CN109758988A - A kind of C-Al2O3-B4The preparation method of C composite aerogel - Google Patents
A kind of C-Al2O3-B4The preparation method of C composite aerogel Download PDFInfo
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- CN109758988A CN109758988A CN201910203846.8A CN201910203846A CN109758988A CN 109758988 A CN109758988 A CN 109758988A CN 201910203846 A CN201910203846 A CN 201910203846A CN 109758988 A CN109758988 A CN 109758988A
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- 239000004964 aerogel Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 33
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 230000000887 hydrating effect Effects 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000019441 ethanol Nutrition 0.000 claims abstract description 15
- 238000000352 supercritical drying Methods 0.000 claims abstract description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 230000032683 aging Effects 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 12
- 239000011240 wet gel Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229960004106 citric acid Drugs 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011810 insulating material Substances 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000004966 Carbon aerogel Substances 0.000 description 4
- 239000004965 Silica aerogel Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of C-Al2O3‑B4The preparation method of C composite aerogel belongs to composite material preparation process technical field.By by aluminum chloride crystals body, water, ethyl alcohol uniform stirring, obtain clear flaxen aluminum chloride crystals body hydrating solution, preferred boron source, citric acid, formaldehyde, resorcinol, water, ethyl alcohol, propylene oxide and catalysts are added into solution again, stir evenly, obtain C-Al2O3‑B4C composite aerogel sol solution stands gel.Sample is handled using Supercritical Drying Technology again, high-temperature heat treatment finally is carried out to sample, finally obtains blocky C-Al2O3‑B4C composite aerogel.The C-Al that the present invention prepares2O3‑B4Not only technical process is simple to operation for C composite aerogel, abundant raw material is simple, have many advantages, such as high specific area, low-density, lower thermal conductivity, and can be low with effective solution aeroge intensity disadvantage, will be had a good application prospect and unlimited potentiality in terms of 1200 DEG C or more high temperature insulating materials.
Description
Technical field
The technical field that the invention belongs to prepare with high temperature insulating feature inorganic nano material is related to a kind of bulk C-
Al2O3-B4The preparation method of C composite aerogel.
Background technique
With the progress of science and technology, more and more fields need high-temperature heat treatment process, however, the guarantor used in the industry
Warm heat-barrier material is mostly the traditional insulation materials such as inorganic fibrous mats, porous ceramic plate, alumina firebrick, heat insulating effect
Difference, and with the raising for using temperature, thermal conductivity also improves rapidly.Aerogel material is for traditional material, heat-insulated
Heat preservation aspect has big advantage, is New-generation efficient energy-saving thermal insulation material, its use, which can greatly reduce, to be produced
Energy consumption in journey.Currently, in high temperature insulating field, oxide silica aerogel is using more, but its intensity is low, high-temperature stability
Difference；Carbon aerogels possess heat-proof quality very significantly under vacuum conditions, but be oxidized easily under aerobic environment and can not
Embody its heat-proof quality.Therefore, C-Al2O3-B4C composite aerogel combines the advantages of oxide silica aerogel and carbon aerogels, phase
For pure Al2O3Aeroge and carbon aerogels are even more to have further breakthrough in performance, can not only efficiently solve oxide gas
The problem of gel poor high temperature stability and carbon aerogels are easily oxidized under aerobic environment, and biggish structural strength make its
Also there is huge application prospect outside high temperature insulating field.
Summary of the invention
The purpose of the invention is to improve studied oxide silica aerogel intensity is lower, high high-temp stability is poor at present etc.
Disadvantage and a kind of C-Al with higher-strength, 1200 DEG C of high temperature resistant or more high temperature insulating types is provided2O3-B4C composite aerogel
Preparation method.
