CN110711543A - Preparation method of fiber composite boron carbide-alumina aerogel material - Google Patents
Preparation method of fiber composite boron carbide-alumina aerogel material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000000835 fiber Substances 0.000 title claims abstract description 50
- 239000004964 aerogel Substances 0.000 title claims abstract description 45
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 24
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 9
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 41
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000000352 supercritical drying Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000002431 foraging effect Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052863 mullite Inorganic materials 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000005261 decarburization Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229910011255 B2O3 Inorganic materials 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- 239000011240 wet gel Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000012774 insulation material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000011819 refractory material Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 230000008676 import Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940063656 aluminum chloride Drugs 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention relates to a preparation method of a fiber composite boron carbide-alumina aerogel material, which comprises the steps of uniformly mixing a boron source, resorcinol, formaldehyde, aluminum chloride hexahydrate, absolute ethyl alcohol and deionized water according to a molar ratio to obtain a light yellow composite sol solution, dipping a cut fiber felt, and standing to obtain a fiber composite wet gel. And (3) replacing the fiber composite wet gel with a solvent, drying to obtain a fiber composite boron carbide-alumina aerogel precursor, and performing carbothermic reduction technology under the protection of inert atmosphere to obtain the fiber composite boron carbide-alumina aerogel. The preparation process is simple, the raw materials are low in price, the problem that the heat insulation material in the existing single/polycrystalline furnace depends on import can be solved, and the preparation method can be applied to the fields of refractory materials, engineering ceramics, nuclear industry, aerospace and the like.
Description
Technical Field
The invention belongs to a preparation process of a composite material, and particularly relates to a preparation method of a fiber composite boron carbide-alumina aerogel material.
Background
The heat preservation and insulation material in the existing single/polycrystalline furnace at home and abroad mainly adopts high-purity graphite felt material, which has high price and high-temperature heat conductivity (0.44 W.m at 1500℃)-1·K-1) And the replacement period is short, and the domestic produced high-purity graphite felt is insufficient in technology, and the heat-insulating property is difficult to meet the technical index of the single/polycrystalline silicon growth furnace crystal furnace. The aerogel material becomes the most ideal heat insulation material at present by virtue of ultralow heat conductivity, but the highest service temperature of the existing commercial aerogel products at home and abroad is less than 1000 ℃, so that the aerogel material is difficult to apply to ultrahigh-temperature equipment. Therefore, in the heat preservation and insulation market of the ultra-high temperature kiln of the single/polycrystalline silicon growth furnace and the like, foreign companies almost monopolize the market by means of the high-purity graphite felt material, and the healthy development of the photovoltaic industry in China is severely restricted. In order to break through the monopoly of foreign technologies, a novel high-temperature-resistant composite carbide aerogel material needs to be developed to replace an imported high-purity graphite felt in a monocrystalline silicon growth furnace, and under the premise of the same heat preservation effect, the composite carbide aerogel has the advantages of lower energy consumption, longer replacement period and low price.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of fiber composite boron carbide-alumina aerogel. The method has the advantages of simple process, low price and easy obtainment of raw materials and excellent sample performance.
