CN104230367A - SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C composite material and preparation method thereof - Google Patents
SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C composite material and a preparation method thereof. A technical scheme adopted by the invention is that the preparation method of the SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C composite material comprises the following steps: mixing 1-5wt% of organic boron, 5-10wt% of organic silicon, 10-20wt% of a ZrC precusor and 65-84wt% of an asphalt methylbenzene soluble component, adding a solvent to dissolve the mixture, reacting the obtained solution for 1-4 hours at 300-450 DEG C to obtain boron-silicon-zirconium-doped asphalt; dipping a carbon fiber prefabricated body with the boron-silicon-zirconium-doped asphalt, and then carrying out pyrolysis treatment to obtain a SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C perform body; and repeatedly dipping and carrying out pyrolysis treatment on the SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C perform body until the density is 1.9-2.5g/cm<3> to obtain the SiC-ZrC-ZrB2 nano complex phase ceramic modified C/C composite material. The composite material prepared by the preparation method has good mechanical performance, self-healing antioxidant ability and superhigh temperature ablation resistance within a wider temperature range.
Description
Technical field
The invention belongs to C/C technical field of composite materials.Relate to a kind of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof.
Background technology
C/C matrix material has a series of premium propertiess such as low density, high specific strength, high ratio modulus, low thermal coefficient of expansion, heat shock resistance and resistance to ablation, has broad application prospects at Aeronautics and Astronautics, nuclear energy and civil area.But, because C/C matrix material just starts oxidation at the aerobic environment of 450 ° of more than C, oxidation directly causes that the hole of C/C matrix material increases, mechanical property reduction, and along with the rising of temperature, the degree of oxidation of matrix material presents remarkable ascendant trend, if do not take effective oxidation protection measure, use C/C matrix material will produce catastrophic consequence for a long time at high-temperature oxidation environment.Along with the continuous lifting of China's aerospace field development to hyperthermal material performance requriements, the oxidant protection under high temperature problem solving C/C matrix material just seems particularly important.
At present, the method improving C/C matrix material high-temperature oxidation resistance mainly contains two kinds: one prepares oxidation resistant coating at composite material surface, utilizes coating to intercept oxidizing atmosphere, reach oxidation resistant object; Another kind carries out modification (Li Hejun to matrices of composite material, Xue Hui, Fu Qiangang, Deng. the status and prospectives of C/C matrix material high-temperature oxidation resistant coating. Journal of Inorganic Materials, 2010,25 (4): 339-42.), by introducing at intrinsic silicon the resistance of oxidation that antioxidant composition improves himself.Effects on surface coating, because the matched coefficients of thermal expansion problem between coated material and C/C matrix material is difficult to be solved at all, in preparation with use procedure, the thermal stresses in material can make coating generation tiny crack even come off; Physical abuse also can make coating occur wound face, loses the provide protection to C/C matrix material.This defect greatly limit the future development (Yang Xing of oxidation resistant coating technology to more elevated operating temperature, more long service live, Cui Hong, Yan Liansheng. C/C matrices of composite material study on the modification present situation. material Leader, 2007,21 (8): 22-9).
Matrix modification method in C/C matrices of composite material, introduces the ceramic phases such as carbide, boride, silicide as oxygen-inhibiting agent by different modes; these oxygen-inhibiting agents can be oxidized to flowable vitreous state Solid solution in high temperature and oxidizing atmosphere; and then form the protective membrane with self-healing function; can effectively masking material surface imperfection and tiny crack; reduce oxidation activity point position; stop oxygen to spread to material internal simultaneously, thus suppress or stop completely the generation of oxidizing reaction to a great extent.Large quantity research shows, in C/C matrices of composite material, introduce SiC, ZrC, ZrB simultaneously
2deng ceramic phase, can greatly improve material anti-oxidant, anti-yaw damper performance (Lee Mangnolia officinalis, Zhang Litong, Cheng Laifei, Wang Yiguang. C/ZrB
2the Burning corrosion resistance of different structure coating under oxy-acetylene flame of – SiC ceramic matrix composite material. international applications ceramic technology, 2009,6 (2): 145-50; Li Zhaoqian, Li Hejun, Zhang Shouyang, Li Kezhi. the overall felt adopting two-step approach to prepare strengthens microstructure and the ablation behavior of C/C – SiC – ZrC matrix material. and pottery is international, and 2012,38 (4): 3419-25).At present by SiC, ZrC, ZrB
2vapor phase process and solid phase method is mainly contained Deng the ceramic phase method be incorporated in C/C matrices of composite material.Vapor phase process adopts chemical vapor infiltration technology (CVI) to be introduced by ceramic phase usually, and because CVI process mostly occurs at precast body near surface, central zone not easily deposits usually and sealing of hole phenomenon easily appears in surface, affects further densification.In addition, usually can produce macro-corrosion gas in CVI process, higher to the requirement of equipment, and preparation cycle is long, production cost is high, and these factors all limit its large-scale application.Solid phase method by slurry infiltration (Tang Sufang, Deng Jingyi, Wang Shijun, Yang Ke. the ablation behavior of ultrahigh temperature ceramic composite. Materials Science and Engineering A. 2007,465 (1-2): 1-7; Tang Sufang, Deng Jingyi, Liu Wenchuan, Yang Ke. the machinery of the two-dimentional C/C matrix material of preimpregnation SiC weighting material and ablative properties. charcoal, 2006,44 (14): 2877-82) or slurry brushing (Lee Mangnolia officinalis, Zhang Litong, Cheng Laifei, Wang Yiguang. C/ZrB
2the Burning corrosion resistance of different structure coating under oxy-acetylene flame of – SiC matrix material. international applications ceramic technology, 2009,6 (2): 145-50) ceramic is incorporated in Carbon fibe precast body or C/C matrix material.But in specific implementation process, there is following two problems: (1) is difficult to realize ceramic particle being uniformly distributed in carbon matrix and Carbon fibe bundle, what thus to greatly limit between various ceramic composition collaborative resistance of oxidation gives full play to (Paul P. P., Schwab S.T. obtains Carbon Materials and oxidation-resistance thereof by the metal organic decoration of pitch. charcoal, 1996,34 (1): 89-95); (2) the adding normally to reduce the high-temperature behavior of C/C matrix material be cost of oxidation-resistant ceramic particle.Add-on too much can make the mechanical property of matrix material obviously decline, and add-on very little, be not enough to form the glass coating met the demands, do not have completely isolated oxygen, prevent its effect diffusing into material matrix (remove group, Cao Liyun, Huang Jianfeng. the anti-oxidant Progress in Modification of carbon/carbon composite material base body. Arms Material scientific and engineering, 2010,33 (2): 98-102).
