CN102643101A - Preparation method of C/SiBNC composite material - Google Patents
Preparation method of C/SiBNC composite material Download PDFInfo
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- CN102643101A CN102643101A CN2012101158827A CN201210115882A CN102643101A CN 102643101 A CN102643101 A CN 102643101A CN 2012101158827 A CN2012101158827 A CN 2012101158827A CN 201210115882 A CN201210115882 A CN 201210115882A CN 102643101 A CN102643101 A CN 102643101A
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Abstract
The invention relates to a preparation method of a C/SiBNC composite material, which comprises the following steps: (1) polymerizing BSZ (borosilazane) monomers to obtain a polyborosilazane precursor polymer; (2) impregnating carbon fiber cloth into the polyborosilazane precursor polymer in a hot pressing mode; (3) carrying out cross-linking treatment on the carbon fiber cloth impregnated with the polyborosilazane precursor polymer obtained in the step (2); (4) carrying out hot pressing on the carbon fiber cloth obtained in the step (3), and cooling to room temperature while gradually relieving the pressure, thereby obtaining a hot-pressed infusible sample; and (5) carrying out high-temperature sintering on the hot-pressed infusible sample obtained in the step (4), thereby obtaining the C/SiBNC composite material. The preparation method is simple, and has the advantages of low cost and low facility request; and the C/SiBNC composite material has the advantages of high density, small bubbles, uniform composition, no cracking and excellent performance.
Description
Technical field
The invention belongs to the preparation field of SIBNC matrix material, particularly a kind of preparation method of C/SIBNC matrix material.
Background technology
The SiBNC pottery has performances such as excellent high temperature resistant, anti-oxidant, anti-thermal shock and creep resistance; Application prospect is extensive, but the fragility of SiBNC pottery is big, big limitations its application; SiBNC makes matrix material with the C fiber reinforcement; Can overcome the fragility of SiBNC pottery, keep excellent properties such as matrix high thermal resistance, anti-oxidant, anti-thermal shock simultaneously, so the C/SiBNC matrix material can be used as the candidate material of radome ablation-supporting region.
But because the C/SiBNC matrix material ceramic matrix that the presoma pickling process obtains has small molecules to overflow in high-temperature sintering process; " foaming " phenomenon can occur, cause matrices of composite material that a lot of pores are arranged, density is very little; There are a lot of crackles inside, and mechanical property is very poor.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of C/SIBNC matrix material, and this method is simple, and cost is low, less demanding to equipment, and the C/SIBNC composite density that obtains is big, and pore is little, and composition is even, flawless, excellent performance.
The preparation method of a kind of C/SIBNC matrix material of the present invention comprises the following steps:
(1) gather the polymerization of silicon nitrogen borine precursor polymer:
Monomers B SZ (n-formyl sarcolysine base silicon nitrogen borine) is obtained gathering silicon nitrogen borine precursor polymer at 80-230 ℃ of polymerization 6-40h.
(2) the carbon cloth dipping gathers silicon nitrogen borine precursor polymer:
Under room temperature to 300 ℃, carbon cloth is dipped in above-mentioned gathering in the silicon nitrogen borine precursor polymer, pressure is vacuum or 10-750Mpa, hot pressing dipping 0.5-30h;
(3) crosslinking Treatment:
The carbon cloth that gathers silicon nitrogen borine precursor polymer that is impregnated with that step (2) is obtained carries out crosslinking Treatment; Concrete operations are raised to 200-500 ℃ for the temperature rise rate with 1-20 ℃/min under inert atmosphere; Insulation 2-30h makes presoma full cross-linked, reaches infusible purpose;
(4) hot pressing:
It is hot-forming that the carbon cloth that under inert atmosphere protection, step (3) is obtained keeps 0.1-5h to carry out under 80-500 ℃ and 40-750Mpa pressure, drops to room temperature then, and in temperature-fall period relief pressure gradually, obtain not melting sample after hot-forming;
(5) high temperature sintering:
Under inert atmosphere, with step (4) obtain hot-forming after the sample that do not melt be heated to 800-2000 ℃ with 0.1-20 ℃/min temperature rise rate, the insulation 0.1-20h, reduce to room temperature then, promptly obtain the C/SIBNC matrix material.
