CN116332654B - BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 Preparation method of composite material - Google Patents

BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 Preparation method of composite material Download PDF

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CN116332654B
CN116332654B CN202310294176.1A CN202310294176A CN116332654B CN 116332654 B CN116332654 B CN 116332654B CN 202310294176 A CN202310294176 A CN 202310294176A CN 116332654 B CN116332654 B CN 116332654B
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汤玉斐
谢章雯
唐晨
罗紫芸
赵康
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Xian University of Technology
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Abstract

The invention discloses a BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material comprises the following steps: firstly, obtaining powder A through high-energy ball milling, and secondly, coating SiO on the surface of the powder A through a sol-gel process 2 Obtaining A@SiO 2 Powder SiBN@Si forming core-shell structure by molten salt sintering, washing and decarbonizing 2 N 2 O, finally obtaining BN/SiBN/Si with onion microstructure through hot-pressed sintering 3 N 4 /Si 2 N 2 O/Si 3 N 4 A composite material; the BN/SiBN/Si with onion-like microstructure prepared by the invention 3 N 4 /Si 2 N 2 O/Si 3 N 4 The composite material realizes the integrated multifunction of excellent dielectric property, high strength, high temperature resistance, ablation resistance and the like, meets the application requirements of the ultra-high speed missile radome material, and has the advantages of simple preparation method, low cost and easy operation.

