CN105967727A - Preparation method of carbon/ zirconium/ aluminum composite aerogel material - Google Patents
Preparation method of carbon/ zirconium/ aluminum composite aerogel material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
Abstract
The invention relates to a preparation method of a carbon/zirconium/aluminum composite aerogel material. The method adopts a sol-gel method, takes resorcinol and formaldehyde as a carbon source, inorganic zirconium salt as a zirconium source, inorganic aluminum salt as an aluminum source, epoxide as a gel accelerant, deionized water as a hydrolytic agent and alcohol as a solvent, and comprises the steps of preparing composite wet gel in presence of a basic catalyst; carrying out aging, solvent replacement, CO2 supercritical drying, high-temperature heat treatment and the like on the wet gel to obtain the high temperature-resistant carbon/zirconium/aluminum composite aerogel material, wherein the apparent density of the composite aerogel material is 0.18-0.35g/ cm<3>, the specific surface area of the composite aerogel material is 430-650m<2>/g, and the pore size distribution is 5-50nm. The method takes the cheap inorganic zirconium salt and inorganic aluminum salt as raw materials; the aerogel material prepared by the method has the excellent performance such as low density, large specific surface area, high strength, high temperature resistance and complete structure, thus having wide application prospect in the fields such as high temperature insulation and coating.
Description
Technical field
The invention belongs to the preparation technology field of nano-porous materials, relate to a kind of carbon/zirconium/aluminum composite aerogel material
The preparation method of material.
Background technology
Nowadays society to lightweight, high intensity, resistant to elevated temperatures high efficiency heat insulation material demand day by day urgent, and
Along with the development in epoch, single aeroge system cannot meet demander requirement increasing to product, only
Prepare performance more prominent, there is the polynary aeroge that meets of lot of advantages and could meet market.And aeroge is
The nano-porous materials that a kind of nano-particle is mutually assembled, has high-specific surface area and porosity, therefore exists
The aspect performance such as calorifics, catalysis highlights, and is significantly better than conventional solid-state material, is a kind of to have the light of extensive use
Matter nano-porous materials.The low skeletal density that aerogel material possesses can reduce solid thermal conduction, and nanoporous is tied
Structure can suppress air heat to conduct, and the infrared light screening agent of introducing can reduce infra-red radiation conduction, and such structure makes
Aeroge demonstrates the heat-proof quality of excellence, is to generally acknowledge the solid material that heat conductivity is minimum at present.The most domestic
Outer many to the comparison of carbon-silicon, carbon-aluminum architectural study, the research to carbon containing ternary system composite aerogel there is no report
Road, tri compound aeroge sample has the excellent properties that binary material does not has, therefore carbon zirconium aluminum ternary system
The preparation of aeroge is great for the performance and application value optimizing material.
Summary of the invention
The invention aims to provide the preparation method of a kind of carbon/zirconium/aluminum aerogel composite, the method
Materials and technique are simple, and with low cost, this material can be used for the field such as high temperature insulating and coating.
The technical scheme is that the preparation method of carbon-zirconium-aluminum aerogel composite, its concrete steps are such as
Under:
(1) just inorganic zirconium salts is dissolved in ethanol with water is (3～5) according to volume ratio: in the solvent of 1 configuration；Again
Inorganic aluminate is dissolved in ethanol and is (1～3) with water according to volume ratio: in the mixed solvent of 1；Then by above-mentioned two
Kind of solution is 1:(1～2 by inorganic zirconium salts with the mol ratio of inorganic aluminate) mix after, addition Polyethylene Glycol, formyl
Amine, prepares ZrO after stirring2/Al2O3Complex sol；Wherein Polyethylene Glycol and inorganic zirconium salts mole
Than being (0.2～1): 1, Methanamide is (0.2～1) with the mol ratio of inorganic zirconium salts: 1；
(2) it is (1～2) according to the mol ratio of formaldehyde, water and resorcinol: (33～55): 1, resorcinol and alkali
The mol ratio of property catalyst is 80～120, by equal to resorcinol, formaldehyde, water and base catalyst mix and blend
Organosol (RF colloidal sol) is obtained after even；Then the ZrO that will obtain in step (1)2/Al2O3Complex sol with
Organosol, by mixing, is stirring evenly and then adding into expoxy propane, obtains mixed sols, be placed on after being sufficiently stirred for
Mould carries out gel；Wherein ZrO2/Al2O3The ratio of colloidal sol and organosol is with reference to inorganic zirconium salts and isophthalic two
Phenol mol ratio i.e. 1:(2～4)；
(3) wet gel adds in the mould of step (2) Ageing solution, put into baking oven and carry out burin-in process
And replace foreign ion, obtain ZrO2/Al2O3/ RF is combined wet gel；
(4) by the ZrO of step (3)2/Al2O3/ RF is combined wet gel and carries out supercritical drying process, thus
Obtain block ZrO2/Al2O3/ RF composite aerogel；
(5) ZrO that will obtain in step (4)2/Al2O3/ RF composite aerogel is heat treatment under protective atmosphere,
Prepare block high temperature resistant carbon/zirconium/aluminum aerogel material.