All steps all are under the situation of secluding air and moisture, to carry out.
The hot pressing dipping carries out in high-purity (99.999%) nitrogen or high-purity argon gas in the said step (2).
Inert atmosphere in said step (3), (4), (5) is high-purity argon gas or high pure nitrogen.
Resulting not the melting after hot-forming of said step (4) contained 3-10 layer carbon cloth in the sample, quality of fiber content is at 15%-70%.
It is little that the present invention adopts hot pressing-sintering process to obtain void content, flawless, the C/SiBNC matrix material of excellent property.
The present invention is through having C cloth dipping in the SIBNC stupalith presoma of certain degree of crosslinking, under certain temperature and pressure, carries out hot-formingly, and the sample with moulding carries out high temperature sintering then, gets final product.
The preparation process of a kind of C/SIBNC matrix material of the present invention is as shown in Figure 1.
Beneficial effect:
(1) preparation method of the present invention is simple, and cost is low, less demanding to equipment;
(2) the C/SIBNC composite density that obtains of the present invention is big, and pore is little, and composition is even, flawless, excellent performance.
Description of drawings
Fig. 1 is the process flow sheet of preparation C/SIBNC matrix material of the present invention;
Fig. 2 for 150 ℃ of polyase 13 2h gather silicon nitrogen borine precursor polymer at 250 ℃, 500Mpa pressure keeps down the photo that obtains behind the 5h
Fig. 3 for 150 ℃ of polyase 13 2h gather silicon nitrogen borine precursor polymer at 250 ℃, 500Mpa pressure keeps down under argon gas atmosphere, being sintered to 1400 ℃ of C/SiBNC matrix material section SEM photos with 1 ℃/min behind the 5h.
Fig. 4 for 150 ℃ of polyase 13 2h gather silicon nitrogen borine precursor polymer at 250 ℃, 500Mpa pressure keeps down behind the 5h under argon gas atmosphere being sintered to 1 ℃/min the infrared curve of 1400 ℃ of matrices of composite materials.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The hexa methyl silazane (0.08mol) of 70g silicon tetrachloride (0.41mol) and 12.5g is placed together the there-necked flask of 250ml; At room temperature stir 20h, the product that obtains is added dropwise under-40 ℃ in the flask of 500ml of the boron trichloride (1.39mol) that 163g is housed slowly.Drip the back temperature and rise to 0 ℃ of reaction 1h, rise to room temperature more slowly, under-78 ℃ of violent stirring, in there-necked flask, slowly be added drop-wise to then 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; Violent stirring to 75 ℃ removal toluene under vacuum can obtain free nitrogen methyl silicon nitrogen borine (BSZ) then.Above-mentioned operating process all needs in the environment of anhydrous and oxygen-free, to carry out.
Embodiment 2
Monomers B SZ is obtained gathering silicon nitrogen borine precursor polymer at 130 ℃ of following polymerization 12h.Carbon cloth vacuum impregnation is at room temperature gathered silicon nitrogen borine precursor polymer 10h; Thomel after will flooding then places sintering oven to make to gather silicon nitrogen borine precursor polymer generation crosslinking reaction; This operates in, and the temperature rise rate with 5 ℃/min is raised to 280 ℃ under the inert atmosphere; Insulation 4h makes presoma full cross-linked.The carbon cloth that obtains after above-mentioned steps handled is put into stainless steel mould, is warmed up to 80 ℃, maintenance 0.5h under 100Mpa pressure, then in cooling to the process of room temperature gradually with discharge degree.Then the sample of the demoulding is packed in the high temperature sintering furnace, under inert atmosphere, be heated to 1400 ℃, be incubated 3 hours, reduce to room temperature then, obtain the C/SIBNC matrix material with 5 ℃/min temperature rise rate.
