CN101698592B - Silicon-aluminium aerogel composite material and manufacturing method thereof - Google Patents
Silicon-aluminium aerogel composite material and manufacturing method thereof Download PDFInfo
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- CN101698592B CN101698592B CN2009102109987A CN200910210998A CN101698592B CN 101698592 B CN101698592 B CN 101698592B CN 2009102109987 A CN2009102109987 A CN 2009102109987A CN 200910210998 A CN200910210998 A CN 200910210998A CN 101698592 B CN101698592 B CN 101698592B
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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Abstract
The invention provides a silicon-aluminium aerogel composite material, comprising (1) silicon-aluminium compound aerogel and (2) inorganic fiber material. The invention further provides a method for manufacturing silicon-aluminium aerogel composite material with simple technology, comprising the steps of preparing silica sol, preparing aluminium sol, preparing silicon-aluminium compound sol, dipping sol, gelatinizing, ageing, overcritical drying, etc. With excellent high-temperature resistant performance, nice mechanical property and lower thermal conductivity at high temperature, the silicon-aluminium aerogel composite material can meet the high demand of thermal protection in respect of aviation, space flight and military affairs and can be applied to the civil heat insulation field.
Description
Technical field
The invention belongs to the material technology field, relate to aerogel composite and preparation method thereof.
Background technology
Along with the flying speed of aircraft is more and more faster; Surface temperature is increasingly high; The conventional alumina silicate or the effect of heat insulation of mullite fiber and mechanical property can not satisfy the thermal protection requirement of space flight and aviation aircraft in high temperature section, and the use of novel nanoporous aerogel heat-insulation composite material has become the dominant direction of effectively insulating.
Aeroge is present optimal light heat-insulating material, is lightweight, amorphous and the porous solid material that is made up of nano-colloid particle or high-polymer molecular, has extremely low density, high-specific surface area and high porosity.The aperture of aeroge (＜50nm) less than the mean free path (about 70nm) of air molecule, in aerogel pores, there is not cross-ventilation, thereby have extremely low gaseous state heat conduction; Have high porosity owing to aeroge simultaneously, the shared volume ratio of solid is very low, so the solid state heat conduction is also very low, makes aeroge have extremely low thermal conductivity, is considered to the best solid material of being found at present of heat-proof quality.
Research at present and application are the aerogel composite of silica system more widely, but because silica aerogel does not have the ability of blocking to the infrared ray of wave band in 2 μ m to 8 mu m ranges.Under the condition of high temperature, the heat radiation energy of this wave band will almost all pass through aeroge.At high temperature simultaneously, SiO
2The aeroge nano-pore caves in easily, and the aeroge structure is tending towards densified, causes SiO
2Temperature can not be higher than 650 ℃ when aeroge used for a long time.Therefore, but the acquisition of the resistant to elevated temperatures aerogel heat-proof composite material of counter infrared ray radiation will be significant to high-speed aircraft development.
In numerous aeroges, Al
2O
3Not only thermal conductivity is low but also high temperature (for example under long-term situation about using, being higher than 1050 ℃ temperature) good stability for aeroge, is the ideal material of preparation high temperature resistant heat insulation material.But there is generation crystal phase transition under the high temperature in alumina aerogels and causes structure to be caved in, and has the shortcoming of shrinking easily under the high temperature.The present invention will adopt through increasing by the second phase silicon and realize the transformation of controlled phase, and transformation is settled out mutually, and the alumina aerogels structure is stable under the maintenance high temperature, thereby improve the temperature tolerance of alumina aerogels through the sial composite aerogel.In addition, there is the shortcoming of poor mechanical property such as intensity is low, fragility is big in simple aeroge structure, is difficult to directly apply to heat insulation field.Therefore, the present invention will adopt inorganic fibers to strengthen the intensity of aeroge, improving the mechanical property of aeroge, thereby prepare resistant to elevated temperatures fiber reinforcement type silicon-aluminium aerogel composite material.
Summary of the invention
In order to overcome one or more or even whole the problems referred to above that prior art exists; Especially single pure alumina aeroge since under the high temperature thermal structure that causes of crystal phase transition unstable thereby influence the problem of its high temperature insulating performance, the invention provides following technical scheme:
1. silicon-aluminium aerogel composite material, wherein, said silicon-aluminium aerogel composite material comprises (1) sial composite aerogel; (2) inorganic fibers.
2. according to technical scheme 1 described silicon-aluminium aerogel composite material, wherein, the SiO in the said sial composite aerogel
2Ratio with said sial composite aerogel the mole count 0.01%～100%.
3. according to technical scheme 1 or 2 described silicon-aluminium aerogel composite materials; Wherein, said inorganic fibers is the one or more kinds of combinations that are selected from the group of being made up of quartz fibre, high silica fiber, alumina silicate fibre, glass fibre, alumina fibre, Zirconium oxide fibre, boron nitride fiber, basalt fibre and mullite fiber; Preferably, the form of said inorganic fibers is one or more the combination that is selected from the group of being made up of fibrofelt, cellucotton, tapetum fibrosum, fiberboard, fiber folded piece, fiber preform and prefabricated component complex.
4. like technical scheme 1 to 3 each described silicon-aluminium aerogel composite material, wherein, the bulk density of said inorganic fibers is 0.01g/cm
3～0.90g/cm
3, individual fiber diameter is 0.1 μ m～10 μ m.
