CN102674875B - Preparation method of SiO2/SiBN composite materials - Google Patents
Preparation method of SiO2/SiBN composite materials Download PDFInfo
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- CN102674875B CN102674875B CN201210115881.2A CN201210115881A CN102674875B CN 102674875 B CN102674875 B CN 102674875B CN 201210115881 A CN201210115881 A CN 201210115881A CN 102674875 B CN102674875 B CN 102674875B
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Abstract
The invention relates to a preparation method of SiO2/SiBN composite materials. The preparation method includes: (1) preparing precursor polymer polyborosilazane; (2) soaking quartz fiber cloth in toluene solution of the polyborosilazane, and soaking in vacuum mode or soaking in hot pressing mode under the pressure of 1-750 Mpa for 0.5-30 hours; (3) performing cross-linking treatment on the quartz fiber cloth soaked by the polyborosilazane and obtained in the step (2) to obtain the quartz fiber cloth experiencing the cross-linking treatment; (4) performing hot-pressing molding on the soaked quartz fiber cloth after the cross-linking treatment to obtain a hot-pressing sample; and (5) sintering the hot-pressing sample at high temperature under reactive atmosphere to obtain the SiO2/SiBN composite materials. The preparation method is simple and convenient to operate. The obtained SiO2/SiBN composite materials are large in density and small in air holes and cracks, and have good mechanical properties and dielectric properties.
Description
Technical field
The invention belongs to the preparation field of SiBN stupalith, particularly a kind of SiO
2the preparation method of/SiBN matrix material.
Background technology
SiBN Ceramic bond Si
3n
4the advantage of pottery and BN pottery, has excellent high thermal resistance, high-strength and high-modulus and dielectric properties, can meet the requirement of the functions such as aerospace applications is high temperature resistant to material, carrying, wave transparent.And silica fiber dielectric properties are very excellent, can realize the characteristic of wideband wave transparent, and resistance to elevated temperatures is better than glass fibre, with silica fiber, strengthen SiBN pottery preparation SiO
2/ SiBN matrix material, is expected to become the candidate material of radome material wave transparent functional zone of new generation, in aerospace wave transparent field, has a extensive future.
But because the organic precursor of ceramic matrix SiBN has a large amount of small molecules to overflow in high-temperature sintering process, there will be " foaming " phenomenon, the matrix material pore that makes to adopt presoma pickling process (PIP) to obtain is many, and density is very little, and material internal has a lot of crackles, poor mechanical property.And it is little to adopt hot pressing-sintering process can obtain void content, flawless, mechanical property, the good SiO of wave penetrate capability
2/ SiBN matrix material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of SiO
2the preparation method of/SiBN matrix material, the method is simple, convenient operation, resulting composite density is large, and pore is few, and crackle is few, has good mechanical property and dielectric properties.
A kind of SiO of the present invention
2the preparation method of/SiBN matrix material, comprising:
(1) poly-silicon nitrogen borine precursor polymer is synthetic
By free nitrogen methyl silicon nitrogen borine (BSZ), at 60-270 ℃, polymerization 6-80h obtains the poly-silicon nitrogen borine of precursor polymer;
(2) the poly-silicon nitrogen borine dipping of precursor polymer silica fiber cloth
At room temperature to 350 ℃, silica fiber cloth is dipped in the anhydrous toluene solution of above-mentioned poly-silicon nitrogen borine that mass concentration is 10-95% to vacuum impregnation or heat pressing dipping 0.5-30h under 1-750Mpa pressure;
(3) crosslinking Treatment
The silica fiber cloth that is impregnated with the poly-silicon nitrogen borine of precursor polymer being obtained by (2) is carried out to crosslinking Treatment, under reactive atmosphere, be warming up to 100-600 ℃, insulation 2-50h, make precursor polymer there is certain degree of crosslinking, obtain the dipping silica fiber cloth after crosslinking Treatment;
(4) hot-forming
Dipping silica fiber cloth after above-mentioned crosslinking Treatment is put into mould, is warmed up to 80-500 ℃, under 10-750Mpa pressure, keep 0.1-5h to carry out hot-forming, then drop to room temperature, and in temperature-fall period relief pressure gradually, obtain hot pressed samples;
(5) high temperature sintering
Under reactive atmosphere, above-mentioned hot pressed samples is carried out to high temperature sintering, be warming up to 300-1200 ℃, insulation 0.1-50h, is then down to room temperature, obtains SiO
2/ SiBN matrix material.
