CN109678476B - Fiber-reinforced ceramic-based wave-transmitting material with FSS and preparation method thereof - Google Patents

Fiber-reinforced ceramic-based wave-transmitting material with FSS and preparation method thereof Download PDF

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CN109678476B
CN109678476B CN201811477220.8A CN201811477220A CN109678476B CN 109678476 B CN109678476 B CN 109678476B CN 201811477220 A CN201811477220 A CN 201811477220A CN 109678476 B CN109678476 B CN 109678476B
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fss
water
soluble film
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wave
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张剑
崔凤单
于长清
吕毅
张天翔
赵英民
裴雨辰
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

The invention provides a fiber reinforced ceramic matrix wave-transmitting material with FSS and a preparation method thereof. The invention realizes the preparation of a single-layer or multi-layer FSS structure in the fiber-reinforced silica-based ceramic material, the FSS structure is stable, the FSS structure has good environmental adaptability under the protection of the fiber-reinforced silica-based ceramic material, the application field is wider, and the invention is beneficial to the engineering application of the technology.

Description

Fiber-reinforced ceramic-based wave-transmitting material with FSS and preparation method thereof
Technical Field
The invention relates to a fiber reinforced ceramic matrix wave-transmitting material with FSS and a preparation method thereof, belonging to the technical field of wave-transmitting composite material preparation.
Background
The wave-transmitting members such as the antenna cover, the antenna window and the like are important components of the main structure of the aircraft, and also are important components of the antenna and the communication system, so that the antenna system can be protected from being influenced by a severe pneumatic environment caused by high-speed flight and can normally transmit signals, and the wave-transmitting member is a part integrating multiple functions of wave transmission, heat prevention, bearing, corrosion resistance and the like. In recent years, the requirements of antenna systems on performance such as omnidirectional wave transmission, broadband wave transmission, frequency-selective wave transmission, stealth and the like are continuously improved, the electrical performance requirements of wave-transmitting members are difficult to meet by simple half-wave wall structures or sandwich structures, and the high performance of the members needs to be realized by more complex electrical structure design.
The Frequency Selective Surface (FSS) is a single-screen or multi-screen periodic array structure composed of a large number of resonance units and is composed of periodically arranged metal patch units or periodically arranged aperture units on a metal screen. Such surfaces may exhibit total reflection (patch type) or full transmission characteristics (aperture type) near the resonant frequency of the cell, referred to as band stop or band pass FSS, respectively. The FSS can adjust the passband of electromagnetic waves, and is expected to enable the radome (window) to realize functions of omnidirectional wave transmission, broadband wave transmission, frequency-selecting wave transmission, stealth and the like. The FSS wave-transmitting material is a wave-transmitting material containing an FSS structure, can improve or change the electromagnetic performance of an antenna, greatly improves the electromagnetic performance of the existing wave-transmitting members such as an antenna cover, an antenna window and the like, is expected to bring great changes to the field of wave-transmitting materials, and has wide application prospects in the field of dual-purpose multifunctional wave-transmitting members for military and civilian use.
At present, research on various FSS materials for electromagnetic windows is vigorously carried out in the fields of aerospace and aviation, and stealth antenna covers partially developed by adopting the FSS materials are also applied to engineering. With chinese patents 201510222218.6 and 201610846579.2 as typical processes, FSS reported in the prior art usually uses metal copper, silver, aluminum, etc. as a resonant structure layer, a resonant structure is prepared on a flexible film such as polyimide, etc. through a photolithography coating process, and then an FSS wave-transmitting material is prepared through integrated molding of the flexible film and a composite material, which is limited by a resin film and a base material, and the FSS wave-transmitting material does not have the capability of withstanding temperatures above 600 ℃. With the development of the technology, high-speed flight, accurate striking and stealth penetration have become the basic requirements of a new generation of flight weapons. The increasingly fast cruising speed brings a harsh pneumatic environment, the long-term service temperature of the radome (window) is over 600 ℃, the application requirements of the ceramic-based wave-transmitting material are increasing, and more requirements point to the ceramic-based FSS wave-transmitting material with higher temperature resistance.
Chinese patent 20140551086.7 proposes a high temperature resistant FSS wave-transparent material and a preparation method thereof. According to the patent, a porous silicon nitride ceramic material is used as a base material, high-temperature-resistant conductive ceramic or high-temperature-resistant metal is used as an FSS material, a high-temperature-resistant resonant structure is directly prepared on the surface of the ceramic base body by adopting a magnetron sputtering coating and laser etching process or a screen printing process, and then the single-layer material with the FSS structure is compounded into a high-temperature-resistant broadband wave-transmitting material with a multi-layer FSS structure through an inorganic adhesive. However, this technique has the following significant disadvantages: 1) the porous silicon nitride ceramic material used as the matrix has poor thermal shock resistance, large brittleness and poor use reliability, and is difficult to meet the use requirements of the high-state aircraft radome; 2) the high-temperature oxidation resistance of the conductive ceramic and the high-temperature-resistant metal is poor, and the problem of conductivity reduction due to oxidation occurs when the conductive ceramic and the high-temperature-resistant metal are used in a high-temperature oxygen-enriched environment, so that the performance of the FSS is influenced; 3) the technical scheme disclosed by the literature does not treat the surface of the porous silicon nitride substrate, the porous substrate can cause capillary diffusion of conductive ceramic or metal slurry, and the precision and the electrical property of the periodic pattern cannot be effectively ensured.
