CN108191416A - BN is modified SiO2Composite material and preparation method thereof - Google Patents

BN is modified SiO2Composite material and preparation method thereof Download PDF

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CN108191416A
CN108191416A CN201810004550.9A CN201810004550A CN108191416A CN 108191416 A CN108191416 A CN 108191416A CN 201810004550 A CN201810004550 A CN 201810004550A CN 108191416 A CN108191416 A CN 108191416A
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sio
composite material
precast body
temperature
coating modified
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吴宝林
侯振华
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Jiangxi Jiajie Xinda New Mstar Technology Ltd
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Jiangxi Jiajie Xinda New Mstar Technology Ltd
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Abstract

The present invention relates to a kind of radome and antenna windows SiO coating modified BN2f/SiO2Composite material and preparation method thereof, described method includes following steps：Surface preparation, BN coating precursors are prepared, BN coatings impregnate, the heat treatment of BN coatings, precast body dipping, precast body is sintered, density measuring and calculating and material are polished.Preparation process of the present invention is simple, and the period is short, and density of material is up to 1.8g/cm3, bending strength is up to 120MPa, and dielectric constant≤3, dielectric loss is not more than 0.02 under 2GPa~18GPa frequencies, can be in 800 DEG C of high temperature continuous firing 10min, and instantaneous operative temperature can reach 1200 DEG C.Anti-moisture absorption ability is good, solves existing SiO2f/SiO2The problem of easy crystallization of composite material, densification degree are low, mechanical strength cannot meet requirement improves the density and mechanical property of material.

Description

BN is modified SiO2Composite material and preparation method thereof
Technical field
The invention belongs to materials processing technology fields, and in particular to a kind of radome and antenna windows are coating modified with BN SiO2f/SiO2Composite material and preparation method thereof.
Background technology
Antenna house is an important component of homing guided missile front end.It is that antenna system is protected not flown at a high speed Severe Airflow Environment caused by row influences, is normally carried out the barrier of signal transmission work, be a kind of collection wave transparent, solar heat protection, carrying and The multi-functional component in one such as against corrosion.With the development of aeronautical and space technology, the flight speed of current all kinds of advanced tactical missiles The reentry velocity of guided missile has reached 8Ma~12Ma to degree mostly in more than 4Ma, ground ground, even higher so that missile-borne radome faces Increasingly acid test.
The radome material of early stage is the monoblock type or sandwich using fiberglass reinforced plastics, but plastics is resistance to Hot property is poor, and free carbon is cracked under high temperature, it is impossible to meet high-speed missile solar heat protection and wave transparent requirement.In contrast, ceramic material Heat-resist, intensity is high, has suitable dielectric properties, is increasingly becoming the first choice of Hypersonic Missile Radomes.
Quartz fibre is from the 1930s applied to spacecraft and military aircraft.Its transmission to radar frequency Property is good, its dielectric constant is held essentially constant in 100MHz~100GHz, and the variation of dielectric loss angle tangent is also very small, only 0.00045 is changed to from 0.0002, and dielectric properties vary with temperature smaller, are optimal wideband wave transparent reinforcing materials.