Description

BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 Preparation method of composite material
Technical Field
The invention belongs to the field of high-temperature wave transmission, and in particular relates to BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 A preparation method of the composite material.
Background
With the high-speed development of aviation technology, the radome at the forefront of the high Mach number aircraft bears larger aerodynamic force and aerodynamic heat, the organic high polymer material can not meet the requirement of service performance, and the inorganic wave-transmitting material meets the requirements of high temperature resistance, broadband wave transmission and bearing integration by the special force, heat and electrical property, so that the radome material becomes the main development direction of the radome material.
Amorphous SiBN fully combines Si 3 N 4 And h-BN has the advantages of low density, high temperature resistance, good mechanical property, oxidation resistance and low dielectric constant, is the high temperature resistant wave transparent ceramic with the development prospect at present, and can still oxidize at the temperature of more than 1300 ℃. Si (Si) 2 N 2 O is a member of the multi-element nitride and has SiO 2 And Si (Si) 3 N 4 The decomposition temperature of the ceramic material is up to 1700 ℃, and the mechanical property and the high-temperature stability of the ceramic material are stable at high temperature, so that the ceramic material can be used in high-temperature and high-pressure extreme environments for a long time, and can be used as excellent high-temperature structural ceramic in the field of aeronautics industry. Studies have shown that by adding Si to the SiBN surface 2 N 2 O is protected, and the high-temperature oxidation resistance of the alloy can be improved. For example, chinese patent (patent publication No. CN 11502857A) discloses Si 2 N 2 SiBN fiber with O microcrystal in-situ coating and its preparation process includes introducing oxygen element to the surface of SiBN fibril through high temperature oxidation, soaking in boiling water, high temperature sintering to convert the oxygen component in the surface of the fiber into Si 2 N 2 The high-temperature oxidation resistance of the O microcrystal is obviously improved, but the SiBN itself is damaged by introducing O into the SiBN. Meanwhile, the method for preparing SiBN mainly comprises the complex means of precursor conversion or vapor deposition, and the like, and has the defects of high cost and long time consumption. Although amorphous nano Si has been reported 3 N 4 And h-BN is used as a raw material, siBN is prepared by a mechanical alloying method, but the sintering temperature is high and the sintering condition is severe.
Second, the radome material needs to have a wide frequency bandAnd high electromagnetic wave transmission efficiency, capable of covering one or more frequency bands (e.g., 1-18GHz, even 0.5-40 GHz). The gradient structure material can be regarded as a multi-layer dielectric material with gradient dielectric property, and can prevent the material from being damaged by interlayer thermal stress at high temperature. In addition, the gradient structure meets the requirements of broadband and ideal dielectric properties by designing microcosmic and optimizing the microwave transmissivity of a single layer, and has a higher application prospect in high Mach number flight, however, at present, technologies such as Chemical Vapor Deposition (CVD), physical Vapor Deposition (PVD), slurry spraying, thermal spraying and the like are mostly adopted to obtain a multilayer structure, and most of the methods require expensive equipment and exquisite technologies, so that the method is unfavorable for mass production. Recently, forest et al (S.J.Lin, F.Ye., J.Ma, J.J.Ding, C.P.Yang, S.L.Dong.Fabrication of multilayer electronic magnetic window material by Si) 2 N 2 Odecomposition[J]Materials and Design,2016, 97:51-55.) by controlling Si 2 N 2 The degree of O decomposition forms an a-sandwich structure in situ (Si 3 N 4 /Si 2 N 2 O/Si 3 N 4 ) The strength can be effectively improved, the dielectric constant is reduced, but the dielectric loss is improved. In addition, the multi-layer structure (more than three layers) with the electromagnetic and mechanical properties regulated is more complicated to prepare, and few researches are reported.
Disclosure of Invention
