CN113321524A - Preparation method of ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers - Google Patents

Preparation method of ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers Download PDF

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CN113321524A
CN113321524A CN202110726911.2A CN202110726911A CN113321524A CN 113321524 A CN113321524 A CN 113321524A CN 202110726911 A CN202110726911 A CN 202110726911A CN 113321524 A CN113321524 A CN 113321524A
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李福平
许卓利
赵康
党薇
汤玉斐
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Xian University of Technology
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Abstract

The invention discloses a preparation method of ultrahigh-temperature ceramic aerogel based on multi-cavity structure fibers, which comprises the steps of carrying out electrostatic spinning by using a spinning needle head and carrying out high-temperature calcination to obtain ultrahigh-temperature ceramic nanofibers with multi-cavity structures; preparing slurry from the nano fibers and the carbon material, freeze-drying, then carrying out vacuum freeze-drying to obtain an aerogel material, and finally carrying out high-temperature carbonization to obtain the ultrahigh-temperature ceramic aerogel material with the fibers in the multi-cavity structure. The method solves the problems of low melting point, poor high temperature resistance, high thermal conductivity, poor structural stability and thermal shock resistance and complex preparation process of the aerogel in the prior art.

Description

Preparation method of ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers
Technical Field
The invention belongs to the technical field of ceramic materials, and relates to a preparation method of an ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers.
Background
Aerogel materials have low densities (up to a minimum of 0.003 g/cm)3) High porosity (up to 99.8%) and high specific surface area (200-1000 m)2The material has the characteristics of/g), is one of solid materials with the lowest density and the lowest thermal conductivity, and becomes a new generation of aerospace heat-insulating material. Aerogels currently the most widely studied include oxide aerogels, such as SiO2、Al2O3、ZrO2Aerogels, and carbon aerogels. The oxide aerogel has a relatively low melting point, is easy to generate crystal form transformation and particle sintering in a high-temperature region (more than 1000 ℃), has poor temperature resistance and is difficult to meet the high-temperature heat insulation requirement. Although the carbon aerogel can reach 2000 ℃ of temperature resistance under inert and vacuum environment, and even reach 3000 ℃ of temperature resistance after graphitization, the carbon aerogel is not oxidation-resistant, and is oxidized above 350 ℃ under aerobic environment, which becomes the difficulty of application. Therefore, the development of a ceramic aerogel heat-insulating material with high temperature resistance, oxidation resistance and low heat conductivity becomes one of the problems to be solved at present.
Ultra-high temperature ceramics, e.g. ZrB2、HfB2ZrC and the like have a series of excellent properties, such as high melting point (more than 3000 ℃), low density, good oxidation and ablation resistance, excellent mechanical properties at high temperature and the like, and are applied to extreme environments of discharge plasma electrode materials, hypersonic velocity reentry aircraft engines and the like. However, its high thermal conductivity (ZrB)257.9W/mk; ZrC:20.52W/mk) limits the application in the field of heat insulation, and if the nano ultrahigh-temperature ceramic fiber with a multi-cavity structure is designed and constructed and prepared into the ultrahigh-temperature ceramic aerogel, the thermal conductivity of the nano ultrahigh-temperature ceramic fiber can be effectively reduced. Therefore, the preparation of ultra-high temperature ceramic aerogel with multi-cavity structure fiber becomes one of the important points of research.
Ye et al 2013 report on zirconium Polyacetylacetonate (PZO) as a zirconium source, 2, 4-dihydroxybenzene, in Journal of Sol-Gel Science Technology, 65 th and 159Formic acid (DA) and formaldehyde (F) as carbon sources, and CO2Preparing zirconium-containing organic aerogel by supercritical drying technology, carbonizing and performing carbothermic reduction reaction under argon to obtain ZrCO/C composite aerogel material which is pure compared with ZrO2The aerogel has higher specific surface area (589 m)2g-1) (ii) a Hao Suo et al used sol-gel to bind CO in SN Applied Sciences journal 2019, Vol.461, No. 12ZrC @ Al prepared by supercritical drying technology2O3@ Carbon aerogel, the aerogel being ZrO2Aerogel and carbon aerogel have better thermal stability and compressive strength; preparation and performance characterization of ZrC/C composite aerogels were described by Sue Ren et al in Journal of the European Ceramic Society, Vol.41, No. 9, No. 4710, No. 4719, at low density (0.262-0.379 g/cm)3) Still has higher compressive strength (0.87-4.42MPa) under the condition of (1); in addition, the thermal conductivity of the material is 0.0896-0.1064W/(m.k), which is lower than that of silicon oxide and carbon fiber; james T et al, in the journal of Chemistry of Materials 2019, volume 31, phase 10, 3700, 3704, introduced that boron nanoparticles and metal (Zr, Hf) oxide precursor are uniformly mixed, and subjected to sol-gel and supercritical drying to obtain B-MO2Performing boron thermal reduction reaction on the composite aerogel to obtain ZrB2、HfB2An aerogel; ZrB obtained2The thermal conductivity of the aerogel is 0.18-0.33W/(m.k), which is far lower than that of the bulk ZrB2The material with excellent performances is expected to be applied to the field of aviation thermal insulation in the near future. However, the aerogel materials are all composed of particles, and the situation of powder falling off exists in the using process, so that the structure is unstable; in addition, the preparation processes of the aerogel materials are all supercritical drying methods, the problems of complex process, high equipment requirement and the like exist, and the prepared aerogel still has a space for improving the porosity and the thermal conductivity.