The Place and Bridges in United States advanced Materials laboratory have developed the high purity quartz fabric enhancing of 4D omnidirectionals SiO2f/SiO2Composite A DL-4D6, the SiO after firing2The matrix porous structure higher for activity, global density 1.6g/ cm3, dielectric constant 2.8-3.1, the tangent value of dielectric loss angle is 0.006 (250MHz), and minimum bending strength reaches 34.5MPa, breaking strain 1.0%, it is considered to be a kind of toughness pottery material.Manocha and Panchal of India etc. pass through Electrophoresis method of impregnation by Ludox repeated impregnations quartz textile and at 600 DEG C sintering be prepared for SiO2f/SiO2Composite material, Density is about 1.6g/cm after 5 impregnation sinterings recycle3, but since fiber/matrix interface cohesion is stronger, and quartz fibre table Very sensitive in face of crackle, the mechanical property of final composite material is poor.The Li Chenghu of the National University of Defense technology passes through urea method work Skill prepares boron nitride (BN) and is prepared for 2.5D SiO with reference to sol-gel technology2f/SiO2- BN composite materials, result of study table It is bright, 2.5D SiO2f/SiO2The density and bending strength of-BN composite materials increase with the increase of urea method technique number；Just Beginning SiO2f/SiO2Composite density is bigger, SiO2f/SiO2The mechanical property of-BN composite materials is better.But to density and The influence of porosity is very limited；With initial SiO2f/SiO2Composite material is compared, the SiO of preparation2f/SiO2- BN composite materials Mechanical property be significantly improved, while its dielectric properties and thermophysical property are also very excellent.The model of Harbin Institute of Technology It is sub- bright with 2D quartz fiber cloths, Ludox, Nano-meter SiO_22Powder and BN powder etc. are raw material, using sol-gal process, are impregnated with reference to slurry Method and hot-pressing sintering technique are prepared for 2D SiO2f/SiO2- BN composite materials.Result of study shows to reach in slurry solid concentration When 40%, composite density can reach 2.068g/cm3, mechanical property also reaches peak；Nano-meter SiO_22The addition of powder can be shown It writes and improves composite materials property, and quartz textile structure grinds silica-base composite material Effect on Mechanical Properties Study carefully composite density to have little effect.The silicon nitride precursor pyrolysismethod such as Qi Gongjin and Zhang Changrui of the National University of Defense technology 2.5D SiO are prepared for reference to Ludox impregnation sintering2f/SiO2–Si3N4Composite material, density is by 1.64g/cm3It increases to 1.79g/cm3, bending strength increases to 95.9MPa, but due to the infiltration of silicon nitride, and precursor pyrolysismethod preparation temperature is too Height, the interface cohesion between fiber and matrix is stronger, and brittle failure feature is presented in composite material.
But to SiO2f/SiO2The history of the research ability decades of material is also many from the preparation angle of material merely Urgent problem to be solved：1st, the crystallization behavior of quartz glass.The crystallization of quartz glass especially quartz fibre, significantly reduces The mechanical property of composite material.2nd, composite material densification behavior.In Ludox method or sol-gel method craft, composite wood Expect that the pickling efficiency in later stage is very low, once and surface crust, density are difficult to be improved again.3rd, reinforcing agent is surface-treated.Stone Strong combine of English fiber and quartz glass substrate causes material that apparent brittle fracture is presented in fracture, does not play quartzy fibre Tie up the effect of activeness and quietness.
Invention content
An object of the present invention is to provide a kind of radome and antenna windows SiO coating modified BN2f/SiO2 The preparation method of composite material.
The radome of the present invention and antenna windows SiO coating modified BN2f/SiO2The preparation method of composite material, Include the following steps：S101：First by SiO2fPrecast body is put into immersion 22h~26h in absolute ethyl alcohol, then places at room temperature 70h~74h is placed into Muffle furnace, 450 DEG C~550 DEG C is warming up under the first heating rate, and keep the temperature 3h~5h, then It is cooled to room temperature；S102：It is 1 by mass ratio：The boric acid and urea of (1.5~2.5) are dissolved in volume ratio as (2~4)：1 second In the mixed solution of alcohol and water, and stir and make it completely dissolved, until solution clear, then adjust the pH value of solution to 5.0~7.0；S103：By the processed SiO of step S1012fPrecast body is put into impregnating autoclave, and injection step S102 obtain it is molten Then liquid vacuumizes simultaneously pressurize 0.3h~0.8h, then be passed through protective gas to 8.104 × 104Pa~1.103 × 105Pa and pressurize 0.3h~0.8h then takes out and dries；S104：By the SiO of step S103 processing2fPrecast body is put into tube furnace, so After be passed through nitrogen and ammonia, then be warming up to 680 DEG C~720 DEG C with the second heating rate and keep the temperature 8h~12h；S105：By described in The SiO of step S104 processing2fPrecast body is put into impregnating autoclave, and injects SiO2Colloidal sol, then vacuumize and pressurize 0.3h~ 0.8h, then protective gas is passed through to 8.104 × 104Pa~1.103 × 105Pa and pressurize 0.3h~0.8h, then take out and do It is dry；S106：By the SiO of step S105 processing2fPrecast body is put into tube furnace, then passes to nitrogen, and heat up with third Rate is warming up to 180 DEG C~220 DEG C and keeps the temperature 0.8h~1.2h, then is warming up to 420 DEG C~480 DEG C with the 4th heating rate and protects Warm 0.8h~1.2h, is subsequently cooled to room temperature；S107：The product obtained with the drainage measuring and calculating step S106, if its density Less than 1.5g/cm3, then the step S105 and the step S106 are repeated in, if its density is not less than 1.5g/cm3, then will It is dried；S108：It is polished with the product that sand paper obtains the step S107, with its surface pore of exposure, then placed it in Ultrasonic vibration 0.3h~0.8h in absolute ethyl alcohol, then be dried, and measure its density；S109：The step S108 is obtained Product be repeated in the step S105 and the step S106, until its density no longer changes, obtain radar antenna Cover and antenna windows SiO coating modified BN2f/SiO2Composite material.