The invention aims at providing BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material solves the problems of complex preparation of SiBN, insufficient high-temperature oxidation resistance and difficult preparation of a multilayer gradient structure at present.
The technical scheme adopted by the invention is as follows:
BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material comprises the following steps:
step 1, amorphous Si 3 N 4 Mixing with h-BN powder, performing high-speed ball milling and sieving to obtain powder A;
step 2, uniformly stirring the powder A, the surfactant, the water, the alcohol and the alkaline substances, then adding the silane precursor liquid for 1-3 times at intervals of 2-8 hours, continuously stirring after the silane precursor liquid is added, centrifuging, washing with water, and drying to obtain the A@SiOO 2 A powder;
step 3, A@SiO 2 Mixing the powder with molten salt, and then sintering to obtain powder B; the A@SiO 2 The molar ratio of powder to molten salt is 1: 1-4, wherein the molten salt is any one of potassium chloride, sodium chloride and calcium chloride, the sintering temperature is 1600-1800 ℃, the sintering time is 1-3h, and the heating rate is 1-8 ℃/min.
Step 4, washing the powder B with hot water, filtering, drying and removing carbon to obtain SiBN@Si 2 N 2 O；
Step 5, siBN@Si 2 N 2 O is sintered by hot pressing to obtain BN/SiBN/Si with onion-like structure 3 N 4 /Si 2 N 2 O/Si 3 N 4 The hot-pressing sintering atmosphere is nitrogen or argon, the sintering temperature is 1600-1800 ℃, the sintering time is 1-2h, and the pressure is 1-2Mpa.
Further, the amorphous Si in step 1 3 N 4 And in the high-speed ball milling process of the h-BN powder, the ball-to-material ratio is 10-20:1, the diameter of the grinding ball is 5-20mm, and the grinding ball is ZrC and Si 3 N 4 Ball milling time is 2-24h, ball milling speed is 400-800rpm, and sieving mesh number is 200-600.
Further, the amorphous Si in step 1 3 N 4 And h-BN powder in a molar ratio of 1 to 3:3 to 1.
Further, the mass percentages of substances added in the step 2 are as follows: 5-10% of powder A, 0.5-5% of surfactant, 1-10% of alkaline substance, 30-50% of alcohol and 25-63.5% of water, wherein the surfactant is at least one of hexadecyl trimethyl ammonium bromide, polyvinyl alkanone and sodium dodecyl benzene sulfonate, the alcohol is any one of ethanol, methanol and ethylene glycol, the alkaline substance is any one of ammonia water, urea and sodium hydroxide, and the silane precursor liquid is at least one of tetraethoxysilane, 1, 2-bis (triethoxysilyl) ethane and 1, 4-bis (triethoxysilyl) propane tetrasulfide.
Further, in the step 4, the hot water washing temperature is 60-100 ℃.
Further, the sintering temperature in the decarbonization treatment in the step 4 is 400-600 ℃, the sintering time is 1-3h, and the heating rate is 1-8 ℃/min.
The beneficial effects of the invention are as follows:
BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 Preparation method of composite material can form BN/SiBN/Si in situ 3 N 4 /Si 2 N 2 O/Si 3 N 4 Can fully improve the oxidation resistance and the bearing capacity of SiBN, has gradient dielectric property and is better than SiO 2 、Si 3 N 4 And h-BN, the material has the characteristics of excellent dielectric property, high strength, high temperature resistance, ablation resistance and the like, meets the application requirements of the ultra-high speed missile radome material, and has the advantages of simple material preparation method, low cost and easy operation.
Drawings
FIG. 1 shows BN/SiBN/Si with onion-like microstructure prepared according to the invention 3 N 4 /Si 2 N 2 O/Si 3 N 4 Schematic cross-sectional morphology of the composite material.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The technical proposal adopted by the invention is that BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material specifically comprises the following steps:
step 1: to amorphous Si 3 N 4 And BN powder in a molar ratio of 1 to 3: 3-1, performing high-speed ball milling and sieving with 200-600 meshes to obtain powder A. Wherein the ball-to-material ratio is 10-20:1, adopt diameterZrC, si of 5-20mm 3 N 4 Any one of grinding balls such as BN, etc., wherein the ball milling time is 2-24 hours, and the ball milling speed is 400-800rpm;
