CN102701771B - Preparation method for SiBNC fiber/SiBNC composite material - Google Patents
Preparation method for SiBNC fiber/SiBNC composite material Download PDFInfo
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- CN102701771B CN102701771B CN2012101693516A CN201210169351A CN102701771B CN 102701771 B CN102701771 B CN 102701771B CN 2012101693516 A CN2012101693516 A CN 2012101693516A CN 201210169351 A CN201210169351 A CN 201210169351A CN 102701771 B CN102701771 B CN 102701771B
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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, particularly the preparation method of 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 the aspects such as Atmosphere System and rocket propulsion system, and is more urgent to the demand of ultrahigh-temperature heat insulation material.Therefore, need further reinforcing fibre to strengthen the fundamental research of ceramic matric composite, technology and theoretical basis are established in the application for it in future aircraft.
As structured material, the SiBNC pottery has the advantages such as heat-resisting ability is strong, resistance of oxidation is strong, high temperature creep resistance is good, hardness is large, wear-resistant, coefficient of linear expansion is little, resistance to chemical attack, shortcoming is plastic deformation ability poor (presenting fragility), can not bear violent mechanical shock and thermal shocking, thereby have a strong impact on its practical application.For this reason, except with control crystal grain and phase toughness method, improving, people are by adopting its characteristic of fiber reinforced method improvement.Crack deflection, fibre breakage and fiber occur in this kind material in breaking-down process extract etc. in, absorb energy, both strengthened intensity and toughness, kept again good high-temperature behavior.Thereby FRCMC not only has the characteristics such as Gao Bimo, high temperature resistant, anti-ablation, anti-particle erosion, anti-oxidant and low density, and its intensity, particularly toughness, is better than one-component ceramic.At present, World Airways engine design and manufacturers have have relatively researched and developed the FRCMC with resistance of oxidation in concentrated area.
SiBNC makes matrix material with the SiBNC fiber reinforcement, can overcome the fragility of SiBNC pottery, keep simultaneously the excellent properties such as matrix high thermal resistance, anti-oxidant, anti-thermal shock, so SiBNC fiber/SiBNC matrix material can be used as aerospace and weapon candidate material.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of a kind of SiBNC fiber/SiBNC matrix material, and the method technique is simple, and is workable, the SiBNC fiber that obtains/the SiBNC composite density is large, 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, comprise the following steps:
(1) preparation of precursor polymer:
Obtain the poly-borosilicate azane of precursor polymer by three kinds of small molecule monomer boron trichlorides, dichloro methyl silane and hexamethyldisilazanes at-40～80 ℃ of polymerase 17 5～85h;
(2) surface treatment of SiBNC fiber and with the precrosslink of precursor polymer:
The poly-borosilicate azane toluene solution of preparation, the SiBNC fiber is placed in after above-mentioned solution floods 1～3h and takes out, the SiBNC fiber that will flood respectively and precursor polymer are placed in tube furnace and are heated to 150～200 ℃ of precrosslink 1-3h, make the polymkeric substance of fiber surface and precursor polymer lightly crosslinked;
(3) hot compacting obtains prefabrication:
With the precursor polymer of precrosslink grinding of ball grinder powdered, with high-speed mixer, above-mentioned powder and surface treated SiBNC fiber are fully mixed, it is that the 4-10MPa temperature is 180～200 ℃ of lower hot pressing at pressure that compound is added in mould, obtains SiBNC fiber/SiBNC composite precast product after the demoulding;
(4) prefabrication melt processed not:
In under the nitrogen atmosphere protection, prefabrication being transferred to tube furnace, the gas displacement in tube furnace is become nitrogen, be warming up to gradually after 60～100 ℃ and pass into trichlorosilane gas with stable flow from room temperature, then be warming up to 240～280 ℃ and thermostatically heating 1～5h;
(5) pyroceramic:
Stop passing into trichlorosilane gas, pass into nitrogen and be warming up to 400～500 ℃ of insulation 1～2h, more slowly be warming up to 1400～1600 ℃, slowly be down to room temperature after constant temperature 2-5h, obtain SiBNC fiber/SiBNC matrix material.