Disclosure of Invention
The invention aims to provide a preparation method of an ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers, and solves the problems of low aerogel melting point, poor high temperature resistance, high thermal conductivity, poor structural stability and thermal shock resistance and complex preparation process in the prior art.
The invention adopts the technical scheme that a preparation method of ultra-high temperature ceramic aerogel based on multi-cavity structure fibers is implemented according to the following steps:
step 1, preparing multi-cavity structure nano fibers;
step 2, preparing aerogel
Adding the multi-cavity structure nanofiber prepared in the step 1 into a cellulose nanofiber solution, stirring to obtain a fiber dispersion solution, injecting the fiber dispersion solution into a plastic mold for freezing and molding, and then performing vacuum freeze drying to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace to obtain the ceramic aerogel.
The present invention is also characterized in that,
the specific process of the step 1 is as follows:
step 1.1, dissolving a carbon source and a spinning auxiliary agent in a solvent A (DMF) to obtain a solution A;
the mass ratio of the carbon source to the spinning auxiliary agent is 0.636-1.272: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent A is 0.636-1.272: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution B;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 4: 2-3: 4;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
and step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tube furnace to calcine in an argon atmosphere to obtain the ZrC nanofiber with a multi-cavity structure.
The specific process of the step 1 is as follows:
step 1.1, dissolving a carbon source, boric acid and a spinning auxiliary agent in a solvent B (DMF) to obtain a solution C;
the mass ratio of the carbon source to the boric acid to the spinning auxiliary agent is 0.636-1.272: 1.108 to 2.771: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent B (DMF) is 0.636-1.272: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution D;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 4: 2-3: 4;
step 1.3, mixing the solution C obtained in the step 1.1 and the solution D obtained in the step 1.2, and uniformly stirring to obtain a spinning solution B;
step 1.4, spinning the spinning solution B obtained in the step 1.3 by using a spinning needle to obtain precursor fiber B;
step 1.5, placing the precursor fiber B obtained in the step 1.4 in a tube furnace to calcine in argon atmosphere to obtain ZrB with a multi-cavity structure2-ZrC nanofibers.
The specific process of the step 1 is as follows:
step 1.1, dissolving a carbon source, boric acid and a spinning auxiliary agent in a solvent C (DMF) to obtain a solution E;
the mass ratio of the carbon source to the boric acid to the spinning auxiliary agent is 0.636-2.031: 1.108 to 2.771: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent C (DMF) is 0.636-2.031: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution F;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 1: 0.5-1: 1;
step 1.3, adding tetraethoxysilane and glacial acetic acid into a solvent D (DMF) to obtain a solution G;
the volume ratio of ethyl orthosilicate, glacial acetic acid and a solvent D (DMF) is 1-4: 0.25-1: 1-4;
step 1.4, mixing the solution E obtained in the step 1.1, the solution F obtained in the step 1.2 and the solution G obtained in the step 1.3, and uniformly stirring to obtain a spinning solution C;
step 1.5, spinning the spinning solution C obtained in the step 1.4 by using a spinning needle to obtain precursor fiber C;
step 1.6, placing the precursor fiber C obtained in the step 1.5 in a tube furnace to calcine in argon atmosphere to obtain ZrB with a multi-cavity structure2-ZrC-SiC nanofibers.
The spinning needle head comprises a shell, two needle heads or three needle heads or four needle heads are arranged in the shell, the three needle heads are arranged in an equilateral triangle, and the four needle heads are arranged in a square;
the size of the shell is 12-13G, and the size of each needle head is 22-25G;
the shell is connected with spinning solution, and the spinning speed is 1.8-2.2 ml.h-1(ii) a The needle head is connected with the oil phase, and the spinning speed is 0.08-0.16 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
the calcining temperature is 1300-1600 ℃, and the calcining time is 2 h.
