CN117165179A - Composite stealth coating resistant to severe environment and preparation method and application thereof - Google Patents
Composite stealth coating resistant to severe environment and preparation method and application thereof Download PDFInfo
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- CN117165179A CN117165179A CN202311245721.4A CN202311245721A CN117165179A CN 117165179 A CN117165179 A CN 117165179A CN 202311245721 A CN202311245721 A CN 202311245721A CN 117165179 A CN117165179 A CN 117165179A
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Abstract
The invention relates to a composite stealth coating resistant to severe environment, and a preparation method and application thereof, comprising the following steps: preparing slurry required by ferroferric oxide/carbon composite material microspheres; preparing microsphere precursors; preparing a fiber-ferroferric oxide/carbon microsphere composite material; preparing stealth wave-absorbing paint containing ferroferric oxide/carbon composite material microspheres; and sequentially coating a layer of mixed solution of an adhesive, a stealth wave-absorbing coating and a curing agent on a substrate, spreading a fiber-ferroferric oxide/carbon microsphere composite material on the surface of the coating, and curing to obtain a composite stealth coating on the surface of the substrate. Compared with the prior art, the high-performance high-absorption wave-absorbing device has the advantages of ensuring high wave-absorbing efficiency, stabilizing stealth performance, flexibly regulating and controlling the structure, resisting high temperature, high humidity and high corrosion, and being suitable for marine environment equipment application.
Description
Technical Field
The invention relates to the field of stealth materials, in particular to a composite stealth coating resistant to severe environment, a preparation method and application thereof.
Background
With the rapid development of information technology and the instantaneous change of war environment, the occurrence of stealth detection technology has profound effects on modern weaponry, the development and application of various stealth detection technologies form a serious threat to the survival of aviation aircrafts, naval vessels and various weaponry, and become a main means for capturing information and detecting targets in new century information electronic war. According to the current actual environment and detection technology, stealth detection is mainly realized through channels such as radar waves, infrared signals, sound waves and the like, so that the method for reducing the radar echo intensity, weakening infrared radiation and reducing noise is a main method for realizing stealth of equipment. In modern stealth technology, the object detectability is reduced mainly by changing the appearance design and preparing the stealth coating on the surface, but the appearance improvement is often difficult and high in cost due to the restrictions of the use condition and environment, and the additional quality is easily added, so that the comprehensive performance is reduced. The performance and the appearance design can not meet the requirements at the same time, the stealth coating just can make up for the defect, and the stealth coating material has the advantages of relatively simple preparation, convenient construction, strong designability selectivity and lower cost.
The stealth coating material is widely applied to various aspects of national defense, military industry, civil use and the like, can play a key role in radar stealth technology, information leakage protection and the like, and is mainly applied to ground and air equipment at present. With the continuous development of the offshore equipment technology in China, the demands of various offshore equipment such as naval vessel mass transfer in China on stealth coating materials are more and more, but due to the fact that the marine environment is greatly different from the application environment in the ground air, the conventional stealth coating materials prepared by taking carbonyl iron powder as a wave absorber are difficult to meet the long-term use demands under the marine environment with high temperature, high humidity, high corrosion and strong illumination, corrosion, sagging and falling of the stealth coating materials are often caused, for example, the invention patent with the application number of CN202211326831.9 discloses a coating material for improving the flexibility and the shock resistance of the coating through an alloy-plated glass flake and carbonyl iron powder combined structure, the invention with the application number of CN202310345108.3 discloses a wave absorber composite graphene coating thickness-adjusting wave absorber material, and the currently studied wave absorber coating materials only focus on optimizing the thickness, strength and other traditional indexes and lack consideration on relevant influence factors of marine special environment application.
In addition, the performance of the stealth coating material commonly used at present is single, the material structure cannot be flexibly regulated and controlled, single components and single structure are often adopted, only a certain single stealth wave absorbing function can be met, for example, the invention patent with the application number of CN202110910391.0 discloses a preparation method of fine adjustment coating performance and double-layer structure through filling proportion, modification, coating thickness design and the like of a magnetic absorbent, the regulation and control effect of the related technology is very limited, the requirements of multiple scenes such as wide frequency band, multiple-field stealth, comprehensive mechanical performance and the like can not be met, and the compound and multiple development requirements of the stealth coating material under the marine environment are difficult to meet.
