CN101792299B - Method for preparing heat-resisting alumina-silox aerogel thermal-protective composite material - Google Patents
Method for preparing heat-resisting alumina-silox aerogel thermal-protective composite material Download PDFInfo
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- CN101792299B CN101792299B CN2010103001120A CN201010300112A CN101792299B CN 101792299 B CN101792299 B CN 101792299B CN 2010103001120 A CN2010103001120 A CN 2010103001120A CN 201010300112 A CN201010300112 A CN 201010300112A CN 101792299 B CN101792299 B CN 101792299B
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Abstract
The invention discloses a method for preparing a heat-resisting alumina-silox aerogel thermal-protective composite material, which comprises the following steps: (1) preparing Al2O3 sol; (2) preparing SiO2 sol; (3) preparing Al2O3-SiO2 sol, (4) preparing SiC coating-containing reinforcing fibers; (5) mixing the SiC coating-containing reinforcing fiber felts or fiber prefabricated members and the Al2O3-SiO2 sol; (6) aging; and (7) carrying out drying treatment by using supercritical fluid. The operating temperature of the Al2O3-SiO2 aerogel composite material prepared by the method can reach 1,200 DEG C; and therefore, the Al2O3-SiO2 aerogel composite material has good heat-insulating property and good mechanical property.
Description
Technical field
The present invention relates to a kind of high temperature resistant aerogel heat-proof composite material and preparation method thereof; Especially relating to a kind of is matrix with the high-temperature resistant aluminium oxide silica aerogel, is aerogel heat-proof composite material of reinforcing phase and preparation method thereof with the SiC coating ceramic fiber that contains the blocks infrared radiation heat transfer effect.
Background technique
Along with the develop rapidly of Aero-Space cause, the flying speed of following aerospace craft is higher, and the flight time is longer, and this pneumatic heating that causes its surface to receive will be more serious, and the thermal environment of bearing will be more abominable.Anti-heat problem has become the great technical barrier that can't avoid and must properly settle in the novel aerospace craft development.
Therefore, in the thermal protection system of aerospace craft, adopting the novel heat insulation material with lightweight, high thermal resistance function, is the retardance heat transfer, guarantees the key of the normal operation of aircraft, and this has proposed harsh more requirement to thermal-protective material.This requires thermal-protective material to have characteristics such as lightweight, high temperature resistant, low thermal conductivity, the good mechanical performance also will be arranged simultaneously, so that can withstand oscillating action strong in the flight course.In addition, aspect civilian, the problem that has become world wide property in short supply day by day of global energy in many high temperature insulatings field, has equally also proposed active demand to new and effective thermal-protective material.Yet in the high temperature using process, its effect of heat insulation more and more has been difficult to satisfy the requirements at the higher level that practical application proposes for traditional thermal-protective material such as refractory fiber (alumina silicate or mullite fiber etc.).Therefore, it is extremely urgent to seek new thermal-protective material high temperature resistant, low thermal conductivity.
Aerogel is one type of thermal-protective material of tool potentiality, and it is to assemble each other with the nanometer scale colloidal particles to constitute the nanoporous network structure, and in hole, is full of a kind of high dispersive solid-state material of gaseous state dispersion medium.Because the very thin skeleton particle of aerogel material can reduce the solid thermal conduction, nano-porous structure can suppress gas transmission of heat, and therefore, aerogel has excellent heat-shielding performance, is to generally acknowledge the minimum solid material (being about 0.015W/mK under the normal temperature) of thermal conductivity at present.
Current, the research of aerogel has become the focus that countries in the world are paid close attention to, and wherein research is SiO more widely
2The aerogel system.But simple SiO
2Aerogel will directly apply to heat insulation field and also have certain difficulty, and main cause is: (1) SiO
2The low density of aerogel, high porosity cause its mechanical property relatively poor, and intensity is low, and fragility is big; (2) SiO
2Aerogel is that the near infrared of 3～8 μ m has stronger breathability to wavelength, and under high temperature condition, infrared radiation heat transfer is occupied an leading position, and this makes SiO
2Aerogel is in the high temperature using process, and thermal conductivity amplification is bigger; (3) at high temperature, SiO
2Airsetting micelle bunch particle shrinks and reunites, and particle is grown up, and hole structure is caved in, and causes its specific surface area and porosity ratio significantly to reduce, and this can have influence on SiO
2The heat-shielding performance of aerogel, in most cases SiO
2The aerogel serviceability temperature can not be above 800 ℃.