Chinese patent 201610837457.7 also proposes a high temperature resistant frequency selective wave-transparent structure and a method for making the same. According to the FSS structure layer, a fiber-reinforced ceramic-based wave-transparent composite material is used as a base material, a plasma spraying process is firstly adopted to prepare a modified bonding layer on the surface of the base material, and then a precious metal physical coating or a precious metal slurry coating on the modified bonding layer is subjected to laser processing to obtain the FSS structure layer. The technology has the following defects: 1) the preparation process is complicated, firstly, a modification bonding layer is prepared through a plurality of processes such as sand blasting, plasma spraying, polishing and the like, and an FSS structure layer is also prepared through a laser processing process; 2) a new substance except the base material and the metal, namely a modified bonding layer substance is introduced, so that the complexity of the design of an electric structure is increased; 3) the preparation process of the FSS structure depends on the technologies of equal particle spraying, magnetron sputtering, laser processing and the like, the dependence degree on equipment is high, and the cost is high; 4) the FSS structure can be prepared only on the surface of the composite material, and is poor in maintenance performance and environmental adaptability and not beneficial to engineering application of the technology.
In addition, the document tries to prepare single-layer and multi-layer ceramic-based FSS wave-transmitting materials based on doped quartz ceramic materials based on a high-temperature co-fired ceramic technology, but the scheme has the outstanding problems that the glue discharging and sintering processes of the tape-casting ceramic chip are difficult to control, the base material is easy to crack and warp in the preparation process, and the reliability is poor.
In the preparation of the wave-transmitting member with a complex structure, the resin-based wave-transmitting material member can conveniently realize the integration of pre-embedded functional components and a multi-layer functional structure by a flexible prepreg hand-pasting process. In the aspect of ceramic matrix composites, however, phosphate-based composites and alumina (mullite) -based composites which can adopt a prepreg hand-lay-up process have good manufacturability but unstable high and low temperature dielectric properties, and the dielectric loss of the composite is obviously changed at 500 ℃ and above 650 ℃ respectively, so that the high temperature application of the composite is limited; the generally poor adhesion of silicon dioxide and nitride matrixes determines that almost all silicon dioxide and nitride-based composite materials need to be prepared into composite materials and components thereof by selecting 2.5D and 3D integrally woven fabrics or sewing and needling fabrics which improve the interlayer strength of cloth layers by using fibers as reinforcements.
If the existing sol-gel process is adopted to prepare the fiber-reinforced silica-based wave-transmitting composite material meeting the prepreg hand-lay process, the interlayer strength only depends on the weak bonding effect of the silica matrix, the material is easy to generate delamination instability, and the product strength is difficult to meet the requirements of the radome.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a frequency-selective fiber reinforced ceramic-based wave-transmitting material which has a stable FSS structure, a simple preparation process and high interlayer strength and can meet the requirement of a prepreg hand-pasting process and a preparation method thereof.
The technical solution of the invention is as follows: a preparation method of a fiber reinforced ceramic-based wave-transmitting material with FSS is realized by the following steps:
the first step, raw material preparation,
the raw materials comprise interlayer reinforcing slurry, silicon dioxide sol, a wave-transmitting fiber fabric and a water-soluble film with an FSS structure, wherein the interlayer reinforcing slurry is formed by mixing an organic solvent, a thickening agent and interlayer reinforcing powder, the interlayer reinforcing powder is formed by uniformly mixing glass powder and gas-phase silicon dioxide, the addition amount of the gas-phase silicon dioxide accounts for 70-90% of the total mass of the interlayer reinforcing powder, and the wave-transmitting fiber fabric is a 2D or 2.5D thin-layer wave-transmitting fiber fabric;
the glass powder is alkali-free and lead-free glass powder with sintering temperature lower than high-temperature heat treatment temperature in silica sol molding, and can be purchased in the market or synthesized by self.
The thickness of the single layer of the wave-transparent fiber fabric of the 2D or 2.5D thin layer is not more than 0.5 mm.
The addition amount of the interlayer reinforcing powder in the interlayer reinforcing slurry accounts for 70-90% of the total mass of the interlayer reinforcing slurry.
The water-soluble film with the FSS structure is formed by printing FSS periodic units on the water-soluble film by using precious metal slurry through various printing technologies.
In the second step, a single-layer prepreg is prepared,
soaking the single-layer wave-transmitting fiber fabric in silica sol, and airing to obtain a single-layer prepreg;
the third step, preparing a combined green body,
a3.1, brushing interlaminar reinforcing slurry on the surface of the single-layer prepreg prepared in the second step;
a3.2, airing the single-layer prepreg coated with the interlayer reinforcing slurry;
a3.3, removing the green body layer and the water-soluble film,
laying an air-dried single-layer prepreg compounded with interlayer reinforcing slurry and a water-soluble film with an FSS structure together according to the design requirements of a combined blank, if the water-soluble film is a cold-soluble film, repeatedly coating silica sol on the surface of the single-layer prepreg when laying the prepreg on the upper layer of the water-soluble film with the FSS structure, so that the laid prepreg is more compliant, bubbles and wrinkles are removed, and on the other hand, glue solution permeates into an impregnated blank, the water-soluble film is removed, an FSS periodic unit is left after the water-soluble film is dissolved, and then the prepreg is fixed; if the water-soluble film is a hot-melt film, laying the single-layer prepreg and the water-soluble film with the FSS structure together for fixing, and then immersing the single-layer prepreg and the water-soluble film in hot water to dissolve the water-soluble film;
fourthly, the combined blank is shaped,
dipping the combined blank obtained in the third step into the silica sol prepared in the first step, and obtaining a shaped combined blank after gelling and drying;
fifthly, carrying out high-temperature heat treatment on the shaped combined blank to obtain a low-density composite material;
and (4) carrying out high-temperature heat treatment on the combined blank shaped in the fourth step, and completing sintering of the interlayer reinforcing slurry and the noble metal electronic slurry while completing the heat treatment of the silica sol.
And sixthly, densifying the low-density composite material to obtain the fiber reinforced ceramic matrix wave-transmitting composite material.