Use demand and current SiO the present invention is based on radar antenna cover material2f/SiO2The Research Challenges of material propose A kind of radome and antenna windows SiO coating modified BN2f/SiO2The preparation method of composite material, preparation process Simply, the period is short, and density of material is up to 1.8g/cm3, bending strength is up to 120MPa.Dielectric constant≤3, in 2GPa~18GPa Dielectric loss is not more than 0.02 under frequency.Can be in 800 DEG C of high temperature continuous firing 10min, and instantaneous operative temperature can reach 1200 ℃.Anti-moisture absorption ability is good, disclosure satisfy that use demand of the middle high Mach aircraft to radome.Solves existing SiO2f/ SiO2The problem of easy crystallization of composite material, densification degree are low, mechanical strength cannot meet requirement is situated between not influencing material The density and its mechanical property of material are improved under the premise of electrical property.
In addition, radome according to the above embodiment of the present invention and antenna windows SiO coating modified BN2f/SiO2 The preparation method of composite material can also have following additional technical characteristic：
Further, the first heating rate is 450 DEG C/h~550 DEG C/h.
Further, in the step S103, drying temperature is 70 DEG C~90 DEG C, and drying time is 3h~5h；Institute It states in step S105, drying temperature is 70 DEG C~90 DEG C, and drying time is 3h~5h；In the step S107, drying temperature It it is 70 DEG C~90 DEG C, drying time is 3h~5h；In the step S108, drying temperature is 70 DEG C~90 DEG C, drying time For 3h~5h.
Further, in the step S104, second heating rate is 8 DEG C/min~12 DEG C/min.
Further, in the step S104, the flow velocity of nitrogen is 300mL/min~500mL/min, the flow velocity of ammonia For 100mL/min~200mL/min.
Further, in the step S106, the third heating rate be 180 DEG C/h~220 DEG C/h, the described 4th Heating rate is 200 DEG C/h~300 DEG C/h.
Further, the SiO2fPrecast body includes at least 2D SiO2fPrecast body, 2.5D SiO2fPrecast body and 3D SiO2fOne kind in precast body.
Further, in the step S105, the SiO2The grain size of colloidal sol is 10 μm~15 μm.
Further, in the step S108, the grain size number of the sand paper is the mesh of 100 mesh~150.
Another object of the present invention is to propose to be applied with BN using the radome and antenna windows of the method preparation The modified SiO of layer2f/SiO2Composite material.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description It obtains significantly or is recognized by the practice of the present invention.
Description of the drawings
Fig. 1 is the radome of the present invention and the coating modified SiO of antenna windows BN2f/SiO2The preparation of composite material Method flow diagram.
Specific embodiment
The embodiment of the present invention is described below in detail, the embodiment is exemplary, it is intended to for explaining the present invention, and It is not considered as limiting the invention.
Embodiment 1
Embodiment 1 proposes a kind of radome and the coating modified SiO of antenna windows BN2f/SiO2Composite material, such as Shown in Fig. 1, preparation method includes the following steps：
(1) first by 2D SiO2fPrecast body, which is put into absolute ethyl alcohol, impregnates 22h, then places 74h at room temperature, then put Enter in Muffle furnace, 550 DEG C are warming up under the heating rate of 450 DEG C/h, and keep the temperature 3h, are subsequently cooled to room temperature.
(2) it is 1 by mass ratio：It is 2 that 2.5 boric acid and urea, which is dissolved in volume ratio,：The mixed solution of 1 second alcohol and water In, and stir and make it completely dissolved, until solution clear, then adjust the pH value of solution to 7.0.