Therefore, for preparing the aerogel heat-insulating material with use value, people have carried out extensive studies, existing both at home and abroad many related patent U.S. Patent No. bibliographical informations.
At first, aspect the raising mechanical property, main method has fiber (comprising short fibre, fibrofelt or prefabricated component) to strengthen, and particle strengthens, and whisker strengthens, nano wire enhancing etc.Chinese patent CN1803602A discloses a kind of brucite fiber and has strengthened SiO
2The preparation method of aerogel heat-insulating material; With industry water glass or Ludox and natural brucite short fibre is raw material; Before solidifying, colloidal sol utilize the high energy ball mill chemical dispersion method to realize the inorganic sunscreen granularity refinement; With the natural brucite fiber tuft separately, through solvent exchange, hydrophobic processing, constant pressure and dry, prepare brucite fiber and strengthen SiO
2Aerogel heat-insulating material, its thermal conductivity are 0.01～0.03W/mK.Chinese patent CN101439957A discloses a kind of aerogel heat-insulating composite material that contains the Nano semiconductor opacifier and preparation method thereof; Through mechanical agitation or ultrasound effect; Ludox is mixed the back with tin-antiomony oxide or aluminum zinc oxide nanometer alcohol slurry flow in fibrofelt or the fiber preform, form the wet gel compound body, carry out supercritical fluid drying again through infiltration process; Obtain aerogel heat-insulating composite material, its mechanical strength is 0.1～2MPa.But, adopt ball milling, mechanical agitation or ultrasound to be used for disperse water magnesite short fibre or tin-antiomony oxide, the pure slurry of aluminum zinc oxide nanometer, its dispersing uniformity is still waiting further improvement.
The applicant discloses a kind of aerogel heat-proof composite material and preparation method thereof in the Chinese patent CN1749214A of application in 2005: be the silicon source with the silicon alkoxide; The titanium alkoxide is that the hydrolysis of titanium source prepares infrared light screening agent; Compound through sol impregnation technology and fibrofelt or fiber preform; Gel is after supercritical drying is prepared aerogel composite, and mechanical strength can reach more than the 2MPa.But, SiO
2The serviceability temperature of aerogel generally is not higher than 800 ℃, and this has limited it and in the heat insulation field of higher temperature, has used.
Secondly, reducing aspect the aerogel Thermal Conductivity at High Temperature, main method is through adding infrared light screening agent to suppress high temp, infrared radiation transmission of heat, and infrared light screening agent commonly used has titanium pigment, SiC, carbon black, potassium titanate crystal whisker, iron oxide, Nano semiconductor etc.Chinese patent CN1730388A discloses a kind of preparation method of stephanoporate powder doped silica aerogel heat-insulation material; Through in the Ludox of hydrolysis, adding fiber, opacifier and porous silica powder; Obtain silica aerogel heat-insulation material with supercritical drying through gel is aging, the compressive strength of material is 1.2～1.8MPa, but since adition process such as SiO 2 powder, opacifier reunite easily; Material thermal conductivity is higher, and its normal temperature thermal conductivity is 0.05～0.08W/mK.
At last, improving SiO
2Aerogel serviceability temperature aspect, main method are to mix other elements to suppress SiO
2The high temperature sintering of aerogel.Chinese patent CN1724354A discloses a kind of raising SiO
2The heat-staple method of aerogel, this method is passed through at SiO
2Doped F e in the aerogel
2O
3Nanoparticle is to overcome shortcomings such as aerogel poor stability, mechanical strength in practical application be lower, and aerogel specific surface area after 1000 ℃ of heat treatment still reaches 138～148m
2/ g.But this manufacturing process is comparatively complicated, and manufacturing cycle is longer, often needs two weeks to accomplish.