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, and object is to provide a kind of SiC-ZrC-ZrB
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, the SiC-ZrC-ZrB prepared by the method
2nano heterogeneous ceramic modification C/C matrix material has good mechanical property, the self-healing anti-oxidation ability of wide temperature range and ultrahigh-temperature anti-yaw damper performance.
For achieving the above object, the technical solution used in the present invention is:
The pre-treatment of step one, Carbon fibe precast body
By Carbon fibe precast body acetone cleaning 30 ~ 60min, under 70 ~ 100 ° of C conditions, dry 1 ~ 2h, obtains pre-treatment Carbon fibe precast body.
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction.
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 1 ~ 5wt%, 5 ~ 10wt%, 10 ~ 20wt% and 65 ~ 84wt% is mixed, obtains mixture.In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution.Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 2 ~ 10 ° of C/min, reactor is warming up to 300 ~ 450 ° of C, insulation 1 ~ 4h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch.
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.2 ~ 0.5) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered.The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 3 ~ 5MPa, heat-insulation pressure keeping 0.5 ~ 2 h.Then under identical pressure condition, be warming up to 350 ~ 500 ° of C, heat-insulation pressure keeping 4 ~ 6h, naturally cools to room temperature, pressure release.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1600 ° of C with the temperature rise rate of 2 ~ 10 ° of C/min, insulation 1 ~ 3h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.2 ~ 0.5), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers.Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, is evacuated to 0.02 ~ 0.08MPa, then reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, and filling with inert gas to the pressure in reactor is 3 ~ 5MPa, heat-insulation pressure keeping 0.5 ~ 2h.Then under identical pressure condition, be warming up to 350 ~ 500 ° of C, heat-insulation pressure keeping 4 ~ 6h, naturally cools to room temperature, and pressure release completes single-steeping.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1600 ° of C with the temperature rise rate of 2 ~ 10 ° of C/min, insulation 1 ~ 3h, is cooled to room temperature, completes a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
Described Carbon fibe precast body is the one in overall felt Carbon fibe precast body, charcoal cloth/net tire lamination needle-punched carbon fiber precast body and 3 D weaving Carbon fibe precast body, and the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
Described pitch is coal-tar pitch or is petroleum pitch.
Described organic boron is the one in polyborazine, pyridine borane and 2-picoline borine.
Described organosilicon is the one in Polycarbosilane, polydimethylsiloxane and trimethysilyl chloride.
The preparation process of described ZrC presoma is: reactor is evacuated to 0.06 ~ 0.08MPa, passes into argon gas to normal pressure, then in reactor, adds toluene, zirconates and dehydrated alcohol successively, stirs.Wherein: zirconates: toluene: the mol ratio of dehydrated alcohol is 1: (3 ~ 5): (4 ~ 10); Then under 10 ~ 10 ° of C conditions, pass into ammonia, the flow passing into ammonia is 40 ~ 60ml/min, and reaction 2 ~ 6h, filters, obtain the toluene solution of alcohol zirconium.
Reactor is evacuated to 0.06 ~ 0.08MPa, pass into argon gas to normal pressure, add the toluene solution of alcohol zirconium, beta-diketon and phenol to reactor successively again, stir, wherein: beta-diketon: phenol: the mol ratio of zirconates is (1 ~ 4): (2 ~ 4): 1; Then by the temperature rise rate of 2 ~ 4 ° of C/min, reaction system is heated to 120 ~ 300 ° of C, insulation 1 ~ 10h, underpressure distillation, is cooled to room temperature, obtains ZrC presoma.
Described solvent is toluene or is dimethylbenzene.
Described churned mechanically rotating speed is 200 ~ 600r/min.
Described rare gas element is argon gas or is nitrogen.
Described medium is the one in acetone, dehydrated alcohol and deionized water.