5. a method for preparing silicon-aluminium aerogel composite material is characterized in that, this method comprises the steps:
(1) preparation of Ludox: silicon alkoxide, Ludox are mixed with Ludox with solvent, Ludox with catalyst and water;
(2) preparation of aluminium colloidal sol: aluminium salt, chelating agent, aluminium colloidal sol are mixed with aluminium colloidal sol with solvent and aluminium colloidal sol with catalyst and water;
(3) preparation of sial complex sol: said Ludox and said aluminium colloidal sol are mixed, make the sial complex sol, preferably, according to the SiO that makes in the said sial composite aerogel
2Mole with said sial composite aerogel is counted 0.01%～100% said Ludox of mixed and said aluminium colloidal sol;
(4) impregnation: through Infiltration Technics said sial complex sol is immersed in the inorganic fibers, obtain the mixture of sial complex sol and inorganic fibers;
(5) gelling: the said mixture that obtains in the step (4) is placed 60 ℃ to 80 ℃ environment, make the said sial complex sol generation gelling in the said mixture, obtain the sial plural gel;
(6) aging: as to carry out 24 hours to 48 hours wearing out with alcoholic solvent through adding to wear out; With
(7) supercritical drying: handle carrying out supercritical drying, obtain said silicon-aluminium aerogel composite material through aging sial plural gel.
6. according to technical scheme 5 described methods, wherein, said Ludox uses catalyst and said aluminium colloidal sol to use catalyst to be base catalyst simultaneously, perhaps is acidic catalyst simultaneously.
7. according to technical scheme 5 or 6 described methods, wherein, said Ludox uses solvent and said aluminium colloidal sol to use solvent to be alcoholic solvent or ketone solvent,
8. according to technical scheme 5 to 7 each described methods, wherein, said aging use alcoholic solvent is one or more the combination that is selected from the group of being made up of ethanol, isopropyl alcohol and sec-butyl alcohol.
9. like technical scheme 5 to 8 each described methods; Wherein, The preparation of said Ludox adopts following one-step method to carry out: at first said silicon alkoxide and Ludox are used solvent, drip said water and Ludox again with catalyst and mix, obtain Ludox; Preferably, said silicon alkoxide: Ludox is used solvent: water: it is 1: 1～20: 1～20: 0.0002～1.0 that Ludox uses the mol ratio of catalyst; In addition preferably, said water is deionized water.
10. like technical scheme 5 to 9 each described methods; Wherein, The preparation of said aluminium colloidal sol adopts following mode to carry out: with said aluminium salt is precursor, adds said chelating agent and mixes, and adds said aluminium colloidal sol again with solvent and mix; Drip said water and aluminium colloidal sol then with catalyst and mix, obtain said aluminium colloidal sol; Preferably, the mol ratio of said aluminium salt, chelating agent, aluminium colloidal sol use solvent, water and aluminium colloidal sol use catalyst is 1: 0.001～0.6: 4～32: 0.6～4: 0.0001～1; In addition preferably, said water is deionized water.
11. like technical scheme 5 to 10 each described methods, wherein, said impregnation carries out through following mode (1) or (2):
(1) directly said sial complex sol adding is placed with in the mould of said inorganic fibers, relies on gravity to carry out impregnation;
(2) use said sial complex sol to flood said inorganic fibers, and will in the said inorganic fibers of dipping packed mould into, re-use said sial complex sol and infiltrate.
12. like technical scheme 11 described methods, wherein, said inorganic fibers is when for big and thick inorganic fibers, said impregnation adopts mode (2) to carry out.
13. like technical scheme 5 to 12 each described methods; Wherein, Said supercritical fluid drying carries out according to following mode: the said inorganic fibers that will be impregnated with said sial complex sol is put into supercritical fluid drying equipment; Squeeze into the drying medium of 2 megapascal (MPa)s～10 megapascal (MPa)s, 0～50 ℃ of insulation 1 hour～30 hours; Be warming up to 20 ℃～80 ℃ again, and utilize drying medium to bring assist medium into separating still and separate with 10 liters/hour～400 liters/hour flow; After assist medium separates fully, again with 1 megapascal (MPa)/hour～6 megapascal (MPa)s/hour speed pressure is released into and the ambient atmosphere equilibrium, obtain said silicon-aluminium aerogel composite material.
14. like technical scheme 13 described methods, wherein, said drying medium is carbon dioxide or ethanol, said assist medium is alcoholic solvent or ketone solvent, and said alcoholic solvent is ethanol and/or isopropyl alcohol, and said ketone solvent is an acetone.
15. according to technical scheme 5 to 14 each described methods, wherein,
Said silicon alkoxide is one or more the combination that is selected from the group of being made up of silester, methyl silicate and silicic acid propyl ester, preferably ethyl orthosilicate;
It is one or more the combination that is selected from the group of being made up of ethanol, methyl alcohol, propyl alcohol and isopropyl alcohol that said Ludox uses alcoholic solvent, is preferably ethanol; And/or
It is one or more the combination that is selected from the group be made up of ammoniacal liquor, NaOH and ammonium fluoride that said Ludox uses base catalyst, is preferably ammoniacal liquor.
16. according to technical scheme 5 to 15 each described methods, wherein,
Said aluminium salt is one or more the combination that is selected from the group of being made up of aluminium isopropoxide, aluminium secondary butylate and aluminum nitrate;
It is one or more the combination that is selected from the group of being made up of ethanol, isopropyl alcohol and n-butanol that said aluminium colloidal sol uses alcoholic solvent;
Said chelating agent is acetylacetone,2,4-pentanedione and/or ethyl acetoacetate; And/or
It is one or more the combination that is selected from the group of being made up of ammoniacal liquor, NaOH or ammonium fluoride that said aluminium colloidal sol uses base catalyst, is preferably ammoniacal liquor.