The oil phase is one of paraffin oil, silicone oil and edible oil.
The carbon source adopts sucrose or glucose, and the zirconium source adopts zirconium n-propoxide or zirconium oxychloride.
In the step 2, the mass fraction of the cellulose nanofiber solution is 0.15-0.2%, the stirring speed is 13000-20000rpm, and the stirring time is 5-15 min; the freezing time is-130 to-40 ℃, the temperature of vacuum freeze drying is-20 ℃, the vacuum degree of vacuum freeze drying is 1Pa, and the time of vacuum freeze drying is 24 hours.
In the step 2, the mass concentration of the cellulose nanofiber solution is 0.1-0.5%, and the mass ratio of the multi-cavity structure nanofiber to the cellulose nanofiber solution is 0.2-2: 100.
in the step 3, the carbonization temperature is 800-850 ℃, and the heat preservation time is 2 hours.
The beneficial effect of the invention is that,
(1) according to the preparation method of the ultrahigh-temperature ceramic aerogel based on the multi-cavity structure fibers, the multi-cavity structure nanofibers are used as structural units of the aerogel, the ultrahigh-temperature ceramic fiber aerogel is obtained after freeze drying and forming, the number of mesopores of the aerogel is increased due to the multi-cavity structure, the gas heat transfer effect is weakened, and the heat conductivity of the aerogel is further reduced;
(2) according to the preparation method of the ultrahigh-temperature ceramic aerogel based on the multi-cavity structure fibers, the high length-diameter ratio of the multi-cavity structure nanofibers improves the structural stability of the aerogel, so that the thermal shock resistance is improved, the application field of the current ultrahigh-temperature ceramic aerogel is expanded, and the blank of the current preparation of the ultrahigh-temperature ceramic aerogel is made up.
Drawings
FIG. 1 is a schematic structural diagram of a spinning needle in a preparation method of an ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers, wherein FIG. 1a is a spinning needle with two needles, FIG. 1b is a spinning needle with three needles, and FIG. 1c is a spinning needle with four needles;
FIG. 2 is an XRD diffraction pattern of ZrC-C fiber aerogel obtained in example 1 in the preparation method of the ultrahigh temperature ceramic aerogel based on multi-cavity structure fibers;
FIG. 3 is an SEM image of a ZrC-C fiber aerogel obtained in example 1 in the preparation method of the ultrahigh temperature ceramic aerogel based on multi-cavity structural fibers;
FIG. 4 shows ZrB obtained in example 4 in a preparation method of an ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers2-XRD diffractogram of ZrC fibrous aerogel;
FIG. 5 shows ZrB obtained in example 7 in a preparation method of an ultrahigh temperature ceramic aerogel based on multi-cavity structural fibers2XRD diffraction pattern of-ZrC-SiC fiber aerogel.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of an ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers, which is implemented according to the following steps:
step 1, preparing multi-cavity structure nano fibers;
step 1.1, dissolving a carbon source and a spinning auxiliary agent in a solvent A to obtain a solution A;
the mass ratio of the carbon source to the spinning auxiliary agent is 0.636-1.272: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent A is 0.636-1.272: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution B;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 4: 2-3: 4;
the molar ratio of carbon in the carbon source to zirconium in the zirconium source is 2.5-5: 1;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tube furnace to calcine in an argon atmosphere to obtain ZrC nano-fibers with a multi-cavity structure;
or, step 1.1, dissolving a carbon source, boric acid and a spinning aid in a solvent B (DFM) to obtain a solution C;
the mass ratio of the carbon source to the boric acid to the spinning auxiliary agent is 0.636-1.272: 1.108 to 2.771: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent B (DFM) is 0.636-1.272: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution D;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 4: 2-3: 4;
the molar ratio of carbon in the carbon source to zirconium in the zirconium source is 2.5-5: 1; the molar ratio of boron in the boric acid to zirconium in the zirconium source is 2-5: 1;
step 1.3, mixing the solution C obtained in the step 1.1 and the solution D obtained in the step 1.2, and uniformly stirring to obtain a spinning solution B;
step 1.4, spinning the spinning solution B obtained in the step 1.3 by using a spinning needle to obtain precursor fiber B;
step 1.5, placing the precursor fiber B obtained in the step 1.4 in a tube furnace to calcine in argon atmosphere to obtain ZrB with a multi-cavity structure2-a ZrC nanofiber;
or, step 1.1, dissolving a carbon source, boric acid and a spinning auxiliary agent in a solvent C (DMF) to obtain a solution E;