The technical solution of the present invention is as follows: a kind of C-Al2O3-B4The preparation method of C composite aerogel, the specific steps of which are as follows:
(1) by aluminum chloride crystals body, water, ethyl alcohol uniform stirring, clear aluminum chloride crystals body hydrating solution is obtained；
(2) formaldehyde, resorcinol, propylene oxide and catalysts are added into aluminum chloride crystals body hydrating solution, stir
It mixes uniformly, obtains solution A；
(3) by boron source, catalysts, deionized water and dehydrated alcohol, example is 1:(0.005~0.03 in molar ratio):
(20~60): after (8~25) ultrasonic disperse, heating stirring is uniform, obtains boron source hydrating solution；
(4) formaldehyde, resorcinol and network former are added into boron source hydrating solution, stirs evenly, obtains solution B；
(5) solution B is added in step (2) after solution A, continues to stir, obtains C-Al2O3-B4C composite aerogel colloidal sol
Solution；
(6) by C-Al obtained in step (5)2O3-B4C composite aerogel sol solution, which pours into mold, to react to gel,
It is put into baking oven and carries out aging process；
(7) dehydrated alcohol is added to gel obtained in step (6) and carries out solvent displacement；
(8) the compound wet gel after solvent displacement in step (7) is subjected to CO2Supercritical drying is handled, wherein CO2It is super to face
Boundary's seasoning uses CO2Gas shield, reaction temperature are 45~50 DEG C, and the control of autoclave pressure is in 10~12MPa, reaction
Time is 1~2d；
(9) sample handled well in step (8) is heated under inert atmosphere protection with the heating rate of 2~4 DEG C/min
To 1350~1600 DEG C, soaking time is to be heat-treated for 5~10 hours, finally obtains C-Al2O3-B4C composite aerogel.
Water and ethyl alcohol molar ratio are 1:(0.2~5 in preferred steps (1)), aluminum chloride crystals body hydrating solution mass concentration
Control is 15%~20%.
Resorcinol in preferred steps (2): formaldehyde: aluminum chloride crystals body: propylene oxide: the molar ratio of catalysts is
1:2:(1~2): (7~15): (0.002~0.02).
Catalysts are one kind of natrium carbonicum calcinatum or sodium hydroxide in preferred steps (2) and step (3).
The temperature of heating stirring is 40 DEG C~50 DEG C in preferred steps (3).
Network former is one kind of anhydrous citric acid, Citric Acid Mono or sodium citrate in preferred steps (4).
Resorcinol, formaldehyde in preferred steps (4): boron source: the molar ratio of network former is 1:2:(0.5~2):
(0.5~2).
The molar ratio of the boron source of the aluminium chloride and solution B of solution A is 1:(0.5~2 in preferred steps (5))
Oven temperature is 40 DEG C~70 DEG C in preferred steps (6), 1~2d of aging；In step (7) solvent be replaced into every 10~
12h replacement is primary, replaces 3~6 times in total.
Inert atmosphere is one kind of helium or argon gas in preferred steps (9).
The utility model has the advantages that
(1) simple process, the prices of raw materials are cheap to be easy to get.This method is using the cheap inorganic salts being easy to get as silicon source, boron
Acid or boron oxide are as boron source, and using sol-gel method combination Supercritical Drying Technology, technological operation is simple and easily repeats.
(2) excellent properties are excellent, have a wide range of application.It is compared to traditional oxide silica aerogel material, C-Al2O3-B4C
There is composite aerogel low-density, high intensity and low-heat the excellent properties such as to lead.Meanwhile C-Al2O3-B4C composite aerogel also has
The excellent properties such as high structural strength, high-temperature physics stable chemical performance, can be widely applied to refractory material, engineering ceramics and
The fields such as aerospace.
Detailed description of the invention
Fig. 1 is C-Al prepared by embodiment 12O3-B4The photo in kind of C aerogel composite.