A fiber reinforced ceramic-based wave-transmitting material with FSS is reinforced by a plurality of fiber layers, an FSS structure is arranged among the fiber layers, and the fiber layers are distributed in a silicon dioxide matrix in parallel.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention realizes the preparation of a single-layer or multi-layer FSS structure in the fiber-reinforced silica-based ceramic material, the FSS structure is stable, the FSS structure has good environmental adaptability under the protection of the fiber-reinforced silica-based ceramic material, the application field is wider, and the invention is beneficial to the engineering application of the technology;
(2) the FSS structure and the silica dipping-gelling process are integrally formed, and compared with direct gluing, the FSS structure is more stable and reliable, the reliability of the FSS structure in the application process under a high-temperature oxygen-enriched environment is ensured, the FSS structure can endure the high temperature of 800 ℃ at most for long-term use under the aerobic environment, and the electromagnetic tuning function of the FSS is exerted;
(3) according to the invention, the interlayer strength of the 2D fiber-reinforced silica-based composite material is greatly improved by bonding the interlayer reinforcing slurry, so that the fiber-reinforced silica-based wave-transmitting composite material can adopt a prepreg hand-lay process, the addition of an FSS structure is facilitated, and the application range of the material is expanded;
(4) the additive component introduced into the composite material is low in content and only exists between layers, and the influence on the comprehensive performance of the composite material is minimum relative to the additive or the modified component dispersed in the matrix;
(5) the additive introduced into the composite material has low sintering temperature, no alkaline gas escapes, the strength of the reinforced fiber is not influenced, and the composite material has good mechanical property and high use reliability;
(6) the preparation method has the advantages of simple process, low requirement on equipment, and good practicability, and is suitable for popularization and application in scientific research and production.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention;
FIG. 2 is a block diagram of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples and accompanying drawings.
The invention provides a preparation method of a fiber reinforced ceramic-based wave-transmitting material with frequency selectivity, which is realized by the following steps as shown in figure 1:
1. raw material preparation
The raw materials comprise interlayer reinforcing slurry, silica sol, wave-transmitting fiber fabric and a water-soluble film with an FSS structure.
The interlayer reinforcing slurry is formed by mixing an organic solvent, a thickening agent and interlayer reinforcing powder, the interlayer reinforcing powder is formed by uniformly mixing glass powder and gas-phase silicon dioxide, the addition amount of the gas-phase silicon dioxide accounts for 70-90% of the total mass of the interlayer reinforcing powder, and the balance is the glass powder. The glass powder is alkali-free lead-free glass powder with sintering temperature lower than high-temperature heat treatment temperature in silica sol molding, and can be purchased from market or synthesized by self (for example, the glass powder comprises the following components in percentage by mass: B)2O3：30-35wt％；BiO2：30-35wt％；Al2O3：10-15wt％；SiO2：20-25wt％)。
The interlaminar reinforcing powder is formed by uniformly mixing glass powder and fumed silica, and the addition amount of the fumed silica accounts for 70-90% of the total mass of the interlaminar reinforcing powder.
According to the invention, the interlaminar strength of the silicon dioxide matrix is increased by adopting the interlaminar reinforcing powder, the glass powder is used as a reinforcing component, the fumed silica is used as a medium, and the matrix is silicon dioxide, so that the interlaminar reinforcing slurry is used as the reinforcing medium, the influence of the interlaminar reinforcing slurry on the material composition and purity of the composite material is minimized, and the stable high-low temperature electrical property of the composite material (the silicon dioxide has stable high-low temperature electrical property) is ensured to the greatest extent. The fumed silica is wrapped by a glass phase (glass powder is melted) in the high-temperature heat treatment process and flows to permeate into the prepreg cloth layer. The glass phase bonds the cloth layers together, and the fumed silica is filled in the glass phase, so that the glass phase is only the interface of the interlayer phase. If the glass powder proportion is too low (the gas-phase silicon dioxide proportion is too high), the influence on the material performance is not obvious, and the interlayer reinforcing effect cannot be achieved; if the glass frit ratio is too high (fumed silica ratio is too low), the dielectric loss increases and the stability in a wide temperature range of a wide frequency range becomes poor; therefore, the addition amount of the fumed silica accounts for 70-90% of the total mass of the interlaminar reinforced powder, and in the range, the interlaminar increasing effect can be ensured, and the influence on the performance is reduced as much as possible. Under the same condition, the interlayer increasing effect is better along with the increase of the glass powder proportion.
The wave-transmitting fiber fabric is a 2D or 2.5D thin layer wave-transmitting fiber fabric. The single-layer thickness of the wave-transmitting fiber fabric with the 2D or 2.5D thin layer is not more than 0.5mm, otherwise, the flexibility and the deformability of the fiber fabric are poor, and the fiber fabric is not suitable for preparing a component with a pre-embedded function and realizing a multi-layer functional structure. The 2D wave-transmitting fiber fabric comprises various 2D fabrics including plain cloth and satin cloth, and the 2.5D thin-layer wave-transmitting fiber fabric is good in flexibility and can be regarded as a 2D fabric. The wave-transmitting fiber fabric can be a wave-transmitting ceramic fiber such as a quartz fiber, an alumina-based fiber or a nitride fiber, and the like, and can be prepared by applying the fiber-reinforced silica-based composite material. The choice of the type of fibers and the structure of the fabric is well known and can be selected by the person skilled in the art according to specific requirements.
Before the wave-transmitting fiber fabric is used, the impregnating compound on the surface of the fabric fiber is generally subjected to pretreatment, the fabric pretreatment is a technology known in the art, and the fabric pretreatment can be selected according to specific requirements, such as removing the impregnating compound on the surface of the fabric by adopting a mode of combining acid washing, high-temperature heat treatment, acetone soaking and boiling.
The silicon dioxide sol can adopt the silicon dioxide sol sold on the market, the solid content is generally 10-30%, the silicon dioxide sol can be prepared by self or the silicon dioxide sol sold on the market is concentrated, the solid content is preferably not higher than 55%, otherwise, the solid content is too high, the stability is poor during dipping, and the manufacturability is influenced.