Though at present to SiO
2Aerogel heat-proof composite material has carried out extensive studies; But can find; Still exist some problem needs further to solve: (1) adopts fiber (comprising short fibre, fibrofelt or prefabricated component) to be reinforcing phase; Be the effective ways that improve the aerogel material mechanical property, but Thermal Conductivity at High Temperature is also than higher; (2) adding infrared light screening agent is the main method that reduces Thermal Conductivity at High Temperature; But; Most of opacifiers be employed in the colloidal sol through mechanical agitation or action of ultrasonic waves and aerogel compound; This causes opacifier to be difficult to be uniformly dispersed easily, even reunites, and can reduce the heat-shielding performance of aerogel composite sometimes on the contrary; (3) although can improve SiO through methods such as doping
2The serviceability temperature of aerogel, but still be difficult to satisfy the requirement to the higher serviceability temperature of thermal-protective material such as following aerospace craft.
More than these several aspects influenced SiO
2Aerogel heat-proof composite material is in the application in high temperature insulating field.Therefore; How further to improve the serviceability temperature of aerogel and the mechanical property and the high temperature insulating performance of composite material thereof; Be the main direction of studying from now on, particularly have very important and practical meanings in high temperature insulating fields such as novel aerospace craft thermal protection systems.
In numerous aerogels, Al
2O
3Aerogel is thermal conductivity low (30 ℃ of thermal conductivitys are merely 0.029W/MK, and 800 ℃, 1atm thermal conductivity are merely 0.098W/MK) not only, and serviceability temperature can reach 950 ℃, is the ideal material of preparation high temperature resistant heat insulation material.The block Al of U.S. Lawrence Livermore National Laboratory preparation
2O
3Aerogel can be anti-950 ℃ of sintering not, 1050 ℃ of heat treatments 4 hours, thermal conductivity was 0.098W/mK (referring to U.S. Pat 6620458B2) when its linear shrinkage was no more than 2%, 800 ℃.But, Al
2O
3Effects limit such as the intrinsic intensity of aerogel material is low, fragility big, retaining infrared radiation ability difference and shaping difficulty Al
2O
3Aerogel is in Industrial Application.
The applicant discloses a kind of high temperature resistant Al in the Chinese patent CN101041770A of application in 2007
2O
3Aerogel heat-proof composite material and preparation method thereof, the serviceability temperature of aerogel and high temperature insulating performance are improved, and 1000 ℃ of thermal conductivitys of material are 0.063～0.069W/mK.But, Al
2O
3Aerogel is severe sinter after being higher than 1000 ℃, collapse of pore structure, and specific surface area reduces, and in the high temperature using process, fiber is still waiting further improvement to the occlusion effect of infrared radiation simultaneously, and therefore, these have all influenced Al
2O
3The high temperature insulating performance of composite material.
Through at Al
2O
3Introduce the inhibition Al that silicon, rare earth elements or alkaline earth element etc. can be in various degree in the aerogel
2O
3The high-temperature phase-change of aerogel and sintering improve Al
2O
3The heat resistance of aerogel.Wherein, through with SiO
2With Al
2O
3It is to improve Al at present that the mode that colloidal sol mixes is introduced element silicon
2O
3The method that the aerogel heat resistance is commonly used.Osaki etc. are raw material with aluminium isopropoxide and ethyl orthosilicate, the Al that obtains
2O
3-SiO
2The specific surface area of aerogel under 1200 ℃ be 47m2/g (J.Non-Cryst.Solids, 2007,353:2436-2442).
But, Al
2O
3-SiO
2Effects limit such as the intrinsic intensity of aerogel material is low, fragility big, retaining infrared radiation ability difference and shaping difficulty Al
2O
3-SiO
2Aerogel is in Industrial Application.Therefore, prepare serviceability temperature and can reach more than 1200 ℃, the better Al of heat-shielding performance and mechanical property
2O
3-SiO
2Aerogel composite has very important and practical meanings.
Summary of the invention
The object of the present invention is to provide a kind of serviceability temperature to reach 1200 ℃, have aluminium oxide silica aerogel composite material of good heat-shielding performance and mechanical property and preparation method thereof simultaneously.
For realizing above-mentioned purpose, the present invention passes through Al
2O
3Colloidal sol and SiO
2Colloidal sol mixes in proportion, forms the Al with nanoporous network structure
2O
3-SiO
2Composite aerogel, to contain the ceramic fiber of blocks infrared radiation effect SiC coating compound with the surface then, thereby obtain the aluminium oxide silica aerogel heat-insulation composite material of high temperature resistant, low thermal conductivity and excellent mechanical performances.