Monomer is gathered silicon nitrogen borine presoma gather silicon nitrogen borine precursor polymer what 150 ℃ of following polymerization 20h obtained having certain polymerization degree.The thomel of handling is dipped in gathers silicon nitrogen borine precursor polymer; At 100 ℃ of vacuum impregnation 10h; Place sintering oven to carry out not melt processed the silicon nitrogen borine precursor polymer of gathering that is immersed on the thomel; This operates in, and the temperature rise rate with 10 ℃/min is raised to 300 ℃ under the inert atmosphere, and insulation 10h makes presoma full cross-linked.The thomel that obtains after then above-mentioned steps the being handled stainless steel mould of packing into is warmed up to 120 ℃, maintenance 1h under 200Mpa pressure, then in cooling to the process of room temperature gradually with discharge degree.Then the sample of the demoulding is packed in the high temperature sintering furnace, under inert atmosphere, be heated to 1600 ℃ with 1 ℃/min temperature rise rate, insulation 0.5h reduces to room temperature then, obtains final sample.
Embodiment 4
Monomer is gathered silicon nitrogen borine presoma be aggregated under 180 ℃, what polymerization 25h obtained having certain polymerization degree gathers silicon nitrogen borine precursor polymer.The thomel of handling is dipped in gathers silicon nitrogen borine precursor polymer; At 80 ℃ of vacuum impregnation 20h; Place sintering oven to carry out not melt processed the silicon nitrogen borine precursor polymer of gathering that is immersed on the thomel; This operates in, and the temperature rise rate with 15 ℃/min is raised to 350 ℃ under the inert atmosphere, and insulation 15h makes presoma full cross-linked.The thomel that obtains after then above-mentioned steps the being handled stainless steel mould of packing into is warmed up to 180 ℃, maintenance 1.5h under 300Mpa pressure, then in cooling to the process of room temperature gradually with discharge degree.Then the sample of the demoulding is packed in the high temperature sintering furnace, under inert atmosphere, be heated to 1000 ℃ with 10 ℃/min temperature rise rate, insulation 2h reduces to room temperature then, obtains final sample.Above-mentioned all steps all are under the situation of secluding air and moisture, to carry out.
Embodiment 5
Monomer is gathered silicon nitrogen borine presoma be aggregated under 200 ℃, what polyase 13 0h obtained having certain polymerization degree gathers silicon nitrogen borine precursor polymer.The thomel of handling is dipped in gathers silicon nitrogen borine precursor polymer; At 100 ℃, 50Mpa hot pressing dipping 10h; Place sintering oven to carry out not melt processed the silicon nitrogen borine precursor polymer of gathering that is immersed on the thomel; This operates in, and the temperature rise rate with 15 ℃/min is raised to 400 ℃ under the inert atmosphere, and insulation 20h makes presoma full cross-linked.The thomel that obtains after then above-mentioned steps the being handled stainless steel mould of packing into is warmed up to 200 ℃, maintenance 0.5h under 100Mpa pressure, then in cooling to the process of room temperature gradually with discharge degree.Then the sample of the demoulding is packed in the high temperature sintering furnace, under inert atmosphere, be heated to 1800 ℃ with 5 ℃/min temperature rise rate, insulation 3h reduces to room temperature then, obtains final sample.