The organic solvent is used for adjusting the viscosity of the interlaminar reinforcing slurry and making the interlaminar reinforcing slurry relatively stable, for example, one or a mixture of common terpineol and tributyl citrate which are not easy to volatilize at room temperature can be selected, but not limited thereto, as long as the viscosity of the slurry can be ensured not to change too fast in storage and use, and the operation is not affected.
The thickening agent is also used for adjusting the viscosity of the interlayer reinforcing slurry, and if the thickening agent is not used, the absolute value of the viscosity of the organic solvent adjusting slurry is low, so that the coating requirement cannot be met. The kind of the thickener is not limited as long as the above purpose can be achieved and no adverse effect is caused to the interlaminar reinforcing slurry, for example, one or more of the common thickeners such as ethyl cellulose and the like are adopted.
The addition amount of the interlayer reinforcing powder in the interlayer reinforcing slurry accounts for 70-90% of the total mass of the interlayer reinforcing slurry, the viscosity of the interlayer reinforcing slurry meets the brush coating process, and the preferable range is 250-500 Pa.S.
The addition amount of the interlayer reinforcing powder in the interlayer reinforcing slurry theoretically influences the interlayer strength, the more the interlayer reinforcing powder is added, the better the interlayer strength is improved, but the manufacturability is reduced; if the addition amount is too low, the reinforcing effect is not obvious, so the addition amount is generally not less than 70 percent of the total mass of the interlayer reinforcing slurry; if the addition amount is too high, the manufacturability of the interlayer reinforcing slurry is reduced, the viscosity meeting the requirements of the brushing process is difficult to adjust, and the improvement effect of the interlayer strength is less obvious along with the increase of the addition amount, so that the addition amount is generally not higher than 90% of the total mass of the interlayer reinforcing slurry; when the total mass of the interlayer reinforced slurry is changed within the range of 70-90%, other conditions are unchanged, and the interlayer strength is higher along with the increase of the addition amount.
The water-soluble film with the FSS structure is characterized in that the FSS periodic units are printed on the water-soluble film by precious metal slurry through various printing technologies.
Preparation of water-soluble film with FSS structure:
and printing the FSS periodic unit on a water-soluble PVA film and the like by adopting a printed circuit board technology through various printing technologies of noble metal electronic paste, wherein the structural size of the FSS unit is designed according to a required frequency tuning function. Preferably, the water-soluble PVA film is a cold-soluble film, and the noble metal is silver or silver alloy.
The basic idea of the preparation method of the high-temperature-resistant FSS structure wave-transmitting material is to print FSS periodic units on a water-soluble film by adopting a printed circuit board technology through various printing technologies of noble metal slurry, fix a water-soluble film with an FSS structure at a required position by using wave-transmitting fiber cloth through a process similar to prepreg paving to form an impregnation blank, then dissolve the water-soluble film by brushing glue or heating, and finish the densification of the wave-transmitting fiber cloth through repeated impregnation and compounding.
2. Single layer prepreg preparation
And (3) soaking the single-layer wave-transmitting fiber fabric in the silica sol, and airing to obtain the single-layer prepreg.
The wave-transmitting fiber fabric is soaked in the silica sol, the wave-transmitting fiber fabric can be soaked in the silica sol or repeatedly brushed with the silica sol, and other modes in the field can also be adopted to fully soak the wave-transmitting fiber fabric.
3. Preparation of a composite blank
A3.1, brushing interlaminar reinforcing slurry on the surface of the single-layer prepreg prepared in the step 2;
a3.2, airing the single-layer prepreg coated with the interlayer reinforcing slurry at room temperature or in a heating device such as an oven at the temperature of not more than 100 ℃;
a3.3, removing the green body layer and the water-soluble film,
laying an air-dried single-layer prepreg compounded with interlayer reinforcing slurry and a water-soluble film with an FSS structure together according to the design requirements of a combined blank, if the water-soluble film is a cold-soluble film, repeatedly coating silica sol on the surface of the single-layer prepreg when laying the prepreg on the upper layer of the water-soluble film with the FSS structure, so that the laid prepreg is more compliant, bubbles and wrinkles are removed, and on the other hand, glue solution permeates into an impregnated blank, the water-soluble film is removed, an FSS periodic unit is left after the water-soluble film is dissolved, and then the prepreg is fixed; if the water-soluble film is a hot-melt film, laying the single-layer prepreg and the water-soluble film with the FSS structure together for fixing, and then immersing the single-layer prepreg and the water-soluble film in hot water to dissolve the water-soluble film;
the water-soluble film with the FSS structure in the step can be arranged into a single layer or multiple layers, the water-soluble film with the FSS structure is distributed among single-layer prepregs, and the specific stacking is determined according to the requirements of the required design materials. When a multilayer water-soluble film of the FSS structure is used, the water-soluble film is preferably the same, so that the water-soluble film is removed the same and the process is easy to control.
After the prepreg is wound or laid by lamination, the prepreg with the FSS structure is distributed among single-layer prepregs and is compacted in a vacuum bag, and the prepreg is fixed by using impregnated quartz yarns after the vacuum bag is removed.
The thickness of the interlayer reinforcing slurry can be controlled by the brushing area and the solid content of the slurry, and the preferred thickness of the slurry is 30-50 μm.
4. Shaping of combined blank
Dipping the combined blank obtained in the third step into the silica sol prepared in the first step, and obtaining a shaped combined blank after gelling and drying;
the dipping-gelling-drying is a known process for preparing the silica-based composite material by a silica sol method, and the drying only removes the moisture in the gel for the silica matrix, but the invention has a multi-layer structure with an FSS structure, and the gelling-drying is used for shaping a combined blank body, so that the subsequent treatment is convenient, and the drying temperature is not only used for removing the moisture in the gel, but also referred to the silica matrix process.
5. And carrying out high-temperature heat treatment on the shaped combined blank to obtain the low-density composite material.