The specific operation step is following:
(1) Al
2O
3The colloidal sol preparation
Al
2O
3Colloidal sol fitting process process is similar with the applicant's the disclosed technological scheme of CN101041770A patent application.With aluminium salt is pioneer, adds alcoholic solvent, deionized water and chelating agent, and the mol ratio of aluminium salt, alcoholic solvent, deionized water and chelating agent is 1: 4～32: 0.6～4: 0～0.6; Through reflux mixed solution is warming up to 60 ℃～80 ℃ constant temperature and stirs more than 45 minutes, form clear colloidal sol, colloidal sol is cooled to room temperature after, obtain Al
2O
3Colloidal sol;
Said aluminium salt can be aluminium isopropoxide, aluminium secondary butylate or aluminum nitrate;
The structural chain of said alcoholic solvent is short more, and structure is simple more, then helps the reaction of aluminium salt hydrolysis more, and therefore, alcoholic solvent can be methyl alcohol, ethanol, isopropanol or n-butanol;
Said chelating agent can be acetylacetone,2,4-pentanedione or ethyl acetoacetate;
Aluminium salt hydrolysis reactive rate is very fast, Al
2O
3The gel time of colloidal sol is often shorter, and is easy to generate deposition, simultaneously, with SiO
2The colloidal sol compound tense require to form comparatively complete porous network structure again, and therefore, it is more abundant to pay particular attention to the aluminium salt hydrolysis in the preparation process, forms more colloidal sol monomer, controls Al well
2O
3The stability of colloidal sol;
(2) SiO
2The colloidal sol preparation
SiO
2Colloidal sol fitting process process is similar with the applicant's the disclosed technological scheme of CN1749214A patent application.With silicon salt is pioneer, adds alcoholic solvent, deionized water and acid catalyst, and the mol ratio of silicon salt, alcoholic solvent, deionized water and acid catalyst is 1: 2～20: 1～6: 1.8～7.2 * 10
-3, stir after 20～60 minutes, left standstill 2～4 hours, make the abundant hydrolysis in silicon source obtain SiO
2Colloidal sol;
Silicon salt can be ethyl orthosilicate, methyl silicate or water glass;
Alcoholic solvent can be methyl alcohol, ethanol, isopropanol or n-butanol;
Acid catalyst can be hydrochloric acid, nitric acid, sulfuric acid, oxalic acid or acetate;
The monomer that requires silicon salt after hydrolysis, to form is more, avoids unnecessary by product to generate.
Because the difference of silicon salt and aluminium salt hydrolysis speed in order to obtain the good compound adhesive of network structure, requires the SiO of preparation
2Sol-hydrolysis is more abundant, is beneficial in complex sol process subsequently and Al
2O
3The colloidal sol monomer interconnects, and forms comparatively complete porous network structure;
Relation according to the hydrolysis of silicon source and polycondensation reaction relative speed and pH value can know that when the pH value was 7 left and right sides, hydrolysis rate was minimum, compiled and gathered the speed maximum, and the pH value was greater than 7 o'clock, and polycondensation reaction speed is greater than hydrolysis reaction, and the silicon source is main with polycondensation reaction; When the pH value less than 7 the time, hydrolysis reaction is greater than polycondensation reaction speed, the silicon source is main with hydrolysis reaction, therefore, preparation SiO
2Colloidal sol should carry out under acid condition;
(3) Al
2O
3-SiO
2The preparation of colloidal sol
With the Al for preparing
2O
3Colloidal sol and SiO
2Colloidal sol mixes by a certain percentage, and adds catalyzer, stirs 15～30 minutes, promptly obtains Al
2O
3-SiO
2Colloidal sol;
When the Al/Si mol ratio is 1: 1～8; Add deionized water, methyl alcohol and acid catalyst mixed solution; Wherein the mol ratio of methyl alcohol, deionized water and acid catalyst and aluminium is 4～10: 0.1～0.3: 0.3～0.8: 1, and catalyzer is selected acid more weak, can be acetic acid, formic acid or oxalic acid;
When the Al/Si mol ratio is 1～8: 1, add deionized water and base catalyst mixed solution, wherein the mol ratio of deionized water, base catalyst and ethyl orthosilicate is 0.10～0.3: 1.8～7.2 * 10
-3: 1, base catalyst can be ammoniacal liquor or urea;
(4) contain the preparation of SiC coated fiber
With total mass ratio is that 5%～20% Polycarbosilane (PCS) mixes with xylene solution, and dipping reinforcing fiber mats or prefabricated component then 900 ℃～1600 ℃ following cracking 2～4 hours, can obtain containing the fibrofelt or the prefabricated component of SiC coating;