(3) by step (1) processed SiO2fPrecast body is put into impregnating autoclave, and the solution that injection step (2) obtains, so After vacuumize and pressurize 0.3h, then be passed through protective gas to 1.103 × 105Pa and pressurize 0.3h, then take out and in 90 DEG C of temperature The lower dry 3h of degree.
(4) by the SiO of the step (3) processing2fPrecast body is put into tube furnace, then passes to nitrogen and ammonia, then with The heating rate of 12 DEG C/min is warming up to 680 DEG C and keeps the temperature 12h.Wherein, the flow velocity of nitrogen be 300mL/min, the flow velocity of ammonia For 200mL/min.
(5) by the SiO of the step (4) processing2fPrecast body is put into impregnating autoclave, and injects the SiO that grain size is 10 μm2It is molten Then glue vacuumizes simultaneously pressurize 0.8h, then be passed through protective gas to 8.104 × 104Pa and pressurize 0.8h, then take out and 70 Dry 5h at a temperature of DEG C.
(6) by the SiO of the step (5) processing2fPrecast body is put into tube furnace, then passes to nitrogen, and with 180 DEG C/h Heating rate be warming up to 220 DEG C and keep the temperature 0.8h, then be warming up to 420 DEG C with the heating rate of 300 DEG C/h and keep the temperature 1.2h, so Postcooling is to room temperature.
(7) product obtained with the drainage measuring and calculating step (6), if its density is less than 1.5g/cm3, then it is repeated in The step (5) and the step (6), if its density is not less than 1.5g/cm3, then it is dried into 5h at a temperature of 70 DEG C.
(8) it is polished with grain size number for the product that the sand paper of 100 mesh obtains the step (7), to expose its surface pore, Then ultrasonic vibration 0.8h in absolute ethyl alcohol is placed it in, then it is dried into 5h, and measure its density at a temperature of 70 DEG C.
(9) product that the step (8) obtains is repeated in the step (5) and the step (6), until its density It no longer changes, obtains radome and the coating modified SiO of antenna windows BN2f/SiO2Composite material.
Embodiment 2
Embodiment 2 proposes a kind of radome and the coating modified SiO of antenna windows BN2f/SiO2Composite material, Preparation method includes the following steps：
(1) first by 2.5D SiO2fPrecast body, which is put into absolute ethyl alcohol, impregnates 26h, then places 70h at room temperature, then It is put into Muffle furnace, 450 DEG C is warming up under the heating rate of 550 DEG C/h, and keep the temperature 5h, is subsequently cooled to room temperature.
(2) it is 1 by mass ratio：It is 4 that 1.5 boric acid and urea, which is dissolved in volume ratio,：The mixed solution of 1 second alcohol and water In, and stir and make it completely dissolved, until solution clear, then adjust the pH value of solution to 5.0.
(3) by step (1) processed SiO2fPrecast body is put into impregnating autoclave, and the solution that injection step (2) obtains, so After vacuumize and pressurize 0.8h, then be passed through protective gas to 8.104 × 104Pa and pressurize 0.8h, then take out and in 70 DEG C of temperature The lower dry 5h of degree.
(4) by the SiO of the step (3) processing2fPrecast body is put into tube furnace, then passes to nitrogen and ammonia, then with 8 DEG C/heating rate of min is warming up to 720 DEG C and keeps the temperature 8h.Wherein, the flow velocity of nitrogen is 500mL/min, and the flow velocity of ammonia is 100mL/min。
(5) by the SiO of the step (4) processing2fPrecast body is put into impregnating autoclave, and injects the SiO that grain size is 15 μm2It is molten Then glue vacuumizes simultaneously pressurize 0.3h, then be passed through protective gas to 1.103 × 105Pa and pressurize 0.3h, then take out and 90 Dry 3h at a temperature of DEG C.
(6) by the SiO of the step (5) processing2fPrecast body is put into tube furnace, then passes to nitrogen, and with 220 DEG C/h Heating rate be warming up to 180 DEG C and keep the temperature 1.2h, then be warming up to 480 DEG C with the heating rate of 200 DEG C/h and keep the temperature 0.8h, so Postcooling is to room temperature.
(7) product obtained with the drainage measuring and calculating step (6), if its density is less than 1.5g/cm3, then it is repeated in The step (5) and the step (6), if its density is not less than 1.5g/cm3, then it is dried into 3h at a temperature of 90 DEG C.