And (4) carrying out high-temperature heat treatment on the combined blank shaped in the step (4), and finishing the sintering of the slurry while finishing the heat treatment of the silica sol.
The high-temperature heat treatment process is a known process for preparing the silica-based composite material by a silica sol method, and as for a silica matrix, the high-temperature heat treatment process is only a high-temperature drying process for further dehydrating gel, and the high-temperature heat treatment temperature is lower than the melting temperature (sintering temperature) of silica.
However, the temperature curve in the high-temperature heat treatment in the step of the invention is the sintering condition of the interlayer reinforcing slurry and the noble metal sintering type slurry.
The high temperature heat treatment process (sintering of the slurry) is as follows:
the water-soluble film with the FSS structure is formed by printing FSS periodic units on the organic film by using noble metal slurry through various printing technologies, so that the sintering of the enhanced slurry is carried out at the same time as the sintering of the sintered noble metal slurry, namely the highest temperature in the sintering stage is higher than the sintering temperature of the enhanced slurry and the sintering temperature of the noble metal slurry and is lower than the sintering temperature of silicon dioxide.
Preferably, the highest temperature point of the high-temperature heat treatment is 750-800, and the heat preservation time at the highest temperature point is not less than 15 min. The time of the high-temperature heat treatment temperature rising section can refer to the prior art on the principle that the component material can be uniformly and thoroughly heated.
The removal of the quartz yarns can be after this step of high temperature heat treatment, but also after the densification of the composite material is completed.
6. And (3) densifying the low-density composite material to obtain the fiber reinforced ceramic matrix wave-transmitting composite material.
And (5) repeatedly dipping the low-density composite material obtained in the step (5) by adopting silica sol, and realizing densification through a sol-gel process until the low-density composite material reaches the required density.
Densification is a technique known in the art, and a person skilled in the art selects process parameters such as solid content of silica sol, gum dipping, gelation and the like according to needs.
The invention also provides a fiber reinforced ceramic-based wave-transmitting material with FSS as shown in figure 2, which is reinforced by a plurality of fiber layers, wherein an FSS structure is arranged among the fiber layers, and the fiber layers are distributed in parallel in a silicon dioxide matrix.
Example 1
Preparing the flat fiber reinforced ceramic matrix wave-transparent composite material containing the single FSS layer structure.
1. Raw material preparation
Mixing commercially available low-temperature sintered alkali-free lead-free glass powder and fumed silica according to the weight ratio of 10: and (5) uniformly mixing the components according to the mass ratio of 90 to obtain the enhanced powder. The glass powder comprises the following components in percentage by mass: b is2O3：30wt％；BiO2:35wt％；Al2O3:10wt％；SiO225 wt%. Mixing terpineol, ethyl cellulose and the reinforced powder according to the weight ratio of 29:1:70, and grinding to obtain the interlaminar reinforcing slurry with the viscosity of 400-500 Pa.S. And printing FSS periodic units on the cold-soluble PVA film by using the sintered silver paste by adopting a screen printing process, wherein the thickness of the FSS periodic units is 10 mu m, and the unit structure is a circular hole.
2. Single layer prepreg preparation
The reinforced 2D wave-transparent fiber fabric is quartz fiber satin cloth with the thickness of 0.28 mm. And (3) boiling the quartz cloth in acetone for three times, and removing the fabric surface sizing agent. After the last time of boiling, cooling the acetone to room temperature, soaking and washing the fabric in new acetone, and airing the fabric in a fume hood for later use.
The single-layer prepreg is obtained by impregnating 2D fabric with silica sol. First, the 2D fabric was cut according to the size of the desired material and soaked to a density of 1.13g/cm3The prepreg is prepared from the commercial silica sol, and is ventilated and aired for standby, and the fabric needs to be fully soaked.
3. Preparation of a composite blank
Firstly, uniformly coating the interlayer reinforcing slurry on the surface of the single-layer prepreg by using a rubber scraper, and then placing the single-layer prepreg with the reinforcing slurry in an oven for 1 hour at 100 ℃. Taking out the prepreg with the reinforcing slurry, stacking the dried single-layer prepreg compounded with the interlayer reinforcing slurry and the PVA film with the FSS structure on a flat plate according to the design requirement of a combined blank body, paving the PVA film on the prepreg, adhering one surface of the water-soluble film with the FSS structure to the prepreg during paving, paving the prepreg on the PVA film, and repeatedly brushing silica sol on the surface of the prepreg to ensure that the paved prepreg is more proper and remove air bubbles and wrinkles on one hand, and ensure that the glue solution permeates into the impregnated blank body on the other hand, and dissolving the water-soluble film to leave an FSS period unit. After the laying is finished, the vacuum bag is used for pressing, the vacuum bag is removed and is fixed by using the impregnated quartz yarns. The thickness of the interlayer reinforcing slurry can be controlled by the brushing area and the solid content of the slurry, and the thickness of the slurry is about 30 μm.
4. Shaping of combined blank
According to the technological process of dipping composite molding of the silicon dioxide-based composite material, silica sol (which is commercially available and has the density of 1.14 g/cm) is used3) Completing the one-time impregnation-gelation-drying process of the combined blank body to complete the shaping of the combined blank body, wherein the maximum drying temperature is 250 ℃.
5. High temperature heat treatment
And carrying out high-temperature heat treatment on the silver paste in a muffle furnace to finish the sintering of the silver paste and the sintering of the reinforced paste.
The high-temperature heat treatment system comprises: the temperature was raised from room temperature to 400 ℃ over 60min, subsequently to 600 ℃ over 100min, subsequently to 800 ℃ over 100min and again for 30 min.
6. Densification
And after the oven is naturally cooled to room temperature, taking out the blank, and finishing the cycle of impregnation-compounding-sintering of the composite material blank by using high-purity acidic silica sol according to the impregnation compounding and molding process flow of the silicon dioxide-based composite material until densification is finished to obtain the final high-temperature-resistant FSS structure wave-transmitting material.