Disclosure of Invention
The invention aims to overcome at least one of the defects in the prior art and provide a composite stealth coating resistant to severe environments, and a preparation method and application thereof. The composite stealth coating ensures high wave absorption efficiency, has stable stealth performance, can flexibly regulate and control the structure, is high-temperature resistant, high-humidity resistant and high-corrosion resistant, and is suitable for marine environment equipment application.
The aim of the invention can be achieved by the following technical scheme:
the invention aims at providing a preparation method of a composite stealth coating resistant to severe environment, which comprises the following steps:
s1, adding ferroferric oxide powder into an organic solvent, and uniformly dispersing to form uniform and stable suspension; adding a polymer, heating and stirring uniformly, cooling to room temperature, and degassing to obtain slurry required by preparing the ferroferric oxide/carbon composite microspheres;
s2, dispersing the slurry into liquid drops through electrospray, and immersing the liquid drops into a coagulation bath to form microsphere precursors; soaking the precursor in a coagulating bath, filtering out from the coagulating bath after the phase inversion is fully performed, and drying to obtain a microsphere precursor;
s3, dispersing the microsphere precursor in a non-organic solvent uniformly to form uniform and stable suspension; arranging carbon fibers in the suspension, fully soaking, taking out, drying and sintering to obtain a fiber-ferroferric oxide/carbon microsphere composite material;
s4, sintering the microsphere precursor to obtain the ferroferric oxide/carbon composite microsphere; adding the ferroferric oxide/carbon composite material microspheres into a mixed solution of an organic film forming agent and a diluent, and uniformly stirring to obtain a stealth wave-absorbing coating;
s5, sequentially coating a layer of mixed solution of an adhesive, a stealth wave-absorbing coating and a curing agent on a substrate, spreading the fiber-ferroferric oxide/carbon microsphere composite material on the surface of the coating, and curing to obtain a composite stealth coating on the surface of the substrate.
The order of S3 and S4 does not require S3 to precede S4, and both may be performed simultaneously, or S3 may precede S4 or S4 may precede S3.
In one embodiment of the present invention, the composite stealth coating comprises, in parts by weight:
in one embodiment of the invention:
the organic film forming agent is organic silicon rubber, preferably 107 silicon rubber;
the curing agent is bis-2, 4-dichlorobenzoyl peroxide;
the ferroferric oxide powder is powder, and the particle size is 25-75nm, preferably 50nm;
the diluent is 120# gasoline;
the organic solvent is N-methyl pyrrolidone;
the polymer is powdery polyethersulfone or cellulose acetate, the particle size is not particularly required, and the polymer is preferably polyethersulfone;
the non-organic solvent is water, preferably deionized water;
the binder is a silane coupling agent, preferably KH550.
In one embodiment of the invention, in S1:
the dispersion is ultrasonic dispersion, and the dispersion time is 10-30min, preferably 20min;
the heating and stirring are oil bath heating and mechanical stirring, the stirring time is 6-18h, the stirring rotating speed is 300-400r/min, preferably, the stirring time is 12h, and the stirring rotating speed is 350r/min;
the degassing is vacuum degassing treatment, and the degassing time is 20-40min, preferably 30min.
In one embodiment of the invention, S2:
the electronic injection is specifically as follows: injecting the slurry into an injector of an electronic injection ball making system, dispersing the slurry into liquid drops in the electronic injection process, and immersing the liquid drops into a coagulation bath to form microsphere precursors; the electric spraying voltage is 15-25kV, the slurry flow speed is 2-4ml/min, the caliber of an electric spraying nozzle is 0.5-1mm, and the distance between the electric spraying nozzle and the coagulating bath is 8-12cm; preferably, the electric spraying voltage is 20kV, the slurry flow rate is 2-4ml/min, the caliber of the electric spraying nozzle is 0.8mm, and the distance between the electric spraying nozzle and the coagulating bath is 10cm.
