CN102701771A - Preparation method for SiBNC fiber/SiBNC composite material - Google Patents
Preparation method for SiBNC fiber/SiBNC composite material Download PDFInfo
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- CN102701771A CN102701771A CN2012101693516A CN201210169351A CN102701771A CN 102701771 A CN102701771 A CN 102701771A CN 2012101693516 A CN2012101693516 A CN 2012101693516A CN 201210169351 A CN201210169351 A CN 201210169351A CN 102701771 A CN102701771 A CN 102701771A
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Abstract
The invention relates to a preparation method for a SiBNC fiber/SiBNC composite material. The preparation method for the SiBNC fiber/SiBNC composite material comprises the following steps: (1) preparing a precursor polymer by polymerizing a micromolecular monomer boron trichloride, methyl hydrogen dichlorosilane and hexamethyldisilazane; (2) pretreating the surface of the SiBNC fiber and performing pre-crosslinking with the precursor polymer; (3) performing thermoforming to obtain a prefabricated product; (4) performing infusible treatment on the prefabricated product; and (5) performing ceramic treatment at high temperature. The SiBNC fiber/SiBNC composite material prepared by the method has high density, uniform components, low porosity, high-temperature resistance and excellent mechanical performance.
Description
Technical field
The invention belongs to the preparation field of ceramic matric composite, the preparation method of particularly a kind of SiBNC fiber/SiBNC matrix material.
Background technology
Along with the develop rapidly of aerospace flight technology, the correlative study of some high-end space crafts is brought into schedule, particularly at supersonic aircraft, is written into aspects such as Atmosphere System and rocket propulsion system, and is more urgent to the demand of ultrahigh-temperature heat insulation material.Therefore, need the fundamental research of further reinforcing fibre enhancing ceramic matric composite, for technology and theoretical basis are established in its application in following aircraft.
As structured material; The SiBNC pottery has that heat-resisting ability is strong, resistance of oxidation is strong, high temperature creep-resisting property is good, hardness is big, wear-resistant, advantages such as coefficient of linear expansion is little, resistance to chemical attack; Shortcoming is plastic deformation ability poor (presenting fragility); Can not bear violent physical shock and thermal shocking, thereby have a strong impact on its practical application.For this reason, except improving with control crystal grain and phase toughness method, people are through adopting its characteristic of fiber reinforced method improvement.When this kind material takes place that in breaking-down process crack deflection, fibre breakage and fiber are extracted etc., absorb energy, both strengthened intensity and toughness, kept the good high-temperature performance again.Thereby FRCMC not only has characteristics such as height ratio mould, high temperature resistant, anti-ablation, anti-particle erosion, anti-oxidant and low density, and its intensity, particularly toughness, is superior to one-component ceramic.At present, World Airways engine design and manufacturers have have relatively researched and developed the FRCMC with resistance of oxidation in the concentrated area.
SiBNC makes matrix material with the SiBNC 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 SiBNC fiber/the SiBNC matrix material can be used as aerospace and weapon is used candidate material.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method of a kind of SiBNC fiber/SiBNC matrix material, and this method technology is simple, workable; SiBNC fiber/SiBNC the composite density that obtains is big; Composition is even, and porosity is low, and is high temperature resistant and mechanical property is excellent.
The preparation method of a kind of SiBNC fiber of the present invention/SiBNC matrix material comprises the following steps:
(1) preparation of precursor polymer:
Obtain gathering the borosilicate azane by three kinds of small molecule monomer boron trichlorides, dichloro methyl silane and hexamethyldisilazane polymerization;
(2) surface treatment of SiBNC fiber and with the precrosslink of precursor polymer:
Preparation gathers borosilicate azane toluene solution; Take out after placing above-mentioned solution to flood 1 ~ 3h the SiBNC fiber; SiBNC fiber and precursor polymer with dipping places tube furnace to be heated to 150 ~ 200 ℃ of precrosslink 1-3h respectively, makes the polymkeric substance of fiber surface and precursor polymer lightly crosslinked;
(3) hot compacting obtains prefabrication:
The precursor polymer of precrosslink is clayed into power with ball mill; With high-speed mixer with above-mentioned powder and surface treated SiBNC fiber thorough mixing; Compound is added in the mould at pressure for the 4-10MPa temperature is 180 ~ 200 ℃ of following hot pressing, obtain SiBNC fiber/SiBNC matrix material prefabrication after the demoulding;
(4) prefabrication melt processed not:
Down prefabrication is transferred in the tube furnace in nitrogen atmosphere protection, the gas displacement in the tube furnace is become nitrogen, feed trichlorosilane gas with stable flow rate after being warming up to 60 ~ 100 ℃ gradually from room temperature, be warming up to 240 ~ 280 ℃ of also thermostatically heating 1 ~ 5h again;
(5) pyroceramicization:
Stop to feed trichlorosilane gas, feed nitrogen and be warming up to 400 ~ 500 ℃ of insulation 1 ~ 2h, slowly be warming up to 1400 ~ 1600 ℃ again, slowly reduce to room temperature behind the constant temperature 2-5h, obtain SiBNC fiber/SiBNC matrix material.