The technical scheme of the invention is as follows: a preparation method of a fiber composite boron carbide-alumina aerogel material comprises the following specific steps:
(1) preparing composite sol: adding a boron source, deionized water and absolute ethyl alcohol according to a molar ratio of 1: (30-70): (10-30) uniformly mixing, heating and uniformly stirring to obtain a solution A; resorcinol, formaldehyde and absolute ethyl alcohol are mixed according to a molar ratio of 1: 2: (8.5-32), and uniformly stirring to obtain a solution B; mixing an aluminum source, ethanol and deionized water according to the weight ratio of 1: (20-40): (10-50), uniformly mixing, heating, uniformly stirring to obtain a solution C; mixing the solution A and the solution C, adding the solution B, adding a network forming agent, and continuously heating and stirring to obtain a light yellow composite sol solution;
(2) compounding with a fiber felt matrix: putting the cut fiber felt material into a container, pouring the light yellow sol solution obtained in the step (1) into the container, and standing until the light yellow sol solution submerges the base material;
(3) putting the fiber felt impregnated by the composite sol obtained in the step (2) into a drying oven together with a container for aging treatment; adding absolute ethyl alcohol into the container to replace the solvent of the aged material;
(4) cutting the composite material subjected to solvent replacement in the step (3) and performing CO2 supercritical drying treatment to obtain a precursor of the composite aerogel material;
(5) and (3) heating the precursor of the composite aerogel material obtained in the step (4) to 750-850 ℃ at a heating rate of 2-5 ℃/min under the protection of inert atmosphere, keeping the temperature for 3-5 hours, then continuously heating to 1350-1650 ℃ at a heating rate of 1-3 ℃/min, keeping the temperature for 3-10 hours, then reducing the temperature to 550-750 ℃, exchanging inert gas into air, continuously keeping the temperature for 1-4 hours, performing decarburization treatment, and cooling to obtain the fiber composite boron carbide-alumina aerogel.
Preferably, the boron source in the step (1) is one of boric acid, boron oxide or triethyl borate; the aluminum source is aluminum chloride hexahydrate.
Preferably, the heating temperature in the step (1) is 50-80 ℃.
Preferably, the network forming agent in step (1) is one of anhydrous citric acid, citric acid monohydrate or sodium citrate.
Preferably, in step (1), resorcinol, formaldehyde: a boron source: an aluminum source: the molar ratio of the network former is 1: 2: (0.5-1.5): (1-2): (0.5-2).
Preferably, in the step (2), the fiber felt substrate is one of alumina fiber felt, mullite fiber felt or carbon fiber felt.
Preferably, the standing time in the step (2) is 30-60 min.
Preferably, the temperature of the oven in the step (3) is 40-70 ℃; and replacing the solvent once every 8-24 hours in the solvent replacement process, wherein the replacement is performed 3-6 times in total.
Preferably, in the step (4), the supercritical drying parameters of CO2 are that the pressure of a kettle body is controlled to be 8-12.5 MPa, the temperature is controlled to be 45-55 ℃, and the drying time is 8-14 hours.
Preferably, the inert atmosphere in step (5) is one of helium and argon.
Has the advantages that:
(1) the process is simple, and compared with imported high-purity graphite felt, the raw material of the fiber composite boron carbide-alumina aerogel is low in price and easy to obtain. The method adopts cheap and easily-obtained boric acid, boron oxide and aluminum chloride as raw materials, utilizes a sol-gel method combined with a supercritical drying technology, and has simple and easily-repeated process operation.
(2) Excellent performance and wide application range. Compared with the traditional oxide aerogel material, the fiber composite boron carbide-alumina aerogel has excellent performances of low density, high strength, low thermal conductivity and the like, can be applied to heat preservation and insulation materials in single/polycrystalline furnaces, has excellent performances of high chemical stability, high neutron absorption cross section, high temperature resistance and the like due to the boron carbide contained in the composite material, and can also be widely applied to the fields of refractory materials, engineering ceramics, nuclear industry, aerospace and the like.
Drawings
Fig. 1 is a photograph of a physical representation of the fiber composite boron carbide-alumina aerogel material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of protection.