17. according to technical scheme 5 to 16 each described methods, wherein,
Said inorganic fibers is the one or more kinds of combinations that are selected from the group of being made up of quartz fibre material, high silica fiber, alumina silicate fibre, glass fibre, alumina fibre, boron nitride fiber, basalt fibre and mullite fiber;
Preferably; The fibers form of said fiber is continuous fiber form and/or short fiber form;
Preferably, the goods form of said inorganic fibers is cellucotton, tapetum fibrosum, fiberboard, fiber folded piece, fiber preform or fiber preform complex form.18. like technical scheme 5 to 17 each described methods, wherein, the bulk density of said inorganic fibers is 0.01～0.90g/cm
3, individual fiber diameter is 0.1～10 μ m.
19. the silicon-aluminium aerogel composite material that makes by technical scheme 5 to 18 each described methods.
Beneficial effect of the present invention: the sial composite aerogel is adopted in (1); Under the high temperature that has overcome single silica aerogel no infrared block capability problems in; The negative effect of also having avoided easy transformation of crystal formation under the aluminium aeroge high temperature and having caused the aeroge structure to cave in and cause; Not only improved its temperature tolerance, also made it at high temperature have lower thermal conductivity simultaneously; In other words, and not through fibre-reinforced or compare through fibre-reinforced single silica aerogel material or alumina aerogels material, high temperature resistant heat insulation composite of the present invention can have better temperature resistance and lower elevated temperature heat conductance under the same conditions.(2), significantly reduced the solid heat transfer of fortifying fibre itself through compound use to one or more inorfils and silicon-aluminium aerogel; (3) can design different sial compositely proportionals according to different heat insulation requirements, can reach different effect of heat insulation; (4) adopt fibre-reinforced aerogel composite, except that having excellent heat insulation and mechanical property, also can coat according to the outward appearance and the pattern of product; (5) prepared silicon-aluminium aerogel composite material except that having excellent heat-proof quality, also has excellent mechanical property, for example through the shop layer design of fiber, can make its hot strength be higher than 2MPa; (6) preparation technology is simple, only needs preparation fiber reinforcement gel rubber material, through supercritical fluid drying, can obtain fibre-reinforced silicon-aluminium aerogel composite material.
The specific embodiment
As stated, the present invention the method that a kind of silicon-aluminium aerogel composite material is provided and has prepared said silicon-aluminium aerogel composite material.
First aspect the invention provides a kind of silicon-aluminium aerogel composite material, and said silicon-aluminium aerogel composite material comprises (1) sial composite aerogel; (2) inorfil.
Preferably, the SiO in the said sial composite aerogel
2Ratio can be following scope (1) or (2): (1) counts 0.01%～100% with the mole of said sial composite aerogel; (2) SiO in the said sial composite aerogel
2Mass ratio with respect to said sial composite aerogel is 0.01%～100%.Those skilled in the art can according to the for example requirement of high temperature insulating performance and mechanical property, prepare SiO according to the disclosed content of this specification
2Silicon-aluminium aerogel composite material in the scope of above-mentioned scope (1) or (2).
In the present invention; Using the topmost purpose of inorganic fibers is to overcome existing fragility difference of aeroge itself and the low defective of inherent strength; Therefore as long as inorganic fibers can tolerate material environment for use temperature, can as expecting, overcome the low defective of the existing fragility difference of aeroge itself and inherent strength and totally it seems and prepared silicon-aluminium aerogel composite material is not caused negative effect; Can be selected to the present invention; The present invention does not have other special requirements to inorganic fibers, and those skilled in the art can select suitable inorganic fibers as required under the situation of reading the disclosed content of this specification.But preferably, said inorganic fibers is the one or more kinds of combinations that are selected from the group of being made up of quartz fibre, high silica fiber, alumina silicate fibre, glass fibre, alumina fibre, Zirconium oxide fibre, boron nitride fiber, basalt fibre and mullite fiber.The form of employed inorganic fibers can be for being selected from one or more the combination in the group of being made up of fibrofelt, cellucotton, tapetum fibrosum, fiberboard, fiber folded piece, fiber preform and prefabricated component complex in the preparation process, those skilled in the art can according to the specific requirement of the concrete material that will prepare select to use the inorganic fibers of appropriate format.
In addition preferably, the bulk density of inorganic fibers is 0.01g/cm
3～0.90g/cm
3, for example be 0.01g/cm
3, 0.05g/cm
3, 0.10g/cm
3, 0.20g/cm
3, 0.30g/cm
3, 0.40g/cm
3, 0.50g/cm
3, 0.60g/cm
3, 0.70g/cm
3, 0.80g/cm
3Or 0.90g/cm
3。In addition further preferably; The individual fiber diameter of inorganic fibers is 0.1 μ m～10 μ m, for example is 0.1 μ m, 0.5 μ m, 1.0 μ m, 2.0 μ m, 3.0 μ m, 4.0 μ m, 5.0 μ m, 6.0 μ m, 7.0 μ m, 8.0 μ m, 9.0 μ m or 10.0 μ m.