Specific embodiment
Example 1
By 1mol aluminum chloride crystals body, 10mol deionized water and the full and uniform stirring of 6mol dehydrated alcohol, until solution is
Faint yellow clarification aluminum chloride crystals body hydrating solution, mass concentration 19.11%.1mol isophthalic two is added into hydrating solution again
Phenol, 2mol formaldehyde, 0.002mol catalysts natrium carbonicum calcinatum and 7mol network former propylene oxide are sufficiently stirred
It is even, obtain solution A.By 0.5mol boric acid, 0.0025mol catalysts natrium carbonicum calcinatum, 10mol deionized water and 4mol without
Water-ethanol, ultrasonic disperse is uniform, and 40 DEG C of heating stirrings obtain clear solution.1mol resorcinol, 2mol is added into solution again
Formaldehyde and 0.5mol network former anhydrous citric acid stir evenly, and obtain solution B.Solution B is poured into sufficiently mixed in solution A
It closes, continues to stir 30min, until solution substantially uniformity, to obtain C-Al2O3-B4C composite aerogel sol solution, pours into mould
Tool waits gel.Room temperature gel time about 8h is put into 40 DEG C of baking ovens after gel and carries out high temperature ageing 2d, reacts it sufficiently,
Then with use ethanol as Ageing solution, the foreign ion in wet gel is replaced, is replaced 3 times, each 12h.Again by C-Al2O3-B4C
Compound wet gel is put into high temperature and high pressure kettle, utilizes CO2Sample is dried in supercritical drying, wherein CO2Pressure control exists
10MPa, for control temperature at 45 DEG C, the supercritical drying time is 1d.Finally, by sample with 2 DEG C/min under helium atmosphere protection
Heating rate be heated to 1350 DEG C, soaking time is 5 hours, obtains C-Al after being cooled to room temperature2O3-B4C composite aerogel.
It is found by characterization: C-Al obtained2O3-B4C composite aerogel specific surface area is 402m2/ g, compressive strength are become by 25% thickness
Shape amount calculates, compressive strength 1776kPa.Prepared C-Al2O3-B4Photo in kind such as Fig. 1 institute of C aerogel composite
Show.
Example 2
By 1mol aluminum chloride crystals body, 11mol deionized water and the full and uniform stirring of 7mol dehydrated alcohol, until solution is
Faint yellow clarification aluminum chloride crystals body hydrating solution, mass concentration 17.50%.1mol isophthalic two is added into hydrating solution again
Phenol, 2mol formaldehyde, 0.002mol catalysts natrium carbonicum calcinatum and 7mol network former propylene oxide are sufficiently stirred
It is even, obtain solution A.2mol boric acid, 0.06mol catalysts natrium carbonicum calcinatum, 120mol deionized water and 50mol is anhydrous
Ethyl alcohol, ultrasonic disperse is uniform, and 40 DEG C of heating stirrings obtain clear solution.1mol resorcinol, 2mol first is added into solution again
Aldehyde and 2mol network former anhydrous citric acid stir evenly, and obtain solution B.Solution B is poured into solution A and is sufficiently mixed, after
Continuous stirring 30min, until solution substantially uniformity, to obtain C-Al2O3-B4C composite aerogel sol solution, pours into mold, etc.
To gel.Room temperature gel time about 8h is put into 70 DEG C of baking ovens after gel and carries out high temperature ageing 1d, reacts it sufficiently, then
With use ethanol as Ageing solution, the foreign ion in wet gel is replaced, is replaced 4 times, each 12h.Again by C-Al2O3-B4C is compound
Wet gel is put into high temperature and high pressure kettle, utilizes CO2Sample is dried in supercritical drying, wherein CO2Pressure control exists
12MPa, for control temperature at 50 DEG C, the supercritical drying time is 2d.Finally, by sample with 3 DEG C/min under argon atmosphere protection
Heating rate be heated to 1400 DEG C, soaking time is 6 hours, obtains C-Al after being cooled to room temperature2O3-B4C composite aerogel.
It is found by characterization: C-Al obtained2O3-B4C composite aerogel specific surface area is 375m2/ g, compressive strength are become by 25% thickness
Shape amount calculates, compressive strength 2142kPa.
Example 3
By 2mol aluminum chloride crystals body, 20mol deionized water and the full and uniform stirring of 16mol dehydrated alcohol, until solution
For faint yellow clarification aluminum chloride crystals body hydrating solution, mass concentration 16.87%.1mol isophthalic is added into hydrating solution again
Diphenol, 2mol formaldehyde, 0.002mol catalysts natrium carbonicum calcinatum and 7mol network former propylene oxide are sufficiently stirred
It is even, obtain solution A.1mol boric acid, 0.005mol catalysts natrium carbonicum calcinatum, 20mol deionized water and 8mol is anhydrous
Ethyl alcohol, ultrasonic disperse is uniform, and 40 DEG C of heating stirrings obtain clear solution.1mol resorcinol, 2mol first is added into solution again
Aldehyde and 1mol network former anhydrous citric acid stir evenly, and obtain solution B.Solution B is poured into solution A and is sufficiently mixed, after
Continuous stirring 30min, until solution substantially uniformity, to obtain C-Al2O3-B4C composite aerogel sol solution, pours into mold, etc.