The precursor is immersed in the coagulating bath for 12-36h, preferably 24h;
the drying is room temperature drying, and the drying time is 24-72h, preferably 48h.
In one embodiment of the invention, S3:
the carbon fiber cloth is treated by removing oil stains on the surface and increasing the surface roughness;
the dispersion is ultrasonic dispersion, and the dispersion time is 10-30min, preferably 20min;
the microsphere precursor is sintered specifically as follows: arranging fully impregnated carbon fibers in a crucible, and sintering in a muffle furnace in two stages, wherein the sintering atmosphere is inert atmosphere, the sintering temperature in the first stage is 500-700 ℃, the sintering time in the second stage is 8-12h, the sintering time in the third stage is 1000-1400 ℃, the sintering time in the fourth stage is 1-3h, and the temperature rising and falling speed is 3-6 ℃/min. Preferably, the sintering temperature in the first stage is 600 ℃, the sintering time is 10 hours, the sintering time in the second stage is 1200 ℃, the sintering time is 2 hours, and the temperature rising speed is 5 ℃/min.
In one embodiment of the invention, in S4, the microsphere precursor sintering step is identical to the sintering step in S3.
In one embodiment of the invention, S5, the curing time is 30-50 hours, preferably 48 hours.
Specifically, the preparation method of the composite stealth coating comprises the following steps:
(1) Adding ferroferric oxide powder into an organic solvent according to a certain proportion, and performing ultrasonic dispersion to form uniform and stable suspension. The polymer powder was then added to the suspension and mechanically stirred in an oil bath. And after the stirring is finished, standing the obtained uniform slurry to room temperature, and then putting the slurry into a vacuum dryer for degassing treatment, and removing air mixed in the stirring process to obtain the slurry required for preparing the ferroferric oxide/carbon composite microsphere.
(2) And injecting the slurry into an injector of an electronic injection ball making system, dispersing the slurry into liquid drops in the electronic injection process, and immersing the liquid drops into a coagulating bath to form microsphere precursors. The precursor is immersed in a coagulating bath, filtered out of the coagulating bath after the phase inversion is fully carried out, and dried in the room temperature environment to obtain the microsphere precursor.
(3) Cutting carbon fiber cloth with a preset knitting structure into a proper size, carrying out surface treatment on the carbon fiber cloth, soaking the carbon fiber cloth with sodium hydroxide solution to remove surface greasy dirt, and then acidizing the carbon fiber cloth with nitric acid and carrying out ultrasonic treatment to increase the surface roughness of the carbon fiber cloth so as to facilitate uniform adhesion of microspheres. And mixing part of microsphere precursors with a certain amount of non-organic solvent, stirring by ultrasonic waves to form stable suspension, immersing the suspension, and continuing ultrasonic waves to fully impregnate the solution into the carbon fiber cloth structure. And then taking out the impregnated carbon fibers, arranging the impregnated carbon fibers in an oven, drying the impregnated carbon fibers, and taking out the impregnated carbon fibers.
(4) The impregnated fibers are arranged in a corundum crucible and sintered in two stages in a muffle furnace under nitrogen atmosphere. In the sintering process, the organic matters are pyrolyzed into carbon materials, ferroferric oxide/carbon composite material microspheres are generated on the surface of the fiber cloth in situ, and after the sintering is completed, the fiber-ferroferric oxide/carbon microsphere composite material can be obtained after the temperature is reduced to room temperature.
(5) And (3) placing a certain amount of microsphere precursors into a crucible for sintering, wherein the sintering step is the same as that of the step (4), so as to obtain the ferroferric oxide/carbon composite microsphere, pouring the organic film forming agent and the diluent into a stirring tank according to the proportion, continuously adding a proper amount of microspheres during the period, and uniformly mixing to obtain the uniform stealth wave-absorbing coating.
(6) After the surface of a substrate is cleaned, a layer of adhesive is coated, then a proper amount of curing agent is added into the uniformly mixed wave-absorbing coating and stirred uniformly, then the coating is sprayed on the surface of the substrate uniformly, then the fiber-ferroferric oxide/carbon microsphere composite material is paved on the surface of the coating, the curing is carried out for a period of time, and after the silicon rubber is crosslinked completely, the organic solvent is volatilized completely, so that the composite stealth coating is obtained on the surface of the substrate.