Wherein, Reinforcing fiber mats or fiber preform mainly are to be made up of ceramic fiber; Preferential good alumina silicate, mullite, quartz fibre, Zirconium oxide fibre, alumina fibre, graphite fiber or the silicon carbide fiber of resistance to high temperature of selecting; Preferred 3～10 μ m of fiber diameter, fiber volume fraction is preferred 3%～10%, the preferred 0.5～10cm of length of staple; Have the SiC coating of good anti-infrared radiation heat transfer through adding one deck at fiber surface, just can be so that the transmission of radiation in fibrous insulating material is inhibited, thus reduction radiation heat conductance;
Traditional interpolation infrared light screening agent mode is difficult to be uniformly dispersed; And if with infrared light screening agent pioneer dipping and fiber surface; Through Pintsch process, then can obtain to have the anti-infrared radiating coating of high extinction coefficient, not only can reach finely dispersed purpose; And can avoid the transmission of heat by contact between the fiber, improve the heat-shielding performance of material;
(5) mix
In the mould that fibrofelt or fiber preform are housed, add Al
2O
3-SiO
2Colloidal sol makes it to mix with reinforcing fiber mats or fiber preform, at room temperature leave standstill 0.5～5 hour after, form gel, obtain fiber composite Al
2O
3-SiO
2Gel rubber material;
(6) aging
With fiber composite Al
2O
3-SiO
2Gel rubber material wears out through adding alcoholic solvent, and the alcoholic solvent consumption only need soak full sample and get final product, and wherein alcoholic solvent can be anhydrous alcohol or isopropanol or sec-butyl alcohol etc., and ageing time was greater than 24 hours;
(7) drying
The Al that will contain fiber
2O
3-SiO
2Wet gel is handled through supercritical fluid drying, and the optimum condition of described supercritical fluid drying does, is drying medium with ethanol or isopropanol, will contain the Al of fiber
2O
3-SiO
2Wet gel is put into supercritical fluid drying equipment, and the nitrogen of preliminary filling 0.5～2MPa is heated to more than the super critical point of alcoholic solvent with 1～2 ℃/min speed again, is incubated 1～2 hour, again with the slow release pressure of 50～100KPa/min speed, at last with N
2Gas dashes and swept 15～60 minutes, promptly obtains Al
2O
3-SiO
2Aerogel heat-proof composite material.
Wherein, it is similar with the applicant's the disclosed technological scheme of CN101041770A patent application with Dry run to mix, wear out.
Compare with CN101041770A, the disclosed technological scheme of CN1749214A, the present invention has following good effect:
(1) than the previous SiO for preparing of the applicant
2The aerogel serviceability temperature generally is not higher than 800 ℃ (CN1749214A), the Al of preparation
2O
3The aerogel serviceability temperature generally is not higher than 1000 ℃ (CN101041770A), the Al of the present invention's preparation
2O
3-SiO
2Aerogel still has higher porosity and specific surface area under 1200 ℃, can use down at 1200 ℃, has further improved the serviceability temperature of aerogel; (2) Al through sol-gel, supercritical fluid drying prepared
2O
3-SiO
2Aerogel density is low; The aperture is little; Solid heat transfer and gas heat-transfer there is good iris action; Have the SiC coating of blocks infrared radiation effect through adding, efficiently solve the problem of the nonuniformity of infrared light screening agent dispersion in the past, more help suppressing high temp, infrared radiation transmission of heat on the ceramic fiber surface; Gained Al
2O
3-SiO
2Aerogel composite minimum thermal conductivity when 800 ℃, 1000 ℃ and 1200 ℃ is respectively 0.042W/mK, 0.048W/mK and 0.053W/mK, with the SiO of the previous preparation of the applicant
2Aerogel heat-proof composite material (CN1749214A) and Al
2O
3Aerogel heat-proof composite material (patent CN101041770A) is compared, and the high temperature insulating effect has obtained further improvement; (3) be reinforcing phase to contain SiC coating ceramic fiber, make Al
2O
3-SiO
2Aerogel material has the good mechanical performance, can prepare various large complicated special-shaped heat insulating components, can satisfy Aeronautics and Astronautics, military affairs and the harsh more usage requirement in heat insulation field such as civilian.