step 2: stirring the powder A, the surfactant, the water, the alcohol and the alkaline substances for 2-12h, then adding quantitative silane precursor liquid for 1-3 times at intervals of 2-8h, continuously stirring for 2-12h after adding the silane precursor liquid, centrifuging, washing with water, and drying to obtain A@SiOO 2 A powder; wherein the mass percentages of the added substances are as follows: 5 to 10 percent of A powder, 0.5 to 5 percent of surfactant, 1 to 10 percent of alkaline substance, 30 to 50 percent of alcohol and 25 to 63.5 percent of water, wherein the surfactant is at least one of cetyl trimethyl ammonium bromide, polyvinylpyrrolidone, sodium dodecyl benzene sulfonate and the like, the alcohol is any one of ethanol, methanol, ethylene glycol and the like, the alkaline substance is any one of ammonia water, urea, sodium hydroxide and the like, and the silane precursor is at least one of Tetraethoxysilane (TEOS), 1, 2-bis (triethoxysilyl) ethane (BTSE), 1, 4-bis (triethoxysilyl) propane tetrasulfide (TESPTS) and the like.
Step 3: A@SiO 2 The molar ratio of the powder to the molten salt is 1: 1-4, and then sintering, wherein the molten salt is any one of potassium chloride, sodium chloride, calcium chloride and the like, the sintering temperature is 1600-1800 ℃, the sintering time is 1-3h, and the heating rate is 1-8 ℃/min, so as to obtain powder B.
Step 4: washing the powder B in hot water at 60-100 deg.c, filtering and drying, setting the heating rate of 1-8 deg.c/min, sintering in air atmosphere at 400-600 deg.c for 1-3 hr, and decarbonizing to obtain SiBN@Si with core-shell structure 2 N 2 O。
Step 5: siBN@Si of core-shell structure 2 N 2 Sintering O under hot pressure at 1600-1800 deg.C in nitrogen or argon for 1-2 hr under 1-2Mpa to obtain BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 A composite material.
The invention selects silane precursor to coat superfine h-BN-Si 3 N 4 Mixing powder, controlling the addition times and the content of silane precursorSo that h-BN-Si 3 N 4 Surface is SiO 2 Cladding, effectively promote h-BN and Si 3 N 4 Bonding, si 3 N 4 With SiO 2 Combining; siO can be improved by controlling the content of molten salt and the calcining temperature 2 Closing and pressurizing to promote h-BN and Si 3 N 4 Form SiBN by reaction between them, and simultaneously enable Si to be 3 N 4 The particles are dissolved in SiO 2 Promoting Si in the liquid phase formed 2 N 2 O is formed to obtain SiBN@Si with a core-shell structure 2 N 2 O; BN/SiBN/Si with onion-like microstructure can be obtained by further hot pressing 3 N 4 /Si 2 N 2 O/Si 3 N 4 The thickness between layers of the composite material can be effectively regulated and controlled by controlling the hot-pressing sintering temperature and time, and the dielectric parameters and mechanical properties of the material are improved.
The invention prepares BN/SiBN/Si with onion-like microstructure by simple sol-gel coating and three-step calcination method 3 N 4 /Si 2 N 2 O/Si 3 N 4 The composite material can fully improve the oxidation resistance and the bearing capacity of SiBN, has gradient dielectric property and is better than SiO 2 、Si 3 N 4 And h-BN, the material has the characteristics of excellent dielectric property, high strength, high temperature resistance, ablation resistance and the like, meets the application requirements of the ultra-high speed missile radome material, and has the advantages of simple material preparation method, low cost and easy operation.
Example 1:
step 1: to amorphous Si 3 N 4 And h-BN powder in a molar ratio of 3: and 1, carrying out mixing high-speed ball milling and 400-mesh sieving treatment to obtain powder A. Wherein the ball-to-material ratio is 20:1, si with a diameter of 20mm is used 3 N 4 Grinding balls, wherein the ball milling time is 12 hours, and the ball milling speed is 600rpm;
step 2: mixing and stirring 4g of A powder, 0.5g of hexadecyl trimethyl ammonium bromide, 30mL of water, 60mL of ethanol and 5.5mL of ammonia water for 6 hours, then adding 12.6mL of Tetraethoxysilane (TEOS) at intervals of 3 times for 6 hours, continuing stirring for 12 hours after the addition of the TEOS, centrifuging, washing with water, and drying to obtain A@SiO 2 A powder;
step 3: A@SiO 2 Powder and NaCl in a molar ratio of 1:4 mixing, setting the heating rate to 8 ℃/min, and adding the mixture into N 2 Sintering for 3 hours at 1600 ℃ in the atmosphere to obtain powder B;
step 4: washing the powder B in hot water at 90 ℃, filtering and drying, setting the heating rate at 1 ℃/min, sintering at 400 ℃ in air atmosphere for 1h, and performing carbon removal treatment to obtain SiBN@Si with a core-shell structure 2 N 2 O；