Owing to adopting technique scheme, the present invention compared with prior art has following positively effect:
(1) boron, silicon and zirconium atom are introduced in the condensed-nuclei aromatics molecule of pitch by the copyrolysis of pitch toluene soluble fraction and organic boron, organosilicon and ZrC presoma by the present invention, other is dispersed to make boron, silicon and zirconium heteroatoms reach molecular level in pitch, and borosilicate zirconium doping pitch can generate the ZrB of even dispersion after high-temperature heat treatment at carbon matrix situ
2, SiC and ZrC nano heterogeneous ceramic.
(2) due to ZrB
2, SiC and ZrC nano heterogeneous ceramic is evenly distributed in carbon matrix, SiC-ZrC-ZrB
2the B that nano heterogeneous ceramic is formed in oxidising process
2o
3, SiO
2, ZrO
2interreaction can dissolve with mutual in different temperature ranges Deng oxide compound, form continuous and stable protective membrane, therefore only need introduce a small amount of ZrB in C/C matrix material
2, SiC and ZrC nano heterogeneous ceramic just can significantly improve self-healing anti-oxidation ability and the ultrahigh-temperature anti-yaw damper performance of material wide temperature range.
(3) generated in-situ ZrB in carbon matrix
2and there is between ZrC and carbon good physics and chemistry consistency, greatly can improve the mechanical property of C/C matrix material.
(4) SiC-ZrC-ZrB for preparing of the present invention
2nano heterogeneous ceramic modification C/C matrix material is oxidized 10h under static atmosphere of air and 1100 ° of C conditions, sample weight gain 0.2 ~ 0.5 wt%; Be oxidized 10 h at 1600 ° of C, oxidation weight loss is 0.1 ~ 0.3 wt% only; Oxidation ablation 120s in the oxy-acetylene flame of 3000 ° of C, its linear ablative rate is only 0.001 ~ 0.0015mm/s.
Therefore, present invention efficiently solves solid phase method and prepare SiC-ZrC-ZrB
2the SiC-ZrC-ZrB that complex phase ceramic modification C/C matrix material exists
2complex phase ceramic disperses uneven problem in carbon matrix, the SiC-ZrC-ZrB of preparation
2nano heterogeneous ceramic modification C/C matrix material has self-healing anti-oxidation ability and the ultrahigh-temperature anti-yaw damper performance of good mechanical property and wide temperature range.
Accompanying drawing explanation
Fig. 1 is a kind of SiC-ZrC-ZrB prepared by the present invention
2the XRD spectra of nano heterogeneous ceramic modification C/C matrix material;
Fig. 2 is SiC-ZrC-ZrB described in Fig. 1
2the SEM photo of nano heterogeneous ceramic modification C/C composite material surface;
Fig. 3 is SiC-ZrC-ZrB shown in Fig. 2
2the distribution plan of nano heterogeneous ceramic modification C/C composite material surface carbon;
Fig. 4 is SiC-ZrC-ZrB shown in Fig. 2
2the distribution plan of nano heterogeneous ceramic modification C/C composite material surface boron;
Fig. 5 is SiC-ZrC-ZrB shown in Fig. 2
2the distribution plan of nano heterogeneous ceramic modification C/C composite material surface element silicon;
Fig. 6 is SiC-ZrC-ZrB shown in Fig. 2
2the distribution plan of nano heterogeneous ceramic modification C/C composite material surface zr element.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, the restriction not to its protection domain.
For avoiding repetition, first by as follows for the preparation process Unify legislation of the ZrC presoma in this embodiment, repeat no more in embodiment:
The preparation process of described ZrC presoma is: reactor is evacuated to 0.06 ~ 0.08MPa, passes into argon gas to normal pressure, then in reactor, adds toluene, zirconates and dehydrated alcohol successively, stirs.Wherein: zirconates: toluene: the mol ratio of dehydrated alcohol is 1: (3 ~ 5): (4 ~ 10); Then under 10 ~ 10 ° of C conditions, pass into ammonia, the flow passing into ammonia is 40 ~ 60ml/min, and reaction 2 ~ 6h, filters, obtain the toluene solution of alcohol zirconium.
Reactor is evacuated to 0.06 ~ 0.08MPa, pass into argon gas to normal pressure, add the toluene solution of alcohol zirconium, beta-diketon and phenol to reactor successively again, stir, wherein: beta-diketon: phenol: the mol ratio of zirconates is (1 ~ 4): (2 ~ 4): 1; Then by the temperature rise rate of 2 ~ 4 ° of C/min, reaction system is heated to 120 ~ 300 ° of C, insulation 1 ~ 10h, underpressure distillation, is cooled to room temperature, obtains ZrC presoma.
embodiment 1
A kind of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof.The concrete steps of described preparation method are:
The pre-treatment of step one, Carbon fibe precast body
By Carbon fibe precast body acetone cleaning 30 ~ 60min, under 70 ~ 100 ° of C conditions, dry 1 ~ 2h, obtains pre-treatment Carbon fibe precast body.
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction.
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 1 ~ 2wt%, 5 ~ 6wt%, 10 ~ 12wt% and 80 ~ 84wt% is mixed, obtains mixture.In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution.Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 2 ~ 5 ° of C/min, reactor is warming up to 300 ~ 350 ° of C, insulation 1 ~ 2h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch.