the mass ratio of the carbon source to the boric acid to the spinning auxiliary agent is 0.636-2.031: 1.108 to 2.771: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent C (DMF) is 0.636-2.031: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution F;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 1: 0.5-1: 1;
step 1.3, adding tetraethoxysilane and glacial acetic acid into a solvent D (DMF) to obtain a solution G;
the volume ratio of ethyl orthosilicate, glacial acetic acid and a solvent D (DMF) is 1-4: 0.25-1: 1-4;
the molar ratio of carbon in the carbon source to zirconium in the zirconium source is 2.5-5: 1; the molar ratio of boron in the boric acid to zirconium in the zirconium source is 2-5: 1; the molar ratio of carbon in the carbon source to silicon in the ethyl orthosilicate is 3-5: 1;
step 1.4, mixing the solution E obtained in the step 1.1, the solution F obtained in the step 1.2 and the solution G obtained in the step 1.3, and uniformly stirring to obtain a spinning solution C;
step 1.5, spinning the spinning solution C obtained in the step 1.4 by using a spinning needle to obtain precursor fiber C;
step 1.6, placing the precursor fiber C obtained in the step 1.5 in a tube furnace to calcine in argon atmosphere to obtain ZrB with a multi-cavity structure2-ZrC-SiC nanofibers;
the ZrC nano-fiber is prepared,ZrB2-ZrC nanofibers, ZrB2The spinning needle structure adopted by the-ZrC-SiC nano fiber is as follows: the syringe comprises a shell, wherein two needles or three needles or four needles are arranged in the shell, the three needles are arranged in an equilateral triangle, and the four needles are arranged in a square; the size of the shell is 12-13G, and the size of each needle head is 22-25G;
the spinning process comprises the following steps: the shell is connected with spinning solution, and the spinning speed is 1.8-2.2 ml.h-1(ii) a The needle head is connected with the oil phase, and the spinning speed is 0.08-0.16 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
the calcining process comprises the following steps: the calcining temperature is 1300-1600 ℃, and the calcining time is 2 h.
The oil phase is one of paraffin oil, silicone oil and edible oil; the carbon source adopts sucrose or glucose; zirconium source adopts zirconium n-propoxide or zirconium oxychloride;
step 2, preparing aerogel
Adding the multi-cavity structure nanofiber prepared in the step 1 into a cellulose nanofiber solution, stirring for 5-15 min at the speed of 13000-20000rpm to obtain a fiber dispersion solution, injecting the fiber dispersion solution into a plastic mold, freezing and molding at-130 to-40 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
the mass concentration of the cellulose nanofiber solution is 0.1-0.5%, and the mass ratio of the multi-cavity structure nanofiber to the cellulose nanofiber solution is 0.2-2: 100, respectively;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 800-850 ℃, and preserving heat for 2 hours to obtain the ceramic aerogel.
Example 1
Step 1, preparing multi-cavity structure nano fibers;
step 1.1, dissolving 1.17g of sucrose and 1.008g of spinning auxiliary agent PVP in 10ml of solvent A (DMF) to obtain solution A;
step 1.2, adding 4ml of zirconium n-propoxide and 2.5ml of glacial acetic acid into 4ml of absolute ethyl alcohol to obtain a solution B;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
wherein, spinning syringe needle structure does: as shown in fig. 1, comprises a shell, two needles are arranged in the shell; the size of the shell is 13G, and the size of each needle is 22G;
the shell is connected with spinning solution, the spinning speed is 2 ml.h-1(ii) a The needle is connected with paraffin oil, and the spinning speed is 0.16 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tube furnace to calcine for 2 hours in an argon atmosphere, wherein the calcining temperature is 1300 ℃, and after the calcination, volatilizing an oil phase to leave a multi-cavity structure to obtain the ZrC nanofiber with the multi-cavity structure;
step 2, preparing aerogel
Adding 0.35g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of a Cellulose Nanofiber (CNF) solution with the mass concentration of 0.15%, stirring at 13000rpm for 10min to obtain a fiber dispersion, injecting the fiber dispersion into a plastic mold, freezing and molding at-40 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain the aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 800 ℃, and the heat preservation time is 2 hours, so that the ceramic aerogel is obtained.
As shown in fig. 2, which shows only the ZrC phase, it is demonstrated that ZrC fibers can be successfully produced in example 1.
As shown in FIG. 3, the aerogel prepared by the method of the present invention has a cellular porous structure, and the pore walls are formed by interweaving fibers.