Embodiment
Below through embodiment the present invention is described further, but these embodiments must not be used to explain the restriction to protection domain of the present invention.
Embodiment 1
(1) aluminium secondary butylate, anhydrous alcohol, deionized water were mixed in 1: 16: 0.6 in molar ratio, adopt reflux to be heated to 60? Stir 45min, form water white transparency colloidal sol, when treating that colloidal sol is reduced to room temperature, obtain Al
2O
3Colloidal sol; (2) with ethyl orthosilicate, anhydrous alcohol, deionized water and hydrochloric acid 1: 5: 1 in molar ratio: 3.6 * 10
-3Mix, stir 20min, leave standstill 1h, obtain SiO
2Colloidal sol; (3) be 3: 1 mixed with two kinds of colloidal sols by the Al/Si mol ratio, add methyl alcohol, deionized water and glacial acetic acid mixed solution, wherein methyl alcohol, deionized water and glacial acetic acid and aluminium secondary butylate mol ratio are 5: 0.168: 0.448: 1, obtain Al
2O
3-SiO
2Colloidal sol; (4) be to mix at 0.05: 0.95 Polycarbosilane (PCS) and xylene solution by mass ratio; The impregnation of fibers volume fraction is 5% mullite fiber felt or prefabricated component; 1200 ℃ of following cracking 2 hours, obtain containing the mullite fiber felt or the prefabricated component of SiC coating then; (5) with Al
2O
3-SiO
2Colloidal sol adds and contains in the mullite fiber felt or prefabricated component mould of SiC coating, makes the two compound, gel after 1 hour; (6) add anhydrous alcohol then, make it to soak full sample, under room temperature, wore out 2 days; (7) put into autoclave, preliminary filling N
2To 2MPa, be heated to 270 ℃ with the speed of 1 ℃/min, constant temperature kept temperature-resistant after 1 hour, with the slow release pressure of speed of 70KPa/min, to normal pressure, with N
2Dash and swept autoclave 15 minutes, powered-down makes its natural cooling, promptly gets aluminium oxide silica aerogel effectively insulating composite material.
1200 ℃ of heat treatments of gained aluminium oxide silica aerogel after 2 hours specific surface area be 115m
2/ g, gained Al
2O
3-SiO
2800 ℃ of thermal conductivitys of aerogel composite are 0.042W/mK, and 1200 ℃ of thermal conductivitys are 0.058W/mK, and tensile strength is 1.12MPa, and flexural strength is 0.92MPa, and compression strength (deformation is 25% o'clock) is 0.98MPa.
Embodiment 2
Aluminum nitrate, isopropanol, deionized water were mixed in 1: 12: 0.6 in molar ratio, adopt reflux to be heated to 80 ℃ and stir 50min, when treating that colloidal sol is reduced to room temperature, obtain Al
2O
3Colloidal sol; With methyl silicate, anhydrous alcohol, deionized water and acetic acid 1: 3: 1 in molar ratio: 1.8 * 10
-3Mix, stir 20min, leave standstill 1h, obtain SiO
2Colloidal sol; Be 8: 1 mixed with two kinds of colloidal sols by the Al/Si mol ratio then, add methyl alcohol, deionized water and glacial acetic acid mixed solution, wherein methyl alcohol, deionized water and glacial acetic acid and aluminium secondary butylate mol ratio are 6: 0.1: 0.622: 1, obtain Al
2O
3-SiO
2Colloidal sol; Is to mix at 0.10: 0.90 Polycarbosilane (PCS) and xylene solution by mass ratio, and the impregnation of fibers volume fraction is 7% Zirconium oxide fibre felt or prefabricated component, then 1200 ℃ of following cracking 2 hours, obtains containing the Zirconium oxide fibre felt or the prefabricated component of SiC coating; With Al
2O
3-SiO
2Colloidal sol adds and contains in the Zirconium oxide fibre felt or prefabricated component mould of SiC coating, makes the two compound, gel after 0.5 hour; Add isopropanol then, make it to soak full sample, under room temperature, wore out 1 day; Put into autoclave then, the N of preliminary filling 1.0MPa
2, be heated to 270 ℃ with 1.5 ℃/min speed again, be incubated 2 hours, again with the slow release pressure of speed of 50KPa/min, at last with N
2Gas dashes and swept 30 minutes, and powered-down makes its natural cooling, promptly makes aluminium oxide silica aerogel effectively insulating composite material.