Inorganic zirconium salts described in preferred steps (1) is the one in zirconium oxychloride or zirconyl nitrate or its mixing
Thing；Described inorganic aluminate is the one in aluminum chloride or aluminum nitrate or its mixture；Described Polyethylene Glycol
Molecular weight is 600～1000.
Base catalyst in preferred steps (2) is the one in natrium carbonicum calcinatum, sodium hydroxide or potassium carbonate.
Preferred steps (2) expoxy propane is (4～12) with the mol ratio of inorganic zirconium salts: 1.
Ageing solution added in preferred steps (3) be the one in ethanol, normal hexane or tetraethyl orthosilicate or
Its mixture.
Oven temperature described in preferred steps (3) is 40～70 DEG C；The number of times of displacement is 5～10 times, every time
The time of displacement is 12～24h.
Supercritical drying described in preferred steps (4) is dried as CO2Supercritical drying, with CO2As
Being dried medium, reaction temperature is 45～60 DEG C, and in autoclave, pressure is 8～12MPa, and drying time is
8～14h.
Protective atmosphere described in preferred steps (5) is the one in nitrogen, argon or helium.Preferred steps
(5) in, heat treatment temperature is 800 DEG C～1500 DEG C, and heat treatment time is 3～10h.
The apparent density of the aeroge obtained by the present invention is 0.18～0.35g/cm3, specific surface area exists
430～650m2/ g, pore-size distribution is 5～50nm.
Beneficial effect:
(1) raw material is inexpensive, reduces cost.What in this method, zirconium source selected is inorganic zirconium salts, and aluminum source selects
Also it is inorganic aluminum source.Abandon Organic Alcohol zirconium, the organo-aluminium alcoholate used during being typically prepared, and inorganic zirconium salts,
The price of inorganic aluminate is low, greatly reduces production cost.
(2) density is low, and the high temperature resistant carbon/zirconium of bulk/aluminum aerogel composite density prepared by this invention is
0.18～0.35g/cm3, density is far below conventional high temperature insulating material.
(3) the high temperature resistant carbon/zirconium/aluminum aerogel composite of bulk that the method prepares, in sol-gel process
Carbon reactant and zirconium reactant, al reactant are not independent reactions, the wet gel obtained be not simple carbon,
Zirconium and the mixing of aluminum, but reaction makes wet gel network structure be interleaved with each other, more each other.Cause
This aeroge good moldability, intensity are big, have good application prospect.
Accompanying drawing explanation
Fig. 1 is the photo in kind of high temperature resistant carbon/zirconium/aluminum aerogel composite that embodiment 1 prepares；
Fig. 2 is the nitrogen adsorption desorption curve that embodiment 1 prepares carbon/zirconium/aluminum composite aerogel；
Fig. 3 is that the SEM of the block carbon zirconium aluminum composite aerogel prepared by embodiment 2 shines.