Example 2
Step 1, preparing multi-cavity structure nano fibers;
step 1.1, dissolving 0.636 of sucrose and 0.756g of a spinning auxiliary agent PVP in 10ml of a solvent A (DMF) to obtain a solution A;
step 1.2, adding 4ml of zirconium n-propoxide and 2ml of glacial acetic acid into 4ml of absolute ethyl alcohol to obtain a solution B;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
wherein, spinning syringe needle structure does: as shown in fig. 3, comprises a shell, three needles are arranged in the shell; the size of the shell is 13G, and the size of each needle is 25G;
the shell is connected with spinning solution, the spinning speed is 1.8 ml.h-1(ii) a The needle is connected with silicone oil, and the spinning speed is 0.08 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tubular furnace to calcine for 2 hours in an argon atmosphere, wherein the calcining temperature is 1450 ℃, and obtaining the ZrC nanofiber with a multi-cavity structure;
step 2, preparing aerogel
Adding 0.2g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of Cellulose Nanofiber (CNF) solution with the mass concentration of 0.1%, stirring at 17000rpm for 5min to obtain fiber dispersion, injecting the fiber dispersion into a plastic mold, freezing and molding at-80 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 820 ℃, and preserving heat for 2h to obtain the ceramic aerogel.
Example 3
Step 1, preparing multi-cavity structure nano fibers;
step 1.1, dissolving 1.272g of glucose and 1.251g of spinning auxiliary agent PVP in 10ml of solvent A (DMF) to obtain solution A;
step 1.2, adding 4ml of zirconium oxychloride and 3ml of glacial acetic acid into 4ml of absolute ethyl alcohol to obtain a solution B;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
wherein, spinning syringe needle structure does: as shown in fig. 4, comprises a shell, wherein four needles are arranged inside the shell; the size of the shell is 13G, and the size of each needle is 25G;
the shell is connected with spinning solution, the spinning speed is 2.2 ml.h-1(ii) a The needle is connected with edible oil, and the spinning speed is 0.1 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tubular furnace to calcine for 2 hours in an argon atmosphere, wherein the calcining temperature is 1600 ℃, and obtaining the ZrC nanofiber with a multi-cavity structure;
step 2, preparing aerogel
Adding 2g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of Cellulose Nanofiber (CNF) solution with the mass concentration of 0.5%, stirring for 15min at the speed of 20000rpm to obtain fiber dispersion liquid, injecting the fiber dispersion liquid into a plastic mold, freezing and molding at-130 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 850 ℃, and the heat preservation time is 2 hours, so that the ceramic aerogel is obtained.
Example 4
Step 1, preparing multi-cavity structure nano fibers;
step 1.1, dissolving 1.17g of sucrose, 1.97g of boric acid and 1.008g of spinning auxiliary agent PVP in 10ml of solvent A (DMF) to obtain solution A;
step 1.2, adding 4ml of zirconium n-propoxide and 2.5ml of glacial acetic acid into 4ml of absolute ethyl alcohol to obtain a solution B;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
wherein, spinning syringe needle structure does: comprises a shell, two needle heads are arranged in the shell; the size of the shell is 12G, and the size of each needle is 22G;
the shell is connected with spinning solution, the spinning speed is 2.2 ml.h-1(ii) a The needle is connected with paraffin oil, and the spinning speed is 0.1 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tube furnace to calcine for 2 hours in argon atmosphere, wherein the calcining temperature is 1400 ℃, and obtaining ZrB with a multi-cavity structure2-a ZrC nanofiber;
step 2, preparing aerogel
Adding 0.5g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of Cellulose Nanofiber (CNF) solution with the mass concentration of 0.2%, stirring at the speed of 15000rpm for 10min to obtain fiber dispersion liquid, injecting the fiber dispersion liquid into a plastic mold, freezing and molding at the temperature of-40 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 850 ℃, and the heat preservation time is 2 hours, so that the ceramic aerogel is obtained.
As shown in FIG. 4, ZrB can be prepared by the method of the invention2-ZrC fibres.