In described step (1), mole proportioning of three kinds of small molecules boron trichlorides, dimethyldichlorosilane(DMCS) and hexamethyldisilazanes is 1.3～2:2～3:8.5～9.
In described step (2), the massfraction of poly-borosilicate azane toluene solution is 10%～50%.
Described step in (3) is clayed into power the precursor polymer of precrosslink, and its particle diameter is 100～300um.
Being heated to the temperature rise rate of 60～100 ℃ from room temperature in described step (4) is 1～2 ℃/min.
After passing into trichlorosilane gas in described step (4), with the speed of 0.5-2 ℃/min, be warming up to 240～280 ℃.
Temperature rise rate with 2-10 ℃/min in described step (5) is heated to 400～500 ℃, with 0.8-1 ℃/min, is warming up to 1400～1600 ℃.
Beneficial effect
(1) preparation technology of the present invention is simple, and is workable, is suitable for industrialization promotion, and business potential is large;
(2) the present invention preparation the SiBNC fiber/the SiBNC composite density is large, composition is even, 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 be the present invention through do not melt and pyroceramic after goods
Embodiment
, below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for explanation the present invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the appended claims limited range of the application equally.
Embodiment 1
Small molecule monomer boron trichloride, dichloro methyl silane and hexamethyldisilazane are reacted 75h by mole proportioning 1.3:2:8.5 under-40 ℃ and obtain the poly-borosilicate azane of precursor polymer.The preparation massfraction is 10% poly-borosilicate azane toluene solution, and the SiBNC fiber is placed in after above-mentioned solution floods 1h and takes out, and the SiBNC fiber that will flood respectively and precursor polymer are placed in tube furnace and are heated to 150 ℃ of precrosslink 1h, make it lightly crosslinked.The precursor polymer of precrosslink being clayed into power and with the SiBNC fiber of processing, fully mix, compound is added in mould, is that the 4MPa temperature is 180 ℃ of lower hot pressing at pressure.In under nitrogen atmosphere protection, prefabrication being transferred to tube furnace, being heated to pass into trichlorosilane gas with stable flow after 60 ℃ from room temperature with the temperature rise rate of 1 ℃/min, then with the speed of 0.5 ℃/min, being warming up to 240 ℃ and constant temperature 1h.Be heated to 400 ℃ and be incubated 1h with the temperature rise rate of 2 ℃/min under nitrogen atmosphere, then with the speed of 0.8 ℃/min, be warming up to 1400 ℃, slowly be down to room temperature after constant temperature 2h.
Embodiment 2
Small molecule monomer boron trichloride, dichloro methyl silane and hexamethyldisilazane are reacted 80h by mole proportioning 1.65:2.5:8.75 under 20 ℃ and obtain the poly-borosilicate azane of precursor polymer.The preparation massfraction is 30% poly-borosilicate azane toluene solution, and the SiBNC fiber is placed in after above-mentioned solution floods 2h and takes out, and the SiBNC fiber that will flood respectively and precursor polymer are placed in tube furnace and are heated to 175 ℃ of precrosslink 2h, make it lightly crosslinked.The precursor polymer of precrosslink being clayed into power and with the SiBNC fiber of processing, fully mix, compound is added in mould, is that the 7MPa temperature is 190 ℃ of lower hot pressing at pressure.In under nitrogen atmosphere protection, prefabrication being transferred to tube furnace, being heated to pass into trichlorosilane gas with stable flow after 80 ℃ from room temperature with the temperature rise rate of 1.5 ℃/min, then with the speed of 1.25 ℃/min, being warming up to 260 ℃ and constant temperature 3h.Be heated to 450 ℃ and be incubated 1.5h with the temperature rise rate of 6 ℃/min under nitrogen atmosphere, then with the speed of 0.9 ℃/min, be warming up to 1500 ℃, slowly be down to room temperature after constant temperature 3.5h.