Second aspect the invention provides a kind of method for preparing silicon-aluminium aerogel composite material, and said method comprises the steps:
(1) preparation of Ludox: silicon alkoxide, Ludox are mixed with Ludox with solvent, Ludox with catalyst and water;
(2) preparation of aluminium colloidal sol: aluminium salt, chelating agent, aluminium colloidal sol are mixed with aluminium colloidal sol with solvent and aluminium colloidal sol with catalyst and water;
(3) preparation of sial complex sol: said Ludox and said aluminium colloidal sol are mixed, make the sial complex sol, preferably, according to the SiO that makes in the said sial composite aerogel
2Mole with said sial composite aerogel is counted 0.01%～100% said Ludox of mixed and said aluminium colloidal sol;
(4) impregnation: through Infiltration Technics said sial complex sol is immersed in the inorganic fibers, obtain the mixture of sial complex sol and inorganic fibers;
(5) gelling: the said mixture that obtains in the step (4) is placed 60 ℃ to 80 ℃ environment, make the said sial complex sol generation gelling in the said mixture, obtain the sial plural gel;
(6) aging: as to carry out 24 hours to 48 hours wearing out with alcoholic solvent through adding to wear out; With
(7) supercritical drying: handle carrying out supercritical drying, obtain said silicon-aluminium aerogel composite material through aging sial plural gel.
The inventive method has no particular limits with catalyst with catalyst and aluminium colloidal sol Ludox; But preferred Ludox uses catalyst and aluminium colloidal sol to use catalyst to be base catalyst simultaneously; Perhaps be acidic catalyst simultaneously; More preferably Ludox is one or more the combination that is selected from the group of being made up of ammoniacal liquor, NaOH and ammonium fluoride with catalyst and aluminium colloidal sol with catalyst; Further preferably be all the combination of ammoniacal liquor or ammoniacal liquor and one or more other said base catalyst, most preferably be all ammoniacal liquor.
The water that prepare silicon colloidal sol or aluminium colloidal sol are used should be selected the water that impurity is few and/or ion is few, for example can pure water, distilled water (for example distilled water or tri-distilled water) or deionized water, preferably deionized water.Integrated cost and effect two aspects consider that the water that preferred prepare silicon colloidal sol uses is same specification or water of the same type with the water that preparation aluminium colloidal sol uses.
In addition; Ludox can be preparation Ludox solvent or solvent combinations commonly used with solvent; For example can be alcoholic solvent or ketone solvent, said alcoholic solvent for example can be for being selected from one or more the combination in the group of being made up of ethanol, methyl alcohol, propyl alcohol and isopropyl alcohol, is preferably the combination of ethanol or ethanol and one or more other said alcoholic solvent; But from for example being easy to get property, ease for use or cost equal angles, more preferably ethanol; Said ketone solvent for example can be acetone or butanone etc.
The present invention has no particular limits with alcoholic solvent aluminium colloidal sol; As long as aluminium colloidal sol can be in order to prepare aluminium colloidal sol and totally it seems and in the preparation process and in the material use, material system not caused harmful effect with alcoholic solvent, for example can be for being selected from one or more the combination in the group of forming by ethanol, isopropyl alcohol and n-butanol; But from for example being easy to get property, ease for use or cost equal angles, more preferably ethanol.In addition, because Ludox and the aluminium colloidal sol prepared will be used to dispose the sial complex sol, therefore, can adopt incompatible prepare silicon colloidal sol of same solvent or group of solvents and aluminium colloidal sol from aspect considerations such as for example acquired, ease for use or compatibilities.
The present invention has no particular limits silicon alkoxide; Generally can select to use suitable esters of silicon acis; For example can be for being selected from one or more the combination in the group of forming by silester, methyl silicate and silicic acid propyl ester; Be preferably ethyl orthosilicate, perhaps the combination of ethyl orthosilicate and one or more other said esters of silicon acis, more preferably ethyl orthosilicate.
The present invention also has no particular limits aluminium salt, and used aluminium salt can be for being selected from one or more the combination in the group of being made up of aluminium isopropoxide, aluminium secondary butylate and aluminum nitrate in the inventive method.
The inventive method also has no particular limits chelating agent, but said chelating agent is preferably acetylacetone,2,4-pentanedione and/or ethyl acetoacetate.
Inorganic fibers that the inventive method is used such as first aspect of the present invention are said.
When prepare silicon colloidal sol, can adopt for example following one-step method to carry out: at first silicon alkoxide and Ludox to be used solvent, drip water and Ludox again with catalyst and mix, obtain Ludox; Preferably; Said silicon alkoxide: Ludox is used solvent: water: it is 1: 1～20: 1～20: 0.0002～1.0 that Ludox uses the mol ratio of catalyst, for example can be 1: (1,2,3,4,5,6,8,10,12,14,16,18 or 20): (1,2,3,4,5,6,8,10,12,14,16,18 or 20): (0.0002,0.0005,0.001,0.01,0.1 or 1.0).
When preparation aluminium colloidal sol, can for example adopt following mode to carry out: with aluminium salt is precursor, adds chelating agent and also mixes, and adds aluminium colloidal sol again with solvent and mix, and drips water and aluminium colloidal sol then with catalyst and mix, and obtains aluminium colloidal sol.Preferably; It is 1: 0.001～0.6: 4～32: 0.6～4: 0.0001～1 that said aluminium salt, chelating agent, aluminium colloidal sol use solvent, water and aluminium colloidal sol to use the mol ratio of catalyst, for example can be 1: (0.001,0.01,0.1,0.2,0.3,0.4,0.5 or 0.6): (4,8,12,16,20,24,28 or 32): (0.6,1.2,1.8,2.4,3.2,3.5,3.8 or 4): (0.0001,0.0002,0.0005,0.001,0.01,0.1 or 1).
When impregnation, carry out through following mode (1) or (2): (1) directly is placed with the adding of sial complex sol in the mould of inorganic fibers, relies on gravity to carry out impregnation; (2) use sial complex sol dipping inorganic fibers, and will in the inorganic fibers of dipping packed mould into, re-use the sial complex sol and infiltrate.When inorganic fibers during, preferably adopt mode (2) to carry out impregnation for big and thick inorganic fibers form.
