CN115583836A - High-temperature-resistant complex-phase ceramic aerogel and preparation method thereof - Google Patents
High-temperature-resistant complex-phase ceramic aerogel and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 62
- 239000011240 wet gel Substances 0.000 claims abstract description 36
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- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000011215 ultra-high-temperature ceramic Substances 0.000 claims abstract description 10
- 238000000197 pyrolysis Methods 0.000 claims abstract description 7
- 238000005336 cracking Methods 0.000 claims abstract description 5
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- 238000003756 stirring Methods 0.000 claims description 22
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- 239000011148 porous material Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003431 cross linking reagent Substances 0.000 claims description 7
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
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- 239000008096 xylene Substances 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
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- 229910026551 ZrC Inorganic materials 0.000 claims description 4
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- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 2
- ZQOBAJVOKBJPEE-UHFFFAOYSA-N [B].[C].[N].[Si] Chemical compound [B].[C].[N].[Si] ZQOBAJVOKBJPEE-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 11
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 238000002679 ablation Methods 0.000 description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 238000002791 soaking Methods 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 12
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- 229960001701 chloroform Drugs 0.000 description 5
- 229910052735 hafnium Inorganic materials 0.000 description 5
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- 238000005245 sintering Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 description 1
- ZILJFRYKLPPLTO-UHFFFAOYSA-N [C].[B].[Si] Chemical compound [C].[B].[Si] ZILJFRYKLPPLTO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention provides a method for preparing high-temperature-resistant complex-phase ceramic aerogel, which comprises the following steps: preparing a ceramic precursor wet gel by using the main ceramic precursor and the ultrahigh-temperature ceramic precursor; sequentially carrying out solvent replacement and drying treatment to obtain a ceramic precursor aerogel; and obtaining the high-temperature resistant complex-phase ceramic aerogel through pyrolysis. The invention also provides the high-temperature resistant complex-phase ceramic aerogel prepared by the method. The method has the advantages of good mixing uniformity, easy quality control, no pulverization by high-temperature cracking, no collapse of a framework, easy preparation and the like, is simple and controllable, has mild preparation conditions and good stability, is convenient for large-scale preparation, can prepare the complex phase ceramic aerogel material with the nano porous structure, has the advantages of low high-temperature resistance and density, high porosity, large specific surface area and the like compared with the traditional complex phase ceramic material, and is applied to the field of thermal protection as a high-temperature resistant heat-insulating material.
Description
Technical Field
The invention relates to the technical field of complex phase ceramic materials, in particular to a high-temperature-resistant complex phase ceramic aerogel and a preparation method thereof.
Background
The rapid development of a new generation of hypersonic aerocraft puts higher requirements on the temperature resistance, ablation resistance, oxidation resistance and other performances of the nano porous heat-proof material. Single phase ceramic aerogel materials such as alumina and silicon carbide have not been able to meet the demand. Adding carbide or boride ceramic of transition metal with higher temperature resistance grade into the single-phase ceramic aerogel material to form complex phase ceramic is a possible way for improving the ablation resistance and oxidation resistance of the existing ceramic aerogel. The traditional method for preparing the complex phase ceramic is to mix carbide or boride ceramic with ceramic powder such as silicon carbide, silicon nitride and the like, and then to sinter the mixture at high temperature and high pressure to obtain the complex phase ceramic. However, the traditional preparation method has the problems of poor mixing uniformity of the two ceramics, high quality control difficulty and the like.
In recent years, a method for preparing the complex phase ceramic by adopting a liquid ceramic precursor appears, but the method is only limited to the preparation of the complex phase ceramic and the composite material thereof, and no research report on the aspect of the nano-porous complex phase ceramic aerogel exists.