Example 1
1mol of boric acid, 30mol of deionized water and 10mol of absolute ethyl alcohol are dispersed uniformly by ultrasonic, and the solution A is obtained by heating and stirring at 50 ℃. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 8.5mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of aluminum chloride hexahydrate, 20mol of absolute ethyl alcohol and 10mol of deionized waterMixing and stirring evenly. And mixing the solution A and the solution C, adding the solution A and the solution C into the solution B, mixing, adding 0.5mol of anhydrous citric acid, and uniformly stirring to obtain a light yellow sol solution. Pouring into a die in which the cut carbon fiber felt is placed, standing for 30min, placing into a 40 ℃ oven for aging treatment for 5 hours, adding absolute ethyl alcohol for solvent replacement, replacing every 8 hours for 3 times in total. Subjecting the displaced wet gel to CO2And (3) performing supercritical drying treatment, wherein the pressure of the kettle body is controlled at 8MPa, the temperature is controlled at 45 ℃, and the drying time is 8 hours, so as to obtain the fiber composite boron carbide-alumina aerogel precursor. And heating the obtained fiber composite boron carbide-alumina aerogel precursor to 750 ℃ at the heating rate of 2 ℃/min under the protection of argon atmosphere, keeping the temperature for 3 hours, then continuously heating to 1350 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 3 hours, then reducing the temperature to 550 ℃, exchanging argon gas into air, continuously keeping the temperature for 1 hour for decarburizing treatment, and cooling to room temperature to obtain the fiber composite boron carbide-alumina aerogel. The photo of the prepared fiber composite boron carbide-alumina aerogel real object is shown in figure 1 and is a black block-shaped object. Tests show that: the density of the prepared fiber composite boron carbide-alumina aerogel is 0.24g/cm3The thermal conductivity was 0.063W/(m.K), and the compressive strength was 1.25 MPa.
Example 2
1mol of boric acid, 70mol of deionized water and 30mol of absolute ethyl alcohol are dispersed evenly by ultrasonic, and solution A is obtained by heating and stirring at 80 ℃. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 32mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of aluminum chloride hexahydrate, 40mol of absolute ethyl alcohol and 50mol of deionized water are mixed uniformly and stirred. And mixing the solution A and the solution C, adding the mixture into the solution B, mixing, adding 2mol of anhydrous citric acid, and uniformly stirring to obtain a light yellow sol solution. Pouring into a mold with cut carbon fiber felt, standing for 60min, aging in a 70 ℃ oven for 5 h, adding absolute ethyl alcohol for solvent replacement, replacing every 24 h for 6 times in total. Subjecting the displaced wet gel to CO2Supercritical drying at 55 deg.C under 12.5MPa for 14 hr to obtain the final productTo the fiber composite boron carbide-alumina aerogel precursor. And heating the obtained fiber composite boron carbide-alumina aerogel precursor to 850 ℃ at the heating rate of 5 ℃/min under the protection of argon atmosphere, keeping the temperature for 5 hours, then continuously heating to 1650 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 10 hours, then reducing the temperature to 750 ℃, exchanging argon gas into air, continuously keeping the temperature for 4 hours for decarburizing treatment, and cooling to room temperature to obtain the fiber composite boron carbide-alumina aerogel. Tests show that: the density of the prepared fiber composite boron carbide-alumina aerogel is 0.41g/cm3The thermal conductivity was 0.057W/(m.K), and the compressive strength was 2.43 MPa.
Example 3
1mol of boric acid, 50mol of deionized water and 20mol of absolute ethyl alcohol are dispersed uniformly by ultrasonic, and the solution A is obtained by heating and stirring at 65 ℃. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 20mol of absolute ethyl alcohol, and stirring to obtain a solution B. 2mol of aluminum chloride hexahydrate, 60mol of absolute ethyl alcohol and 60mol of deionized water are mixed uniformly and stirred. And mixing the solution A and the solution C, adding the mixture into the solution B, mixing, adding 1mol of anhydrous citric acid, and uniformly stirring to obtain a light yellow sol solution. Pouring into a mold with cut carbon fiber felt, standing for 45min, aging in a 60 ℃ oven for 5 hours, adding absolute ethyl alcohol for solvent replacement, replacing every 16 hours for 5 times in total. Subjecting the displaced wet gel to CO2And (3) performing supercritical drying treatment, wherein the pressure of the kettle body is controlled at 10MPa, the temperature is controlled at 50 ℃, and the drying time is 11 hours, so as to obtain the fiber composite boron carbide-alumina aerogel precursor. Heating the obtained fiber composite boron carbide-alumina aerogel precursor to 800 ℃ at the heating rate of 3 ℃/min under the protection of argon atmosphere, keeping the temperature for 4 hours, then continuously heating to 1550 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 7 hours, then reducing the temperature to 600 ℃, exchanging argon gas into air, continuously keeping the temperature for 2 hours for decarburizing treatment, and cooling to room temperature to obtain the fiber composite boron carbide-alumina aerogel. Tests show that: the density of the prepared fiber composite boron carbide-alumina aerogel is 0.34g/cm3The thermal conductivity was 0.053W/(m.K), and the compressive strength was 2.60 MPa.