When wearing out, the present invention has no particular limits aging temperature, can in the temperature range of room temperature to 60 for example ℃, wear out.Aging used solvent is preferably alcoholic solvent, for example is ethanol, isopropyl alcohol and/or sec-butyl alcohol.
When carrying out supercritical fluid drying; Can for example adopt in such a way and carry out: the inorganic fibers that will be impregnated with said sial complex sol is put into supercritical fluid drying equipment; Squeeze into the drying medium of 2 megapascal (MPa)s～10 megapascal (MPa)s, 0～50 ℃ of insulation 1 hour～30 hours; Be warming up to 20 ℃～80 ℃ again, and utilize drying medium to bring assist medium into separating still and separate with 10 liters/hour～400 liters/hour flow; After assist medium separates fully, again with 1 megapascal (MPa)/hour～6 megapascal (MPa)s/hour speed pressure is released into and the ambient atmosphere equilibrium, obtain silicon-aluminium aerogel composite material.In the supercritical drying process, can use carbon dioxide or ethanol as drying medium, use alcoholic solvent or ketone solvent as assist medium, said alcoholic solvent is ethanol and/or isopropyl alcohol, said ketone solvent is an acetone.
The third aspect, the silicon-aluminium aerogel composite material that the present invention also provides above-described the inventive method to make.
In this article, except as otherwise noted, otherwise " high temperature " described in this specification is meant the temperature more than 650 ℃.
Except as otherwise noted, otherwise " sial complex sol " as herein described be meant by Ludox and the formulated colloidal sol that contains silicon and aluminium of aluminium colloidal sol.
Except as otherwise noted, otherwise " sial composite aerogel " as herein described is meant the aeroge that contains silicon and aluminium that is made by the sial complex sol.Sial composite aerogel of the present invention has formed the Al-O-Si key and has made after Ludox and aluminium colloidal sol are compound.Sial composite aerogel of the present invention can overcome single aeroge unstable properties at high temperature, but also reaches the optimum efficiency of two kinds of single aeroges (being silica aerogel and aluminium aeroge) combination.
Except as otherwise noted, then otherwise " compound " of " silicon-aluminium aerogel composite material " as herein described refers to play the inorganic fibers of effects such as enhancing and combining of the sial composite aerogel that is made by the sial complex sol that is impregnated in the inorganic fibers.
Except as otherwise noted, otherwise term " be selected from " and be meant and be selected from any one of said group, or two or more combination in any arbitrarily in said group by ... the combination of one or more in the group.
Except as otherwise noted, otherwise in the term used herein " two or more " " more than " comprise given figure, promptly comprise two kinds situation and more than two kinds situation.
Except as otherwise noted, otherwise described herein and number range comprise the arbitrary value between end value and the endpoints thereof (being upper and lower bound).
Embodiment
Hereinafter will be described further the present invention with the form of embodiment.Yet these embodiment just are illustrated with regard to preferred implementation of the present invention, and protection scope of the present invention should not be construed as and only limits to these embodiment.The chemical reagent that following examples adopted is available from Beijing chemical reagents corporation, and inorganic fibers is available from Shandong Luyang share co.,ltd.
For the water as the raw material of prepare silicon colloidal sol or aluminium colloidal sol, in all following embodiment, being of use is used for illustrational deionized water.
Embodiment 1
The prepared silicon-aluminium aerogel composite material of present embodiment is that alumina silicate fibre strengthens silicon-aluminium aerogel composite material, the SiO in the sial composite aerogel
2Mol ratio with respect to said sial composite aerogel is 10%.The Ludox preparation condition is for being 1: 1: 1 with methyl silicate, absolute ethyl alcohol, deionized water, ammoniacal liquor in molar ratio: 0.0002, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.001: 16 with aluminium secondary butylate, ethyl acetoacetate, ethanol, water and ammoniacal liquor in molar ratio: 3: 0.002; Be made into aluminium colloidal sol with base catalyst; After prepared Ludox and aluminium colloidal sol mixed make the sial complex sol, the mixed proportion of Ludox and aluminium colloidal sol is according to making the SiO in the sial composite aerogel
2With respect to the mol ratio of said sial composite aerogel is 10% to calculate.Then, directly bulk density being equipped with in the adding of sial complex sol is 0.2g/cm
3, individual fiber diameter is in the mould of alumina silicate fibre material of 1 μ m, relies on gravity to flood.60 ℃ of gellings of carrying out 6 hours, then in ethanol, wore out 48 hours in room temperature, put into autoclave again, squeeze into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature be 0.081 watt of/meter Kelvin (testing standard: YB/T 4130-2005, down with), linear shrinkage is less than 5%.
Embodiment 2
The prepared silicon-aluminium aerogel composite material of present embodiment is that mullite fiber strengthens sial composite aerogel, the SiO in the sial composite aerogel
2Mol ratio with respect to said sial composite aerogel is 40%.The Ludox preparation condition is for being 1: 1: 1 with ethyl orthosilicate, absolute ethyl alcohol, deionized water, ammoniacal liquor in molar ratio: 0.0002, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.01: 12 with aluminium isopropoxide, acetylacetone,2,4-pentanedione, ethanol, water and ammoniacal liquor in molar ratio: 4: 0.002; Be made into aluminium colloidal sol with base catalyst, after prepared Ludox and aluminium colloidal sol mixed make the sial complex sol.Directly bulk density being equipped with in the adding of sial complex sol is 0.2g/cm
3, individual fiber diameter is in the mould of mullite fiber of 0.1 μ m, relies on the gravity dipping, 60 ℃ of following gels 6 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature is 0.081 watt of/meter Kelvin, and shrinkage factor is less than 5%.