Example 5
Step 1, preparing multi-cavity structure nano fibers;
step 1.1, dissolving 0.636g of sucrose, 1.108g of boric acid and 0.756g of spinning auxiliary agent PVP in 10ml of solvent A (DMF) to obtain solution A;
step 1.2, adding 4ml of zirconium n-propoxide and 2ml of glacial acetic acid into 4ml of absolute ethyl alcohol to obtain a solution B;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
wherein, spinning syringe needle structure does: comprises a shell, three needle heads are arranged in the shell; the size of the shell is 13G, and the size of each needle is 25G;
the shell is connected with spinning solution, the spinning speed is 1.8 ml.h-1(ii) a The needle is connected with silicone oil, and the spinning speed is 0.08 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tube furnace to calcine for 2 hours in argon atmosphere, wherein the calcining temperature is 1300 ℃, and obtaining ZrB with a multi-cavity structure2-a ZrC nanofiber;
step 2, preparing aerogel
Adding 0.2g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of a Cellulose Nanofiber (CNF) solution with the mass concentration of 0.1%, stirring at 13000rpm for 5min to obtain a fiber dispersion, injecting the fiber dispersion into a plastic mold, freezing and molding at-80 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 800 ℃, and the heat preservation time is 2 hours, so that the ceramic aerogel is obtained.
Example 6
Step 1, preparing multi-cavity structure nano fibers;
step 1.1, dissolving 1.272g of glucose, 2.771g of boric acid and 1.251g of spinning auxiliary agent PVP in 10ml of solvent A (DMF) to obtain solution A;
step 1.2, adding 4ml of zirconium oxychloride and 3ml of glacial acetic acid into 4ml of absolute ethyl alcohol to obtain a solution B;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
wherein, spinning syringe needle structure does: comprises a shell, wherein four needle heads are arranged in the shell; the size of the shell is 12G, and the size of each needle is 25G;
the shell is connected with spinning solution, the spinning speed is 1.8 ml.h-1(ii) a The needle is connected with edible oil, and the spinning speed is 0.16 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tube furnace to calcine for 2 hours in argon atmosphere, wherein the calcining temperature is 1600 ℃, and obtaining ZrB with a multi-cavity structure2-a ZrC nanofiber;
step 2, preparing aerogel
Adding 2g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of Cellulose Nanofiber (CNF) solution with the mass concentration of 0.5%, stirring for 15min at the speed of 20000rpm to obtain fiber dispersion liquid, injecting the fiber dispersion liquid into a plastic mold, freezing and molding at-130 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 820 ℃, and preserving heat for 2h to obtain the ceramic aerogel.
Example 7
Step 1.1, dissolving 2.031g sucrose, 0.97g boric acid, 0.886g spinning auxiliary agent PVP in 10ml solvent C (DMF) to obtain solution E;
step 1.2, adding 2ml of zirconium n-propoxide and 1.25ml of glacial acetic acid into 2ml of absolute ethyl alcohol to obtain a solution F;
step 1.3, 2ml of ethyl orthosilicate and 0.5ml of glacial acetic acid are added into 2ml of solvent D (DMF) to obtain solution G;
step 1.4, mixing the solution E obtained in the step 1.1, the solution F obtained in the step 1.2 and the solution G obtained in the step 1.3, and uniformly stirring to obtain a spinning solution C;
step 1.5, spinning the spinning solution C obtained in the step 1.4 by using a spinning needle to obtain precursor fiber C;
wherein, spinning syringe needle structure does: comprises a shell, three needle heads are arranged in the shell; the size of the shell is 13G, and the size of each needle is 25G;
the shell is connected with spinning solution, the spinning speed is 1.8 ml.h-1(ii) a The needle is connected with paraffin oil, and the spinning speed is 0.08 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.6, placing the precursor fiber C obtained in the step 1.5 in a tube furnace to calcine for 2 hours in argon atmosphere, wherein the calcining temperature is 1550 ℃, and obtaining ZrB with a multi-cavity structure2-ZrC-SiC nanofibers;
step 2, preparing aerogel
Adding 0.7g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of Cellulose Nanofiber (CNF) solution with the mass concentration of 0.2%, stirring at 20000rpm for 5min to obtain fiber dispersion, injecting the fiber dispersion into a plastic mold, freezing and molding at-130 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 850 ℃, and the heat preservation time is 2 hours, so that the ceramic aerogel is obtained.
As shown in FIG. 5, the method of the present inventionCan prepare ZrB2-ZrC-SiC fibers.