Detailed description of the invention
Example 1
According to zirconium oxychloride, aluminum chloride and resorcinol mol ratio are that 1:1:3 is respectively configured ZrO2/Al2O3Colloidal sol
With RF colloidal sol.Zirconium oxychloride being dissolved in ethanol with water volume ratio is the mixed solvent of 4:1, is dissolved in by aluminum chloride
Ethanol and water volume ratio are the mixed solvent of 2:1, then by both according to 1:1 mixed in molar ratio.Add wherein
The mol ratio entering Macrogol 600, Methanamide, Macrogol 600 and Methanamide and zirconium oxychloride is 0.5:1,
Mixing and stirring, obtains ZrO2/Al2O3Colloidal sol.According to formaldehyde: water: the mol ratio of resorcinol is 2:55:1,
Resorcinol: the mol ratio of sodium carbonate=100 obtains organosol (RF colloidal sol) after uniformly mixing and being sufficiently stirred for.
The mixing of above two colloidal sol being stirred, being added thereto to the most afterwards with zirconium oxychloride mol ratio is 4:1
The expoxy propane of amount, pour in mould after stirring about 15min, about 10h gel.Obtain above-mentioned
RF/ZrO2Gel is put at room temperature after 12h, adds ethanol as the foreign ion in Ageing solution displacement wet gel,
Then it is put in the baking oven of 50 DEG C, replaces 8 times, each 24h.Again by the RF/Al after aging2O3/ZrO2Multiple
Close wet gel and put into high temperature and high pressure kettle, utilize CO2Sample is dried by supercritical drying, wherein CO2
Stress control is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 9h, thus prepares mouldability
Good block RF/Al2O3/ZrO2Composite aerogel.Again by this composite aerogel under the protection of argon in
At 1500 DEG C, heat treatment 3h obtains block carbon/zirconium/aluminum aerogel composite.High temperature resistant carbon/zirconium/the aluminum of shape prepared
The photo in kind of aerogel composite is as shown in Figure 1: can be seen that this composite aerogel is complete block, table
Face flawless, and possess certain mechanical strength, and its nitrogen adsorption desorption curve is as shown in Figure 2: can see
Going out this curve is typical IV type curve, shows that material is typical mesoporous material, and specific surface area is big, is conducive to
Use as a kind of high temperature resistant heat insulation material.Its density 0.22g/cm is found through characterizing3, specific surface area is
650m2/ g, pore-size distribution is 5～30nm.
Example 2
According to zirconium oxychloride, aluminum nitrate and resorcinol mol ratio are that 1:1:3 is respectively configured ZrO2/Al2O3Colloidal sol
With RF colloidal sol, zirconium oxychloride being dissolved in ethanol with water volume ratio is the mixed solvent of 4:1, is dissolved in by aluminum nitrate
Ethanol and water volume ratio are the mixed solvent of 2:1, then by both according to 1:1 mixed in molar ratio.Add wherein
Enter the mol ratio of Macrogol 600, Methanamide, Macrogol 600 and Methanamide and zirconium oxychloride and be 0.2:
1, mixing and stirring, obtain ZrO2/Al2O3Colloidal sol.According to formaldehyde: water: the mol ratio of resorcinol is
2:55:1, resorcinol: the mol ratio of potassium carbonate=100 obtains organosol (RF after uniformly mixing and being sufficiently stirred for
Colloidal sol).Above-mentioned 2 kinds of colloidal sols mixing is stirred, is added thereto to the most afterwards and zirconium oxychloride mole
Than the expoxy propane of the amount for 12:1, pour in mould after stirring 10min, about 3h gel.Obtain above-mentioned
To RF/ZrO2Gel is put at room temperature after 12h, add ethanol as the impurity in Ageing solution displacement wet gel from
Son, is then put in the baking oven of 40 DEG C, replaces 10 times, each 24h.Again by the RF/Al after aging2O3/ZrO2
Compound wet gel puts into high temperature and high pressure kettle, utilizes CO2Sample is dried by supercritical drying, wherein
CO2Stress control is at 8MPa, and temperature controls at 60 DEG C, and the supercritical drying time is 12h, thus prepares into
The block RF/Al that type is good2O3/ZrO2Composite aerogel.Again by this composite aerogel under the protection of argon
At 1500 DEG C, heat treatment 10h obtains block carbon/zirconium/aluminum aerogel composite.Prepared carbon/zirconium/aluminum is multiple
The SEM closing aerogel material schemes as it is shown on figure 3, the block carbon-zirconium as can be seen from the figure obtained is combined airsetting
Glue is porous network structure, composite aerogel density 0.34g/cm3, specific surface area is 579m2/ g, pore-size distribution
10～40nm.