The second object of the invention is a composite stealth coating resistant to severe environments obtained by the preparation method.
The invention also aims at the application of the composite stealth coating which is resistant to severe environments and is applied to various corrosion environments such as acid and/or alkali and/or salt, and the like, and is particularly suitable for special application scenes such as marine environments.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, composite wave-absorbing material microspheres are generated on the surface of the carbon fiber in situ through processes of electronic spraying, sintering and the like, so that the fiber-ferroferric oxide/carbon microsphere composite material is obtained. The magnetic component has high saturation magnetization intensity and high absorption rate, the carbon material component has the characteristics of high thermal stability, corrosion resistance, low density, adjustable dielectric property and the like, and the fiber structure of the mutually-carried fiber braiding bodies constructs a proper attenuation space for electromagnetic waves, so that the magnetic carbon-based wave absorbing material can greatly improve the wave absorbing capacity of the coating through the combined effects of a magneto-dielectric double-loss mechanism, magneto-electric cooperation and the like.
(2) The organic silicon rubber matrix has excellent insulativity, and the composite material prepared by adding the conductive filler (ferroferric oxide/carbon microsphere) has wide conductivity regulation and control range, high infrared transmittance and high intrinsic medium-low frequency sound wave absorptivity.
(3) The composite material adopts a new research thought of material and structure integrated design, and the porous structure, the carbon fiber cloth weaving structure and the distribution structure of the silicon rubber interlayer wave-absorbing microspheres in the composite material microsphere are adjustable, i.e. the material microsphere can adjust and control the shape of the internal hole such as a finger-shaped hole, a spherical hole and the like; the weaving structure of the carbon fiber cloth can regulate and control the weaving density, the weaving direction, the weaving pattern and the like; the distribution density of the microspheres can be adjusted by the distribution of the microspheres of the silicon rubber, and the electromagnetic performance of the coating can be designed by combining different application scenes, so that the coating has good impedance matching characteristics and electromagnetic wave absorption efficiency.
(4) The coating is a wave-absorbing coating with a multilayer gradient structure, can realize stealth detection protection, and has excellent protection capability and usability. The carbon fiber cloth substrate applied to the surface layer has the advantages of high strength, high modulus, light dead weight, good durability, corrosion resistance and the like, and can further prolong the service performance and service life of the coating. The intermediate layer matrix is silicon rubber, has wide use temperature range, good compatibility with powder (ferroferric oxide/carbon microsphere), oxidation resistance, excellent use performance in various corrosive environments such as acid, alkali, salt and the like, and can be well suitable for special application scenes such as marine environments and the like.
Drawings
Fig. 1 is a photograph of carbon fiber cloth with different knitting structures of the coating surface layer in example 1.
FIG. 2 is a photograph showing the morphology of the ferroferric oxide/carbon composite microsphere (i.e., the wave-absorbing microsphere) obtained in example 1.
FIG. 3 is a graph of electromagnetic parameters of the composite stealth coating and the coating without ferroferric oxide/carbon microsphere in example 1, wherein ε 'is the real part of permittivity, ε "is the imaginary part of permittivity, μ' is the real part of permeability, and μ" is the imaginary part of permeability.
Fig. 4 is a graph of experimental data for the attenuation constant α of the composite stealth coating of example 1 and a coating without ferroferric oxide/carbon microspheres.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments.