Embodiment 3
The prepared silicon-aluminium aerogel composite material of present embodiment is that high silica fiber strengthens sial composite aerogel, the SiO in the sial composite aerogel
2Mol ratio with respect to said sial composite aerogel is 60%, and the Ludox preparation condition is for being 1: 1: 1 with positive silicic acid propyl ester, isopropyl alcohol, deionized water and ammoniacal liquor in molar ratio: 0.0008, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.1: 15 with aluminium isopropoxide, acetylacetone,2,4-pentanedione, isopropyl alcohol, water and ammoniacal liquor in molar ratio: 4: 0.002; Be made into aluminium colloidal sol with base catalyst, after prepared Ludox and aluminium colloidal sol mixed make the sial complex sol.Directly bulk density being equipped with in the adding of sial complex sol is 0.22g/cm
3, individual fiber diameter is in the mould of high silica fiber of 0.5 μ m, relies on the gravity dipping, 60 ℃ of following gels 8 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature is 0.081 watt of/meter Kelvin, and linear shrinkage is less than 5%.
Embodiment 4
The prepared silicon-aluminium aerogel composite material of present embodiment is a silica wool fiber reinforcement sial composite aerogel, the SiO in the sial composite aerogel
2Mol ratio with respect to said sial composite aerogel is 90%, and the Ludox preparation condition is for being 1: 1: 1 with positive silicic acid propyl ester, isopropyl alcohol, deionized water and ammoniacal liquor in molar ratio: 0.0008, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.5: 15 with aluminium isopropoxide, ethyl acetoacetate, isopropyl alcohol, water and ammoniacal liquor in molar ratio: 4: 0.002; Be made into aluminium colloidal sol with base catalyst, after prepared Ludox and aluminium colloidal sol mixed make the sial complex sol.Directly bulk density being equipped with in the adding of sial complex sol is 0.2g/cm
3, individual fiber diameter be 5 μ m the mould of silica wool fiber in, rely on the gravity dipping, 60 ℃ of following gels 4 hours; Wore out 48 hours in alcoholic solvent in room temperature in the back; Put into autoclave, squeeze into the carbon dioxide of 2 megapascal (MPa)s, be incubated 15 hours down at 30 ℃.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature is 0.081 watt of/meter Kelvin, and linear shrinkage is less than 5%.
Embodiment 5
The prepared silicon-aluminium aerogel composite material of present embodiment is that basalt fibre strengthens sial composite aerogel, the SiO in the sial composite aerogel
2Mol ratio with respect to said sial composite aerogel is 90%, and the Ludox preparation condition is for being 1: 1: 1 with ethyl orthosilicate, isopropyl alcohol, deionized water and ammoniacal liquor in molar ratio: 0.0008, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.6: 16 with aluminium secondary butylate, acetylacetone,2,4-pentanedione, isopropyl alcohol, water and ammoniacal liquor in molar ratio: 4: 0.002; Be made into aluminium colloidal sol with base catalyst, after prepared Ludox and aluminium colloidal sol mixed make the sial complex sol.Directly bulk density being equipped with in the adding of sial complex sol is 0.21g/cm
3, individual fiber diameter is in the mould of basalt fibre of 10 μ m, relies on the gravity dipping, 60 ℃ of following gels 6 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature is 0.081 watt of/meter Kelvin, and linear shrinkage is less than 5%.
Embodiment 6
The prepared silicon-aluminium aerogel composite material of present embodiment is that glass fibre strengthens sial composite aerogel, the wherein SiO in the sial composite aerogel
2Ratio be 10% with the molar ratio computing of said sial composite aerogel, the Ludox preparation condition is for being 1: 1: 1 with ethyl orthosilicate, isopropyl alcohol, deionized water and ammoniacal liquor in molar ratio: 0.0008, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.6: 16 with aluminium secondary butylate, acetylacetone,2,4-pentanedione, isopropyl alcohol, water and ammoniacal liquor in molar ratio: 4: 0.004; Be made into aluminium colloidal sol with base catalyst, after prepared Ludox and aluminium colloidal sol mixed make the sial complex sol.Directly bulk density being equipped with in the adding of sial complex sol is 0.23g/cm
3, individual fiber diameter is in the mould of glass fibre of 1 μ m, relies on the gravity dipping, 60 ℃ of following gels 6 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature is 0.081 watt of/meter Kelvin, and linear shrinkage is less than 5%.
Embodiment 7
The prepared silicon-aluminium aerogel composite material of present embodiment is that alumina fibre strengthens sial composite aerogel, the wherein SiO in the sial composite aerogel
2Ratio be 50% with the molar ratio computing of said sial composite aerogel, the Ludox preparation condition is for being 1: 1: 1 with ethyl orthosilicate, ethanol, deionized water and ammoniacal liquor in molar ratio: 0.0008, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.6: 16 with aluminium secondary butylate, ethyl acetoacetate, ethanol, water and ammoniacal liquor in molar ratio: 4: 0.002; Be made into aluminium colloidal sol with base catalyst, after prepared Ludox and aluminium colloidal sol mixed make the sial complex sol.Directly bulk density being equipped with in the adding of sial complex sol is 0.25g/cm
3, individual fiber diameter is in the mould of alumina fibre of 1 μ m, relies on the gravity dipping, 60 ℃ of following gels 6 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature is 0.090 watt of/meter Kelvin, and linear shrinkage is less than 5%.