1000 ℃ of thermal conductivitys of gained aluminium oxide silica aerogel composite material are 0.048 W/mK, and resistance to flexure is 1.09MPa.
Embodiment 3
Aluminium isopropoxide, anhydrous alcohol, deionized water were mixed in 1: 32: 4 in molar ratio, adopt reflux to be heated to 60 ℃ and stir 50min, when treating that colloidal sol is reduced to room temperature, obtain Al
2O
3Colloidal sol; With water glass, anhydrous alcohol, deionized water and hydrochloric acid 1: 5: 2 in molar ratio: 3.6 * 10
-3Mix, stir 20min, leave standstill 1h, obtain SiO
2Colloidal sol; Be 1: 4 mixed with two kinds of colloidal sols by the Al/Si mol ratio then, add ammoniacal liquor and deionized water, wherein deionized water and ammoniacal liquor and water glass mol ratio are 0.25: 7.2 * 10
-3: 1, obtain Al
2O
3-SiO
2Colloidal sol; Is to mix at 0.15: 0.85 Polycarbosilane (PCS) and xylene solution by mass ratio, and the impregnation of fibers volume fraction is 9% quartz fibre felt or prefabricated component; 900 ℃ of following cracking 2 hours, obtain containing the quartz fibre felt or the prefabricated component of SiC coating then; With Al
2O
3-SiO
2Colloidal sol adds and contains in the quartz fibre felt or prefabricated component mould of SiC coating, makes the two compound, behind 1.5 hours gels, adds anhydrous alcohol, makes it to soak full sample, under room temperature, wears out 1.5 days; Put into autoclave then, preliminary filling N
2To 0.5MPa, be heated to 270 ℃ with the speed of 1 ℃/min, constant temperature kept temperature-resistant after 1 hour, with the slow release pressure of speed of 100KPa/min, to normal pressure, with N
2Dash and swept autoclave 50 minutes, powered-down makes its natural cooling, promptly gets aluminium oxide silica aerogel effectively insulating composite material.
1200 ℃ of thermal conductivitys of gained aluminium oxide-silicon oxide aerogel composite are 0.053W/mK, and tensile strength is 1.29MPa.
Embodiment 4
With aluminium secondary butylate, anhydrous alcohol, deionized water and ethyl acetoacetate 1: 8: 0.6 in molar ratio: 0.188 mixed, and adopts reflux to be heated to 60 ℃ and stirs 50min, when treating that colloidal sol is reduced to room temperature, obtains Al
2O
3Colloidal sol; With ethyl orthosilicate, anhydrous alcohol, deionized water and oxalic acid 1: 5: 2 in molar ratio: 3.6 * 10
-3Mix, stir 20min, leave standstill 1h, obtain SiO
2Colloidal sol; Be 1: 8 mixed with two kinds of colloidal sols by the Al/Si mol ratio then, add ammoniacal liquor and deionized water, wherein deionized water and ammoniacal liquor and ethyl orthosilicate mol ratio are 0.15: 3.6 * 10
-3: 1, obtain Al
2O
3-SiO
2Colloidal sol; Is to mix at 0.08: 0.92 Polycarbosilane (PCS) and xylene solution by mass ratio, and the impregnation of fibers volume fraction is 7% alumina silicate fiber felt or prefabricated component, then 1000 ℃ of following cracking 2 hours, obtains containing the alumina silicate fiber felt or the prefabricated component of SiC coating; With Al
2O
3-SiO
2Colloidal sol adds and contains in the alumina silicate fiber felt or prefabricated component mould of SiC coating, makes the two compound, behind 5 hours gels, adds anhydrous alcohol, makes it to soak full sample, under room temperature, wears out 1.5 days; Put into autoclave then, preliminary filling N
2To 0.8MPa, be heated to 270 ℃ with the speed of 2 ℃/min, constant temperature kept temperature-resistant after 1 hour, with the slow release pressure of speed of 60KPa/min, to normal pressure, with N
2Dash and swept autoclave 45 minutes, powered-down makes its natural cooling, promptly gets aluminium oxide silica aerogel effectively insulating composite material.