Embodiment 6
Monomer is gathered silicon nitrogen borine presoma be aggregated under 150 ℃, polyase 13 2h obtains having the polymkeric substance of certain polymerization degree.The thomel of handling is dipped in gathers silicon nitrogen borine precursor polymer; Hot pressing dipping 20h under 200 ℃, 500Mpa; Place sintering oven to carry out not melt processed the silicon nitrogen borine precursor polymer of gathering that is immersed on the thomel; This operates in, and the temperature rise rate with 15 ℃/min is raised to 400 ℃ under the inert atmosphere, and insulation 24h makes presoma full cross-linked.The thomel that obtains after then above-mentioned steps the being handled stainless steel mould of packing into is warmed up to 250 ℃, maintenance 5h under 500Mpa pressure, then in cooling to the process of room temperature gradually with discharge degree.Then the sample of the demoulding is packed in the high temperature sintering furnace, under inert atmosphere, be heated to 1600 ℃ with 5 ℃/min temperature rise rate, insulation 5h reduces to room temperature then, obtains final sample.
Claims (5)
1. the preparation method of a C/SIBNC matrix material comprises:
(1) free nitrogen methyl silicon nitrogen borine BSZ is obtained gathering silicon nitrogen borine precursor polymer at 80-230 ℃ of polymerization 6-40h;
(2) under room temperature to 300 ℃, carbon cloth is dipped in above-mentioned gathering in the silicon nitrogen borine precursor polymer, pressure is vacuum or 10-750Mpa, hot pressing dipping 0.5-30h;
(3) carbon cloth that gathers silicon nitrogen borine precursor polymer that is impregnated with that step (2) is obtained carries out crosslinking Treatment, and concrete operations are raised to 200-500 ℃ for the temperature rise rate with 1-20 ℃/min under inert atmosphere, insulation 2-30h;
(4) carbon cloth that under inert atmosphere protection, step (3) is obtained keeps 0.1-5h to carry out hot-forming under 80-500 ℃ and 40-750Mpa pressure; Drop to room temperature then; And in temperature-fall period relief pressure gradually, obtain not melting sample after hot-forming;
(5) under inert atmosphere, with step (4) obtain hot-forming after the sample that do not melt be heated to 800-2000 ℃ with 0.1-20 ℃/min temperature rise rate, the insulation 0.1-20h, reduce to room temperature then, promptly get.
2. the preparation method of a kind of C/SIBNC matrix material according to claim 1 is characterized in that: described whole preparation method all is under the situation of secluding air and moisture, to carry out.
3. the preparation method of a kind of C/SIBNC matrix material according to claim 1 is characterized in that: the hot pressing dipping carries out in high pure nitrogen or high-purity argon gas in the said step (2).
4. the preparation method of a kind of C/SIBNC matrix material according to claim 1 is characterized in that: the inert atmosphere in said step (3), (4), (5) is high-purity argon gas or high pure nitrogen.
5. the preparation method of a kind of C/SIBNC matrix material according to claim 1 is characterized in that: resulting not the melting after hot-forming of said step (4) contained 3-10 layer carbon cloth in the sample, quality of fiber content is at 15%-70%.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965767A (en) * | 2012-11-23 | 2013-03-13 | 中国科学院化学研究所 | Hybrid carbon nanofiber and preparation method thereof |
| CN103243548A (en) * | 2013-05-22 | 2013-08-14 | 东华大学 | Preparation method of high-temperature-resistant SiBN(C) carbon fiber coating |
| CN103880449A (en) * | 2014-03-27 | 2014-06-25 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of low-carbon aluminum-carbon refractory material for use in continuous casting |
