CN110818423A - Zirconium carbide-boron carbide composite aerogel and preparation method thereof - Google Patents
Zirconium carbide-boron carbide composite aerogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses zirconium carbide-boron carbide composite aerogel and a preparation method thereof, wherein a boron source, deionized water and absolute ethyl alcohol are mixed, heated and uniformly stirred to obtain a solution A; mixing resorcinol, formaldehyde and absolute ethyl alcohol, and stirring uniformly to obtain a solution B; uniformly mixing and stirring a zirconium source, absolute ethyl alcohol and deionized water to obtain a solution C; mixing the solution B and the solution C, adding the mixture into the solution A, then adding a network forming agent, and uniformly stirring to obtain a composite sol solution; pouring the composite sol solution into a mold, standing, placing the mold in an oven for aging, performing solvent replacement on the aged material with absolute ethyl alcohol to obtain composite wet gel, and performing CO (carbon monoxide) treatment2Supercritical drying partAnd finally, carrying out heat treatment and carbon removal under the protection of inert atmosphere to obtain the zirconium carbide-boron carbide composite aerogel which has excellent performances such as low density, high strength and low thermal conductivity.
Description
Technical Field
The invention belongs to a preparation process of a composite material, and particularly relates to a zirconium carbide-boron carbide composite aerogel material and a preparation method thereof.
Background
With the continuous breakthrough of the flight speed technical barrier and the accompanied severe service environment of the aerospace craft, the requirements on the thermal protection material of the high-performance aerospace craft are higher and higher. The aerogel is a nano porous material with a three-dimensional network structure and excellent performances such as low density, high specific surface area, low thermal conductivity and the like. Currently, in the field of thermal insulation, most researches are carried out on silica aerogel, but the temperature resistance is not high, and severe pore collapse and material structure damage can occur when the temperature exceeds 800 ℃. In order to break through the application of aerogel in ultra-high temperature in the aerospace field, a novel high-temperature-resistant aerogel material needs to be developed urgently. Zirconium carbide has excellent physicochemical properties as a high-melting-point material with high hardness and an excellent high-temperature refractory material; boron carbide is one of the three hardest known materials, and has the characteristics of low density, high strength, high-temperature stability and good chemical stability, so that the preparation method of the zirconium-boron carbide composite aerogel is developed by combining carbide with excellent performance and aerogel, the application of the aerogel in the ultrahigh-temperature field can be widened, and the potential advantages of the aerogel in the aerospace field can be expected.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a zirconium carbide-boron carbide composite aerogel material, which has the advantages of simple process, low price and easy obtainment of raw materials and excellent sample performance, aiming at the defects of the prior art.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of zirconium carbide-boron carbide composite aerogel comprises the following steps:
(1) mixing a boron source, deionized water and absolute ethyl alcohol, heating and stirring uniformly to obtain a solution A;
(2) mixing resorcinol, formaldehyde and absolute ethyl alcohol, and stirring uniformly to obtain a solution B;
(3) uniformly mixing and stirring a zirconium source, absolute ethyl alcohol and deionized water to obtain a solution C;
(4) mixing the solution B and the solution C, adding the mixture into the solution A, then adding a network forming agent, and uniformly stirring to obtain a composite sol solution;
(5) pouring the composite sol solution obtained in the step (4) into a mold, standing, putting into an oven for aging treatment, and then performing solvent replacement on the aged material by using absolute ethyl alcohol to obtain a composite wet gel;
(6) subjecting the composite wet gel obtained in the step (5) to CO2Performing supercritical drying treatment to obtain a precursor of the composite aerogel material;
(7) and (3) heating the precursor of the composite aerogel material obtained in the step (6) to 650-850 ℃ at a heating rate of 5-10 ℃/min under the protection of inert atmosphere, carrying out carbonization treatment for 5-7 hours, then continuously heating to 1450-1750 ℃ at a heating rate of 2-4 ℃/min, carrying out carbothermic reduction reaction for 5-10 hours, then reducing the temperature to 300-600 ℃, changing the inert gas into air, continuously carrying out decarburization treatment for 2-5 hours, and cooling to obtain the zirconium carbide-boron carbide composite aerogel.
Specifically, in the step (1), the boron source is trimethyl borate or triethyl borate, and the molar ratio of the boron source, deionized water and absolute ethyl alcohol is 1: (60-100): (30-50) mixing; the temperature for heating and stirring is 75-85 ℃.
Preferably, in step (2), resorcinol, formaldehyde and anhydrous ethanol are mixed in a molar ratio of 1: 2: (10-40), and taking the solution B as a carbon source and a part of a skeleton structure of the aerogel precursor.
Specifically, in the step (3), the zirconium source is zirconium oxychloride octahydrate, and the zirconium source, absolute ethyl alcohol and deionized water are mixed according to a molar ratio of 1: (30-50): (40-60) mixing.