Small molecule monomer boron trichloride, dichloro methyl silane and hexamethyldisilazane are reacted 85h by mole proportioning 2:3:9 under 80 ℃ and obtain the poly-borosilicate azane of precursor polymer.The preparation massfraction is 50% poly-borosilicate azane toluene solution, and the SiBNC fiber is placed in after above-mentioned solution floods 3h and takes out, and the SiBNC fiber that will flood respectively and precursor polymer are placed in tube furnace and are heated to 200 ℃ of precrosslink 3h, make it lightly crosslinked.The precursor polymer of precrosslink being clayed into power and with the SiBNC fiber of processing, fully mix, compound is added in mould, is that the 10MPa temperature is 200 ℃ of lower hot pressing at pressure.In under nitrogen atmosphere protection, prefabrication being transferred to tube furnace, being heated to pass into trichlorosilane gas with stable flow after 100 ℃ from room temperature with the temperature rise rate of 2 ℃/min, then with the speed of 2 ℃/min, being warming up to 280 ℃ and constant temperature 5h.Be heated to 500 ℃ and be incubated 2h with the temperature rise rate of 10 ℃/min under nitrogen atmosphere, then with the speed of 1 ℃/min, be warming up to 1600 ℃, slowly be down to room temperature after constant temperature 5h.
Claims (7)
1. the preparation method of SiBNC fiber/SiBNC matrix material comprises:
(1) obtain the poly-borosilicate azane of precursor polymer by small molecule monomer boron trichloride, monomethyl hydrogen dichlorosilane and hexamethyldisilazane at-40 ~ 80 ℃ of polymerase 17 5 ~ 85h;
(2) the poly-borosilicate azane toluene solution of preparation, be placed in the SiBNC fiber after above-mentioned solution floods 1 ~ 3h and take out, and the SiBNC fiber that will flood respectively and precursor polymer are heated to 150 ~ 200 ℃ of precrosslink 1-3h;
(3) precursor polymer of precrosslink is clayed into power, above-mentioned powder and surface treated SiBNC fiber are fully mixed, it is 4-10MPa at pressure that compound is added in mould, and temperature is 180 ~ 200 ℃ of lower hot pressing, obtains SiBNC fiber/SiBNC composite precast product after the demoulding;
(4) under the nitrogen atmosphere protection, prefabrication being transferred to tube furnace, the gas displacement in tube furnace is become nitrogen, be warming up to after 60 ~ 100 ℃ and pass into trichlorosilane gas with stable flow from room temperature, then be warming up to 240 ~ 280 ℃ and thermostatically heating 1 ~ 5h;
(5) stop passing into trichlorosilane gas, pass into nitrogen and be warming up to 400 ~ 500 ℃ of insulation 1 ~ 2h, then be warming up to 1400 ~ 1600 ℃, slowly be down to room temperature after 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: in described step (1), mole proportioning of three kinds of small molecules boron trichlorides, dimethyldichlorosilane(DMCS) and hexamethyldisilazanes is 1.3 ~ 2:2 ~ 3:8.5 ~ 9.
3. the preparation method of a kind of SiBNC fiber according to claim 1/SiBNC matrix material is characterized in that: in described step (2), the massfraction of poly-borosilicate azane toluene solution 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: described 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 the temperature rise rate of 60 ~ 100 ℃ from room temperature in described 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 passing into trichlorosilane gas in described step (4), with the speed of 0.5-2 ℃/min, be warming up to 240 ~ 280 ℃.
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 described step (5), then with 0.8-1 ℃/min, be warming up to 1400 ~ 1600 ℃.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880449B (en) * | 2014-03-27 | 2015-09-16 | 中钢集团洛阳耐火材料研究院有限公司 | A kind of low-carbon aluminous-carbon refractory material for continuous casting preparation method |
| CN104072785B (en) * | 2014-05-30 | 2017-04-05 | 西北工业大学 | A kind of dissaving polymer and preparation method thereof |
| CN104532551B (en) * | 2014-12-12 | 2016-07-06 | 哈尔滨工业大学 | A kind of method that carbon fiber surface original position prepares Si-B-C-N ceramic coating |
| CN104529499B (en) * | 2014-12-19 | 2016-09-07 | 东华大学 | A kind of preparation method of self-sealing silicon carbide fiber reinforcement silicon boron nitrogen carbon composite |
| CN105152670B (en) * | 2015-07-01 | 2017-06-06 | 西北工业大学 | A kind of preparation method of SiC nanowire enhancing SiBCN ceramics |
| 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 |
| 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 |
| 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 |
| 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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| 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 |
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