The whole operating process of described step (1)～(5) is all carried out in the environment of anhydrous and oxygen-free.
In described step (3), reactive atmosphere is ammonia.
The temperature rise rate heating up in described step (3) is 0.1-20 ℃/min.
In the hot pressed samples that described step (4) obtains, contain 3-10 layer silica fiber cloth, in hot pressed samples, silica fiber mass content is 15%-70%.
The temperature rise rate heating up in described step (5) is 0.1-20 ℃/min.
In described step (5), reactive atmosphere is ammonia.
The SiO obtaining in described step (5)
2in/SiBN matrix material, the weight percent of silica fiber is 15%-70%.
The present invention is by adopting SiBNC precursor solution dipping SiO
2cloth, carry out after crosslinked hot-forming, finally by hot-forming sample high temperature sintering.Present method is prepared SiO
2/ SIBN matrix material.
Beneficial effect
(1) preparation method of the present invention is simple, convenient operation;
(2) SiO that the present invention obtains
2/ SIBN composite density is large, and pore is few, and crackle is few, has good mechanical property and dielectric properties.
Accompanying drawing explanation
In Fig. 1, curve a is the infrared curve at the poly-silicon nitrogen borine of precursor polymer of 150 ℃ of polymerization 40h;
Curve b is for being warming up to 230 ℃, insulation 12h, the infrared curve of crosslinked precursor polymer at the poly-silicon nitrogen borine of the precursor polymer of 150 ℃ of polymerization 40h with the temperature rise rate of 4 ℃/min;
Curve c, for take the poly-silicon nitrogen borine precursor polymer of 150 ℃ of polymerization 40h as matrix is at 250 ℃, keeps 1h to carry out hot-forming under 550Mpa pressure, under ammonia atmosphere, with 3 ℃/min, be sintered to the SiO that 800 ℃ of insulation 3h obtain
2the infrared spectrum of/SiBN matrices of composite material;
Fig. 2, for take the poly-silicon nitrogen borine precursor polymer of 150 ℃ of polymerization 40h as matrix is at 250 ℃, keeps 1h to carry out hot-forming under 550Mpa pressure, under ammonia atmosphere, with 3 ℃/min, be sintered to the SiO that 800 ℃ of insulation 3h obtain
2the SEM photo of/SiBN matrix material section.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
The hexa methyl silazane (0.08mol) of 70g silicon tetrachloride (0.41mol) and 12.5g is placed in together to the there-necked flask of 250ml, at room temperature stir 20h, the product obtaining is added dropwise to slowly in the flask of 500ml of the boron trichloride (1.39mol) that 163g is housed at-40 ℃.Drip rear temperature and rise to 0 ℃ of reaction 1h, rise to slowly again room temperature, then under-78 ℃ of violent stirring to being slowly added drop-wise in there-necked flask in the anhydrous toluene solution of methylamine of 100ml, after dripping, temperature rises to 0 ℃, and reaction 5h, is rising to room temperature reaction 10h, then under vacuum, violent stirring to 75 ℃ is removed toluene, can obtain free nitrogen methyl silicon nitrogen borine (BSZ).Above-mentioned operating process all need be carried out in the environment of anhydrous and oxygen-free.