The method comprises the following specific steps: concentrating the silica sol crude gel by reduced pressure distillation ultrafiltration method, wherein the density of the treated silica sol is 1.40g/cm3. And (3) placing the low-density composite material into a closed pressure container, and after die assembly, ensuring that the container is sealed and airtight. Vacuumizing the closed pressure container until the vacuum degree is lower than 0.095MPa, and pre-treating to obtain the product with the density of 1.40g/cm3Injecting the silica sol into a closed pressure container through vacuum suction and injection, injecting the silica sol for 12 times, injecting 4L of the silica sol each time, wherein the injection rate is 1L/min, and injecting the silica sol for the next time after the injection of the silica sol is finished and then vacuumizing for 30min until the container is filled. And (3) pressurizing the closed pressure container to 3.6MPa, wherein the pressurized gas is nitrogen, and maintaining the pressure for 20 hours. Will be secretClosing the pressure container, putting the pressure container into an oven, heating to 90 ℃, and preserving heat for 48 hours. And demolding after the sealed pressure container is naturally cooled.
Slowly drying the blank piece removed from the pressure container in a constant temperature and humidity box according to a constant temperature and humidity drying system: the temperature is constantly 25 ℃; the relative humidity is 95%, the relative humidity is kept for 48h, then the relative humidity is reduced to 85% in 30min, the relative humidity is kept for 48h, then the relative humidity is reduced to 75% in 30min, the relative humidity is kept for 48h, then the relative humidity is reduced to 65% in 30min, and the relative humidity is kept for 48 h; the humidity was then reduced to 55% over 30min and held for 48 h. Putting the blank after constant temperature and humidity drying into an oven for drying, wherein the oven drying system is as follows: the temperature was raised from room temperature to 50 ℃ over 15min for 1h, then 15min to 70 ℃ for 1h, then 15min to 100 ℃ for 1h, then 25min to 150 ℃ for 1h, then 25min to 200 ℃ for 1h, and finally 25min to 250 ℃ for 1 h. And after the oven is naturally cooled to room temperature, taking out the blank to carry out ceramic heat treatment, wherein the heat treatment temperature is 800 ℃, the heating rate is 10 ℃/min, and the blank is kept warm for 2h after reaching 800 ℃.
Repeating the above processes for three times to obtain the final product. Wherein the density of the second impregnation of the silica sol was changed to 1.38g/cm3The density of the third dipping silica sol is changed to 1.34g/cm3The density of the fourth dipping silica sol is changed to 1.30g/cm3。
Standard bending test pieces (without FSS unit, bending strength is a comprehensive embodiment of tensile and compressive strength of a material, bending strength of a laminated material can reflect the strength between layers of the material, the strength between layers is low, and the laminated material is easy to delaminate during bending, the same applies below) are processed from the prepared material of the example, and the performance test results are as follows:
density (g/cm)3)：1.64；
Dielectric constant: 3.05;
dielectric loss: 0.006;
flexural Strength (GB/T1449-: 55.7.
example 2
Preparing the curved fiber reinforced ceramic matrix wave-transmitting composite material containing the single-layer FSS layer structure.
1. Mixing commercially available low-temperature sintered alkali-free lead-free glass powder and fumed silica according to the weight ratio of 30: 70, and mixing uniformly to obtain the reinforced powder. The glass powder comprises the following components in percentage by mass: b is2O3：35wt％；BiO2:30wt％；Al2O3:15wt％；SiO220 wt%. And mixing tributyl citrate, ethyl cellulose and the reinforcing powder according to the mass ratio of 9.4:0.6:90, and grinding to obtain the interlayer reinforcing slurry with the viscosity of 250-300 Pa.S. The sintered silver-palladium alloy slurry is printed with FSS periodic units on a cold-soluble PVA film by adopting a printed circuit board technology, the thickness of the FSS periodic units is 30 mu m, and the unit structure is Y-shaped.
The reinforced 2D wave-transparent fiber fabric is made of alumina fiber plain cloth with the thickness of 0.14 mm. And (3) placing the alumina cloth into a muffle furnace for high-temperature heat treatment to remove the fabric surface sizing agent for later use.
2. And (3) preparing a single-layer prepreg.
Cutting the 2D fabric according to the size of the required material, and using the fabric with the density of 1.16g/cm3The silica sol is repeatedly coated on fiber cloth to prepare prepreg, and the prepreg is ventilated and aired for later use. The fabric needs to be fully saturated.
3. The surface of the prepreg is uniformly coated with the interlaminar reinforcing slurry by a rubber scraper, and then the prepreg with the reinforcing slurry is placed in an oven to be treated for 1 hour at 100 ℃. The thickness of the interlayer reinforcing slurry can be controlled by the brushing area and the solid content of the slurry, and the thickness of the slurry is about 40 mu m.
The prepreg was wound onto a cylindrical mold and the PVA film was spread into the desired position. Covering the PVA film by using the prepreg, wherein the surface of the water-soluble film with the FSS structure faces the direction of the core mold, covering the surface by using the prepreg, tightening, and repeatedly brushing silica sol on the surface of the prepreg during paving, so that the paved prepreg layer is more fitted, bubbles and folds are removed, the glue solution permeates into the impregnated blank, and the water-soluble film is dissolved to leave an FSS periodic unit.
4. According to the dipping composite molding process flow of the silicon dioxide-based composite material, the one-time dipping-gel curing-medium temperature drying process of the combined blank body is completed by using high-purity acidic silica sol. The maximum drying temperature is 250 ℃.
5. And carrying out high-temperature heat treatment on the slurry in a muffle furnace, and sintering the slurry. The high-temperature heat treatment system comprises: the temperature was raised from room temperature to 400 ℃ over 60min, subsequently to 600 ℃ over 100min, subsequently to 800 ℃ over 100min and again for 30 min.