Embodiment 8
The prepared silicon-aluminium aerogel composite material of present embodiment is that boron nitride fiber strengthens sial composite aerogel, the wherein SiO in the sial composite aerogel
2Ratio be 80% with the molar ratio computing of said sial composite aerogel, the Ludox preparation condition is for being 1: 1: 1 with methyl silicate, ethanol, deionized water and ammoniacal liquor in molar ratio: 0.0008, be made into Ludox with base catalyst.The preparation condition of aluminium colloidal sol is for being 1: 0.2: 16 with aluminium secondary butylate, ethyl acetoacetate, ethanol, water and ammoniacal liquor in molar ratio: 4: 0.005; Be made into aluminium colloidal sol with base catalyst, after prepared Ludox and aluminium colloidal sol mixed make the sial complex sol.Directly bulk density being equipped with in the adding of sial complex sol is 0.24g/cm
3, individual fiber diameter is in the mould of boron nitride fiber of 1 μ m, relies on the gravity dipping, 60 ℃ of following gels 6 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out the fibre-reinforced aerogel composite at last.Through measuring, the thermal conductivity of this silicon-aluminium aerogel composite material under 800 ℃ of high temperature is 0.08 watt of/meter Kelvin, and linear shrinkage is less than 5%.
Embodiment 9
The prepared silica aerogel composite of present embodiment is that glass fibre strengthens silica aerogel, and the Ludox preparation condition is for being 1: 1: 1 with ethyl orthosilicate, isopropyl alcohol, deionized water and ammoniacal liquor in molar ratio: 0.0008, be made into Ludox with base catalyst.Directly bulk density being equipped with in the Ludox adding is 0.23g/cm
3, the individual fiber diameter 1 μ m glass fibre that is mould in, rely on the gravity dipping, 60 ℃ of following gels 6 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out fiber reinforcement silica aerogel material at last.Through measuring, linear shrinkage is 40%.
Embodiment 10
The prepared aluminium aerogel composite of present embodiment is that alumina silicate fibre strengthens the aluminium aeroge; Aluminium colloidal sol preparation condition is for being 1: 0.6: 16 with aluminium secondary butylate, ethyl acetoacetate, ethanol, water and ammoniacal liquor in molar ratio: 3: 0.002, be made into aluminium colloidal sol with base catalyst.Directly bulk density being equipped with in the adding of aluminium colloidal sol is 0.23g/cm
3, individual fiber diameter is in the mould of alumina silicate fibre of 1 μ m, relies on the gravity dipping, 60 ℃ of following gels 6 hours, autoclave was put in room temperature in ethanol aging 48 hours in the back, squeezes into the carbon dioxide of 2 megapascal (MPa)s, 30 ℃ of insulations 15 hours down.Be warming up to 50 ℃ again, and with 200 liters/hour flow ethanol brought carbon dioxide into separating still and separate.After ethanol separates fully, again with 3 megapascal (MPa)s/hour the slow release pressure of speed, until with the ambient atmosphere equilibrium, take out fiber reinforcement aluminium aerogel material at last.Through measuring, linear shrinkage is 20%.
Because silica aerogel among the embodiment 9 and the aluminium aeroge among the embodiment 10 all shrink easily, therefore can't test thermal conductivity in 800 ℃.
The process conditions of each embodiment of table 2 and measured performance parameter
| The embodiment numbering | Gelling time (h) | Drying medium pressure (MPa) | Holding temperature (℃) | Temperature retention time (h) | Separation temperature (℃) | Flow (L/h) | Pressure decay rate (MPa/h) | Elevated temperature heat conductance (W/ (mK)) | Linear shrinkage |
| 1 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | 0.081 | ＜5％ |
| 2 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | 0.081 | ＜5％ |
| 3 | 8 | 2 | 30 | 15 | 50 | 200 | 3 | 0.081 | ＜5％ |
| 4 | 4 | 2 | 30 | 15 | 50 | 200 | 3 | 0.081 | ＜5％ |
| 5 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | 0.081 | ＜5％ |
| 6 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | 0.081 | ＜5％ |
| 7 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | 0.090 | ＜5％ |
| 8 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | 0.080 | ＜5％ |
| 9 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | Can't measure | 40％ |
| 10 | 6 | 2 | 30 | 15 | 50 | 200 | 3 | Can't measure | 20％ |
Annotate: the gelation temperature among the embodiment is 60 ℃, wears out and is ethanol with solvent, and aging temperature is room temperature, and ageing time is 48 hours, and drying medium is carbon dioxide.
Embodiment described herein illustrates what the preferred embodiments of the present invention were done.Person of ordinary skill in the field of the present invention can content disclosed according to the present invention carry out various modifications to described embodiment, but revises thus and the technical scheme that does not depart from essence of the present invention that obtains still drops within the appended claims institute restricted portion.