(8) it is polished with grain size number for the product that the sand paper of 150 mesh obtains the step (7), to expose its surface pore, Then ultrasonic vibration 0.3h in absolute ethyl alcohol is placed it in, then it is dried into 3h, and measure its density at a temperature of 90 DEG C.
(9) product that the step (8) obtains is repeated in the step (5) and the step (6), until its density It no longer changes, obtains radome and the coating modified SiO of antenna windows BN2f/SiO2Composite material.
Embodiment 3
Embodiment 3 proposes a kind of radome and the coating modified SiO of antenna windows BN2f/SiO2Composite material, Preparation method includes the following steps：
(1) first by 3D SiO2fPrecast body, which is put into absolute ethyl alcohol, to be impregnated for 24 hours, then places 72h at room temperature, then put Enter in Muffle furnace, 500 DEG C are warming up under the heating rate of 500 DEG C/h, and keep the temperature 4h, are subsequently cooled to room temperature.
(2) it is 1 by mass ratio：It is 3 that 2 boric acid and urea, which is dissolved in volume ratio,：In the mixed solution of 1 second alcohol and water, And stir and make it completely dissolved, until solution clear, the pH value of solution is then adjusted to 6.0.
(3) by step (1) processed SiO2fPrecast body is put into impregnating autoclave, and the solution that injection step (2) obtains, so After vacuumize and pressurize 0.5h, then be passed through protective gas to 9.927 × 104Pa and pressurize 0.5h, then take out and in 80 DEG C of temperature The lower dry 4h of degree.
(4) by the SiO of the step (3) processing2fPrecast body is put into tube furnace, then passes to nitrogen and ammonia, then with The heating rate of 10 DEG C/min is warming up to 700 DEG C and keeps the temperature 10h.Wherein, the flow velocity of nitrogen be 400mL/min, the flow velocity of ammonia For 150mL/min.
(5) by the SiO of the step (4) processing2fPrecast body is put into impregnating autoclave, and injects the SiO that grain size is 12 μm2It is molten Then glue vacuumizes simultaneously pressurize 0.5h, then be passed through protective gas to 9.927 × 104Pa and pressurize 0.5h, then take out and 80 Dry 4h at a temperature of DEG C.
(6) by the SiO of the step (5) processing2fPrecast body is put into tube furnace, then passes to nitrogen, and with 200 DEG C/h Heating rate be warming up to 200 DEG C and keep the temperature 1h, then be warming up to 450 DEG C with the heating rate of 250 DEG C/h and keep the temperature 1h, Ran Houleng But to room temperature.
(7) product obtained with the drainage measuring and calculating step (6), if its density is less than 1.5g/cm3, then it is repeated in The step (5) and the step (6), if its density is not less than 1.5g/cm3, then it is dried into 4h at a temperature of 80 DEG C.
(8) it is polished with grain size number for the product that the sand paper of 120 mesh obtains the step (7), to expose its surface pore, Then ultrasonic vibration 0.5h in absolute ethyl alcohol is placed it in, then it is dried into 4h, and measure its density at a temperature of 80 DEG C.
(9) product that the step (8) obtains is repeated in the step (5) and the step (6), until its density It no longer changes, obtains radome and the coating modified SiO of antenna windows BN2f/SiO2Composite material.
Use demand and current SiO the present invention is based on radar antenna cover material2f/SiO2The Research Challenges of material propose A kind of radome and antenna windows SiO coating modified BN2f/SiO2The preparation method of composite material, preparation process Simply, the period is short, and density of material is up to 1.8g/cm3, bending strength is up to 120MPa.Dielectric constant≤3, in 2GPa~18GPa Dielectric loss is not more than 0.02 under frequency.Can be in 800 DEG C of high temperature continuous firing 10min, and instantaneous operative temperature can reach 1200 ℃.Anti-moisture absorption ability is good, disclosure satisfy that use demand of the middle high Mach aircraft to radome.Solves existing SiO2f/ SiO2The problem of easy crystallization of composite material, densification degree are low, mechanical strength cannot meet requirement is situated between not influencing material The density and its mechanical property of material are improved under the premise of electrical property.