Specifically, in the step (4), the network forming agent is propylene oxide to promote the formation of the aerogel network skeleton, and the molar ratio of resorcinol, formaldehyde, boron source, zirconium source and network forming agent in the obtained composite sol solution is 1: 2: 1: 1: (0.5-2).
Preferably, in the step (5), the standing time is 60-180 min, and the temperature of an oven is 100-150 ℃; the absolute ethyl alcohol is replaced once every 8-24 hours, and the total replacement time is 6-8 times.
Preferably, in step (6), the CO2The conditions of the supercritical drying treatment are as follows: 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.
Preferably, in step (7), the inert atmosphere is argon.
The zirconium carbide-boron carbide composite aerogel prepared by the preparation method is also in the protection scope of the invention.
Further, the invention also provides application of the zirconium carbide-boron carbide composite aerogel as a heat insulation material.
Has the advantages that:
1. the invention has simple process, and compared with other heat-insulating composite materials in the field of aerospace, the zirconium carbide-boron carbide composite aerogel material has low price and is easy to obtain. The method adopts cheap and easily-obtained triethyl borate and zirconium chloride as raw materials, utilizes a sol-gel method combined with a supercritical drying technology, and has simple and easily-repeated process operation.
2. The zirconium carbide-boron carbide composite aerogel prepared by the invention has excellent performance and wide application range. Compared with the traditional oxide aerogel material, the zirconium carbide-boron carbide composite aerogel has excellent performances of low density, high strength, low thermal conductivity and the like, can be applied to the field of aerospace, and can also be used on heat-insulating materials of civil high-temperature kilns, such as high-temperature single/polycrystalline furnaces and the like. And because the composite material contains boron carbide, the composite material has excellent performances of high chemical stability, high neutron absorption cross section, high temperature resistance and the like, and can be widely applied to the fields of nuclear industry and the like.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a photograph of a physical representation of the zirconium carbide-boron carbide composite aerogel material prepared in example 1.
FIG. 2 is a scanning electron micrograph of the zirconium carbide-boron carbide composite aerogel material prepared in example 2.
Detailed Description
The invention will be better understood from the following examples.
Example 1
1mol of triethyl borate, 60mol of deionized water and 30mol 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 10mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of zirconium oxychloride octahydrate, 30mol of absolute ethyl alcohol and 40mol of deionized water are uniformly mixed and stirred. And mixing the solution B and the solution C, adding the mixture into the solution A, mixing, adding 0.5mol of propylene oxide, and uniformly stirring to obtain an orange sol solution. Pouring into a mold, standing for 60min, aging in an oven at 100 deg.C for 24 hr, adding anhydrous ethanol for solvent replacement, and replacing once every 8 hr for 6 times in total. Subjecting the displaced wet gel to CO2And (3) 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 zirconium carbide-boron carbide composite aerogel precursor. And heating the obtained zirconium carbide-boron carbide composite aerogel precursor to 650 ℃ at the heating rate of 5 ℃/min under the protection of argon atmosphere, keeping the temperature for 5 hours, then continuously heating to 1450 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 5 hours, then reducing the temperature to 300 ℃, changing argon into air, continuously keeping the temperature for 2 hours to perform decarburizing treatment, and cooling to room temperature to obtain the zirconium carbide-boron carbide composite aerogel. The photo of the prepared zirconium carbide-boron carbide composite aerogel is shown in figure 1 and is a black block-shaped object. Tests show that: the density of the prepared zirconium carbide-boron carbide composite aerogel is 0.36g/cm3The thermal conductivity was 0.048W/(mK).
Example 2
1mol of triethyl borate, 100mol of deionized water and 50mol of boric acidUltrasonically dispersing with water ethanol, and heating and stirring at 85 ℃ to obtain a solution A. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 40mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of zirconium oxychloride octahydrate, 50mol of absolute ethyl alcohol and 60mol of deionized water are uniformly mixed and stirred. And mixing the solution B and the solution C, adding the mixture into the solution A, mixing, adding 2mol of propylene oxide, and uniformly stirring to obtain an orange sol solution. Pouring into a mold, standing for 180min, aging in an oven at 150 deg.C for 24 hr, adding anhydrous ethanol for solvent replacement, and replacing once every 24 hr for 8 times. Subjecting the displaced wet gel to CO2And (3) performing supercritical drying treatment, wherein the pressure of the kettle body is controlled at 12.5MPa, the temperature is controlled at 55 ℃, and the drying time is 14 hours, so as to obtain the zirconium carbide-boron carbide composite aerogel precursor. And heating the obtained zirconium carbide-boron carbide composite aerogel precursor to 850 ℃ at the heating rate of 10 ℃/min under the protection of argon atmosphere, keeping the temperature for 7 hours, then continuously heating to 1750 ℃ at the heating rate of 4 ℃/min, keeping the temperature for 10 hours, then reducing the temperature to 600 ℃, changing argon into air, continuously keeping the temperature for 5 hours to perform decarburizing treatment, and cooling to room temperature to obtain the zirconium carbide-boron carbide composite aerogel. The scanning electron microscope image of the prepared zirconium carbide-boron carbide composite aerogel is shown in fig. 2, and the prepared zirconium carbide-boron carbide composite aerogel presents a regular aerogel three-dimensional structure. Tests show that: the density of the prepared zirconium carbide-boron carbide composite aerogel is 0.22g/cm3The thermal conductivity was 0.062W/(m.K).