Step 5: siBN@Si of core-shell structure 2 N 2 Placing O in nitrogen gas, hot-pressing and sintering at 1700 deg.C for 2 hr, wherein the pressure is 2Mpa, to obtain BN/SiBN/Si with onion microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 A composite material.
Example 2:
step 1: to amorphous Si 3 N 4 And h-BN powder in a molar ratio of 1: and 1, carrying out mixing high-speed ball milling and 600-mesh sieving treatment to obtain powder A. Wherein the ball-to-material ratio is 15:1, si with a diameter of 10mm is used 3 N 4 Grinding balls, wherein the ball milling time is 24 hours, and the ball milling speed is 800rpm;
step 2: mixing 5g of A powder, 1g of hexadecyl trimethyl ammonium bromide, 20mL of water, 70mL of ethanol and 4g of NaOH, stirring for 6h, adding 12mL of Tetraethoxysilane (TEOS) 2 times at intervals of 2h, continuously stirring for 6h after the TEOS is added, centrifuging, washing with water, and drying to obtain A@SiO 2 A powder;
step 3: A@SiO 2 Powder and NaCl in a molar ratio of 1:3 mixing, setting the heating rate to 3 ℃/min, and adding the mixture into N 2 Sintering for 1h at 1700 ℃ in the atmosphere to obtain powder B;
step 4: washing the powder B in hot water at 80 ℃, filtering and drying, setting the heating rate to be 3 ℃/min, sintering for 2 hours at 500 ℃ in air atmosphere, and performing carbon removal treatment to obtain SiBN@Si with a core-shell structure 2 N 2 O；
Step 5: siBN@Si of core-shell structure 2 N 2 Hot pressing and sintering O in argon at 1600 deg.c for 1.5 hr, whereinApplying pressure of 1.5Mpa to obtain BN/SiBN/Si with onion microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 A composite material.
Example 3
Step 1: to amorphous Si 3 N 4 And BN powder in a molar ratio of 1: and 3, carrying out mixing high-speed ball milling and 200-mesh sieving treatment to obtain powder A. Wherein the ball-to-material ratio is 10:1, si with a diameter of 5mm is used 3 N 4 Grinding balls, wherein the ball milling time is 2 hours, and the ball milling speed is 400rpm;
step 2: mixing 3g of A powder, 0.3g of polyvinylpyrrolidone, 30mL of water, 60mL of ethanol and 6.5mL of ammonia water, stirring for 12h, adding 12.8mL of Tetraethoxysilane (TEOS) at intervals of 8h for 1 time, continuously stirring for 2h after the TEOS is added, centrifuging, washing with water, and drying to obtain A@SiO 2 A powder;
step 3: A@SiO 2 Powder and KCl in a molar ratio of 1:1 mixing, setting the heating rate to be 2 ℃/min, and adding the mixture into N 2 Sintering for 2 hours at 1800 ℃ in the atmosphere to obtain powder B;
step 4: washing the powder B in hot water at 60 ℃, filtering and drying, setting the heating rate to be 6 ℃/min, sintering for 3 hours at 600 ℃ in air atmosphere, and performing carbon removal treatment to obtain SiBN@Si with a core-shell structure 2 N 2 O；
Step 5: siBN@Si of core-shell structure 2 N 2 Placing O in argon gas at 1600 deg.C, hot-pressing and sintering for 1 hr, wherein the pressure is 1Mpa, to obtain BN/SiBN/Si with onion microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 A composite material.
Example 4:
step 1: to amorphous Si 3 N 4 And BN powder in a molar ratio of 1: and 3, carrying out mixed high-speed ball milling and 300-mesh sieving treatment to obtain powder A. Wherein the ball-to-material ratio is 10:1, si with a diameter of 15mm is used 3 N 4 Grinding balls, wherein the ball milling time is 24 hours, and the ball milling speed is 500rpm;
step 2: 6g of A powder, 0.6g of sodium dodecyl benzene sulfonate, 10mL of water, 80mL of ethanol and 4Mixing and stirring 4g of urea for 6 hours, then adding 10mL of Tetraethoxysilane (TEOS) for 2 times at intervals of 5 hours, continuously stirring for 10 hours after the TEOS is added, centrifuging, washing with water, and drying to obtain A@SiO 2 A powder;
step 3: A@SiO 2 Powder and CaCl 2 The molar ratio is 1:2 mixing, setting the heating rate to be 1 ℃/min, and adding the mixture into N 2 Sintering for 3 hours at 1750 ℃ in the atmosphere to obtain powder B;
step 4: washing the powder B in hot water at 100deg.C, filtering, drying, heating at 8deg.C/min, sintering at 550deg.C in air atmosphere for 2 hr, and removing carbon to obtain SiBN@Si with core-shell structure 2 N 2 O；
Step 5: siBN@Si of core-shell structure 2 N 2 Placing O in nitrogen gas, hot-pressing and sintering at 1800 deg.C for 2 hr under 1.5Mpa to obtain BN/SiBN/Si with onion microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 A composite material.
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the principles and spirit of the invention, but such changes and modifications fall within the scope of the invention.