Example 4
0.5mol of triethyl borate, 20mol of deionized water and 10mol of absolute ethyl alcohol are dispersed uniformly by ultrasonic, and the solution A is obtained by heating and stirring at 60 ℃. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 25mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of aluminum chloride hexahydrate, 25mol of absolute ethyl alcohol and 35mol of deionized water are mixed uniformly and stirred. And mixing the solution A and the solution C, adding the mixture into the solution B, mixing, adding 1mol of anhydrous citric acid, and uniformly stirring to obtain a light yellow sol solution. Pouring into a die in which a cut mullite fibrofelt is placed, standing for 40min, placing into a 65 ℃ oven for aging treatment for 5 hours, adding absolute ethyl alcohol for solvent replacement, and replacing once every 10 hours for 6 times in total. Subjecting the displaced wet gel to CO2And (3) performing supercritical drying treatment, wherein the pressure of the kettle body is controlled at 9MPa, the temperature is controlled at 50 ℃, and the drying time is 10 hours, so as to obtain the fiber composite boron carbide-alumina aerogel precursor. And heating the obtained fiber composite boron carbide-alumina aerogel precursor to 800 ℃ at the heating rate of 4 ℃/min under the protection of argon atmosphere, keeping the temperature for 3 hours, then continuously heating to 1600 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 5 hours, then reducing the temperature to 600 ℃, exchanging argon gas into air, continuously keeping the temperature for 3 hours for decarburizing treatment, and cooling to room temperature to obtain the fiber composite boron carbide-alumina aerogel. Tests show that: the density of the prepared fiber composite boron carbide-alumina aerogel is 0.40g/cm3The thermal conductivity was 0.051W/(m.K), and the compressive strength was 1.88 MPa.
Example 5
1mol of boric acid, 50mol of deionized water and 20mol of absolute ethyl alcohol are dispersed uniformly by ultrasonic, and the solution A is obtained by heating and stirring at 75 ℃. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 18mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of aluminum chloride hexahydrate, 30mol of absolute ethyl alcohol and 40mol of deionized water are mixed uniformly and stirred. And mixing the solution A and the solution C, adding the solution A and the solution C into the solution B, mixing, adding 1mol of sodium citrate, and uniformly stirring to obtain a light yellow sol solution. Pouring into a die with cut carbon fiber felt, standing for 40min, and aging in a 60 deg.C oven for 5 hrAnd adding absolute ethyl alcohol to perform solvent replacement, and replacing once every 10 hours for 6 times in total. Subjecting the displaced wet gel to CO2And (3) performing supercritical drying treatment, wherein the pressure of the kettle body is controlled at 10MPa, the temperature is controlled at 55 ℃, and the drying time is 12 hours, so as to obtain the fiber composite boron carbide-alumina aerogel precursor. Heating the obtained fiber composite boron carbide-alumina aerogel precursor to 800 ℃ at the heating rate of 3 ℃/min under the protection of argon atmosphere, keeping the temperature for 3 hours, then continuously heating to 1650 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 5 hours, then reducing the temperature to 600 ℃, exchanging argon gas into air, continuously keeping the temperature for 3 hours for decarburizing treatment, and cooling to room temperature to obtain the fiber composite boron carbide-alumina aerogel. Tests show that: the density of the prepared fiber composite boron carbide-alumina aerogel is 0.32g/cm3The thermal conductivity was 0.067W/(m.K), and the compressive strength was 2.65 MPa.