Example 3
Ultrasonically dispersing 1mol of trimethyl borate, 80mol of deionized water and 40mol of absolute ethyl alcohol uniformly, and heating and stirring at 80 ℃ to obtain a solution A. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 15mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of zirconium oxychloride octahydrate, 40mol of absolute ethyl alcohol and 50mol of deionized water are uniformly mixed and stirred. And mixing the solution B and the solution C, adding the mixture into the solution A, mixing, adding 1mol of propylene oxide, and uniformly stirring to obtain an orange sol solution. Pouring into a mold, standing for 100min, aging in a 120 ℃ oven for 24 h, adding absolute ethanol for solvent replacement, and replacing once every 16 h for 7 times in total. The displaced wet gel is driedCarrying out CO2And (3) supercritical drying treatment, wherein the pressure of the kettle body is controlled at 10MPa, the temperature is controlled at 52 ℃, and the drying time is 10 hours, so as to obtain the zirconium carbide-boron carbide composite aerogel precursor. And heating the obtained zirconium carbide-boron carbide composite aerogel precursor to 700 ℃ at the heating rate of 7 ℃/min under the protection of argon atmosphere, keeping the temperature for 6 hours, then continuously heating to 1680 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 7 hours, then reducing the temperature to 400 ℃, changing argon into air, continuously keeping the temperature for 3 hours to perform decarburizing treatment, and cooling to room temperature to obtain the zirconium carbide-boron carbide composite aerogel. Tests show that: the density of the prepared zirconium carbide-boron carbide composite aerogel is 0.40g/cm3The thermal conductivity was 0.053W/(mK).
Example 4
Ultrasonically dispersing 1mol of trimethyl borate, 70mol of deionized water and 45mol of absolute ethyl alcohol uniformly, and heating and stirring at 82 ℃ to obtain a solution A. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 25mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of zirconium oxychloride octahydrate, 45mol of absolute ethyl alcohol and 55mol of deionized water are uniformly mixed and stirred. And mixing the solution B and the solution C, adding the mixture into the solution A, mixing, adding 1.5mol of propylene oxide, and uniformly stirring to obtain an orange sol solution. Pouring into a mold, standing for 120min, aging in an oven at 100 deg.C for 24 hr, adding anhydrous ethanol for solvent replacement, and replacing once every 12 hr for 8 times. Subjecting the displaced wet gel to CO2And (3) performing supercritical drying treatment, wherein the pressure of the kettle body is controlled at 11MPa, the temperature is controlled at 50 ℃, and the drying time is 11 hours, so as to obtain the zirconium carbide-boron carbide composite aerogel precursor. Heating the obtained zirconium carbide-boron carbide composite aerogel precursor to 700 ℃ at the heating rate of 7 ℃/min under the protection of argon atmosphere, keeping the temperature for 6 hours, then continuously heating to 1650 ℃ at the heating rate of 4 ℃/min, keeping the temperature for 8 hours, then reducing the temperature to 450 ℃, changing argon into air, continuously keeping the temperature for 2 hours to remove carbon, and cooling to room temperature to obtain the zirconium carbide-boron carbide composite aerogel. Tests show that: the density of the prepared zirconium carbide-boron carbide composite aerogel is 0.38g/cm3The thermal conductivity was 0.045W/(m·K)。
Example 5
1mol of triethyl borate, 90mol of deionized water and 45mol of absolute ethyl alcohol are dispersed uniformly by ultrasonic, and the solution A is obtained by heating and stirring at 80 ℃. Uniformly mixing 1mol of resorcinol, 2mol of formaldehyde and 35mol of absolute ethyl alcohol, and stirring to obtain a solution B. 1mol of zirconium oxychloride octahydrate, 40mol of absolute ethyl alcohol and 50mol of deionized water are uniformly mixed and stirred. And mixing the solution B and the solution C, adding the mixture into the solution A, mixing, adding 0.5mol of propylene oxide, and uniformly stirring to obtain an orange sol solution. Pouring into a mold, standing for 160min, aging in an oven at 100 deg.C for 15 hr, adding anhydrous ethanol for solvent replacement, and replacing once every 24 hr for 6 times in total. Subjecting the displaced wet gel to CO2And (3) 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 12 hours, so as to obtain the zirconium carbide-boron carbide composite aerogel precursor. And heating the obtained zirconium carbide-boron carbide composite aerogel precursor to 800 ℃ at the heating rate of 8 ℃/min under the protection of argon atmosphere, keeping the temperature for 6 hours, then continuously heating to 1600 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 8 hours, then reducing the temperature to 500 ℃, changing argon into air, continuously keeping the temperature for 4 hours to perform decarburizing treatment, and cooling to room temperature to obtain the zirconium carbide-boron carbide composite aerogel. Tests show that: the density of the prepared zirconium carbide-boron carbide composite aerogel is 0.31g/cm3The thermal conductivity was 0.051W/(mK).