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.2 ~ 0.3) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered.The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 3 ~ 3.5MPa, heat-insulation pressure keeping 0.5 ~ 1 h.Then under identical pressure condition, be warming up to 350 ~ 400 ° of C, heat-insulation pressure keeping 4 ~ 4.5h, naturally cools to room temperature, pressure release.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1450 ° of C with the temperature rise rate of 2 ~ 5 ° of C/min, insulation 1 ~ 1.5h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.3 ~ 0.4), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers.Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in reactor is 3.5 ~ 4.5MPa, heat-insulation pressure keeping 1 ~ 1.5h.Then under identical pressure condition, be warming up to 400 ~ 450 ° of C, heat-insulation pressure keeping 4.5 ~ 5.5h, naturally cools to room temperature, and pressure release completes single-steeping.Metallic cylinder is taken out in autoclave, puts into high temperature carbonization furnace, under argon gas atmosphere protection; be warming up to 1450 ~ 1550 ° of C with the temperature rise rate of 5 ~ 8 ° of C/min, insulation 1.5 ~ 2.5h, is cooled to room temperature; complete a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
In the present embodiment: described Carbon fibe precast body is overall felt Carbon fibe precast body, and the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
Described pitch is coal-tar pitch.
Described organic boron is polyborazine.
Described organosilicon is Polycarbosilane.
Described solvent is toluene.
Described churned mechanically rotating speed is 200 ~ 300r/min.
Described rare gas element is argon gas.
Described medium is acetone.
embodiment 2
A kind of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof.The concrete steps of described preparation method are:
Step one, step one with embodiment one.
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction.
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 2 ~ 3wt%, 6 ~ 7wt%, 12 ~ 14wt% and 76 ~ 80wt% is mixed, obtains mixture.In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution.Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 2 ~ 5 ° of C/min, reactor is warming up to 300 ~ 350 ° of C, insulation 1 ~ 2h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch.
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.2 ~ 0.3) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered.The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 3 ~ 3.5MPa, heat-insulation pressure keeping 0.5 ~ 1 h.Then under identical pressure condition, be warming up to 350 ~ 400 ° of C, heat-insulation pressure keeping 4 ~ 4.5h, naturally cools to room temperature, pressure release.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1450 ° of C with the temperature rise rate of 2 ~ 5 ° of C/min, insulation 1 ~ 1.5h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.3 ~ 0.4), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers.Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in reactor is 3.5 ~ 4.5MPa, heat-insulation pressure keeping 1 ~ 1.5h.Then under identical pressure condition, be warming up to 400 ~ 450 ° of C, heat-insulation pressure keeping 4.5 ~ 5.5h, naturally cools to room temperature, and pressure release completes single-steeping.Metallic cylinder is taken out in autoclave, puts into high temperature carbonization furnace, under argon gas atmosphere protection; be warming up to 1450 ~ 1550 ° of C with the temperature rise rate of 5 ~ 8 ° of C/min, insulation 1.5 ~ 2.5h, is cooled to room temperature; complete a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
In the present embodiment: described Carbon fibe precast body is charcoal cloth/net tire lamination needle-punched carbon fiber precast body, and the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
Described pitch is coal-tar pitch.
Described organic boron is pyridine borane.
Described organosilicon is Polycarbosilane.
Described solvent is toluene.
Described churned mechanically rotating speed is 300 ~ 400r/min.
Described rare gas element is nitrogen.
Described medium is acetone.
embodiment 3
A kind of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof.The concrete steps of described preparation method are:
Step one, step one with embodiment one.
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction.
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 3 ~ 4wt%, 7 ~ 8wt%, 14 ~ 16wt% and 72 ~ 76wt% is mixed, obtains mixture.In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution.Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 5 ~ 8 ° of C/min, reactor is warming up to 350 ~ 400 ° of C, insulation 2 ~ 3h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch.
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.3 ~ 0.4) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered.The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 3.5 ~ 4.5MPa, heat-insulation pressure keeping 1 ~ 1.5 h.Then under identical pressure condition, be warming up to 400 ~ 450 ° of C, heat-insulation pressure keeping 4.5 ~ 5.5h, naturally cools to room temperature, pressure release.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1450 ~ 1550 ° of C with the temperature rise rate of 5 ~ 8 ° of C/min, insulation 1.5 ~ 2.5h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.4 ~ 0.5), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers.Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, is evacuated to 0.02 ~ 0.08MPa, then reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, and filling with inert gas to the pressure in reactor is 4 ~ 5MPa, heat-insulation pressure keeping 1.5 ~ 2h.Then under identical pressure condition, be warming up to 450 ~ 500 ° of C, heat-insulation pressure keeping 5.5 ~ 6h, naturally cools to room temperature, and pressure release completes single-steeping.Metallic cylinder is taken out in autoclave, puts into high temperature carbonization furnace, under argon gas atmosphere protection; be warming up to 1550 ~ 1600 ° of C with the temperature rise rate of 8 ~ 10 ° of C/min, insulation 2.5 ~ 3h, is cooled to room temperature; complete a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
In the present embodiment: described Carbon fibe precast body is 3 D weaving Carbon fibe precast body, the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
Described pitch is coal-tar pitch.
Described organic boron is 2-picoline borine.
Described organosilicon is polydimethylsiloxane.