Claims (10)
1. A preparation method of a fiber composite boron carbide-alumina aerogel material comprises the following specific steps:
(1) preparing composite sol: adding a boron source, deionized water and absolute ethyl alcohol according to a molar ratio of 1: (30-70): (10-30) uniformly mixing, heating and uniformly stirring to obtain a solution A; resorcinol, formaldehyde and absolute ethyl alcohol are mixed according to a molar ratio of 1: 2: (8.5-32), and uniformly stirring to obtain a solution B; mixing an aluminum source, ethanol and deionized water according to the weight ratio of 1: (20-40): (10-50), uniformly mixing, heating, uniformly stirring to obtain a solution C; mixing the solution A and the solution C, adding the solution B, adding a network forming agent, and continuously heating and stirring to obtain a light yellow composite sol solution;
(2) compounding with a fiber felt matrix: putting the cut fiber felt material into a container, pouring the light yellow sol solution obtained in the step (1) into the container, and standing until the light yellow sol solution submerges the base material;
(3) putting the fiber felt impregnated by the composite sol obtained in the step (2) into a drying oven together with a container for aging treatment; adding absolute ethyl alcohol into the container to replace the solvent of the aged material;
(4) cutting the composite material subjected to solvent replacement in the step (3) and carrying out CO (carbon monoxide)2Performing supercritical drying treatment to obtain a precursor of the composite aerogel material;
(5) and (3) heating the precursor of the composite aerogel material obtained in the step (4) to 750-850 ℃ at a heating rate of 2-5 ℃/min under the protection of inert atmosphere, keeping the temperature for 3-5 hours, then continuously heating to 1350-1650 ℃ at a heating rate of 1-3 ℃/min, keeping the temperature for 3-10 hours, then reducing the temperature to 550-750 ℃, exchanging inert gas into air, continuously keeping the temperature for 1-4 hours, performing decarburization treatment, and cooling to obtain the fiber composite boron carbide-alumina aerogel.
2. The production method according to claim 1, characterized in that the boron source in the step (1) is one of boric acid, boric oxide or triethyl borate; the aluminum source is aluminum chloride hexahydrate.
3. The method according to claim 1, wherein the heating temperature in the step (1) is 50 to 80 ℃.
4. The method of claim 1, wherein the network forming agent in the step (1) is one of anhydrous citric acid, citric acid monohydrate or sodium citrate.
5. The production method according to claim 1, characterized in that in step (1), the ratio of resorcinol, formaldehyde: a boron source: an aluminum source: the molar ratio of the network former is 1: 2: (0.5-1.5): (1-2): (0.5-2).
6. The method according to claim 1, wherein the fiber mat base in the step (2) is one of alumina fiber mat, mullite fiber mat, or carbon fiber mat.
7. The method according to claim 1, wherein the standing time in the step (2) is 30 to 60 min.
8. The preparation method according to claim 1, wherein the temperature of the oven in the step (3) is 40-70 ℃; and replacing the solvent once every 8-24 hours in the solvent replacement process, wherein the replacement is performed 3-6 times in total.
9. The process according to claim 1, wherein the CO in the step (4)2The supercritical drying parameters are that the pressure of the kettle body is controlled to be 8-12.5 MPa, the temperature is controlled to be 45-55 ℃, and the drying time is 8-14 hours.
10. The method according to claim 1, wherein the inert gas atmosphere in the step (5) is one of helium gas and argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911082398.7A CN110711543A (en) | 2019-11-07 | 2019-11-07 | Preparation method of fiber composite boron carbide-alumina aerogel material |
Applications Claiming Priority (1)
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