The invention provides a zirconium carbide-boron carbide composite aerogel and a preparation method thereof, and a method and a way for realizing the technical scheme are numerous, the above description is only a preferred embodiment of the invention, and it should be noted that, for a person skilled in the art, a plurality of improvements and decorations can be made without departing from the principle of the invention, and the improvements and decorations should also be regarded as the protection scope of the invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (10)
1. The preparation method of the zirconium carbide-boron carbide composite aerogel is characterized by comprising the following steps of:
(1) mixing a boron source, deionized water and absolute ethyl alcohol, heating and stirring uniformly to obtain a solution A;
(2) mixing resorcinol, formaldehyde and absolute ethyl alcohol, and stirring uniformly to obtain a solution B;
(3) uniformly mixing and stirring a zirconium source, absolute ethyl alcohol and deionized water to obtain a solution C;
(4) mixing the solution B and the solution C, adding the mixture into the solution A, then adding a network forming agent, and uniformly stirring to obtain a composite sol solution;
(5) pouring the composite sol solution obtained in the step (4) into a mold, standing, putting into an oven for aging treatment, and then performing solvent replacement on the aged material by using absolute ethyl alcohol to obtain a composite wet gel;
(6) subjecting the composite wet gel obtained in the step (5) to CO2Performing supercritical drying treatment to obtain a precursor of the composite aerogel material;
(7) and (3) heating the precursor of the composite aerogel material obtained in the step (6) to 650-850 ℃ at a heating rate of 5-10 ℃/min under the protection of inert atmosphere, keeping the temperature for 5-7 hours, then continuously heating to 1450-1750 ℃ at a heating rate of 2-4 ℃/min, keeping the temperature for 5-10 hours, then reducing the temperature to 300-600 ℃, changing the inert gas into air, continuously keeping the temperature for 2-5 hours, performing decarburization treatment, and cooling to obtain the zirconium carbide-boron carbide composite aerogel.
2. The method for preparing the zirconium carbide-boron carbide composite aerogel according to claim 1, wherein in the step (1), the boron source is trimethyl borate or triethyl borate, and the molar ratio of the boron source to the deionized water to the absolute ethyl alcohol is 1: (60-100): (30-50) mixing; the temperature for heating and stirring is 75-85 ℃.
3. The method for preparing zirconium carbide-boron carbide composite aerogel according to claim 1, wherein in the step (2), the molar ratio of resorcinol, formaldehyde and absolute ethyl alcohol is 1: 2: (10-40) mixing.
4. The method for preparing the zirconium carbide-boron carbide composite aerogel according to claim 1, wherein in the step (3), the zirconium source is zirconium oxychloride octahydrate, and the zirconium source, the absolute ethyl alcohol and the deionized water are mixed according to a molar ratio of 1: (30-50): (40-60) mixing.
5. The method for preparing the zirconium carbide-boron carbide composite aerogel according to claim 1, wherein in the step (4), the network forming agent is propylene oxide, and the molar ratio of resorcinol, formaldehyde, the boron source, the zirconium source and the network forming agent in the obtained composite sol solution is 1: 2: 1: 1: (0.5-2).
6. The preparation method of the zirconium carbide-boron carbide composite aerogel according to claim 1, wherein in the step (5), the standing time is 60-180 min, and the oven temperature is 100-150 ℃; the absolute ethyl alcohol is replaced once every 8-24 hours, and the total replacement time is 6-8 times.
7. The method for preparing zirconium carbide-boron carbide composite aerogel according to claim 1, wherein in the step (6), the CO is introduced into the reaction vessel2The conditions of the supercritical drying treatment are as follows: 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.
8. The method for preparing the zirconium carbide-boron carbide composite aerogel according to claim 1, wherein in the step (7), the inert atmosphere is argon.
9. The zirconium carbide-boron carbide composite aerogel prepared by the preparation method of any one of claims 1 to 8.
10. Use of the zirconium carbide-boron carbide composite aerogel according to claim 9 as a thermal insulation material.
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