Disclosure of Invention
The present invention is directed to overcoming the disadvantages of the prior art, and provides in a first aspect a method for preparing a high temperature resistant complex phase ceramic aerogel, the method comprising the steps of:
(1) Dissolving a main ceramic precursor and an ultrahigh-temperature ceramic precursor in an organic solvent to obtain a precursor mixed solution;
(2) Sequentially adding a cross-linking agent and a catalyst into the precursor mixed solution, uniformly stirring, and reacting to obtain a ceramic precursor wet gel;
(3) Sequentially carrying out solvent replacement on the ceramic precursor wet gel to obtain solvent replacement wet gel;
(4) Drying the solvent-replaced wet gel to obtain a ceramic precursor aerogel;
(5) And heating the ceramic precursor aerogel to perform pyrolysis under an inert atmosphere to obtain the high-temperature-resistant complex-phase ceramic aerogel.
The invention provides a high-temperature-resistant complex-phase ceramic aerogel in a second aspect, wherein the high-temperature-resistant complex-phase ceramic aerogel is prepared by the method in the first aspect.
The invention has the following technical effects:
compared with the traditional complex phase ceramic material, the complex phase ceramic aerogel material with the nano porous structure (the average pore diameter is 80-200 nm) is successfully prepared by the method, and has the advantages of high temperature resistance, low density, high porosity, large specific surface area and the like.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail and fully hereinafter. It is to be understood that the specific embodiments described are merely a few possible embodiments of the invention, and not all possible embodiments. All other embodiments made by those skilled in the art without any inventive step based on the disclosure of the present invention are within the scope of the present invention.
The present invention is directed to overcoming the disadvantages of the prior art, and provides in a first aspect a method for preparing a high temperature resistant complex phase ceramic aerogel, the method comprising the steps of:
(1) Dissolving a main ceramic precursor and an ultrahigh-temperature ceramic precursor in an organic solvent to obtain a precursor mixed solution;
(2) Sequentially adding a cross-linking agent and a catalyst into the precursor mixed solution, uniformly stirring, and reacting to obtain a ceramic precursor wet gel;
(3) Sequentially carrying out solvent replacement on the ceramic precursor wet gel to obtain solvent replacement wet gel;
(4) Drying the solvent replacement wet gel to obtain a ceramic precursor aerogel;
(5) And heating the ceramic precursor aerogel to perform pyrolysis under an inert atmosphere to obtain the high-temperature-resistant complex-phase ceramic aerogel.
In some preferred embodiments, the primary ceramic precursor is selected from one of a silicon carbide ceramic precursor, a silicon nitride ceramic precursor, and a silicon boron carbon nitride ceramic precursor.
In other preferred embodiments, the ultra-high temperature ceramic precursor is selected from one or more of a zirconium boride precursor, a hafnium boride precursor, a zirconium carbide precursor, a poly-hafnoxane, and a poly-tantaloxane.
In other preferred embodiments, the mass ratio of the ultrahigh-temperature ceramic precursor to the main ceramic precursor is 1 (2-20), such as 1:2, 1:5, 1.
In other preferred embodiments, the organic solvent is selected from one or more of n-hexane, cyclohexane, petroleum ether, tetrahydrofuran, chloroform, toluene, xylene, ethyl acetate, and butyl acetate.
In other preferred embodiments, the solvent replacement comprises a first solvent replacement with a first solvent and a second solvent replacement with a second solvent performed sequentially.
In some more preferred embodiments, the first solvent is selected from one or more of n-hexane, cyclohexane, petroleum ether, tetrahydrofuran, chloroform, toluene, xylene, ethyl acetate, and butyl acetate. The first solvent and the organic solvent may be the same or different.
In some preferred embodiments, the second solvent is ethanol and/or cyclohexane.
In other preferred embodiments, the concentration of the main ceramic precursor and the ultra-high temperature ceramic in the ceramic precursor solution is 5wt% to 35wt%, such as 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt% or 35wt%.
In other preferred embodiments, the crosslinking agent is divinylbenzene.
In other preferred embodiments, the mass ratio of the cross-linking agent to the ceramic precursor is (1.
In other preferred embodiments, the catalyst is one of Karstedt's catalyst, dicumyl peroxide, azobisisobutyronitrile, or dibenzoyl peroxide.