To gel.Room temperature gel time about 8h is put into 50 DEG C of baking ovens after gel and carries out high temperature ageing 2d, reacts it sufficiently, then
With use ethanol as Ageing solution, the foreign ion in wet gel is replaced, is replaced 5 times, each 12h.Again by C-Al2O3-B4C is compound
Wet gel is put into high temperature and high pressure kettle, utilizes CO2Sample is dried in supercritical drying, wherein CO2Pressure control exists
11MPa, for control temperature at 50 DEG C, the supercritical drying time is 1d.Finally, by sample with 4 DEG C/min under argon atmosphere protection
Heating rate be heated to 1450 DEG C, soaking time is 7 hours, obtains C-Al after being cooled to room temperature2O3-B4C composite aerogel.
It is found by characterization: C-Al obtained2O3-B4C composite aerogel specific surface area is 309m2/ g, compressive strength are become by 25% thickness
Shape amount calculates, compressive strength 2890kPa.
Example 4
By 2mol aluminum chloride crystals body, 24mol deionized water and the full and uniform stirring of 18mol dehydrated alcohol, until solution
For faint yellow clarification aluminum chloride crystals body hydrating solution, mass concentration 15.29%.1mol isophthalic is added into hydrating solution again
Diphenol, 2mol formaldehyde, 0.02mol catalysts natrium carbonicum calcinatum and 15mol network former propylene oxide are sufficiently stirred
It is even, obtain solution A.2mol boric acid, 0.06mol catalysts natrium carbonicum calcinatum, 120mol deionized water and 50mol is anhydrous
Ethyl alcohol, ultrasonic disperse is uniform, and 40 DEG C of heating stirrings obtain clear solution.1mol resorcinol, 2mol first is added into solution again
Aldehyde and 2mol network former sodium citrate stir evenly, and obtain solution B.Solution B is poured into solution A and is sufficiently mixed, is continued
30min is stirred, until solution substantially uniformity, to obtain C-Al2O3-B4C composite aerogel sol solution, pours into mold, waits
Gel.Room temperature gel time about 8h is put into 60 DEG C of baking ovens after gel and carries out high temperature ageing 1d, reacts it sufficiently, then sharp
It uses ethyl alcohol as Ageing solution, replaces the foreign ion in wet gel, replace 6 times, each 12h.Again by C-Al2O3-B4C is compound wet
Gel is put into high temperature and high pressure kettle, utilizes CO2Sample is dried in supercritical drying, wherein CO2Pressure is controlled in 12MPa,
Temperature is controlled at 50 DEG C, the supercritical drying time is 2d.Finally, by sample with the heating of 4 DEG C/min under argon atmosphere protection
Rate is heated to 1600 DEG C, and soaking time is 10 hours, obtains C-Al after being cooled to room temperature2O3-B4C composite aerogel.By table
It levys existing: C-Al obtained2O3-B4C composite aerogel specific surface area is 218m2/ g, compressive strength press 25% thickness deformation meter
It calculates, compressive strength 3489kPa.
Example 5
By 1mol aluminum chloride crystals body, 12mol deionized water and the full and uniform stirring of 8mol dehydrated alcohol, until solution is
Faint yellow clarification aluminum chloride crystals body hydrating solution, mass concentration 16.14%.1mol isophthalic two is added into hydrating solution again
Phenol, 2mol formaldehyde, 0.01mol catalysts sodium hydroxide and 10mol network former propylene oxide, stir,
Obtain solution A.By 1.5mol boric acid, 0.03mol catalysts sodium hydroxide, 60mol deionized water and the anhydrous second of 25mol
Alcohol, ultrasonic disperse is uniform, and 50 DEG C of heating stirrings obtain clear solution.1mol resorcinol, 2mol formaldehyde is added into solution again
It is stirred evenly with 1.5mol network former Citric Acid Mono, obtains solution B.Solution B is poured into solution A and is sufficiently mixed, after
Continuous stirring 30min, until solution substantially uniformity, to obtain C-Al2O3-B4C composite aerogel sol solution, pours into mold, etc.