Embodiment 2
By monomers B SZ (n-formyl sarcolysine base silicon nitrogen borine), at 120 ℃, polymerization 15h obtains poly-silicon nitrogen borine precursor polymer.Silica fiber cloth is dipped in the toluene solution that mass concentration is 70% above-mentioned poly-silicon nitrogen borine precursor polymer, at room temperature vacuum impregnation 20h.Then the silica fiber cloth that is soaked with poly-silicon nitrogen borine precursor polymer obtained above is put into sintering oven and carry out crosslinking Treatment, under ammonia reactive atmosphere, temperature rise rate with 5 ℃/min is warming up to 180 ℃, insulation 10h, carry out crosslinking Treatment, the presoma that makes to be immersed on silica fiber cloth has certain degree of crosslinking.Under the environment of anhydrous and oxygen-free, the silica fiber cloth that is soaked with certain degree of crosslinking presoma obtaining is put into mould, be warmed up to 230 ℃, under 350Mpa pressure, keep 1h to carry out hot-forming, then drop to room temperature, and in temperature-fall period relief pressure gradually, in resulting sample, fibre content is 60%.Last resulting hot pressed samples is put into high temperature sintering furnace, under ammonia reactive atmosphere, with 1 ℃/min temperature rise rate, is warming up to 800 ℃, and insulation 10h, carries out high temperature sintering, is then down to room temperature, obtains SiO
2/ SiBN matrix material, fiber weight percentage is 40%.
By monomers B SZ (n-formyl sarcolysine base silicon nitrogen borine), at 150 ℃, polymerization 40h obtains poly-silicon nitrogen borine precursor polymer.Silica fiber cloth is dipped in the toluene solution that mass concentration is 40% above-mentioned poly-silicon nitrogen borine precursor polymer, at room temperature vacuum impregnation 15h.Then the silica fiber cloth that is soaked with poly-silicon nitrogen borine precursor polymer obtained above is put into sintering oven and carry out crosslinking Treatment, under ammonia reactive atmosphere, temperature rise rate with 4 ℃/min is warming up to 230 ℃, insulation 12h, carry out crosslinking Treatment, the presoma that makes to be immersed on silica fiber cloth has certain degree of crosslinking.Under the environment of anhydrous and oxygen-free, the silica fiber cloth that is soaked with certain degree of crosslinking presoma obtaining is put into mould, be warmed up to 250 ℃, under 550Mpa pressure, keep 1h to carry out hot-forming, then drop to room temperature, and in temperature-fall period relief pressure gradually, in resulting sample, fibre content is 70%.Last resulting hot pressed samples is put into high temperature sintering furnace, under ammonia reactive atmosphere, with 3 ℃/min temperature rise rate, is warming up to 1000 ℃, and insulation 10h, carries out high temperature sintering, is then down to room temperature, obtains SiO
2/ SiBN matrix material, fiber weight percentage is 60%.
Embodiment 4
By monomers B SZ (n-formyl sarcolysine base silicon nitrogen borine), at 180 ℃, polymerization 40h obtains poly-silicon nitrogen borine precursor polymer.Silica fiber cloth is dipped in the toluene solution that mass concentration is 80% above-mentioned poly-silicon nitrogen borine precursor polymer, at 200 ℃, heat pressing dipping 20h under 250Mpa.Then the silica fiber cloth that is soaked with poly-silicon nitrogen borine precursor polymer obtained above is put into sintering oven and carry out crosslinking Treatment, under ammonia reactive atmosphere, temperature rise rate with 3 ℃/min is warming up to 280 ℃, insulation 15h, carry out crosslinking Treatment, the presoma that makes to be immersed on silica fiber cloth has certain degree of crosslinking.Under the environment of anhydrous and oxygen-free, the silica fiber cloth that is soaked with certain degree of crosslinking presoma obtaining is put into mould, be warmed up to 280 ℃, under 350Mpa pressure, keep 1h to carry out hot-forming, then drop to room temperature, and in temperature-fall period relief pressure gradually, in resulting sample, fibre content is 80%.Last resulting hot pressed samples is put into high temperature sintering furnace, under ammonia reactive atmosphere, with 3 ℃/min temperature rise rate, is warming up to 800 ℃, and insulation 3h, carries out high temperature sintering, is then down to room temperature, obtains SiO
2/ SiBN matrix material, fiber weight percentage is 65%.