| CN104532551A (en) * | 2014-12-12 | 2015-04-22 | 哈尔滨工业大学 | Method for in-situ preparing silicon-boron-carbon-nitrogen ceramic coating on surface of carbon fiber |
| CN104649699A (en) * | 2015-01-30 | 2015-05-27 | 中国人民解放军国防科学技术大学 | Carbon fiber of externally-deposited SiBCN gradient coating and preparation method thereof |
| CN105152670A (en) * | 2015-07-01 | 2015-12-16 | 西北工业大学 | Preparation method of SiC nanowire reinforced SiBCN ceramic |
| CN106966748A (en) * | 2016-11-23 | 2017-07-21 | 北京航空航天大学 | Superhigh temperature resistant and there is ceramic matric composite of self-healing capability and preparation method thereof |
| CN107675110A (en) * | 2017-09-08 | 2018-02-09 | 东华大学 | A kind of carbon fiber reinforced metal aluminium composite material and preparation method thereof |
| WO2018205156A1 (en) * | 2017-05-09 | 2018-11-15 | 南通纺织丝绸产业技术研究院 | Carborane-ceramic-coating-based heat-resistant textile and preparation method therefor |
| CN109320275A (en) * | 2018-10-09 | 2019-02-12 | 中国航空工业集团公司基础技术研究院 | A kind of preparation method of anti-oxidant SiC fiber reinforced ceramic matrix composites |
| CN114656922A (en) * | 2022-03-28 | 2022-06-24 | 北京理工大学 | Preparation method of SiBCN ceramic-based continuous adhesive film |
| CN115724674A (en) * | 2022-11-16 | 2023-03-03 | 航天特种材料及工艺技术研究所 | Impregnation-curing treatment method of polysilaborazane, composite material and preparation method |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965767A (en) * | 2012-11-23 | 2013-03-13 | 中国科学院化学研究所 | Hybrid carbon nanofiber and preparation method thereof |
| CN102965767B (en) * | 2012-11-23 | 2014-08-13 | 中国科学院化学研究所 | Hybrid carbon nanofiber and preparation method thereof |
| CN103243548A (en) * | 2013-05-22 | 2013-08-14 | 东华大学 | Preparation method of high-temperature-resistant SiBN(C) carbon fiber coating |
| CN103880449A (en) * | 2014-03-27 | 2014-06-25 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of low-carbon aluminum-carbon refractory material for use in continuous casting |
| CN104532551A (en) * | 2014-12-12 | 2015-04-22 | 哈尔滨工业大学 | Method for in-situ preparing silicon-boron-carbon-nitrogen ceramic coating on surface of carbon fiber |
| CN104649699A (en) * | 2015-01-30 | 2015-05-27 | 中国人民解放军国防科学技术大学 | Carbon fiber of externally-deposited SiBCN gradient coating and preparation method thereof |
| CN105152670A (en) * | 2015-07-01 | 2015-12-16 | 西北工业大学 | Preparation method of SiC nanowire reinforced SiBCN ceramic |
| CN106966748A (en) * | 2016-11-23 | 2017-07-21 | 北京航空航天大学 | Superhigh temperature resistant and there is ceramic matric composite of self-healing capability and preparation method thereof |
| CN106966748B (en) * | 2016-11-23 | 2018-04-03 | 北京航空航天大学 | Superhigh temperature resistant and there is ceramic matric composite of self-healing capability and preparation method thereof |
| WO2018205156A1 (en) * | 2017-05-09 | 2018-11-15 | 南通纺织丝绸产业技术研究院 | Carborane-ceramic-coating-based heat-resistant textile and preparation method therefor |
| CN107675110A (en) * | 2017-09-08 | 2018-02-09 | 东华大学 | A kind of carbon fiber reinforced metal aluminium composite material and preparation method thereof |
| CN109320275A (en) * | 2018-10-09 | 2019-02-12 | 中国航空工业集团公司基础技术研究院 | A kind of preparation method of anti-oxidant SiC fiber reinforced ceramic matrix composites |
| CN114656922A (en) * | 2022-03-28 | 2022-06-24 | 北京理工大学 | Preparation method of SiBCN ceramic-based continuous adhesive film |
| CN115724674A (en) * | 2022-11-16 | 2023-03-03 | 航天特种材料及工艺技术研究所 | Impregnation-curing treatment method of polysilaborazane, composite material and preparation method |
| CN115724674B (en) * | 2022-11-16 | 2023-12-19 | 航天特种材料及工艺技术研究所 | Impregnation-curing treatment method of polysilabozane, composite material and preparation method |
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Application publication date: 20120822 |