A preparation method of a composite stealth coating resistant to severe environment comprises the following steps:
s1, adding ferroferric oxide powder into an organic solvent, and uniformly dispersing to form uniform and stable suspension; adding a polymer, heating and stirring uniformly, cooling to room temperature, and degassing to obtain slurry required by preparing the ferroferric oxide/carbon composite microspheres;
s2, dispersing the slurry into liquid drops through electrospray, and immersing the liquid drops into a coagulation bath to form microsphere precursors; soaking the precursor in a coagulating bath, filtering out from the coagulating bath after the phase inversion is fully performed, and drying to obtain a microsphere precursor;
s3, dispersing the microsphere precursor in a non-organic solvent uniformly to form uniform and stable suspension; arranging carbon fibers in the suspension, fully soaking, taking out, drying and sintering to obtain a fiber-ferroferric oxide/carbon microsphere composite material;
s4, sintering the microsphere precursor to obtain the ferroferric oxide/carbon composite microsphere; adding the ferroferric oxide/carbon composite material microspheres into a mixed solution of an organic film forming agent and a diluent, and uniformly stirring to obtain a stealth wave-absorbing coating;
s5, sequentially coating a layer of mixed solution of an adhesive, a stealth wave-absorbing coating and a curing agent on a substrate, spreading the fiber-ferroferric oxide/carbon microsphere composite material on the surface of the coating, and curing to obtain a composite stealth coating on the surface of the substrate.
Preferably, the composite stealth coating comprises, in parts by weight:
preferably:
the organic film forming agent is organic silicon rubber;
the curing agent is bis-2, 4-dichlorobenzoyl peroxide;
the ferroferric oxide powder is powder, and the particle size is 25-75nm;
the diluent is 120# gasoline;
the organic solvent is N-methyl pyrrolidone;
the polymer is polyethersulfone or cellulose acetate;
the non-organic solvent is water;
the binder is a silane coupling agent.
Preferably, in S1:
the dispersion is ultrasonic dispersion, and the dispersion time is 10-30min;
the heating and stirring are oil bath heating mechanical stirring, the stirring time is 6-18h, and the stirring rotating speed is 300-400r/min;
the degassing is vacuum degassing treatment, and the degassing time is 20-40min.
Preferably, in S2:
the electronic injection is specifically as follows: injecting the slurry into an injector of an electronic injection ball making system, dispersing the slurry into liquid drops in the electronic injection process, and immersing the liquid drops into a coagulation bath to form microsphere precursors; the electric spraying voltage is 15-25kV, the slurry flow speed is 2-4ml/min, the caliber of an electric spraying nozzle is 0.5-1mm, and the distance between the electric spraying nozzle and the coagulating bath is 8-12cm;
the dipping time of the precursor in the coagulating bath is 12-36h;
the drying is room temperature drying, and the drying time is 24-72h.
Preferably, in S3:
the carbon fiber cloth is treated by removing oil stains on the surface and increasing the surface roughness;
the dispersion is ultrasonic dispersion, and the dispersion time is 10-30min;
the microsphere precursor is sintered specifically as follows: arranging fully impregnated carbon fibers in a crucible, and sintering in a muffle furnace in two stages, wherein the sintering atmosphere is inert atmosphere, the sintering temperature in the first stage is 500-700 ℃, the sintering time in the second stage is 8-12h, the sintering time in the third stage is 1000-1400 ℃, the sintering time in the fourth stage is 1-3h, and the temperature rising and falling speed is 3-6 ℃/min.
Preferably, in S4, the sintering step of the microsphere precursor is consistent with the sintering step in S3.
Preferably, in S5, the curing time is 30 to 50 hours.
Example 1
The embodiment provides a composite silicone rubber stealth coating resistant to severe environment, which comprises the following raw material components in parts by weight;
a preparation method of the composite silicone rubber stealth coating is as follows.
(1) 10 parts of ferroferric oxide powder is added into 20 parts of N-methylpyrrolidone, and the mixture is dispersed for 20 minutes by ultrasonic waves to form uniform and stable suspension. Subsequently, 2 parts of polyethersulfone powder were added to the suspension and mechanically stirred in an oil bath at a temperature of 50℃for 12 hours with a stirrer bar rotation of 350r/min. And after the stirring is finished, standing the obtained uniform slurry to room temperature, then putting the slurry into a vacuum dryer for degassing treatment for 30min, and removing air mixed in the stirring process to obtain the slurry required for preparing the microwave absorbing microspheres.