In other preferred embodiments, the catalyst is added in an amount of 0.01wt% to 0.5wt%, such as 0.01wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, or 0.5wt% of the ceramic precursor.
In other preferred embodiments, the reaction in step (2) is carried out at a temperature of from 50 ℃ to 160 ℃ (e.g., 50, 80, 100, 120 or 150 ℃) and for a time of from 6 to 24 hours (e.g., 6, 12, 18 or 24 hours).
In other preferred embodiments, the drying treatment is supercritical drying of CO 2 Drying, freeze drying or drying under normal pressure.
In other preferred embodiments, the pyrolysis is carried out at a ramp rate of 1 to 10 ℃/min, a pyrolysis temperature of 1000 to 1800 ℃ (e.g., 1000, 1200, 1400, 1600 or 1800 ℃), and a pyrolysis time of 1 to 4 hours (e.g., 1, 2, 3 or 4 hours).
The invention provides a high-temperature-resistant complex-phase ceramic aerogel in a second aspect, wherein the high-temperature-resistant complex-phase ceramic aerogel is prepared by the method in the first aspect.
In other preferred embodiments, the refractory complex phase ceramic aerogel has a porosity of 60 to 85% (e.g., 65, 70, or 75%) and a density of 0.2 to 0.8g/cm 3 (e.g., 0.3, 0.4, 0.5, 0.6, 0.7, or 0.8g/cm 3 ) The specific surface area is 100-300m 2 G (e.g. 150, 200 or 250 m) 2 In g) and an average pore diameter of 80 to 200nm (for example 100, 150 or 200 nm).
The method breaks through the traditional idea of preparing the nano porous material by adopting ceramic powder high-temperature pressure-resistant sintering, and obtains the high-temperature-resistant complex-phase ceramic aerogel with nano-sized pores by adopting a means of combining a ceramic precursor conversion method and a sol-gel method.
The multiphase ceramic aerogel prepared by the invention utilizes the high temperature resistance and oxidation resistance of the transition metal carbide or boride to obviously improve the temperature resistance level of the silicon carbide ceramic aerogel.
The invention discloses a controllable preparation method of a three-dimensional nano-pore structure of a complex-phase ceramic aerogel, which solves the problems of high-temperature cracking pulverization, skeleton collapse and the like of the ceramic aerogel. The prepared multiphase ceramic aerogel has the characteristics of high porosity, high specific surface area and the like, and is particularly suitable for high-temperature heat-proof and heat-insulating materials of a thermal protection system of a space vehicle due to the excellent mechanical property of the multiphase ceramic.
Examples
The present invention is further described below with reference to examples. The following examples are not to be construed as limiting the scope of the invention, and any modifications made on the basis of the present invention without departing from the spirit of the present invention are within the scope of the present invention.
Example 1
Under the protection of flowing nitrogen, sequentially adding 20g of polycarbosilane, 5g of zirconium boride precursor and 209g of n-hexane into a three-necked bottle, and stirring uniformly; then adding 1.25g of divinylbenzene and 0.0025g of Karstedt catalyst (CAS: 68478-92-2), continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting for 6h at 70 ℃ to obtain ceramic precursor wet gel; taking out, soaking in n-hexane for 3 days, and replacing n-hexane for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1000 ℃ at the speed of 1 ℃/min under high-purity argon, and preserving heat for 2 hours to obtain the zirconium boride-silicon carbide composite ceramic aerogel with the density of 0.24g/cm 3 Porosity of 70% and specific surface area of 100m 2 (ii)/g, the average pore diameter is 80nm, the room-temperature compressive strength is 3.52 +/-0.21MPa, and the ablation rate of the thread is 8.7 multiplied by 10 after being ablated for 600s at 1850 DEG C -4 mm/s, mass ablation rate of 1.5X 10 -3 g/s。
Example 2