Example 3
According to zirconium oxychloride, aluminum chloride and resorcinol mol ratio are that 1:1:2 is respectively configured ZrO2/Al2O3Colloidal sol
With RF colloidal sol, zirconium oxychloride being dissolved in ethanol with water volume ratio is the mixed solvent of 4:1, is dissolved in by aluminum chloride
Ethanol and water volume ratio are the mixed solvent of 3:1, then by both according to 1:1 mixed in molar ratio.Add wherein
The mol ratio entering cetomacrogol 1000, Methanamide, cetomacrogol 1000 and Methanamide and zirconium oxychloride is
0.8:1, mixing and stirring, obtain ZrO2/Al2O3Colloidal sol.According to formaldehyde: water: resorcinol mol ratio
For 2:55:1, resorcinol: the mol ratio of sodium carbonate=100 obtains organic molten after uniformly mixing and being sufficiently stirred for
Glue (RF colloidal sol).Above-mentioned 2 kinds of colloidal sols mixing is stirred, is added thereto to the most afterwards and oxychlorination
Zirconium mol ratio is the expoxy propane of the amount of 5:1, pours in mould, about 5h gel after stirring 15min.By upper
State and obtain RF/Al2O3/ZrO2Gel is put at room temperature after 12h, adds tetraethyl orthosilicate and puts as Ageing solution
Change the foreign ion in wet gel, be then put in the baking oven of 70 DEG C, replace 5 times, each 12h.Again will be old
RF/Al after change2O3/ZrO2Compound wet gel puts into high temperature and high pressure kettle, utilizes CO2Supercritical drying pair
Sample is dried, wherein CO2Stress control is at 12MPa, and temperature controls at 45 DEG C, during supercritical drying
Between be 8h, thus prepare good forming ability block carbon/zirconium/aluminum composite aerogel.Again this composite aerogel is existed
Under the protection of argon, at 1500 DEG C, heat treatment 3h obtains block carbon/zirconium/aluminum aerogel composite.Through characterizing
Find its density 0.31g/cm3, specific surface area is 430m2/ g, pore-size distribution is 5～40nm.
Example 4
According to zirconyl nitrate, aluminum chloride and resorcinol mol ratio are that 1:1:4 is respectively configured ZrO2/Al2O3Colloidal sol
With RF colloidal sol, zirconyl nitrate being dissolved in ethanol with water volume ratio is the mixed solvent of 3:1, is dissolved in by aluminum chloride
Ethanol and water volume ratio are the mixed solvent of 1:1, then by both according to 1:1 mixed in molar ratio.Add wherein
The mol ratio entering Macrogol 600, Methanamide, Macrogol 600 and Methanamide and zirconyl nitrate is 1:1,
Mixing and stirring, obtains ZrO2/Al2O3Colloidal sol.According to formaldehyde: water: resorcinol mol ratio is 2:55:1,
Resorcinol: the mol ratio of sodium hydroxide=80 obtains organosol after uniformly mixing and being sufficiently stirred for, and (RF is molten
Glue).Above-mentioned 2 kinds of colloidal sols mixing is stirred, is added thereto to the most afterwards and zirconium oxychloride mol ratio
For the expoxy propane of the amount of 4:1, pour in mould after stirring 10min, about 15h gel.Obtain above-mentioned
RF/Al2O3/ZrO2Gel is put at room temperature after 12h, adds normal hexane as in Ageing solution displacement wet gel
Foreign ion, be then put in the baking oven of 50 DEG C, replace 7 times, each 24h.Again by after aging
RF/Al2O3/ZrO2Compound wet gel puts into high temperature and high pressure kettle, utilizes CO2Sample is entered by supercritical drying
Row is dried, wherein CO2Stress control is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 10h,
Thus prepare the block carbon/zirconium/aluminum composite aerogel of good forming ability.Again by this composite aerogel the guarantor of helium
Protect down heat treatment 5h at 1500 DEG C and obtain block carbon/zirconium/aluminum aerogel composite.The compound airsetting prepared
Glue density 0.25g/cm3, specific surface area is 490m2/ g, pore-size distribution is 10～50nm.