Claims (17)
1. a method for preparing silicon-aluminium aerogel composite material is characterized in that, this method comprises the steps:
(1) preparation of Ludox: esters of silicon acis, Ludox are mixed with Ludox with solvent, Ludox with catalyst and water, and said esters of silicon acis: Ludox is used solvent: water: it is 1: 1～20: 1～20: 0.0002～1.0 that Ludox uses the mol ratio of catalyst;
(2) preparation of aluminium colloidal sol: aluminium salt, chelating agent, aluminium colloidal sol are mixed with aluminium colloidal sol with solvent and aluminium colloidal sol with catalyst and water, and it is 1: 0.001～0.6: 4～32: 0.6～4: 0.0001～1 that said aluminium salt, chelating agent, aluminium colloidal sol use solvent, water and aluminium colloidal sol to use the mol ratio of catalyst;
(3) preparation of sial complex sol: said Ludox and said aluminium colloidal sol are mixed, make the sial complex sol;
(4) impregnation: through Infiltration Technics said sial complex sol is immersed in the inorganic fibers, obtain the mixture of sial complex sol and inorganic fibers;
(5) gelling: the said mixture that obtains in the step (4) is placed 60 ℃ to 80 ℃ environment, make the said sial complex sol generation gelling in the said mixture, obtain the sial plural gel;
(6) aging: as to carry out 24 hours to 48 hours wearing out with alcoholic solvent through adding to wear out; With
(7) supercritical fluid drying: handle carrying out supercritical fluid drying, obtain said silicon-aluminium aerogel composite material through aging sial plural gel;
Wherein, said Ludox uses catalyst and said aluminium colloidal sol to use catalyst to be base catalyst simultaneously;
Said esters of silicon acis is one or more the combination that is selected from the group of being made up of silester, methyl silicate and silicic acid propyl ester.
2. the method for claim 1, wherein according to the SiO that makes in the said silicon-aluminium aerogel composite material
2Mole with said silicon-aluminium aerogel composite material is counted 0.01%～90% said Ludox of mixed and said aluminium colloidal sol.
3. the method for claim 1, wherein said Ludox uses solvent and said aluminium colloidal sol to use solvent to be alcoholic solvent or ketone solvent.
4. the method for claim 1, wherein the preparation of said Ludox adopts following one-step method to carry out: at first said esters of silicon acis and Ludox are used solvent, drip said water and Ludox again with catalyst and mix, obtain Ludox.
5. method as claimed in claim 4, wherein, said water is deionized water.
6. the method for claim 1; Wherein, The preparation of said aluminium colloidal sol adopts following mode to carry out: with said aluminium salt is precursor, adds said chelating agent and mixes, and adds said aluminium colloidal sol again with solvent and mix; Drip said water and aluminium colloidal sol then with catalyst and mix, obtain said aluminium colloidal sol.
7. method as claimed in claim 6, wherein, said water is deionized water.
8. like each described method of claim 1 to 7, wherein, said impregnation carries out through following mode (1) or (2):
(1) directly said sial complex sol adding is placed with in the mould of said inorganic fibers, relies on gravity to carry out impregnation;
(2) use said sial complex sol to flood said inorganic fibers, and will in the said inorganic fibers of dipping packed mould into, re-use said sial complex sol and infiltrate.
9. like each described method of claim 1 to 7; Wherein, Said supercritical fluid drying carries out according to following mode: the said inorganic fibers that will be impregnated with said sial complex sol is put into supercritical fluid drying equipment; Squeeze into the drying medium of 2 megapascal (MPa)s～10 megapascal (MPa)s, 0～50 ℃ of insulation 1 hour～30 hours; Be warming up to 20 ℃～80 ℃ again, and utilize drying medium to bring assist medium into separating still and separate with 10 liters/hour～400 liters/hour flow; After assist medium separates fully, again with 1 megapascal (MPa)/hour～6 megapascal (MPa)s/hour speed pressure is released into and the ambient atmosphere equilibrium, obtain said silicon-aluminium aerogel composite material.
10. according to each described method of claim 1 to 7, wherein,
It is one or more the combination that is selected from the group of being made up of ethanol, methyl alcohol, propyl alcohol and isopropyl alcohol that said Ludox uses solvent; And/or
It is one or more the combination that is selected from the group be made up of ammoniacal liquor, NaOH and ammonium fluoride that said Ludox uses catalyst.
11. method as claimed in claim 10, wherein, said esters of silicon acis is an ethyl orthosilicate; Said Ludox uses solvent to be ethanol; Said Ludox uses catalyst to be ammoniacal liquor.
12. according to each described method of claim 1 to 7, wherein,
Said aluminium salt is one or more the combination that is selected from the group of being made up of aluminium isopropoxide, aluminium secondary butylate and aluminum nitrate;
It is one or more the combination that is selected from the group of being made up of ethanol, isopropyl alcohol and n-butanol that said aluminium colloidal sol uses solvent;
Said chelating agent is acetylacetone,2,4-pentanedione and/or ethyl acetoacetate; And/or
It is one or more the combination that is selected from the group of being made up of ammoniacal liquor, NaOH or ammonium fluoride that said aluminium colloidal sol uses catalyst.
13. method as claimed in claim 12, wherein, said aluminium colloidal sol uses catalyst to be ammoniacal liquor.
14. the silicon-aluminium aerogel composite material that makes by each described method of claim 1 to 13.
15. silicon-aluminium aerogel composite material according to claim 14; Wherein, said inorganic fibers is the one or more kinds of combinations that are selected from the group of being made up of quartz fibre, high silica fiber, alumina silicate fibre, glass fibre, alumina fibre, Zirconium oxide fibre, boron nitride fiber, basalt fibre and mullite fiber.
16. silicon-aluminium aerogel composite material as claimed in claim 15; Wherein, the form of said inorganic fibers is one or more the combination that is selected from the group of being made up of fibrofelt, cellucotton, tapetum fibrosum, fiberboard, fiber folded piece, fiber preform and prefabricated component complex.
17. like each described silicon-aluminium aerogel composite material of claim 14 to 16, wherein, the bulk density of said inorganic fibers is 0.01g/cm
3～0.90g/cm
3, individual fiber diameter is 0.1 μ m～10 μ m.
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