdenum disulfide reaction solution is prepared in the step 2, raw materials comprise sodium molybdate dihydrate, thiourea, water and hydrochloric acid or sulfuric acid, the mass ratio of the sodium molybdate dihydrate to the thiourea is 1: 2-3, 140ml of water is used, and the use amount of the hydrochloric acid or sulfuric acid is determined according to the pH value, so that the pH value of the molybdenum disulfide reaction solution is not more than 3.
6. The method for preparing the dielectric fiber composite wave-absorbing material with the surface coated with the molybdenum disulfide/iron cobalt alloy/carbon according to claim 3,
in the step 3, the dielectric fiber is uniformly dispersed in the molybdenum disulfide reaction solution by ultrasonic dispersion, and the energy density of the ultrasonic dispersion is not lower than 2000J/ml; and (3) continuously stirring after ultrasonic dispersion, wherein the stirring speed is 300-600 rpm, the stirring time is 2-5 hours, and the mass ratio of the fiber to the molybdenum disulfide reaction solution is 1: 28.
7. The preparation method of the dielectric fiber composite wave-absorbing material with the surface coated with the molybdenum disulfide/iron-cobalt alloy/carbon according to claim 3, wherein in the step 4, the molybdenum disulfide reaction solution and the dielectric fiber are placed in a hydrothermal reaction kettle for reaction, the hydrothermal reaction temperature is 120-180 ℃, and the reaction time is 15-20 hours;
and after the hydrothermal reaction is finished, naturally cooling, soaking and cleaning the product in deionized water for 3-5 times, soaking and cleaning in absolute ethyl alcohol for 1-2 times, and drying.
8. The preparation method of the dielectric fiber composite wave-absorbing material coated with the molybdenum disulfide/iron-cobalt alloy/carbon surface according to claim 3, wherein the reaction solution in the step 5 comprises an iron source, a cobalt source, glucose, polyvinyl alcohol, hydrogen peroxide, ammonia water and water, the iron source and the cobalt source are dissolved in 140ml of water according to a molar mass ratio of 2:1, 0.2-0.8 g of glucose and 0.25-0.75 g of polyvinyl alcohol are added, after uniform mixing, 1-2 ml of 10% hydrogen peroxide is added dropwise, and the ammonia water is added dropwise until the pH value of the solution is not less than 10.
9. The method for preparing the dielectric fiber composite wave-absorbing material with the surface coated with the molybdenum disulfide/iron-cobalt alloy/carbon as claimed in claim 3, wherein in step 6, the composite fiber product prepared in step 4 is dispersed in the reaction solution prepared in step 5, and is stirred for 5-8 hours at the stirring speed of 100-200 rpm;
and after the reaction is finished, filtering the composite fiber material, washing the composite fiber material for 3-5 times by using deionized water, soaking and washing the composite fiber material for 1-2 times by using absolute ethyl alcohol, and drying the composite fiber material.
10. The preparation method of the dielectric fiber composite wave-absorbing material with the surface coated with the molybdenum disulfide/iron-cobalt alloy/carbon as claimed in claim 3, wherein in the step 7, the calcining temperature is 650-750 ℃, the heating rate is 5-10 ℃/min, the calcining time is 3-6 hours, the atmosphere is a mixed atmosphere of nitrogen and hydrogen or argon and hydrogen, and the volume ratio of hydrogen is 5-7%.
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