Example 8
Step 1.1, dissolving 0.636g of sucrose, 1.108g of boric acid and 0.756g of spinning auxiliary agent PVP in 10ml of solvent C (DMF) to obtain solution E;
step 1.2, adding 2ml of zirconium n-propoxide and 1ml of glacial acetic acid into 2ml of absolute ethyl alcohol to obtain a solution F;
step 1.3, adding 3ml of ethyl orthosilicate and 1ml of glacial acetic acid into 3ml of solvent D (DMF) to obtain a solution G;
step 1.4, mixing the solution E obtained in the step 1.1, the solution F obtained in the step 1.2 and the solution G obtained in the step 1.3, and uniformly stirring to obtain a spinning solution C;
step 1.5, spinning the spinning solution C obtained in the step 1.4 by using a spinning needle to obtain precursor fiber C;
wherein, spinning syringe needle structure does: comprises a shell, two needle heads are arranged in the shell; the size of the shell is 13G, and the size of each needle is 22G;
the shell is connected with spinning solution, the spinning speed is 2 ml.h-1(ii) a The needle is connected with silicone oil, and the spinning speed is 0.1 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.6, placing the precursor fiber C obtained in the step 1.5 in a tube furnace to calcine for 2 hours in argon atmosphere, wherein the calcining temperature is 1300 ℃, and obtaining ZrB with a multi-cavity structure2-ZrC-SiC nanofibers;
step 2, preparing aerogel
Adding 0.2g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of a Cellulose Nanofiber (CNF) solution with the mass concentration of 0.1%, stirring at 13000rpm for 10min to obtain a fiber dispersion, injecting the fiber dispersion into a plastic mold, freezing and molding at-80 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 830 ℃, and the heat preservation time is 2 hours, so that the ceramic aerogel is obtained.
Example 9
Step 1.1, dissolving 1.272g of glucose, 2.771g of boric acid and 1.251g of spinning auxiliary agent PVP in 10ml of solvent C (DMF) to obtain solution E;
step 1.2, adding 2ml of zirconium oxychloride and 2ml of glacial acetic acid into 2ml of absolute ethyl alcohol to obtain a solution F;
step 1.3, adding 4ml of ethyl orthosilicate and 1ml of glacial acetic acid into 4ml of solvent D (DFM) to obtain solution G;
step 1.4, mixing the solution E obtained in the step 1.1, the solution F obtained in the step 1.2 and the solution G obtained in the step 1.3, and uniformly stirring to obtain a spinning solution C;
step 1.5, spinning the spinning solution C obtained in the step 1.4 by using a spinning needle to obtain precursor fiber C;
wherein, spinning syringe needle structure does: comprises a shell, wherein four needle heads are arranged in the shell; the size of the shell is 13G, and the size of each needle is 25G;
the shell is connected with spinning solution, the spinning speed is 2.2 ml.h-1(ii) a The needle is connected with edible oil, and the spinning speed is 0.16 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
step 1.6, placing the precursor fiber C obtained in the step 1.5 in a tube furnace to calcine for 2 hours in argon atmosphere, wherein the calcining temperature is 1600 ℃, and obtaining the ZrB with a multi-cavity structure2-ZrC-SiC nanofibers;
step 2, preparing aerogel
Adding 2g of the multi-cavity structure nanofiber prepared in the step 1 into 100g of Cellulose Nanofiber (CNF) solution with the mass concentration of 0.5%, stirring for 15min at the speed of 20000rpm to obtain fiber dispersion liquid, injecting the fiber dispersion liquid into a plastic mold, freezing and molding at the temperature of-40 ℃, and then carrying out vacuum freeze drying for 24h under the conditions that the temperature is-20 ℃ and the vacuum degree is 1Pa to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace, wherein the carbonization temperature is 800 ℃, and the heat preservation time is 2 hours, so that the ceramic aerogel is obtained.

Claims (10)

1. A preparation method of ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers is characterized by comprising the following steps:
step 1, preparing multi-cavity structure nano fibers;
step 2, preparing aerogel
Adding the multi-cavity structure nanofiber prepared in the step 1 into a cellulose nanofiber solution, stirring to obtain a fiber dispersion solution, injecting the fiber dispersion solution into a plastic mold for freezing and molding, and then performing vacuum freeze drying to obtain aerogel;
step 3, carbonizing aerogel
And (3) carbonizing the aerogel obtained in the step (2) in a nitrogen furnace to obtain the ceramic aerogel.
2. The preparation method of the ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers according to claim 1, wherein the specific process of the step 1 is as follows:
step 1.1, dissolving a carbon source and a spinning auxiliary agent in a solvent A to obtain a solution A;
the mass ratio of the carbon source to the spinning auxiliary agent is 0.636-1.272: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent A is 0.636-1.272: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution B;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 4: 2-3: 4;
step 1.3, mixing the solution A obtained in the step 1.1 and the solution B obtained in the step 1.2, and uniformly stirring to obtain a spinning solution A;
step 1.4, spinning the spinning solution A obtained in the step 1.3 by using a spinning needle to obtain precursor fiber A;
and step 1.5, placing the precursor fiber A obtained in the step 1.4 in a tube furnace to calcine in an argon atmosphere to obtain the ZrC nanofiber with a multi-cavity structure.