Claims (6)
1. a SiO
2the preparation method of/SiBN matrix material, comprising:
(1) by free nitrogen methyl silicon nitrogen borine at 60-270 ℃, polymerization 6-80h obtains the poly-silicon nitrogen borine of precursor polymer;
(2), at room temperature to 350 ℃, silica fiber cloth is dipped in the anhydrous toluene solution of above-mentioned poly-silicon nitrogen borine that mass concentration is 10-95% to vacuum impregnation or heat pressing dipping 0.5-30h under 1-750Mpa pressure;
(3) the silica fiber cloth that is impregnated with poly-silicon nitrogen borine step (2) being obtained carries out crosslinking Treatment, under reactive atmosphere, is warming up to 100-600 ℃, and insulation 2-50h, obtains the dipping silica fiber cloth after crosslinking Treatment;
(4) the dipping silica fiber cloth after above-mentioned crosslinking Treatment is put into mould, be warmed up to 80-500 ℃, under 10-750Mpa pressure, keep 0.1-5h to carry out hot-forming, obtain hot pressed samples;
(5) under reactive atmosphere, above-mentioned hot pressed samples is carried out to high temperature sintering, be warming up to 300-1200 ℃, insulation 0.1-50h, is then down to room temperature, obtains SiO
2/ SiBN matrix material;
In described step (3), reactive atmosphere is ammonia;
In described step (5), reactive atmosphere is ammonia.
2. a kind of SiO according to claim 1
2the preparation method of/SiBN matrix material, is characterized in that: the whole operating process of described step (1)～(5) is all carried out in the environment of anhydrous and oxygen-free.
3. a kind of SiO according to claim 1
2the preparation method of/SiBN matrix material, is characterized in that: the temperature rise rate heating up in described step (3) is 0.1-20 ℃/min.
4. a kind of SiO according to claim 1
2the preparation method of/SiBN matrix material, is characterized in that: in the hot pressed samples that described step (4) obtains, contain 3-10 layer silica fiber cloth, in hot pressed samples, silica fiber mass content is 15%-70%.
5. a kind of SiO according to claim 1
2the preparation method of/SiBN matrix material, is characterized in that: the temperature rise rate heating up in described step (5) is 0.1-20 ℃/min.
6. a kind of SiO according to claim 1
2the preparation method of/SiBN matrix material, is characterized in that: the SiO obtaining in described step (5)
2in/SiBN matrix material, the weight percent of silica fiber is 15%-70%.
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| CN106957179B (en) * | 2017-02-24 | 2020-05-29 | 东华大学 | SiBN fiber reinforced SiO2-BN-Al2O3Preparation method of wave-transparent composite material |
| CN108147841B (en) * | 2017-12-27 | 2019-09-24 | 江西嘉捷信达新材料科技有限公司 | Quartz ceramic-base wave-penetrating composite material and preparation method thereof |
| CN108892521B (en) * | 2018-07-06 | 2021-04-02 | 东华大学 | Preparation method of wave-transparent ceramic matrix composite material containing silicon-boron-nitrogen interface |
| CN115724675B (en) * | 2022-11-16 | 2023-12-19 | 航天特种材料及工艺技术研究所 | Polysilazane impregnation-curing treatment method, composite material and preparation method thereof |
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Non-Patent Citations (2)
| Title |
|---|
| "Processing and properties of C/Si-B-C-N fiber-reinforced ceramic matrix composites prepared by precursor impregnation and pyrolysis";See Hoon Lee et al.;《Acta Materialia》;20080128;第56卷;第1529-1538页 * |
| See Hoon Lee et al.."Processing and properties of C/Si-B-C-N fiber-reinforced ceramic matrix composites prepared by precursor impregnation and pyrolysis".《Acta Materialia》.2008,第56卷 |
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