Under the protection of flowing nitrogen, sequentially adding 10g of polycarbosilane, 1g of hafnium boride precursor and 126g of cyclohexane into a three-necked bottle, and stirring uniformly; then 0.88g of divinylbenzene and 0.0055g of dicumyl peroxide catalyst were added thereto, and the mixture was stirred and mixed uniformly and transferred to a nitrogen-filled autoclaveReacting at 90 ℃ for 8h to obtain a ceramic precursor wet gel; taking out, soaking in cyclohexane for 3 days, and replacing n-hexane for 3 times; freeze-drying the wet gel to obtain a ceramic precursor aerogel; placing the aerogel in a high-temperature tube furnace, heating to 1100 ℃ at the speed of 2 ℃/min under high-purity argon, and preserving heat for 1h to obtain the hafnium boride-silicon carbide composite ceramic aerogel with the density of 0.4g/cm 3 Porosity of 75% and specific surface area of 120m 2 Per g, average pore diameter of 100nm, room temperature compressive strength of 4.24 + -0.25MPa, and a line ablation rate of 9.2 × 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.7X 10 -3 g/s。
Example 3
Under the protection of flowing nitrogen, sequentially adding 20g of polycarbosilane, 3g of zirconium carbide precursor and 85g of petroleum ether into a three-necked bottle, and stirring uniformly; then adding 2.3g of divinylbenzene and 0.023g of azodiisobutyronitrile catalyst, continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting at 100 ℃ for 10 hours to obtain ceramic precursor wet gel; taking out, soaking in petroleum ether for 3 days while changing petroleum ether for 3 times, and soaking in ethanol for 3 days while changing ethanol for 3 times; drying the wet gel at normal pressure to obtain a ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1200 ℃ at the speed of 4 ℃/min under high-purity argon, and preserving heat for 1.5h to obtain the zirconium carbide-silicon carbide composite ceramic aerogel with the density of 0.3g/cm 3 Porosity 65%, specific surface area 150m 2 G, average pore diameter of 85nm, room temperature compressive strength of 3.87 +/-0.16MPa, and linear ablation rate of 8.6 x 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.8X 10 -3 g/s。
Example 4
Under the protection of flowing nitrogen, 25g of polycarbosilane, 5g of hafnioxane and 100g of tetrahydrofuran are sequentially added into a three-mouth bottle and stirred uniformly; adding 4.5g of divinylbenzene and 0.06g of dibenzoyl peroxide catalyst, continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting at 60 ℃ for 15h to obtain ceramic precursor wet gel;taking out, soaking in tetrahydrofuran for 3 days while replacing tetrahydrofuran for 3 times, and soaking in ethanol for 3 days while replacing ethanol for 3 times; freeze-drying the wet gel to obtain a ceramic precursor aerogel; placing the aerogel in a high-temperature tube furnace, heating to 1300 ℃ at the speed of 5 ℃/min under high-purity argon, and preserving heat for 2.5 hours to obtain the hafnium carbide-silicon carbide composite ceramic aerogel with the density of 0.5g/cm 3 Porosity of 60%, specific surface area of 180m 2 Per g, average pore diameter of 120nm, room temperature compressive strength of 3.96 +/-0.16MPa, and linear ablation rate of 8.7 x 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.9X 10 -3 g/s。
Example 5
Under the protection of flowing nitrogen, sequentially adding 20g of polycarbosilane, 5g of polytantalkane and 75g of trichloromethane into a three-neck flask, and stirring uniformly; then adding 5g of divinylbenzene and 0.075g of Karstedt catalyst, continuously stirring and uniformly mixing, transferring the mixture to a pressure reaction kettle filled with nitrogen, and reacting for 20 hours at 50 ℃ to obtain ceramic precursor wet gel; taking out, soaking in chloroform for 3 days while changing chloroform for 3 times, and soaking in ethanol for 3 days while changing ethanol for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1400 ℃ at the speed of 10 ℃/min under high-purity argon, and preserving heat for 3 hours to obtain the hafnium carbide-silicon carbide composite ceramic aerogel with the density of 0.63g/cm 3 The porosity is 80%, and the specific surface area is 200m 2 (ii)/g, average pore diameter of 90nm, room temperature compressive strength of 4.52 + -0.21MPa, and ablation rate of 8.7 × 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.6X 10 - 3 g/s。
Example 6