Described solvent is toluene.
Described churned mechanically rotating speed is 400 ~ 500r/min.
Described rare gas element is argon gas.
Described medium is dehydrated alcohol.
embodiment 4
A kind of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof.The concrete steps of described preparation method are:
Step one, step one with embodiment one.
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction.
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 4 ~ 5wt%, 8 ~ 9wt%, 16 ~ 18wt% and 68 ~ 72wt% is mixed, obtains mixture.In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution.Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 5 ~ 8 ° of C/min, reactor is warming up to 350 ~ 400 ° of C, insulation 2 ~ 3h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch.
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.3 ~ 0.4) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered.The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 3.5 ~ 4.5MPa, heat-insulation pressure keeping 1 ~ 1.5 h.Then under identical pressure condition, be warming up to 400 ~ 450 ° of C, heat-insulation pressure keeping 4.5 ~ 5.5h, naturally cools to room temperature, pressure release.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1450 ~ 1550 ° of C with the temperature rise rate of 5 ~ 8 ° of C/min, insulation 1.5 ~ 2.5h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.4 ~ 0.5), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers.Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, is evacuated to 0.02 ~ 0.08MPa, then reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, and filling with inert gas to the pressure in reactor is 4 ~ 5MPa, heat-insulation pressure keeping 1.5 ~ 2h.Then under identical pressure condition, be warming up to 450 ~ 500 ° of C, heat-insulation pressure keeping 5.5 ~ 6h, naturally cools to room temperature, and pressure release completes single-steeping.Metallic cylinder is taken out in autoclave, puts into high temperature carbonization furnace, under argon gas atmosphere protection; be warming up to 1550 ~ 1600 ° of C with the temperature rise rate of 8 ~ 10 ° of C/min, insulation 2.5 ~ 3h, is cooled to room temperature; complete a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
In the present embodiment: described Carbon fibe precast body is overall felt Carbon fibe precast body, and the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
Described pitch is coal-tar pitch.
Described organic boron is polyborazine.
Described organosilicon is trimethysilyl chloride.
Described solvent is dimethylbenzene.
Described churned mechanically rotating speed is 500 ~ 600r/min.
Described rare gas element is nitrogen.
Described medium is dehydrated alcohol.
embodiment 5
A kind of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof.The concrete steps of described preparation method are:
Step one, step one with embodiment one.
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction.
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 4 ~ 5wt%, 9 ~ 10wt%, 18 ~ 20wt% and 65 ~ 69wt% is mixed, obtains mixture.In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution.Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 8 ~ 10 ° of C/min, reactor is warming up to 400 ~ 450 ° of C, insulation 3 ~ 4h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch.
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.4 ~ 0.5) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered.The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 4 ~ 5MPa, heat-insulation pressure keeping 1.5 ~ 2 h.Then under identical pressure condition, be warming up to 450 ~ 500 ° of C, heat-insulation pressure keeping 5.5 ~ 6h, naturally cools to room temperature, pressure release.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1550 ~ 1600 ° of C with the temperature rise rate of 8 ~ 10 ° of C/min, insulation 2.5 ~ 3h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.2 ~ 0.3), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers.Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, is evacuated to 0.02 ~ 0.08MPa, then reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, and filling with inert gas to the pressure in reactor is 3 ~ 3.5MPa, heat-insulation pressure keeping 0.5 ~ 1h.Then under identical pressure condition, be warming up to 350 ~ 400 ° of C, heat-insulation pressure keeping 4 ~ 4.5h, naturally cools to room temperature, and pressure release completes single-steeping.Metallic cylinder is taken out in autoclave, puts into high temperature carbonization furnace, under argon gas atmosphere protection; be warming up to 1400 ~ 1450 ° of C with the temperature rise rate of 2 ~ 5 ° of C/min, insulation 1 ~ 1.5h, is cooled to room temperature; complete a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
In the present embodiment: described Carbon fibe precast body is charcoal cloth/net tire lamination needle-punched carbon fiber precast body, and the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
Described pitch is coal-tar pitch.
Described organic boron is 2-picoline borine.
Described organosilicon is polydimethylsiloxane.
Described solvent is dimethylbenzene.
Described churned mechanically rotating speed is 300 ~ 400r/min.
Described rare gas element is argon gas.
Described medium is deionized water.
embodiment 6
A kind of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material and preparation method thereof.The concrete steps of described preparation method are:
Step one, step one with embodiment one.
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction.
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 3 ~ 4wt%, 7 ~ 8wt%, 13 ~ 15wt% and 73 ~ 77wt% is mixed, obtains mixture.In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution.Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 8 ~ 10 ° of C/min, reactor is warming up to 400 ~ 450 ° of C, insulation 3 ~ 4h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch.