(2) The slurry is injected into an injector of an electronic spray ball system, the electronic spray voltage is 20kV, the slurry flow rate is 2ml/min, the caliber of a nozzle is 0.8mm, and the height from the nozzle to a coagulating bath is 10cm. The slurry is dispersed into liquid drops in the electronic spraying process, and the liquid drops are immersed in the coagulating bath to form the ceramic microsphere precursor. The precursor is immersed in the coagulating bath for 24 hours, filtered out of the coagulating bath after the phase inversion is sufficiently carried out, and dried in the room temperature environment for 48 hours.
(3) Cutting carbon fiber cloth with a preset knitting structure into a proper size, carrying out surface treatment on the carbon fiber cloth, soaking the carbon fiber cloth with sodium hydroxide solution to remove surface greasy dirt, then acidizing the carbon fiber cloth with nitric acid, carrying out ultrasonic treatment for 20min, increasing the surface roughness of the carbon fiber cloth, and facilitating uniform adhesion of microspheres. And then mixing 5 parts of microsphere precursors with a proper amount of deionized water, stirring by ultrasonic waves to form stable suspension, immersing in the suspension, and continuing ultrasonic waves for 20min to fully impregnate the solution into the fiber cloth structure. And then taking out the immersed fiber, placing the immersed fiber in an oven, drying and taking out the immersed fiber.
(4) The impregnated fibers are arranged in a corundum crucible and sintered in two stages in a muffle furnace under nitrogen atmosphere. The sintering temperature in the first stage is 600 ℃, the sintering time is 10 minutes, the sintering time in the second stage is 1200 ℃, the sintering time is 2 hours, and the temperature rising speed is 5 ℃/min. In the sintering process, the organic matters are pyrolyzed into carbon materials, ferroferric oxide/carbon composite material microspheres are generated on the surface of the fiber cloth in situ, as shown in fig. 2, after the sintering is completed, the fiber-ferroferric oxide/carbon microsphere composite material can be obtained after the temperature is reduced to room temperature.
(5) And 5 parts of microsphere precursors are placed in a crucible for sintering, the sintering step is the same as that of (4), ferroferric oxide/carbon composite microspheres are obtained, as shown in figure 2, 90 parts of 107 silicon rubber and 100 parts of gasoline are poured into a stirring tank, 5 parts of ferroferric oxide/carbon composite microspheres are gradually added during the period of time, and uniformly mixed, and then uniform stealth wave-absorbing coating is obtained.
(6) After the surface of a substrate is cleaned, a layer of KH550 is thinly coated, 3 parts of curing agent is added into the uniformly mixed wave-absorbing coating and uniformly stirred, the coating is uniformly sprayed on the surface of the substrate, the fiber-ferroferric oxide/carbon microsphere composite material is paved on the surface of the coating, the curing is carried out for 40 hours, and after the silicon rubber is completely crosslinked, the organic solvent is completely volatilized, so that the composite stealth coating is obtained on the surface of the substrate.
In this embodiment, the substrate is metal, such as high-strength steel, aluminum alloy, and the like.
Referring to fig. 1 in detail, there are a plurality of weave structures of carbon fiber cloth used in the present invention, which are specifically different in weave density, and the weave structure used in this embodiment is fig. 1a.
Fig. 2 is a morphology diagram of the ferroferric oxide/carbon composite microsphere (i.e., the wave absorber microsphere) in this example.
Fig. 3 is a graph of experimental data of various electromagnetic parameters of the composite stealth coating (experimental group) and the coating (control group) without ferroferric oxide/carbon microsphere in this embodiment, and it can be seen from the graph that the parameters of each part of the dielectric constant and the magnetic permeability of the experimental group are higher than those of the control group in the range of 2-8GHz, which indicates that the electric field energy absorbing, storing and losing capability of the experimental group at low frequency and the absorbing, storing and losing capability of the magnetic field energy are better than those of the control group. The preparation method of the control group is identical to that of the experimental group, and the ferroferric oxide/carbon microspheres are not added in the preparation process.
Fig. 4 is a graph of experimental data of attenuation constants α of the composite stealth coating and the coating without ferroferric oxide/carbon microsphere in this example, and as can be obtained from the graph, the attenuation constants of the experimental group are higher than those of the control group in the ranges of 2-8GHz and 14-18Hz, which indicates that the attenuation capability of the experimental group to electromagnetic waves in the low frequency and the high frequency ranges is better than that of the control group.