Under the protection of flowing nitrogen, sequentially adding 10g of polycarbosilane, 3g of zirconium boride precursor and 70g of toluene into a three-mouth bottle, and stirring uniformly; adding 3.25g of divinylbenzene and 0.052g of dicumyl peroxide catalyst, continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting at 120 ℃ for 24 hours to obtain potteryWet gelling of a ceramic precursor; taking out, soaking in toluene for 3 days while changing toluene for 3 times, and soaking in ethanol for 3 days while changing ethanol for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1500 ℃ at the speed of 6 ℃/min under high-purity argon, and preserving heat for 3.5 hours to obtain the zirconium boride-silicon carbide composite ceramic aerogel with the density of 0.76g/cm 3 Porosity of 85% and specific surface area of 220m 2 Per g, average pore diameter of 150nm, room temperature compressive strength of 4.67 + -0.23MPa, and a line ablation rate of 8.9 × 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.5X 10 -3 g/s。
Example 7
Under the protection of flowing nitrogen, sequentially adding 20g of polycarbosilane, 7g of hafnium boride precursor and 50g of dimethylbenzene into a three-mouth bottle, and stirring uniformly; adding 8.1g of divinylbenzene and 0.04g of azodiisobutyronitrile catalyst, continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting at 140 ℃ for 22 hours to obtain ceramic precursor wet gel; taking out, soaking in xylene for 3 days while replacing xylene for 3 times, and soaking in ethanol for 3 days while replacing glycol for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1600 ℃ at the speed of 8 ℃/min under high-purity argon, and preserving heat for 4 hours to obtain the hafnium boride-silicon carbide composite ceramic aerogel with the density of 0.85g/cm 3 The porosity was 73%, and the specific surface area was 250m 2 (ii)/g, average pore diameter of 180nm, room-temperature compressive strength of 5.02 + -0.18MPa, and a line ablation rate of 9.8X 10 after ablation at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.7X 10 -3 g/s。
Example 8
Under the protection of flowing nitrogen, sequentially adding 10g of polycarbosilane, 4g of zirconium carbide precursor and 87g of ethyl acetate into a three-neck flask, and stirring uniformly; then 1.4g of divinylbenzene and 0.063g of dibenzoyl peroxide catalyst were added thereto, and the mixture was stirred and mixed uniformly and transferred to a nitrogen-filled pressure reactorReacting at 80 ℃ for 18h to obtain a ceramic precursor wet gel; taking out, soaking in ethyl acetate for 3 days, replacing ethyl acetate for 3 times, soaking in ethanol for 3 days, and replacing ethanol for 3 times; drying the wet gel at normal pressure to obtain a ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1700 ℃ at the speed of 9 ℃/min under high-purity argon, and preserving heat for 2h to obtain the zirconium boride-silicon carbide composite ceramic aerogel with the density of 0.65g/cm 3 Porosity of 68% and specific surface area of 280m 2 (g) an average pore diameter of 200nm, a room-temperature compressive strength of 5.82 + -0.26MPa, and a line ablation rate of 9.6 × 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.8X 10 -3 g/s。
Example 9
Under the protection of flowing nitrogen, sequentially adding 10g of polycarbosilane, 5g of hafnoxan and 77g of butyl acetate into a three-mouth bottle, and stirring uniformly; then adding 5.25g of divinylbenzene and 0.075g of Karstedt catalyst, continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting at 160 ℃ for 12h to obtain a ceramic precursor wet gel; taking out, soaking in butyl acetate for 3 days, replacing butyl acetate for 3 times, soaking in cyclohexane for 3 days, and replacing cyclohexane for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1800 ℃ at the speed of 3 ℃/min under high-purity argon, and preserving heat for 3 hours to obtain the hafnium carbide-silicon carbide composite ceramic aerogel with the density of 0.48g/cm 3 The porosity was 82%, the specific surface area was 300m 2 (ii)/g, average pore diameter of 190nm, room temperature compressive strength of 4.67 + -0.21MPa, and ablation rate of 8.2 × 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.9X 10 -3 g/s。
Example 10
Under the protection of flowing nitrogen, sequentially adding 20g of polysilazane, 5g of zirconium boride precursor and 209g of n-hexane into a three-necked bottle, and stirring uniformly; 1.25g of divinylbenzene and 0.0025g of Karstedt's catalyst were added thereto, and the mixture was stirred and mixed well and transferred to a nitrogen-filled containerReacting for 6 hours at 70 ℃ in a pressure reaction kettle to obtain ceramic precursor wet gel; taking out, soaking in n-hexane for 3 days, and replacing n-hexane for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1000 ℃ at the speed of 1 ℃/min under high-purity argon, and preserving heat for 2 hours to obtain the silicon nitride-zirconium boride complex phase ceramic aerogel with the density of 0.26g/cm 3 The porosity was 72%, and the specific surface area was 110m 2 G, average pore diameter of 90nm, room temperature compressive strength of 5.32 +/-0.25MPa, and linear ablation rate of 7.5 x 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 1.0X 10 -3 g/s。