Claims (6)

1. BN/SiBN/Si with onion-like microstructure 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material is characterized by comprising the following steps:
step 1, amorphous Si 3 N 4 Mixing with h-BN powder, performing high-speed ball milling and sieving to obtain powder A;
step 2, uniformly stirring the powder A, the surfactant, the water, the alcohol and the alkaline substances, then adding the silane precursor liquid for 2-8 hours at 1-3 times, continuously stirring after the silane precursor liquid is added, centrifuging, washing with water, and drying to obtainObtaining A@SiO 2 A powder;
step 3, A@SiO 2 Mixing the powder with molten salt, and then sintering to obtain powder B; the A@SiO 2 The molar ratio of powder to molten salt is 1: 1-4, wherein the molten salt is any one of potassium chloride, sodium chloride and calcium chloride, the sintering temperature is 1600-1800 ℃, the sintering time is 1-3h, and the heating rate is 1-8 ℃/min;
step 4, washing the powder B with hot water, filtering, drying and removing carbon to obtain SiBN@Si 2 N 2 O；
Step 5, siBN@Si 2 N 2 O is sintered by hot pressing to obtain BN/SiBN/Si with onion-like structure 3 N 4 /Si 2 N 2 O/Si 3 N 4 The hot-pressing sintering atmosphere is nitrogen or argon, the sintering temperature is 1600-1800 ℃, the sintering time is 1-2h, and the pressure is 1-2Mpa.
2. A BN/SiBN/Si having onion-like microstructure according to claim 1 3 N 4 /Si 2 N 2 O/Si 3 N 4 A method for producing a composite material, characterized in that the amorphous Si in step 1 3 N 4 And in the high-speed ball milling process of the h-BN powder, the ball-to-material ratio is 10-20:1, the diameter of the grinding ball is 5-20mm, and the grinding ball is ZrC and Si 3 N 4 Ball milling time is 2-24h, ball milling speed is 400-800rpm, and sieving mesh number is 200-600.
3. A BN/SiBN/Si having onion-like microstructure according to claim 1 3 N 4 /Si 2 N 2 O/Si 3 N 4 A method for producing a composite material, characterized by comprising the step 1 of amorphous Si 3 N 4 And h-BN powder in a molar ratio of 1 to 3:3 to 1.
4. A BN/SiBN/Si having onion-like microstructure according to claim 1 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material is characterized in that the mass percentages of substances added in the step 2 are as follows: 5-10% of powder A, 0.5-5% of surfactant, 1-10% of alkaline substance, 30-50% of alcohol and 25-63.5% of water, wherein the surfactant is at least one of hexadecyl trimethyl ammonium bromide, polyvinyl alkanone and sodium dodecyl benzene sulfonate, the alcohol is any one of ethanol, methanol and ethylene glycol, the alkaline substance is any one of ammonia water, urea and sodium hydroxide, and the silane precursor liquid is at least one of tetraethoxysilane, 1, 2-bis (triethoxysilyl) ethane and 1, 4-bis (triethoxysilyl) propane tetrasulfide.
5. A BN/SiBN/Si having onion-like microstructure according to claim 1 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material is characterized in that the hot water washing temperature in the step 4 is 60-100 ℃.
6. A BN/SiBN/Si having onion-like microstructure according to claim 1 3 N 4 /Si 2 N 2 O/Si 3 N 4 The preparation method of the composite material is characterized in that the sintering temperature in the carbon removal treatment in the step 4 is 400-600 ℃, the sintering time is 1-3h, and the heating rate is 1-8 ℃/min.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60200881A (en) * 1984-03-27 1985-10-11 株式会社東芝 Ceramic sintered body and manufacture
CN103145112A (en) * 2013-03-29 2013-06-12 哈尔滨工业大学 BN-Si2N2O composite ceramic and preparation method thereof
WO2016023200A1 (en) * 2014-08-11 2016-02-18 河海大学 Preparation method for high-density hexagonal boron nitride ceramic material
CN106957179A (en) * 2017-02-24 2017-07-18 东华大学 A kind of SiBN fiber reinforcements SiO2‑BN‑Al2O3The preparation method of wave-penetrating composite material
CN115073195A (en) * 2022-06-05 2022-09-20 西北工业大学 Silicon nitride whisker reinforced nitride composite material for 3D printing radome and preparation and printing methods

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100454715B1 (en) * 2002-03-14 2004-11-05 한국과학기술연구원 MoSi2-Si3N4 COMPOSITE COATING AND MANUFACTURING METHOD THEREOF
US20230036697A1 (en) * 2021-07-30 2023-02-02 Raytheon Technologies Corporation Cvd functionalized particles for cmc applications

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60200881A (en) * 1984-03-27 1985-10-11 株式会社東芝 Ceramic sintered body and manufacture
CN103145112A (en) * 2013-03-29 2013-06-12 哈尔滨工业大学 BN-Si2N2O composite ceramic and preparation method thereof
WO2016023200A1 (en) * 2014-08-11 2016-02-18 河海大学 Preparation method for high-density hexagonal boron nitride ceramic material
CN106957179A (en) * 2017-02-24 2017-07-18 东华大学 A kind of SiBN fiber reinforcements SiO2‑BN‑Al2O3The preparation method of wave-penetrating composite material
CN115073195A (en) * 2022-06-05 2022-09-20 西北工业大学 Silicon nitride whisker reinforced nitride composite material for 3D printing radome and preparation and printing methods

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
梯度复合材料制备技术研究进展;袁秦鲁, 胡锐, 李金山, 吕振林;兵器材料科学与工程(06) *

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