Example 2
The embodiment provides a composite silicone rubber stealth coating resistant to severe environment, which comprises the following raw material components in parts by weight;
a preparation method of the composite silicone rubber stealth coating is as follows.
(1) 10 parts of ferroferric oxide powder is added into 20 parts of N-methylpyrrolidone, and the mixture is dispersed for 20 minutes by ultrasonic waves to form uniform and stable suspension. Subsequently, 1 part of cellulose acetate was added to the suspension and mechanically stirred in an oil bath at a temperature of 50℃for 12 hours with a stirrer bar rotation of 350r/min. And after the stirring is finished, standing the obtained uniform slurry to room temperature, then putting the slurry into a vacuum dryer for degassing treatment for 30min, and removing air mixed in the stirring process to obtain the slurry required for preparing the microwave absorbing microspheres.
(2) The slurry is injected into an injector of an electronic spray ball system, the electronic spray voltage is 20kV, the slurry flow rate is 4ml/min, the caliber of a nozzle is 0.8mm, and the height from the nozzle to a coagulating bath is 10cm. The slurry is dispersed into liquid drops in the electronic spraying process, and the liquid drops are immersed in the coagulating bath to form the ceramic microsphere precursor. The precursor is immersed in the coagulating bath for 24 hours, filtered out of the coagulating bath after the phase inversion is sufficiently carried out, and dried in the room temperature environment for 48 hours.
(3) Cutting carbon fiber cloth with a preset knitting structure into a proper size, carrying out surface treatment on the carbon fiber cloth, soaking the carbon fiber cloth with sodium hydroxide solution to remove surface greasy dirt, then acidizing the carbon fiber cloth with nitric acid, carrying out ultrasonic treatment for 20min, increasing the surface roughness of the carbon fiber cloth, and facilitating uniform adhesion of microspheres. And then mixing 2.5 parts of microsphere precursors with a proper amount of deionized water, stirring by ultrasonic waves to form stable suspension, immersing in the suspension, and continuing ultrasonic waves for 20min to fully impregnate the solution into the fiber cloth structure. And then taking out the immersed fiber, placing the immersed fiber in an oven, drying and taking out the immersed fiber.
(4) The impregnated fibers are arranged in a corundum crucible and sintered in two stages in a muffle furnace under nitrogen atmosphere. The sintering temperature in the first stage is 600 ℃, the sintering time is 10min, the sintering time in the second stage is 1200 ℃, the sintering time is 2h, and the temperature rising speed is 5 ℃/min. In the sintering process, the organic matters are pyrolyzed into carbon materials, ferroferric oxide/carbon composite material microspheres are generated on the surface of the fiber cloth in situ, and after the sintering is completed, the fiber-ferroferric oxide/carbon microsphere composite material can be obtained after the temperature is reduced to room temperature.
(5) 2.5 parts of microsphere precursor is placed in a crucible for sintering, the sintering step is the same as that of (4), ferroferric oxide/carbon composite material microspheres are obtained, 95 parts of 108 silicon rubber and 100 parts of gasoline are poured into a stirring tank, 2.5 parts of ferroferric oxide/carbon composite material microspheres are gradually added during the period of time, and uniformly mixed, and then uniform stealth wave-absorbing coating is obtained.