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.4 ~ 0.5) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered.The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 4 ~ 5MPa, heat-insulation pressure keeping 1.5 ~ 2 h.Then under identical pressure condition, be warming up to 450 ~ 500 ° of C, heat-insulation pressure keeping 5.5 ~ 6h, naturally cools to room temperature, pressure release.Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1550 ~ 1600 ° of C with the temperature rise rate of 8 ~ 10 ° of C/min, insulation 2.5 ~ 3h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.2 ~ 0.3), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers.Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, is evacuated to 0.02 ~ 0.08MPa, then reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, and filling with inert gas to the pressure in reactor is 3 ~ 3.5MPa, heat-insulation pressure keeping 0.5 ~ 1h.Then under identical pressure condition, be warming up to 350 ~ 400 ° of C, heat-insulation pressure keeping 4 ~ 4.5h, naturally cools to room temperature, and pressure release completes single-steeping.Metallic cylinder is taken out in autoclave, puts into high temperature carbonization furnace, under argon gas atmosphere protection; be warming up to 1400 ~ 1450 ° of C with the temperature rise rate of 2 ~ 5 ° of C/min, insulation 1 ~ 1.5h, is cooled to room temperature; complete a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate.By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries.
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
In the present embodiment: described Carbon fibe precast body is 3 D weaving Carbon fibe precast body, the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
Described pitch is petroleum pitch.
Described organic boron is polyborazine.
Described organosilicon is trimethysilyl chloride.
Described solvent is dimethylbenzene.
Described churned mechanically rotating speed is 400 ~ 500r/min.
Described rare gas element is nitrogen.
Described medium is deionized water.
This embodiment compared with prior art has following positively effect:
(1) boron, silicon and zirconium atom are introduced in the condensed-nuclei aromatics molecule of pitch by the copyrolysis of pitch toluene soluble fraction and organic boron, organosilicon and ZrC presoma by this embodiment, other is dispersed to make boron, silicon and zirconium heteroatoms reach molecular level in pitch, and borosilicate zirconium doping pitch can generate the ZrB of even dispersion after high-temperature heat treatment at carbon matrix situ
2, SiC and ZrC nano heterogeneous ceramic.Fig. 1 is a kind of SiC-ZrC-ZrB prepared by embodiment 1
2the XRD spectra of nano heterogeneous ceramic modification C/C matrix material, as seen from Figure 1, the complex phase ceramic that borosilicate zirconium doping pitch is formed through high-temperature heat treatment is primarily of ZrC, ZrB
2with SiC composition, do not occur the characteristic diffraction peak of carbon in XRD spectra, this is mainly because carbon matrix is with caused by the existence of the form of decolorizing carbon.
(2) due to ZrB
2, SiC and ZrC nano heterogeneous ceramic is evenly distributed in carbon matrix, SiC-ZrC-ZrB
2the B that nano heterogeneous ceramic is formed in oxidising process
2o
3, SiO
2, ZrO
2interreaction can dissolve with mutual in different temperature ranges Deng oxide compound, form continuous and stable protective membrane, therefore only need introduce a small amount of ZrB in C/C matrix material
2, SiC and ZrC nano heterogeneous ceramic just can significantly improve self-healing anti-oxidation ability and the ultrahigh-temperature anti-yaw damper performance of material wide temperature range.Fig. 2 is SiC-ZrC-ZrB shown in Fig. 1
2the SEM photo of nano heterogeneous ceramic modification C/C composite material surface.As can be seen from Figure 2, material surface is made up of carbon matrix and ceramic particle, and structure is comparatively fine and close.Fig. 3, Fig. 4, Fig. 5 and Fig. 6 are carbon, boron, silicon and the zr element SiC-ZrC-ZrB shown in Fig. 2 successively
2the distribution plan of nano heterogeneous ceramic modification C/C composite material surface.As can be seen from Fig. 3 ~ Fig. 6, carbon, boron, silicon and zr element are evenly distributed in the surface of described matrix material, and boron, silicon and zirconium are mainly with ZrB
2, SiC and ZrC form exist.
(3) generated in-situ ZrB in carbon matrix
2and there is between ZrC and carbon good physics and chemistry consistency, greatly can improve the mechanical property of C/C matrix material.
(4) SiC-ZrC-ZrB for preparing of this embodiment
2nano heterogeneous ceramic modification C/C matrix material is oxidized 10 h under static atmosphere of air and 1100 ° of C conditions, sample weight gain 0.2 ~ 0.5 wt%; Be oxidized 10 h at 1600 ° of C, oxidation weight loss is 0.1 ~ 0.3 wt% only; Oxidation ablation 120 s in the oxy-acetylene flame of 3000 ° of C, its linear ablative rate is only 0.001 ~ 0.0015 mm/s.
Therefore, this embodiment efficiently solves solid phase method and prepares SiC-ZrC-ZrB
2the SiC-ZrC-ZrB that complex phase ceramic modification C/C matrix material exists
2complex phase ceramic disperses uneven problem in carbon matrix, prepared SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material has good mechanical property, the self-healing anti-oxidation ability of wide temperature range and ultrahigh-temperature anti-yaw damper performance.