The mole proportioning of three kinds of small molecules boron trichlorides, dimethyldichlorosilane(DMCS) and hexamethyldisilazanes is 1.3 ~ 2:2 ~ 3:8.5 ~ 9 in the said step (1).
The massfraction that gathers borosilicate azane toluene solution in the said step (2) is 10% ~ 50%.
Said step in (3) is clayed into power the precursor polymer of precrosslink, and its particle diameter is 100 ~ 300um.
Being heated to 60 ~ 100 ℃ temperature rise rate from room temperature in the said step (4) is 1 ~ 2 ℃/min.
After feeding trichlorosilane gas in the said step (4), be warming up to 240 ~ 280 ℃ with the speed of 0.5-2 ℃/min.
Temperature rise rate with 2-10 ℃/min in the said step (5) is heated to 400 ~ 500 ℃, is warming up to 1400 ~ 1600 ℃ with 0.8-1 ℃/min.
Beneficial effect
(1) preparation technology of the present invention is simple, and is workable, is suitable for industrialization promotion, and business potential is big;
(2) the SiBNC fiber/SiBNC composite density of the present invention preparation is big, and composition is even, and porosity is little, and is high temperature resistant and mechanical property is excellent.
Description of drawings
Fig. 1 is the preform of the present invention after hot-forming
Fig. 2 for the present invention through do not melt and pyroceramicization after goods
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 appended claims of the application institute restricted portion equally.
Embodiment 1
Small molecule monomer boron trichloride, dichloro methyl silane and hexamethyldisilazane are obtained precursor polymer by mole proportioning 1.3:2:8.5 reaction 75h under-40 ℃ gather the borosilicate azane.The preparation massfraction be 10% gather borosilicate azane toluene solution, take out after the SiBNC fiber is placed above-mentioned solution dipping 1h, SiBNC fiber and the precursor polymer with dipping places tube furnace to be heated to 150 ℃ of precrosslink 1h respectively, makes it lightly crosslinked.With the precursor polymer of precrosslink clay into power and with the SiBNC fiber thorough mixing of handling, compound is added in the mould, be 180 ℃ of following hot pressing at pressure for the 4MPa temperature.Down prefabrication is transferred in the tube furnace in nitrogen atmosphere protection, feeds trichlorosilane gas with stable flow rate after being heated to 60 ℃ with the temperature rise rate of 1 ℃/min from room temperature, the speed with 0.5 ℃/min is warming up to 240 ℃ of also constant temperature 1h again.Under nitrogen atmosphere, be heated to 400 ℃ and be incubated 1h with the temperature rise rate of 2 ℃/min, the speed with 0.8 ℃/min is warming up to 1400 ℃ again, slowly reduces to room temperature behind the constant temperature 2h.
Embodiment 2
Small molecule monomer boron trichloride, dichloro methyl silane and hexamethyldisilazane are obtained precursor polymer by mole proportioning 1.65:2.5:8.75 reaction 80h under 20 ℃ gather the borosilicate azane.The preparation massfraction be 30% gather borosilicate azane toluene solution, take out after the SiBNC fiber is placed above-mentioned solution dipping 2h, SiBNC fiber and the precursor polymer with dipping places tube furnace to be heated to 175 ℃ of precrosslink 2h respectively, makes it lightly crosslinked.With the precursor polymer of precrosslink clay into power and with the SiBNC fiber thorough mixing of handling, compound is added in the mould, be 190 ℃ of following hot pressing at pressure for the 7MPa temperature.Down prefabrication is transferred in the tube furnace in nitrogen atmosphere protection, feeds trichlorosilane gas with stable flow rate after being heated to 80 ℃ with the temperature rise rate of 1.5 ℃/min from room temperature, the speed with 1.25 ℃/min is warming up to 260 ℃ of also constant temperature 3h again.Under nitrogen atmosphere, be heated to 450 ℃ and be incubated 1.5h with the temperature rise rate of 6 ° of C/min, the speed with 0.9 ℃/min is warming up to 1500 ℃ again, slowly reduces to room temperature behind the constant temperature 3.5h.