(6) After the surface of a substrate is cleaned, a layer of KH550 is thinly coated, 4 parts of curing agent is added into the uniformly mixed wave-absorbing coating and uniformly stirred, the coating is uniformly sprayed on the surface of the substrate, the fiber-ferroferric oxide/carbon microsphere composite material is paved on the surface of the coating, the curing is carried out for 40 hours, and after the silicon rubber is completely crosslinked, the organic solvent is completely volatilized, so that the composite stealth coating is obtained on the surface of the substrate.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the composite stealth coating resistant to severe environment is characterized by comprising the following steps:
s1, adding ferroferric oxide powder into an organic solvent, and uniformly dispersing to form uniform and stable suspension; adding a polymer, heating and stirring uniformly, cooling to room temperature, and degassing to obtain slurry required by preparing the ferroferric oxide/carbon composite microspheres;
s2, dispersing the slurry into liquid drops through electrospray, and immersing the liquid drops into a coagulation bath to form microsphere precursors; soaking the precursor in a coagulating bath, filtering out from the coagulating bath after the phase inversion is fully performed, and drying to obtain a microsphere precursor;
s3, dispersing the microsphere precursor in a non-organic solvent uniformly to form uniform and stable suspension; arranging carbon fibers in the suspension, fully soaking, taking out, drying and sintering to obtain a fiber-ferroferric oxide/carbon microsphere composite material;
s4, sintering the microsphere precursor to obtain the ferroferric oxide/carbon composite microsphere; adding the ferroferric oxide/carbon composite material microspheres into a mixed solution of an organic film forming agent and a diluent, and uniformly stirring to obtain a stealth wave-absorbing coating;
s5, sequentially coating a layer of mixed solution of an adhesive, a stealth wave-absorbing coating and a curing agent on a substrate, spreading the fiber-ferroferric oxide/carbon microsphere composite material on the surface of the coating, and curing to obtain a composite stealth coating on the surface of the substrate.
2. The method for preparing the composite stealth coating resistant to severe environments according to claim 1, wherein the composite stealth coating comprises, in parts by weight:
3. the method for preparing the composite stealth coating resistant to severe environments according to claim 1, wherein the method comprises the following steps:
the organic film forming agent is organic silicon rubber;
the curing agent is bis-2, 4-dichlorobenzoyl peroxide;
the ferroferric oxide powder is powder, and the particle size is 25-75nm;
the diluent is 120# gasoline;
the organic solvent is N-methyl pyrrolidone;
the polymer is polyethersulfone or cellulose acetate;
the non-organic solvent is water;
the binder is a silane coupling agent.
4. The method for preparing the composite stealth coating resistant to severe environments according to claim 1, wherein in S1:
the dispersion is ultrasonic dispersion, and the dispersion time is 10-30min;
the heating and stirring are oil bath heating mechanical stirring, the stirring time is 6-18h, and the stirring rotating speed is 300-400r/min;
the degassing is vacuum degassing treatment, and the degassing time is 20-40min.
5. The method for preparing the composite stealth coating resistant to severe environments according to claim 1, wherein in S2:
the electronic injection is specifically as follows: injecting the slurry into an injector of an electronic injection ball making system, dispersing the slurry into liquid drops in the electronic injection process, and immersing the liquid drops into a coagulation bath to form microsphere precursors; the electric spraying voltage is 15-25kV, the slurry flow speed is 2-4ml/min, the caliber of an electric spraying nozzle is 0.5-1mm, and the distance between the electric spraying nozzle and the coagulating bath is 8-12cm;
the dipping time of the precursor in the coagulating bath is 12-36h;
the drying is room temperature drying, and the drying time is 24-72h.
6. The method for preparing the composite stealth coating resistant to severe environments according to claim 1, wherein in S3:
the carbon fiber cloth is treated by removing oil stains on the surface and increasing the surface roughness;
the dispersion is ultrasonic dispersion, and the dispersion time is 10-30min;
the microsphere precursor is sintered specifically as follows: arranging fully impregnated carbon fibers in a crucible, and sintering in a muffle furnace in two stages, wherein the sintering atmosphere is inert atmosphere, the sintering temperature in the first stage is 500-700 ℃, the sintering time in the second stage is 8-12h, the sintering time in the third stage is 1000-1400 ℃, the sintering time in the fourth stage is 1-3h, and the temperature rising and falling speed is 3-6 ℃/min.
7. The method for preparing a composite stealth coating resistant to harsh environments according to claim 1, wherein in S4, the microsphere precursor sintering step is identical to the sintering step in S3.
8. A method of preparing a composite stealth coating resistant to harsh environments according to claim 1, wherein in S5, the curing time is 30-50h.
9. A composite stealth coating resistant to harsh environments obtainable by the method of any one of claims 1 to 8.
10. Use of a composite stealth coating resistant to harsh environments according to claim 9, wherein the composite stealth coating is applied in acid and/or alkali and/or salt corrosive environments.
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