Example 11
Under the protection of flowing nitrogen, sequentially adding 20g of polyborosilazane, 5g of zirconium boride precursor and 209g of n-hexane into a three-necked bottle, and stirring uniformly; then adding 1.25g of divinylbenzene and 0.0025g of Karstedt catalyst, continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting at 70 ℃ for 6h to obtain ceramic precursor wet gel; taking out, soaking in n-hexane for 3 days, and changing n-hexane for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tubular furnace, heating to 1000 ℃ at the speed of 1 ℃/min under high-purity argon, and preserving heat for 2h to obtain the zirconium boride-silicon boron carbon nitrogen composite ceramic aerogel with the density of 0.29g/cm 3 The porosity was 74%, and the specific surface area was 105m 2 (ii)/g, an average pore diameter of 94nm, a room-temperature compressive strength of 7.42 + -0.18MPa, and a line ablation rate of 6.3X 10 after ablation at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 0.6X 10 -3 g/s。
Comparative example 1
60g of silicon carbide powder and 15g of zirconium boride are mixed in a ball milling tank with ethanol as a medium for 12 hours, and 2wt% of polyvinyl butyral is added to be used as a binder. The dried premix was sieved through a 50 mesh sieve, and the finally obtained mixture was uniaxially pressed at 36MPa to prepare a rectangular strip sample of 3 mm. Times.4 mm. Times.40 mm. The sample is dried in an oven for 24h and then placed in a closed crucibleHeating to 900 ℃ in an atmosphere furnace, preserving heat for 1h, then sintering at 1400 ℃ for 3h to obtain the zirconium boride-silicon carbide complex phase porous ceramic with the density of 0.24g/cm 3 Porosity of 37% and specific surface area of 48m 2 (ii)/g, the average pore diameter is 275nm, the room-temperature compressive strength is 0.73 +/-0.87MPa, and the ablation rate of the thread is 9.3 multiplied by 10 after being ablated for 600s at 1850 DEG C -4 mm/s, mass ablation rate of 1.9X 10 -3 g/s。
Comparative example 2
Under the protection of flowing nitrogen, 25g of polycarbosilane and 209g of n-hexane are sequentially added into a three-necked bottle, and the mixture is stirred uniformly; then adding 1.25g of divinylbenzene and 0.0025g of Karstedt catalyst, continuously stirring and uniformly mixing, transferring to a pressure reaction kettle filled with nitrogen, and reacting at 70 ℃ for 6h to obtain ceramic precursor wet gel; taking out, soaking in n-hexane for 3 days, and replacing n-hexane for 3 times; passing the wet gel through supercritical CO 2 Drying to obtain ceramic precursor aerogel; placing the aerogel in a high-temperature tube furnace, heating to 1000 ℃ at the speed of 1 ℃/min under high-purity argon, and preserving heat for 2 hours to obtain the silicon carbide ceramic aerogel with the density of 0.20g/cm 3 Porosity of 74% and specific surface area of 180m 2 (ii)/g, average pore diameter of 70nm, room temperature compressive strength of 1.52 + -0.21MPa, and ablation rate of 12.6 × 10 after being ablated at 1850 ℃ for 600s -4 mm/s, mass ablation rate of 2.1 × 10 -3 g/s。
TABLE 1 Properties of the materials obtained in the examples.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing high-temperature-resistant complex-phase ceramic aerogel is characterized by comprising the following steps:
(1) Dissolving a main ceramic precursor and an ultrahigh-temperature ceramic precursor in an organic solvent to obtain a precursor mixed solution;
(2) Sequentially adding a cross-linking agent and a catalyst into the precursor mixed solution, uniformly stirring, and reacting to obtain a ceramic precursor wet gel;
(3) Sequentially carrying out solvent replacement on the ceramic precursor wet gel to obtain solvent replacement wet gel;
(4) Drying the solvent replacement wet gel to obtain a ceramic precursor aerogel;
(5) And heating the ceramic precursor aerogel to perform pyrolysis in an inert atmosphere to obtain the high-temperature-resistant complex-phase ceramic aerogel.