Example 5
According to zirconium oxychloride, aluminum chloride and resorcinol mol ratio are that 1:2:4 is respectively configured ZrO2/Al2O3Colloidal sol
With RF colloidal sol, zirconium oxychloride being dissolved in ethanol with water volume ratio is the mixed solvent of 4:1, is dissolved in by aluminum chloride
Ethanol and water volume ratio are the mixed solvent of 2:1, then by both according to 1:2 mixed in molar ratio.Add wherein
The mol ratio entering cetomacrogol 1000, Methanamide, cetomacrogol 1000 and Methanamide and zirconium oxychloride is
0.5:1, mixing and stirring, obtain ZrO2/Al2O3Colloidal sol.According to formaldehyde: water: resorcinol mol ratio
For 1:33:1, resorcinol: the mol ratio of sodium carbonate=120 obtains organic molten after uniformly mixing and being sufficiently stirred for
Glue (RF colloidal sol).Above-mentioned 2 kinds of colloidal sols mixing is stirred, is added thereto to the most afterwards and oxychlorination
Zirconium mol ratio is the expoxy propane of the amount of 4:1, pours in mould, about 8h gel after stirring 10min.By upper
State and obtain RF/Al2O3/ZrO2Gel is put at room temperature after 12h, adds ethanol and replaces wet gel as Ageing solution
In foreign ion, be then put in the baking oven of 50 DEG C, replace 8 times, each 24h.Again by after aging
RF/Al2O3/ZrO2Compound wet gel puts into high temperature and high pressure kettle, utilizes CO2Sample is entered by supercritical drying
Row is dried, wherein CO2Stress control is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 14h,
Thus prepare the block carbon/zirconium/aluminum composite aerogel of good forming ability.Again by this composite aerogel the guarantor of nitrogen
Protect down heat treatment 3h at 800 DEG C and obtain block carbon-zirconium aerogel composite.The composite aerogel prepared is close
Degree 0.28g/cm3, specific surface area is 521m2/ g, pore-size distribution is 5～20nm.
Example 6
According to zirconium oxychloride, aluminum chloride and resorcinol mol ratio are that 1:1:3 is respectively configured ZrO2/Al2O3Colloidal sol
With RF colloidal sol, zirconium oxychloride being dissolved in ethanol with water volume ratio is the mixed solvent of 5:1, is dissolved in by aluminum chloride
Ethanol and water ratio are the mixed solvent of 2:1, then by both according to 1:1 mixed in molar ratio.It is added thereto to
Macrogol 600, Methanamide, Macrogol 600 and Methanamide are 0.5:1 with the mol ratio of zirconium oxychloride,
Mixing and stirring, obtains ZrO2/Al2O3Colloidal sol.According to formaldehyde: water: the mol ratio of resorcinol is 2:55:1,
Resorcinol: the mol ratio of sodium carbonate=100 obtains organosol (RF colloidal sol) after uniformly mixing and being sufficiently stirred for.
Above-mentioned 2 kinds of colloidal sols mixing being stirred, being added thereto to the most afterwards with zirconium oxychloride mol ratio is 8:1
The expoxy propane of amount, pour in mould after stirring 10min, about 3h gel.Obtain above-mentioned
RF/Al2O3/ZrO2Gel is put at room temperature after 12h, adds miscellaneous as in Ageing solution displacement wet gel of ethanol
Matter ion, is then put in the baking oven of 50 DEG C, replaces 10 times, each 24h.Again by after aging
RF/Al2O3/ZrO2Compound wet gel puts into high temperature and high pressure kettle, utilizes CO2Sample is entered by supercritical drying
Row is dried, wherein CO2Stress control is at 10MPa, and temperature controls at 50 DEG C, and the supercritical drying time is 11h,
Thus prepare the block carbon/zirconium/aluminum composite aerogel of good forming ability.Again by this composite aerogel the guarantor of argon
Protect down heat treatment 3h at 1500 DEG C and obtain block carbon/zirconium/aluminum aerogel composite.The compound airsetting prepared
Glue density 0.26g/cm3, specific surface area is 636m2/ g, pore-size distribution is 5～40nm.