6. And after the oven is naturally cooled to room temperature, taking out the blank, and finishing the cycle of impregnation-compounding-sintering of the composite material blank by using high-purity acidic silica sol according to the impregnation compounding and molding process flow of the silicon dioxide-based composite material until the densification of the composite material is finished to obtain the final high-temperature resistant FSS structure wave-transmitting material.
The thickness of the composite material prepared in the example is only 0.5mm, and the performance test results are as follows:
density (g/cm)3)：1.64；
Dielectric constant: 3.05;
dielectric loss: 0.006.
example 3
Preparing the curved fiber reinforced ceramic matrix wave-transmitting composite material containing the double-layer FSS layer structure.
1. The low-temperature sintering alkali-free and lead-free glass powder synthesized by self and gas phase silicon dioxide are mixed according to the proportion of 20: 80 to obtain the reinforced powder. The glass powder comprises the following components in percentage by mass: b is2O3：30wt％；BiO2:35wt％；Al2O3:10wt％；SiO225 wt%. Terpineol, ethyl cellulose and the reinforcing powder are mixed according to the mass ratio of 29:1:70, and the mixture is ground to obtain interlayer reinforcing slurry with the viscosity of 350-450 Pa.S.
The sintered silver paste is printed with FSS periodic units on a thermosol PVA film by adopting a printed circuit board technology, the thickness of the FSS periodic units is 20 mu m, and the unit structure is cross-shaped.
The reinforced 2D wave-transmitting fiber fabric is woven plain cloth of silicon-boron-nitrogen fibers. And (3) boiling the woven fabric in acetone for three times, wherein the size of the fabric surface is removed after 12 hours each time. After the last time of boiling, cooling the acetone to room temperature, soaking and washing the fabric in new acetone, and airing the fabric in a fume hood for later use.
2. Cutting the 2D fabric according to the size of the required material and soaking the fabric to the density of 1.13g/cm3The prepreg is prepared from the commercial silica sol, and is ventilated and aired for standby, and the fabric needs to be fully soaked.
3. The interlayer reinforcing slurry is firstly uniformly coated on the surface of the prepreg by a rubber scraper, and then the prepreg with the reinforcing slurry is placed in an oven to be treated for 1 hour at 100 ℃. The thickness of the interlayer reinforcing slurry can be controlled by the brushing area and the solid content of the slurry, and the thickness of the slurry is about 30 μm.
The prepreg was wound onto a cylindrical mold and the PVA film was spread into the desired position. And covering the PVA film with a prepreg, tightening, fixing the PVA film on a cylindrical die in a winding mode by using gum dipping quartz fiber yarns, and facing the core die direction of one surface of the water-soluble film with the FSS structure during paving. And immersing the impregnated blank body into high-purity water, heating to 70 ℃, keeping the temperature for 3 hours, taking out, repeating twice, and dissolving out the PVA film to leave an FSS periodic unit.
4. According to the dipping composite molding process flow of the silicon dioxide-based composite material, the one-time dipping-gel curing-medium temperature drying process of the combined blank body is completed by using high-purity acidic silica sol. The maximum drying temperature is 250 ℃.
5. And carrying out high-temperature heat treatment on the slurry in a muffle furnace, and sintering the slurry. The high-temperature heat treatment system comprises: the temperature was raised from room temperature to 400 ℃ over 60min, subsequently to 600 ℃ over 100min, subsequently to 800 ℃ over 100min and again for 30 min.
6. And after the oven is naturally cooled to room temperature, taking out the blank, and finishing the cycle of impregnation-compounding-sintering of the composite material blank by using high-purity acidic silica sol according to the impregnation compounding and molding process flow of the silicon dioxide-based composite material until the densification of the composite material is finished to obtain the final high-temperature resistant FSS structure wave-transmitting material.
The example was prepared as a standard bend test piece with the following performance test results:
density (g/cm)3)：1.72；
Dielectric constant: 3.5;
dielectric loss: 0.008;
flexural Strength (GB/T1449-: 43.5.
example 4
The wave-transparent fiber fabric is a 2.5D thin layer with the thickness of 0.45mm, and the rest of the example is the same as the example 1, the example is prepared into a standard bending test piece, and the performance test results are as follows:
density (g/cm)3)：1.61；
Dielectric constant: 2.95;
dielectric loss: 0.005;
flexural Strength (GB/T1449-: 49.3.
examples 5 and 6
The proportion of the reinforcing powder was 80% and 90% of the proportion of the interlaminar reinforcing slurry, respectively, and the properties of the composite material obtained in example 1 were similar to those of example 1 in terms of density, dielectric constant, dielectric loss and the like, and the flexural strength (interlaminar strength) was improved as the proportion of the reinforcing powder was increased.
Examples 7 and 8
The glass powder content in the reinforced powder is 20% and 30%, respectively, and the performance of the obtained composite material is similar to that of the composite material in the example 1 in comparison with the performance of the composite material in the example 1 in terms of density, dielectric constant, dielectric loss and the like, and the bending strength (interlayer strength) is improved along with the increase of the glass powder content.
The invention has not been described in detail and is in part known to those of skill in the art.