In the description of this specification, reference term " one embodiment ", " example ", " is specifically shown " some embodiments " The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description Point is contained at least one embodiment of the present invention or example.In the present specification, schematic expression of the above terms are not It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office It is combined in an appropriate manner in one or more embodiments or example.In addition, without conflicting with each other, the skill of this field Art personnel can tie the different embodiments or examples described in this specification and the feature of different embodiments or examples It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example Property, it is impossible to limitation of the present invention is interpreted as, those of ordinary skill in the art within the scope of the invention can be to above-mentioned Embodiment is changed, changes, replacing and modification.

Claims (10)

1. a kind of radome and antenna windows SiO coating modified BN2f/SiO2The preparation method of composite material, feature It is, includes the following steps：
S101：First by SiO2fPrecast body is put into immersion 22h~26h in absolute ethyl alcohol, then places 70h~74h at room temperature, It places into Muffle furnace, 450 DEG C~550 DEG C is warming up under the first heating rate, and keep the temperature 3h~5h, is subsequently cooled to room Temperature；
S102：It is 1 by mass ratio：The boric acid and urea of (1.5~2.5) are dissolved in volume ratio as (2~4)：1 second alcohol and water It in mixed solution, and stirs and makes it completely dissolved, until solution clear, then adjust the pH value of solution to 5.0~7.0；
S103：By the processed SiO of step S1012fPrecast body is put into impregnating autoclave, and the solution that injection step S102 is obtained, so After vacuumize and pressurize 0.3h~0.8h, then be passed through protective gas to 8.104 × 104Pa~1.103 × 105Pa and pressurize 0.3h ~0.8h then takes out and dries；
S104：By the SiO of step S103 processing2fPrecast body is put into tube furnace, then passes to nitrogen and ammonia, then with Two heating rates are warming up to 680 DEG C~720 DEG C and keep the temperature 8h~12h；
S105：By the SiO of step S104 processing2fPrecast body is put into impregnating autoclave, and injects SiO2Then colloidal sol vacuumizes And pressurize 0.3h~0.8h, then protective gas is passed through to 8.104 × 104Pa~1.103 × 105Pa and pressurize 0.3h~0.8h, so It takes out afterwards and dry；
S106：By the SiO of step S105 processing2fPrecast body is put into tube furnace, then passes to nitrogen, and heat up with third Rate is warming up to 180 DEG C~220 DEG C and keeps the temperature 0.8h~1.2h, then is warming up to 420 DEG C~480 DEG C with the 4th heating rate and protects Warm 0.8h~1.2h, is subsequently cooled to room temperature；
S107：The product obtained with the drainage measuring and calculating step S106, if its density is less than 1.5g/cm3, then it is repeated in institute Step S105 and the step S106 are stated, if its density is not less than 1.5g/cm3, then it is dried；
S108：It is polished with the product that sand paper obtains the step S107, with its surface pore of exposure, then placed it in anhydrous Ultrasonic vibration 0.3h~0.8h in ethyl alcohol, then be dried, and measure its density；
S109：The obtained products of the step S108 are repeated in the step S105 and the step S106, until its is close Degree no longer changes, and obtains radome and the coating modified SiO of antenna windows BN2f/SiO2Composite material.
2. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that the first heating rate is 450 DEG C/h~550 DEG C/h.
3. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that in the step S103, drying temperature is 70 DEG C~90 DEG C, and drying time is 3h~5h； In the step S105, drying temperature is 70 DEG C~90 DEG C, and drying time is 3h~5h；In the step S107, dry temperature It is 70 DEG C~90 DEG C to spend, and drying time is 3h~5h；In the step S108, drying temperature is 70 DEG C~90 DEG C, when dry Between be 3h~5h.
4. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that in the step S104, second heating rate is 8 DEG C/min~12 DEG C/min.
5. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that in the step S104, the flow velocity of nitrogen is 300mL/min~500mL/min, ammonia Flow velocity is 100mL/min~200mL/min.
6. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that in the step S106, the third heating rate is 180 DEG C/h~220 DEG C/h, described 4th heating rate is 200 DEG C/h~300 DEG C/h.
7. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that the SiO2fPrecast body includes at least 2D SiO2fPrecast body, 2.5D SiO2fPrecast body and 3D SiO2fOne kind in precast body.
8. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that in the step S105, the SiO2The grain size of colloidal sol is 10 μm~15 μm.