2. The method of claim 1, wherein:
the main ceramic precursor is selected from one of a silicon carbide ceramic precursor, a silicon nitride ceramic precursor and a silicon-boron-carbon-nitrogen ceramic precursor; and/or the ultrahigh-temperature ceramic precursor is selected from one or more of a zirconium boride precursor, a hafnium boride precursor, a zirconium carbide precursor, poly-hafnoxane and poly-tantalaxane;
preferably, the mass ratio of the ultrahigh-temperature ceramic precursor to the main ceramic precursor is 1 (2-20).
3. The method of claim 1, wherein:
the solvent replacement comprises a first solvent replacement and a second solvent replacement which are sequentially carried out, wherein the first solvent replacement is carried out by adopting a first solvent, and the second solvent replacement is carried out by adopting a second solvent;
the organic solvent and the first solvent are independently selected from one or more of n-hexane, cyclohexane, petroleum ether, tetrahydrofuran, chloroform, toluene, xylene, ethyl acetate and butyl acetate;
the first solvent is selected from one or more of n-hexane, cyclohexane, petroleum ether, tetrahydrofuran, chloroform, toluene, xylene, ethyl acetate and butyl acetate; and/or
The second solvent is ethanol and/or cyclohexane.
4. The method of claim 1, wherein:
in the ceramic precursor solution, the total concentration of the main ceramic precursor and the ultrahigh-temperature ceramic precursor is 5wt% -35 wt%.
5. The method of claim 1, wherein:
the crosslinking agent is divinylbenzene;
preferably, the mass ratio of the crosslinking agent to the ceramic precursor is (1.
6. The method of claim 1, wherein:
the catalyst is one of Karstedt catalyst, dicumyl peroxide, azodiisobutyronitrile or dibenzoyl peroxide;
preferably, the catalyst is added in an amount of 0.01wt% to 0.5wt% of the ceramic precursor.
7. The method of claim 1, wherein:
the reaction temperature of the reaction in the step (2) is 50-160 ℃, and the reaction time is 6-24h.
8. The method of claim 1, wherein:
the drying treatment is supercritical drying CO 2 Drying, freeze drying or drying under normal pressure.
9. The method of claim 4, wherein:
the heating rate of the high-temperature cracking is 1-10 ℃/min, the cracking temperature is 1000-1800 ℃, and the cracking time is 1-4h.
10. A high-temperature resistant complex phase ceramic aerogel is characterized in that:
the high temperature resistant complex phase ceramic aerogel is prepared by the method of any one of claims 1 to 9;
preferably, the porosity of the high-temperature resistant complex-phase ceramic aerogel is 60-85%, and the density of the high-temperature resistant complex-phase ceramic aerogel is 0.2-0.8g/cm 3 The specific surface area is 100-300m 2 (ii)/g, the average pore diameter is 80-200nm.
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