Small molecule monomer boron trichloride, dichloro methyl silane and hexamethyldisilazane are obtained precursor polymer by mole proportioning 2:3:9 reaction 85h under 80 ℃ gather the borosilicate azane.The preparation massfraction be 50% gather borosilicate azane toluene solution, take out after the SiBNC fiber is placed above-mentioned solution dipping 3h, SiBNC fiber and the precursor polymer with dipping places tube furnace to be heated to 200 ℃ of precrosslink 3h respectively, makes it lightly crosslinked.With the precursor polymer of precrosslink clay into power and with the SiBNC fiber thorough mixing of handling, compound is added in the mould, be 200 ℃ of following hot pressing at pressure for the 10MPa temperature.Down prefabrication is transferred in the tube furnace in nitrogen atmosphere protection, feeds trichlorosilane gas with stable flow rate after being heated to 100 ℃ with the temperature rise rate of 2 ℃/min from room temperature, the speed with 2 ℃/min is warming up to 280 ℃ of also constant temperature 5h again.Under nitrogen atmosphere, be heated to 500 ℃ and be incubated 2h with the temperature rise rate of 10 ℃/min, the speed with 1 ℃/min is warming up to 1600 ℃ again, slowly reduces to room temperature behind the constant temperature 5h.
Claims (7)
1. the preparation method of SiBNC fiber/SiBNC matrix material comprises:
(1) obtains precursor polymer by small molecule monomer boron trichloride, monomethyl hydrogen dichlorosilane and hexamethyldisilazane at-40 ~ 80 ℃ of polymerase 17 5 ~ 85h and gather the borosilicate azane;
(2) preparation gathers borosilicate azane toluene solution, takes out after placing above-mentioned solution to flood 1 ~ 3h the SiBNC fiber, and SiBNC fiber and the precursor polymer with dipping is heated to 150 ~ 200 ℃ of precrosslink 1-3h respectively;
(3) precursor polymer of precrosslink is clayed into power; With above-mentioned powder and surface treated SiBNC fiber thorough mixing; It is 4-10MPa that compound is added in the mould at pressure, and temperature is 180 ~ 200 ℃ of following hot pressing, obtains SiBNC fiber/SiBNC matrix material prefabrication after the demoulding;
(4) down prefabrication is transferred in the tube furnace in nitrogen atmosphere protection, the gas displacement in the tube furnace is become nitrogen, feed trichlorosilane gas with stable flow rate after being warming up to 60 ~ 100 ℃ from room temperature, be warming up to 240 ~ 280 ℃ of also thermostatically heating 1 ~ 5h again;
(5) stop to feed trichlorosilane gas, feed nitrogen and be warming up to 400 ~ 500 ℃ of insulation 1 ~ 2h, be warming up to 1400 ~ 1600 ℃ again, slowly reduce to room temperature behind the constant temperature 2-5h, obtain SiBNC fiber/SiBNC matrix material.
2. the preparation method of a kind of SiBNC fiber according to claim 1/SiBNC matrix material, it is characterized in that: the mole proportioning of three kinds of small molecules boron trichlorides, dimethyldichlorosilane(DMCS) and hexamethyldisilazanes is 1.3 ~ 2:2 ~ 3:8.5 ~ 9 in the said step (1).
3. the preparation method of a kind of SiBNC fiber according to claim 1/SiBNC matrix material, it is characterized in that: the massfraction that gathers borosilicate azane toluene solution in the said step (2) is 10 ~ 50%.
4. the preparation method of a kind of SiBNC fiber according to claim 1/SiBNC matrix material, it is characterized in that: said step in (3) is clayed into power the precursor polymer of precrosslink, and its particle diameter is 100 ~ 300 μ m.
5. the preparation method of a kind of SiBNC fiber according to claim 1/SiBNC matrix material is characterized in that: being heated to 60 ~ 100 ℃ temperature rise rate from room temperature in the said step (4) is 1 ~ 2 ℃/min.
6. the preparation method of a kind of SiBNC fiber according to claim 1/SiBNC matrix material is characterized in that: after feeding trichlorosilane gas in the said step (4), be warming up to 240 ~ 280 ℃ with the speed of 0.5-2 ℃/min.