9. radome according to claim 1 and antenna windows SiO coating modified BN2f/SiO2Composite material Preparation method, which is characterized in that in the step S108, the grain size number of the sand paper is the mesh of 100 mesh~150.
10. the radome and antenna windows that are prepared using claim 1-9 any one of them method are coating modified with BN SiO2f/SiO2Composite material.
CN201810004550.9A 2018-01-03 2018-01-03 BN is modified SiO2Composite material and preparation method thereof Pending CN108191416A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109761630A (en) * 2019-03-19 2019-05-17 江西嘉捷信达新材料科技有限公司 From growth silicon nitride crystal whisker enhancing radar antenna window/antenna house and preparation method thereof
CN109761628A (en) * 2019-03-19 2019-05-17 江西嘉捷信达新材料科技有限公司 Chopped strand enhances radar antenna window/antenna house wave transparent ceramic matric composite and preparation method thereof
CN110511049A (en) * 2019-09-27 2019-11-29 中国人民解放军国防科技大学 BN interface phase-containing quartz/quartz composite material and preparation method thereof
CN110668836A (en) * 2019-10-24 2020-01-10 江西嘉捷信达新材料科技有限公司 Composite material for radome/antenna window and preparation method thereof
CN114044698A (en) * 2021-11-04 2022-02-15 广东先导微电子科技有限公司 Preparation method of boron nitride film of graphite stirrer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101348379A (en) * 2008-09-11 2009-01-21 北京航空航天大学 Method for preparing hexagonal boron nitride coating on fibrage body
CN102167609A (en) * 2010-12-23 2011-08-31 中国人民解放军国防科学技术大学 Quartz/quartz-boron nitride high-temperature wave-permeable material and preparation method thereof
CN103664215A (en) * 2012-09-13 2014-03-26 南京航空航天大学 Preparation method of quartz fiber-toughened multiphase ceramic wave-transparent composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101348379A (en) * 2008-09-11 2009-01-21 北京航空航天大学 Method for preparing hexagonal boron nitride coating on fibrage body
CN102167609A (en) * 2010-12-23 2011-08-31 中国人民解放军国防科学技术大学 Quartz/quartz-boron nitride high-temperature wave-permeable material and preparation method thereof
CN103664215A (en) * 2012-09-13 2014-03-26 南京航空航天大学 Preparation method of quartz fiber-toughened multiphase ceramic wave-transparent composite material

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
YONG LIU等: "Mechanical behavior of 2.5D (shallow bend-joint) and 3D orthogonal quartzf/silica composites by silicasol-infiltration-sintering", 《MATERIALS SCIENCE AND ENGINEERING A》 *
李端等: "SiO2f/SiO2-BN复合材料的制备及其性能", 《复合材料学报》 *
王海丽等: "石英纤维表面低温制备氮化硼涂层", 《人工晶体学报》 *
陈照峰: "《无机非金属材料学》", 29 February 2016, 西北工业大学出版社 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109761630A (en) * 2019-03-19 2019-05-17 江西嘉捷信达新材料科技有限公司 From growth silicon nitride crystal whisker enhancing radar antenna window/antenna house and preparation method thereof
CN109761628A (en) * 2019-03-19 2019-05-17 江西嘉捷信达新材料科技有限公司 Chopped strand enhances radar antenna window/antenna house wave transparent ceramic matric composite and preparation method thereof
CN109761628B (en) * 2019-03-19 2022-06-07 江西嘉捷信达新材料科技有限公司 Chopped fiber reinforced wave-transmitting ceramic matrix composite material for radar antenna window/antenna housing and preparation method thereof
CN110511049A (en) * 2019-09-27 2019-11-29 中国人民解放军国防科技大学 BN interface phase-containing quartz/quartz composite material and preparation method thereof
CN110668836A (en) * 2019-10-24 2020-01-10 江西嘉捷信达新材料科技有限公司 Composite material for radome/antenna window and preparation method thereof
CN110668836B (en) * 2019-10-24 2021-11-02 江西嘉捷信达新材料科技有限公司 Composite material for radome/antenna window and preparation method thereof
CN114044698A (en) * 2021-11-04 2022-02-15 广东先导微电子科技有限公司 Preparation method of boron nitride film of graphite stirrer

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