To gel.Room temperature gel time about 8h is put into 70 DEG C of baking ovens after gel and carries out high temperature ageing 1d, reacts it sufficiently, then
With use ethanol as Ageing solution, the foreign ion in wet gel is replaced, is replaced 5 times, each 10h.Again by C-Al2O3-B4C is compound
Wet gel is put into high temperature and high pressure kettle, utilizes CO2Sample is dried in supercritical drying, wherein CO2Pressure control exists
12MPa, for control temperature at 47 DEG C, the supercritical drying time is 36h.Finally, by sample with 3 DEG C/min under argon atmosphere protection
Heating rate be heated to 1500 DEG C, soaking time is 8 hours, obtains C-Al after being cooled to room temperature2O3-B4C composite aerogel.
It is found by characterization: C-Al obtained2O3-B4C composite aerogel specific surface area is 296m2/ g, compressive strength are become by 25% thickness
Shape amount calculates, compressive strength 3008kPa.
Claims (10)
1. a kind of C-Al2O3-B4The preparation method of C composite aerogel, the specific steps of which are as follows:
(1) by aluminum chloride crystals body, water, ethyl alcohol uniform stirring, clear aluminum chloride crystals body hydrating solution is obtained；
(2) formaldehyde, resorcinol, propylene oxide and catalysts are added into aluminum chloride crystals body hydrating solution, stirring is equal
It is even, obtain solution A；
(3) by boron source, catalysts, deionized water and dehydrated alcohol, example is 1:(0.005~0.03 in molar ratio): (20~
60): after (8~25) ultrasonic disperse, heating stirring is uniform, obtains boron source hydrating solution；
(4) formaldehyde, resorcinol and network former are added into boron source hydrating solution, stirs evenly, obtains solution B；
(5) solution B is added in step (2) after solution A, continues to stir, obtains C-Al2O3-B4C composite aerogel sol solution；
(6) by C-Al obtained in step (5)2O3-B4C composite aerogel sol solution pours into reaction in mold and is put into gel
Aging process is carried out in baking oven；
(7) dehydrated alcohol is added to gel obtained in step (6) and carries out solvent displacement；
(8) the compound wet gel after solvent displacement in step (7) is subjected to CO2Supercritical drying is handled, wherein CO2Supercritical drying
Dry method uses CO2Gas shield, reaction temperature are 45~50 DEG C, and autoclave pressure controlled in 10~12MPa, reaction time
For 1~2d；
(9) sample handled well in step (8) is heated under inert atmosphere protection with the heating rate of 2~4 DEG C/min
1350~1600 DEG C, soaking time is to be heat-treated for 5~10 hours, finally obtains C-Al2O3-B4C composite aerogel.
2. preparation method according to claim 1, it is characterised in that in step (1) water and ethyl alcohol molar ratio be 1:(0.2~
5), the control of aluminum chloride crystals body hydrating solution mass concentration is 15%~20%.
3. preparation method according to claim 1, it is characterised in that resorcinol in step (2): formaldehyde: aluminum chloride crystals
Body: propylene oxide: the molar ratio of catalysts is 1:2:(1~2): (7~15): (0.002~0.02).
4. preparation method according to claim 1, it is characterised in that catalysts are in step (2) and step (3)
One kind of natrium carbonicum calcinatum or sodium hydroxide.
5. preparation method according to claim 1, it is characterised in that the temperature of heating stirring is 40 DEG C~50 in step (3)
℃。
6. preparation method according to claim 1, it is characterised in that in step (4) network former be anhydrous citric acid,
One kind of Citric Acid Mono or sodium citrate.
7. preparation method according to claim 1, it is characterised in that resorcinol, formaldehyde in step (4): boron source: network
The molar ratio of forming agent is 1:2:(0.5~2): (0.5~2).
8. preparation method according to claim 1, it is characterised in that the aluminium chloride of solution A and the boron of solution B in step (5)
The molar ratio in source is 1:(0.5~2).
9. preparation method according to claim 1, it is characterised in that oven temperature is 40 DEG C~70 DEG C in step (6), always
Change 1~2d；Solvent is replaced into every 10~12h replacement once in step (7), replaces 3~6 times in total.
10. preparation method according to claim 1, it is characterised in that inert atmosphere is helium or argon gas in step (9)
It is a kind of.
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