Claims (8)

1. A preparation method of a fiber reinforced ceramic-based wave-transmitting material with FSS is characterized by comprising the following steps:
the first step, raw material preparation,
the raw materials comprise interlayer reinforcing slurry, silica sol, a wave-transmitting fiber fabric and a water-soluble film with an FSS structure, wherein the interlayer reinforcing slurry is formed by mixing an organic solvent, a thickening agent and interlayer reinforcing powder, the interlayer reinforcing powder is formed by uniformly mixing glass powder and gas-phase silica, the addition amount of the gas-phase silica accounts for 70-90% of the total mass of the interlayer reinforcing powder, and the addition amount of the interlayer reinforcing powder accounts for 70-90% of the total mass of the interlayer reinforcing slurry;
in the second step, a single-layer prepreg is prepared,
soaking the single-layer wave-transmitting fiber fabric in silica sol, and airing to obtain a single-layer prepreg;
the third step, preparing a combined green body,
a3.1, brushing interlaminar reinforcing slurry on the surface of the single-layer prepreg prepared in the second step;
a3.2, airing the single-layer prepreg coated with the interlayer reinforcing slurry;
a3.3, laying the dried single-layer prepreg compounded with the interlayer reinforcing slurry and the water-soluble film with the FSS structure together according to the design requirement of the combined blank body, and removing the water-soluble film, wherein the water-soluble film with the FSS structure is formed by printing FSS periodic units on the water-soluble film by using precious metal slurry through a printing technology;
fourthly, the combined blank is shaped,
dipping the combined blank obtained in the third step into the silica sol prepared in the first step, and obtaining a shaped combined blank after gelling and drying;
fifthly, performing high-temperature heat treatment on the shaped combined blank to finish sintering of the interlayer reinforcing slurry and the precious metal slurry with the FSS structure to obtain a low-density composite material, wherein the highest temperature of the high-temperature heat treatment is higher than the higher value of the sintering temperature of the reinforcing slurry and the sintering temperature of the precious metal slurry and lower than the sintering temperature of silicon dioxide;
and sixthly, densifying the low-density composite material to obtain the fiber reinforced ceramic matrix wave-transmitting composite material.
2. The method of claim 1, wherein the FSS-containing fiber reinforced ceramic based wave transparent material is prepared by: the wave-transmitting fiber fabric in the first step is a 2D or 2.5D thin layer wave-transmitting fiber fabric; the glass powder is alkali-free and lead-free glass powder with sintering temperature lower than the high-temperature heat treatment temperature in silica sol molding; the thickness of the single layer of the wave-transparent fiber fabric of the 2D or 2.5D thin layer is not more than 0.5 mm.
3. The method of claim 1, wherein the FSS-containing fiber reinforced ceramic based wave transparent material is prepared by: the thickness of the interlayer reinforcing slurry in the step A3.1 is 30-50 μm.
4. The method of claim 1, wherein the FSS-containing fiber reinforced ceramic based wave transparent material is prepared by: in the step a3.3, if the water-soluble film is a cold-soluble film, when a prepreg with an FSS structure on the upper layer of the water-soluble film is laid, silica sol is repeatedly coated on the surface of the single-layer prepreg, the water-soluble film is dissolved away to leave FSS periodic units, and then the prepreg is fixed.
5. The method of claim 1, wherein the FSS-containing fiber reinforced ceramic based wave transparent material is prepared by: in the step A3.3, if the water-soluble film is a hot-melt film, the single-layer prepreg and the water-soluble film with the FSS structure are laid together and fixed, and then the single-layer prepreg and the water-soluble film are immersed in hot water to dissolve the water-soluble film.
6. The method for preparing a fiber reinforced ceramic based wave transparent material with FSS according to claim 4 or 5, wherein: the water-soluble film with the FSS structure in the step A3.3 can be arranged in a single layer or multiple layers, the water-soluble film with the FSS structure is distributed among single-layer prepregs, specific stacking is determined according to the requirement of required design materials, and if multiple layers of water-soluble films with the FSS structure are adopted, the types of the water-soluble films are the same.
7. A fiber reinforced ceramic based wave transparent material with FSS prepared according to the method of any of claims 1 to 5, wherein: the silica fiber reinforced composite material is reinforced by a plurality of fiber layers, at least one layer of FSS structure is arranged among the fiber layers, and the fiber layers are distributed in parallel in a silica matrix.
8. A fiber reinforced ceramic based wave transmitting material with FSS according to claim 7, wherein: the water-soluble film with the FSS structure can be arranged in a single layer or multiple layers, the water-soluble film with the FSS structure is distributed among single-layer prepregs, specific stacking is determined according to the requirements of required design materials, and if the water-soluble film with the multiple FSS structures is adopted, the water-soluble films are the same in type.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446584A (en) * 2014-11-03 2015-03-25 湖北三江航天江北机械工程有限公司 Moulding method of variable-density broadband wave-transparent quartz composite ceramic antenna housing body
CN104446580A (en) * 2014-12-16 2015-03-25 中国人民解放军国防科学技术大学 Method for preparing continuous fiber cloth reinforced silica ceramic-based composite material
CN105254320A (en) * 2015-11-13 2016-01-20 中航复合材料有限责任公司 Preparation method of continuous oxide fiber reinforced oxide ceramic based composite
CN108840694A (en) * 2018-08-02 2018-11-20 西北工业大学 A kind of wave transparent type Si3N4f/Si3N4The preparation method of composite material surface coating
CN108911776A (en) * 2018-06-28 2018-11-30 航天特种材料及工艺技术研究所 A kind of surface antiscour flexibility heat-insulation composite material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104446584A (en) * 2014-11-03 2015-03-25 湖北三江航天江北机械工程有限公司 Moulding method of variable-density broadband wave-transparent quartz composite ceramic antenna housing body
CN104446580A (en) * 2014-12-16 2015-03-25 中国人民解放军国防科学技术大学 Method for preparing continuous fiber cloth reinforced silica ceramic-based composite material
CN105254320A (en) * 2015-11-13 2016-01-20 中航复合材料有限责任公司 Preparation method of continuous oxide fiber reinforced oxide ceramic based composite
CN108911776A (en) * 2018-06-28 2018-11-30 航天特种材料及工艺技术研究所 A kind of surface antiscour flexibility heat-insulation composite material and preparation method thereof
CN108840694A (en) * 2018-08-02 2018-11-20 西北工业大学 A kind of wave transparent type Si3N4f/Si3N4The preparation method of composite material surface coating

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
2.5D衍生结构SiO2f/SiO2复合材料的经向力学性能;张剑等;《宇航材料工艺》;20150815;全文 *

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