Example 7
According to zirconium oxychloride, aluminum chloride and resorcinol mol ratio are that 1:1:3 is respectively configured ZrO2/Al2O3Colloidal sol
With RF colloidal sol, zirconium oxychloride being dissolved in ethanol with water volume ratio is the mixed solvent of 4:1, is dissolved in by aluminum chloride
Ethanol and water ratio are the mixed solvent of 2:1, then by both according to 1:1 mixed in molar ratio.It is added thereto to
Cetomacrogol 1000, Methanamide, cetomacrogol 1000 and Methanamide are 0.5:1 with the mol ratio of zirconium oxychloride,
Mixing and stirring, obtains ZrO2/Al2O3Colloidal sol.According to formaldehyde: water: the mol ratio of resorcinol is 2:55:1,
Resorcinol: the mol ratio of sodium carbonate=100 obtains organosol (RF colloidal sol) after uniformly mixing and being sufficiently stirred for.
Above-mentioned 2 kinds of colloidal sols mixing being stirred, being added thereto to the most afterwards with zirconium oxychloride mol ratio is 6:1
The expoxy propane of amount, pour in mould after stirring 12min, about 7h gel.Obtain above-mentioned
RF/Al2O3/ZrO2Gel is put at room temperature after 12h, adds miscellaneous as in Ageing solution displacement wet gel of ethanol
Matter ion, is then put in the baking oven of 50 DEG C, replaces 8 times, each 24h.Again by after aging
RF/Al2O3/ZrO2Compound wet gel puts into high temperature and high pressure kettle, utilizes CO2Sample is entered by supercritical drying
Row is dried, wherein CO2Stress control is at 12MPa, and temperature controls at 45 DEG C, and the supercritical drying time is 8h,
Thus prepare the block carbon/zirconium/aluminum composite aerogel of good forming ability.Again by this composite aerogel the guarantor of argon
Protect down heat treatment 5h at 1500 DEG C and obtain block carbon/zirconium/aluminum aerogel composite.The compound airsetting prepared
Glue density 0.23g/cm3, specific surface area is 631m2/ g, pore-size distribution is 5～30nm.
Claims (10)
1. the preparation method of carbon-zirconium-aluminum aerogel composite, it specifically comprises the following steps that
(1) just inorganic zirconium salts is dissolved in ethanol with water is (3～5) according to volume ratio: in the solvent of 1 configuration；Again
Inorganic aluminate is dissolved in ethanol and is (1～3) with water according to volume ratio: in the mixed solvent of 1；Then by above-mentioned two
Kind of solution is 1:(1～2 by inorganic zirconium salts with the mol ratio of inorganic aluminate) mix after, addition Polyethylene Glycol, formyl
Amine, prepares ZrO after stirring2/Al2O3Complex sol；Wherein Polyethylene Glycol and inorganic zirconium salts mole
Than being (0.2～1): 1, Methanamide is (0.2～1) with the mol ratio of inorganic zirconium salts: 1；
(2) it is (1～2) according to the mol ratio of formaldehyde, water and resorcinol: (33～55): 1, resorcinol and alkali
The mol ratio of property catalyst is 80～120, by equal to resorcinol, formaldehyde, water and base catalyst mix and blend
Organosol is obtained after even；Then the ZrO that will obtain in step (1)2/Al2O3Complex sol and organosol
By mixing, it is stirring evenly and then adding into expoxy propane, obtains mixed sols after being sufficiently stirred for, be placed in mould
Row gel；Wherein ZrO2/Al2O3The ratio of colloidal sol and organosol is with reference to inorganic zirconium salts and resorcinol mol ratio
I.e. 1:(2～4)；
(3) wet gel adds in the mould of step (2) Ageing solution, put into baking oven and carry out burin-in process
And replace foreign ion, obtain ZrO2/Al2O3/ RF is combined wet gel；
(4) by the ZrO of step (3)2/Al2O3/ RF is combined wet gel and carries out supercritical drying process, thus
Obtain block ZrO2/Al2O3/ RF composite aerogel；
(5) ZrO that will obtain in step (4)2/Al2O3/ RF composite aerogel is heat treatment under protective atmosphere,
Prepare block high temperature resistant carbon/zirconium/aluminum aerogel material.