Claims (11)
1. a SiC-ZrC-ZrB
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that the concrete steps of described preparation method are:
The pre-treatment of step one, Carbon fibe precast body
By Carbon fibe precast body acetone cleaning 30 ~ 60min, under 70 ~ 100 ° of C conditions, dry 1 ~ 2h, obtains pre-treatment Carbon fibe precast body;
The preparation of step 2, borosilicate zirconium doping pitch
First be dissolved in toluene by pitch, leave standstill 1 ~ 2h at ambient temperature, solid-liquid separation, distills the solution after solid-liquid separation under 110 ~ 150 ° of C conditions, obtains pitch toluene soluble fraction;
The pitch toluene soluble fraction of the ZrC presoma of the organosilicon of the organic boron of 1 ~ 5wt%, 5 ~ 10wt%, 10 ~ 20wt% and 65 ~ 84wt% is mixed, obtains mixture; In mixture, add solvent, the mass ratio of mixture and solvent is 1 ︰ (1 ~ 2), and magnetic agitation 0.5 ~ 1h, obtains mixed solution; Proceed in reactor by mixed solution again, pass into rare gas element, under mechanical agitation, with the temperature rise rate of 2 ~ 10 ° of C/min, reactor is warming up to 300 ~ 450 ° of C, insulation 1 ~ 4h, naturally cools to room temperature, obtains borosilicate zirconium doping pitch;
The dipping of step 3, pre-treatment Carbon fibe precast body and pyrolysis
Be 1 ︰ (0.2 ~ 0.5) by the mass ratio of the doping of borosilicate zirconium pitch and pre-treatment Carbon fibe precast body, pre-treatment Carbon fibe precast body is placed in metallic cylinder, with the borosilicate zirconium pitch that adulterates, pre-treatment Carbon fibe precast body is covered; The metallic cylinder that borosilicate zirconium doping pitch and pre-treatment Carbon fibe precast body are housed is placed in autoclave, first be evacuated to 0.02 ~ 0.08MPa, again reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, filling with inert gas to the pressure in autoclave is 3 ~ 5MPa, heat-insulation pressure keeping 0.5 ~ 2 h; Then under identical pressure condition, be warming up to 350 ~ 500 ° of C, heat-insulation pressure keeping 4 ~ 6h, naturally cools to room temperature, pressure release; Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1600 ° of C with the temperature rise rate of 2 ~ 10 ° of C/min, insulation 1 ~ 3h, is cooled to room temperature, obtains SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate; By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries;
Step 4, SiC-ZrC-ZrB
2the densification of nano heterogeneous ceramic modification C/C base substrate
By borosilicate zirconium doping pitch and SiC-ZrC-ZrB
2the mass ratio of nano heterogeneous ceramic modification C/C base substrate is 1 ︰ (0.2 ~ 0.5), by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate is placed in metallic cylinder, with borosilicate zirconium doping pitch by SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C base substrate covers; Borosilicate zirconium doping pitch and SiC-ZrC-ZrB will be housed
2the metallic cylinder of nano heterogeneous ceramic modification C/C base substrate is placed in autoclave, is evacuated to 0.02 ~ 0.08MPa, then reaction under high pressure temperature in the kettle is risen to 250 ~ 300 ° of C, and filling with inert gas to the pressure in reactor is 3 ~ 5MPa, heat-insulation pressure keeping 0.5 ~ 2h; Then under identical pressure condition, be warming up to 350 ~ 500 ° of C, heat-insulation pressure keeping 4 ~ 6h, naturally cools to room temperature, and pressure release completes single-steeping; Metallic cylinder taken out in autoclave, put into high temperature carbonization furnace, under argon gas atmosphere protection, be warming up to 1400 ~ 1600 ° of C with the temperature rise rate of 2 ~ 10 ° of C/min, insulation 1 ~ 3h, is cooled to room temperature, completes a pyrolysis, obtain the SiC-ZrC-ZrB of density
2nano heterogeneous ceramic modification C/C base substrate; By described C/C billet surface sanding and polishing, ultrasonic cleaning in media as well, dries;
Repeat above-mentioned dipping, pyrolysis, sanding and polishing and drying and processing process, until SiC-ZrC-ZrB
2the density of nano heterogeneous ceramic modification C/C base substrate reaches 1.9 ~ 2.5g/cm
3, obtain SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material.
2. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, it is characterized in that described Carbon fibe precast body is the one in overall felt Carbon fibe precast body, charcoal cloth/net tire lamination needle-punched carbon fiber precast body and 3 D weaving Carbon fibe precast body, the density of Carbon fibe precast body is 0.2 ~ 0.6 g/cm
3.
3. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described pitch is coal-tar pitch or is petroleum pitch.
4. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described organic boron is the one in polyborazine, pyridine borane and 2-picoline borine.
5. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described organosilicon is the one in Polycarbosilane, polydimethylsiloxane and trimethysilyl chloride.
6. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, it is characterized in that the preparation process of described ZrC presoma is: reactor is evacuated to 0.06 ~ 0.08MPa, pass into argon gas to normal pressure, toluene, zirconates and dehydrated alcohol is added successively again in reactor, stir, wherein: zirconates: toluene: the mol ratio of dehydrated alcohol is 1: (3 ~ 5): (4 ~ 10); Then under 10 ~ 10 ° of C conditions, pass into ammonia, the flow passing into ammonia is 40 ~ 60ml/min, and reaction 2 ~ 6h, filters, obtain the toluene solution of alcohol zirconium;
Reactor is evacuated to 0.06 ~ 0.08MPa, pass into argon gas to normal pressure, add the toluene solution of alcohol zirconium, beta-diketon and phenol to reactor successively again, stir, wherein: beta-diketon: phenol: the mol ratio of zirconates is (1 ~ 4): (2 ~ 4): 1; Then by the temperature rise rate of 2 ~ 4 ° of C/min, reaction system is heated to 120 ~ 300 ° of C, insulation 1 ~ 10h, underpressure distillation, is cooled to room temperature, obtains ZrC presoma.
7. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described solvent is toluene or is dimethylbenzene.
8. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described churned mechanically rotating speed is 200 ~ 600r/min.
9. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described rare gas element is argon gas or is nitrogen.
10. SiC-ZrC-ZrB according to claim 1
2the preparation method of nano heterogeneous ceramic modification C/C matrix material, is characterized in that described medium is the one in acetone, dehydrated alcohol and deionized water.
11. 1 kinds of SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material, is characterized in that described SiC-ZrC-ZrB
2nano heterogeneous ceramic modification C/C matrix material is SiC-ZrC-ZrB according to any one of claim 1 ~ 9
2the SiC-ZrC-ZrB prepared by preparation method of nano heterogeneous ceramic modification C/C matrix material
2nano heterogeneous ceramic modification C/C matrix material.
Priority Applications (1)
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| CN104926306A (en) * | 2015-05-22 | 2015-09-23 | 武汉科技大学 | Soluble zirconium carbide ceramic precursor and preparation method thereof |
| CN104944998A (en) * | 2015-05-20 | 2015-09-30 | 合肥工业大学 | Method for enhancing strength of carbon/carbon composite material |
| CN106747668A (en) * | 2017-02-17 | 2017-05-31 | 南通市苏中纺织有限公司 | The modifies high heat conduction C/C composites of ZrC organosilane precursors |
| CN107056334A (en) * | 2017-04-28 | 2017-08-18 | 哈尔滨理工大学 | A kind of ZrC ceramic material surfaces ZrB2The preparation method of SiC composite coatings |
| CN110156468A (en) * | 2019-04-25 | 2019-08-23 | 巩义市泛锐熠辉复合材料有限公司 | A kind of ZrC-ZrB2The presoma conversion method preparation process of SiC ceramic composite granule |
| CN109851798B (en) * | 2019-02-25 | 2021-10-29 | 华东理工大学 | Boron, zirconium and silicon-containing single-source ceramic precursor and preparation method thereof |
| CN113800935A (en) * | 2021-09-27 | 2021-12-17 | 陕西科技大学 | Preparation method of in-situ synthesized SiC (nw, np) -ZrB2-ZrC modified carbon/carbon composite material |
| CN114394844A (en) * | 2021-12-28 | 2022-04-26 | 华中科技大学 | Method for preparing silicon carbide ceramic by 3D printing of waste and silicon carbide ceramic |
| CN116120080A (en) * | 2023-02-21 | 2023-05-16 | 无锡博智复合材料有限公司 | ZrB (ZrB) 2 ZrC-SiC modified carbon/carbon composite material and preparation method and application thereof |
| CN116813386A (en) * | 2023-06-30 | 2023-09-29 | 广西大学 | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof |
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| CN104944998A (en) * | 2015-05-20 | 2015-09-30 | 合肥工业大学 | Method for enhancing strength of carbon/carbon composite material |
| CN104926306A (en) * | 2015-05-22 | 2015-09-23 | 武汉科技大学 | Soluble zirconium carbide ceramic precursor and preparation method thereof |
| CN106747668A (en) * | 2017-02-17 | 2017-05-31 | 南通市苏中纺织有限公司 | The modifies high heat conduction C/C composites of ZrC organosilane precursors |
| CN107056334A (en) * | 2017-04-28 | 2017-08-18 | 哈尔滨理工大学 | A kind of ZrC ceramic material surfaces ZrB2The preparation method of SiC composite coatings |
| CN107056334B (en) * | 2017-04-28 | 2020-04-17 | 哈尔滨理工大学 | ZrB ceramic material surface ZrB2Preparation method of-SiC composite coating |
| CN109851798B (en) * | 2019-02-25 | 2021-10-29 | 华东理工大学 | Boron, zirconium and silicon-containing single-source ceramic precursor and preparation method thereof |
| CN110156468A (en) * | 2019-04-25 | 2019-08-23 | 巩义市泛锐熠辉复合材料有限公司 | A kind of ZrC-ZrB2The presoma conversion method preparation process of SiC ceramic composite granule |
| CN113800935A (en) * | 2021-09-27 | 2021-12-17 | 陕西科技大学 | Preparation method of in-situ synthesized SiC (nw, np) -ZrB2-ZrC modified carbon/carbon composite material |
| CN114394844A (en) * | 2021-12-28 | 2022-04-26 | 华中科技大学 | Method for preparing silicon carbide ceramic by 3D printing of waste and silicon carbide ceramic |
| CN116120080A (en) * | 2023-02-21 | 2023-05-16 | 无锡博智复合材料有限公司 | ZrB (ZrB) 2 ZrC-SiC modified carbon/carbon composite material and preparation method and application thereof |
| CN116120080B (en) * | 2023-02-21 | 2023-11-21 | 无锡博智复合材料有限公司 | ZrB (ZrB) 2 ZrC-SiC modified carbon/carbon composite material and preparation method and application thereof |
| CN116813386A (en) * | 2023-06-30 | 2023-09-29 | 广西大学 | Self-healing high-oxygen-resistance high-temperature-oxidation-prevention composite coating for aluminum electrolysis carbon anode and preparation method thereof |
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