3. The preparation method of the ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers according to claim 1, wherein the specific process of the step 1 is as follows:
step 1.1, dissolving a carbon source, boric acid and a spinning auxiliary agent in a solvent B to obtain a solution C;
the mass ratio of the carbon source to the boric acid to the spinning auxiliary agent is 0.636-1.272: 1.108 to 2.771: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent B is 0.636-1.272: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution D;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 4: 2-3: 4;
step 1.3, mixing the solution C obtained in the step 1.1 and the solution D obtained in the step 1.2, and uniformly stirring to obtain a spinning solution B;
step 1.4, spinning the spinning solution B obtained in the step 1.3 by using a spinning needle to obtain precursor fiber B;
step 1.5, placing the precursor fiber B obtained in the step 1.4 in a tube furnace to calcine in argon atmosphere to obtain ZrB with a multi-cavity structure2-ZrC nanofibers.
4. The preparation method of the ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers according to claim 1, wherein the specific process of the step 1 is as follows:
step 1.1, dissolving a carbon source, boric acid and a spinning auxiliary agent in a solvent C to obtain a solution E;
the mass ratio of the carbon source to the boric acid to the spinning auxiliary agent is 0.636-2.031: 1.108 to 2.771: 0.756 to 1.251;
the volume ratio of the mass of the carbon source to the solvent C is 0.636-2.031: 10, the mass unit is g, and the volume unit is ml;
step 1.2, adding a zirconium source and glacial acetic acid into absolute ethyl alcohol to obtain a solution F;
the volume ratio of the zirconium source to the glacial acetic acid to the absolute ethyl alcohol is 1: 0.5-1: 1;
step 1.3, adding tetraethoxysilane and glacial acetic acid into a solvent D to obtain a solution G;
the volume ratio of the ethyl orthosilicate to the glacial acetic acid to the solvent D is 1-4: 0.25-1: 1-4;
step 1.4, mixing the solution E obtained in the step 1.1, the solution F obtained in the step 1.2 and the solution G obtained in the step 1.3, and uniformly stirring to obtain a spinning solution C;
step 1.5, spinning the spinning solution C obtained in the step 1.4 by using a spinning needle to obtain precursor fiber C;
step 1.6, placing the precursor fiber C obtained in the step 1.5 in a tube furnace to calcine in argon atmosphere to obtain ZrB with a multi-cavity structure2-ZrC-SiC nanofibers.
5. The preparation method of the ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers according to any one of claims 2 to 4, wherein the spinning needle comprises a shell, two needles or three needles or four needles are arranged inside the shell, the three needles are arranged in an equilateral triangle, and the four needles are arranged in a square;
the size of the shell is 12-13G, and the size of each needle head is 22-25G;
the shell is connected with spinning solution, and the spinning speed is 1.8-2.2 ml.h-1(ii) a The needle head is connected with an oil phase, and the spinning speed is 0.08-0.16 ml.h-1(ii) a The spinning voltage of the shell and the spinning voltage of the needle are both 16kV, the spinning receiving distance is 15cm, the spinning time is 2h, and the humidity in the spinning environment is 35% -45%;
the calcining temperature is 1300-1600 ℃, and the calcining time is 2 h.
6. The method for preparing the ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers according to claim 5, wherein the oil phase is one of paraffin oil, silicone oil and edible oil.
7. The method for preparing the ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers according to any one of claims 2 to 4, wherein the carbon source is sucrose or glucose, and the zirconium source is zirconium n-propoxide or zirconium oxychloride.
8. The preparation method of the ultrahigh-temperature ceramic aerogel based on multi-cavity structural fibers as claimed in claim 1, wherein in the step 2, the stirring speed is 13000-20000rpm, and the stirring time is 5-15 min; the freezing time is-130 to-40 ℃, the temperature of vacuum freeze drying is-20 ℃, the vacuum degree of vacuum freeze drying is 1Pa, and the time of vacuum freeze drying is 24 hours.
9. The method for preparing the ultrahigh-temperature ceramic aerogel based on multi-cavity structure fibers according to claim 1, wherein in the step 2, the mass concentration of the cellulose nanofiber solution is 0.1-0.5%, and the mass ratio of the multi-cavity structure nanofibers to the cellulose nanofiber solution is 0.2-2: 100.
10. the method for preparing the ultrahigh-temperature ceramic aerogel based on the multi-cavity structural fibers according to claim 1, wherein in the step 3, the carbonization temperature is 800-850 ℃, and the heat preservation time is 2 hours.
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