Preparation method the most according to claim 1, it is characterised in that the inorganic zirconium described in step (1)
Salt is the one in zirconium oxychloride or zirconyl nitrate or its mixture；Described inorganic aluminate is aluminum chloride or nitric acid
One in aluminum or its mixture；The molecular weight of described Polyethylene Glycol is 600～1000.
Preparation method the most according to claim 1, it is characterised in that the base catalyst in step (2)
For the one in natrium carbonicum calcinatum, sodium hydroxide or potassium carbonate.
Preparation method the most according to claim 1, it is characterised in that step (2) expoxy propane is with inorganic
The mol ratio of zirconates is (4～12): 1.
Preparation method the most according to claim 1, it is characterised in that Ageing solution added in step (3)
For the one in ethanol, normal hexane or tetraethyl orthosilicate or its mixture.
Preparation method the most according to claim 1, it is characterised in that the baking oven temperature described in step (3)
Degree is 40～70 DEG C；The number of times of displacement is 5～10 times, and the time of displacement is 12～24h every time.
Preparation method the most according to claim 1, it is characterised in that the supercritical described in step (4)
It is dried as CO2Supercritical drying, with CO2As dry medium, reaction temperature is 45～60 DEG C, high
In pressure reactor, pressure is 8～12MPa, and drying time is 8～14h.
Preparation method the most according to claim 1, it is characterised in that the protection gas described in step (5)
Atmosphere is the one in nitrogen, argon or helium.
Preparation method the most according to claim 1, it is characterised in that in step (5), heat treatment temperature is
800 DEG C～1500 DEG C, heat treatment time is 3～10h.
Preparation method the most according to claim 1, the apparent density of its obtained aeroge is
0.18～0.35g/cm3, specific surface area is 430～650m2/ g, pore-size distribution is 5～50nm.
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| CN108675331A (en) * | 2018-05-27 | 2018-10-19 | 南京航空航天大学 | A kind of Al2O3The preparation method of aeroge/carbon foam composite insulation material |
| CN109304134A (en) * | 2017-07-28 | 2019-02-05 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of aluminium oxide-zirconium oxide aerogel composite |
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| CN109304134A (en) * | 2017-07-28 | 2019-02-05 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of aluminium oxide-zirconium oxide aerogel composite |
| CN109985578A (en) * | 2017-12-30 | 2019-07-09 | 卢斌 | A kind of preparation method of composite aerogel |
| CN108675331A (en) * | 2018-05-27 | 2018-10-19 | 南京航空航天大学 | A kind of Al2O3The preparation method of aeroge/carbon foam composite insulation material |
| CN108479687A (en) * | 2018-06-12 | 2018-09-04 | 中国工程物理研究院激光聚变研究中心 | A kind of stratiform calcium aluminium hydroxide aeroge and its preparation method and application |
| CN110937915A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Integral titanium-doped aluminum oxide material and preparation method thereof |
| CN110937914A (en) * | 2018-09-25 | 2020-03-31 | 中国石油化工股份有限公司 | Integral titanium modified aluminum oxide material and preparation method thereof |
| CN110937914B (en) * | 2018-09-25 | 2022-04-05 | 中国石油化工股份有限公司 | Integral titanium modified aluminum oxide material and preparation method thereof |
| CN110937915B (en) * | 2018-09-25 | 2022-04-08 | 中国石油化工股份有限公司 | Integral titanium-doped aluminum oxide material and preparation method thereof |
| CN110818423A (en) * | 2019-11-04 | 2020-02-21 | 江苏一夫新材料产业技术研究院有限公司 | Zirconium carbide-boron carbide composite aerogel and preparation method thereof |
| CN111346678A (en) * | 2020-03-30 | 2020-06-30 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration catalyst with aerogel as carrier and prepared catalyst |
| CN113019853A (en) * | 2021-03-19 | 2021-06-25 | 南京工业大学 | Preparation method of fiber-reinforced zirconium carbide composite aerogel based high-emissivity coating |
| CN116443878A (en) * | 2023-04-12 | 2023-07-18 | 北京理工大学 | Method for synthesizing zirconium carbide aerogel by using inorganic zirconium salt and phenolic resin |
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