7. the preparation method of a kind of SiBNC fiber according to claim 1/SiBNC matrix material is characterized in that: be heated to 400 ~ 500 ℃ with 2-10 ℃/min temperature rise rate in the said step (5), be warming up to 1400 ~ 1600 ℃ with 0.8-1 ℃/min again.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104529499A (en) * | 2014-12-19 | 2015-04-22 | 东华大学 | Preparation method of self-healing silicon-carbide-fiber-reinforced silicon-boron-nitrogen-carbon composite material |
| 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 |
| CN105152670A (en) * | 2015-07-01 | 2015-12-16 | 西北工业大学 | Preparation method of SiC nanowire reinforced SiBCN ceramic |
| CN106518087A (en) * | 2016-11-16 | 2017-03-22 | 哈尔滨工业大学 | Preparation method of Si-B-C-N (silicon-boron-carbon-nitrogen) ceramic with PBSZ (polyborosilazane) as additive |
| CN104072785B (en) * | 2014-05-30 | 2017-04-05 | 西北工业大学 | A kind of dissaving polymer and preparation method thereof |
| 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 |
| CN109797459A (en) * | 2019-01-23 | 2019-05-24 | 中国人民解放军国防科技大学 | Preparation method of SiBCN nano ceramic fiber |
| CN115340379A (en) * | 2021-05-14 | 2022-11-15 | 中国科学院化学研究所 | High-carbon-content silicon-boron-carbon-nitrogen ceramic fiber and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800098A (en) * | 2005-01-05 | 2006-07-12 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of Si-B-C-N amorphous ceramic material for high temperature sensing device |
-
2012
- 2012-05-28 CN CN2012101693516A patent/CN102701771B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800098A (en) * | 2005-01-05 | 2006-07-12 | 中国科学院长春光学精密机械与物理研究所 | Preparation method of Si-B-C-N amorphous ceramic material for high temperature sensing device |
Non-Patent Citations (6)
| Title |
|---|
| 《无机材料学报》 20080531 唐云 等 "聚硼硅氮烷的合成及其热解产物的组成及结构" 第23卷, 第3期 * |
| 《有机硅材料》 20100630 李文华 等 "SiBNC陶瓷先驱体的热裂解过程研究" 第24卷, 第3期 * |
| 《稀有金属材料与工程》 20080131 唐云 等 "先驱体转化法制备SiBNC陶瓷" 第37卷, 第S1期 * |
| 唐云 等: ""先驱体转化法制备SiBNC陶瓷"", 《稀有金属材料与工程》, vol. 37, no. 1, 31 January 2008 (2008-01-31) * |
| 唐云 等: ""聚硼硅氮烷的合成及其热解产物的组成及结构"", 《无机材料学报》, vol. 23, no. 3, 31 May 2008 (2008-05-31) * |
| 李文华 等: ""SiBNC陶瓷先驱体的热裂解过程研究"", 《有机硅材料》, vol. 24, no. 3, 30 June 2010 (2010-06-30) * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104072785B (en) * | 2014-05-30 | 2017-04-05 | 西北工业大学 | A kind of dissaving polymer and preparation method thereof |
| 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 |
| CN104529499A (en) * | 2014-12-19 | 2015-04-22 | 东华大学 | Preparation method of self-healing silicon-carbide-fiber-reinforced silicon-boron-nitrogen-carbon composite material |
| CN105152670A (en) * | 2015-07-01 | 2015-12-16 | 西北工业大学 | Preparation method of SiC nanowire reinforced SiBCN ceramic |
| CN106518087B (en) * | 2016-11-16 | 2019-07-05 | 哈尔滨工业大学 | It is a kind of using poly- silicon boron azane as the preparation method of the Si-B-C-N ceramic of additive |
| CN106518087A (en) * | 2016-11-16 | 2017-03-22 | 哈尔滨工业大学 | Preparation method of Si-B-C-N (silicon-boron-carbon-nitrogen) ceramic with PBSZ (polyborosilazane) as additive |
| 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 |
| CN109797459A (en) * | 2019-01-23 | 2019-05-24 | 中国人民解放军国防科技大学 | Preparation method of SiBCN nano ceramic fiber |
| CN109797459B (en) * | 2019-01-23 | 2021-04-02 | 中国人民解放军国防科技大学 | Preparation method of SiBCN nano ceramic fiber |
| CN115340379A (en) * | 2021-05-14 | 2022-11-15 | 中国科学院化学研究所 | High-carbon-content silicon-boron-carbon-nitrogen ceramic fiber and preparation method and application thereof |
| CN115340379B (en) * | 2021-05-14 | 2023-09-01 | 中国科学院化学研究所 | High-carbon-content silicon-boron-carbon-nitrogen ceramic fiber as well as preparation method and application thereof |
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