1200 ℃ of heat treatments of gained aluminium oxide silica aerogel after 2 hours specific surface area be 92m
2/ g, gained Al
2O
3-SiO
21200 ℃ of thermal conductivitys of aerogel composite are 0.057W/mK.
Claims (2)
1. the preparation method of a heat-resisting alumina-silox aerogel thermal-protective composite material is characterized in that, comprises the steps:
(1) Al
2O
3The colloidal sol preparation
With aluminium salt is pioneer, adds alcoholic solvent, deionized water and chelating agent, and the mol ratio of aluminium salt, alcoholic solvent, deionized water and chelating agent is 1: 4 ~ 32: 0.6 ~ 4: 0 ~ 0.6; Through reflux mixed solution is warming up to 60 ℃ ~ 80 ℃ constant temperature and stirs more than 45 minutes, form clear colloidal sol, colloidal sol is cooled to room temperature after, obtain Al
2O
3Colloidal sol;
Said aluminium salt is aluminium isopropoxide, aluminium secondary butylate or aluminum nitrate;
Said alcoholic solvent is methyl alcohol, ethanol, isopropanol or n-butanol;
Said chelating agent is acetylacetone,2,4-pentanedione or ethyl acetoacetate;
(2) SiO
2The colloidal sol preparation
With silicon salt is pioneer, adds alcoholic solvent, deionized water and acid catalyst, and the mol ratio of silicon salt, alcoholic solvent, deionized water and acid catalyst is 1:2 ~ 20:1 ~ 6:1.8 ~ 7.2 * 10
-3, stir after 20 ~ 60 minutes, left standstill 2 ~ 4 hours, make the abundant hydrolysis in silicon source obtain SiO
2Colloidal sol;
Said silicon salt is ethyl orthosilicate, methyl silicate or water glass;
Said alcoholic solvent can be methyl alcohol, ethanol, isopropanol or n-butanol;
Said acid catalyst is hydrochloric acid, nitric acid, sulfuric acid, oxalic acid or acetate;
(3) Al
2O
3-SiO
2The preparation of colloidal sol
With the Al for preparing
2O
3Colloidal sol and SiO
2Colloidal sol mixes by a certain percentage, and adds catalyzer, stirs 15 ~ 30 minutes, promptly obtains Al
2O
3-SiO
2Colloidal sol;
When the Al/Si mol ratio is 1:1 ~ 8, add deionized water, methyl alcohol and acid catalyst mixed solution, in the said mixed solution, the mol ratio of methyl alcohol, deionized water and acid catalyst and aluminium is 4 ~ 10: 0.1 ~ 0.3: 0.3 ~ 0.8: 1;
Catalyzer is acetic acid, formic acid or oxalic acid;
When the Al/Si mol ratio greater than 1, be less than or equal at 8 o'clock, add deionized water and base catalyst mixed solution, in the said mixed solution, the mol ratio of deionized water, base catalyst and ethyl orthosilicate is 0.10 ~ 0.3:1.8 ~ 7.2 * 10
-3: 1, base catalyst is ammoniacal liquor or urea;
(4) contain the preparation of SiC coated fiber
Be that 5% ~ 20% Polycarbosilane mixes with xylene solution with total mass ratio, dipping reinforcing fiber mats or prefabricated component then 900 ℃ ~ 1600 ℃ following cracking 2 ~ 4 hours, promptly obtain containing the reinforcing fiber mats or the prefabricated component of SiC coating;
(5) mix
In the mould that the reinforcing fiber mats that contains the SiC coating or fiber preform are housed, add Al
2O
3-SiO
2Colloidal sol makes it to mix with reinforcing fiber mats or fiber preform, at room temperature leave standstill 0.5 ~ 5 hour after, form gel, the fiber composite that is enhanced Al
2O
3-SiO
2Gel rubber material;
(6) aging
With the compound Al of reinforcing fiber
2O
3-SiO
2Gel rubber material wears out through adding alcoholic solvent, and said alcoholic solvent is anhydrous alcohol, isopropanol or sec-butyl alcohol, and ageing time was greater than 24 hours;
(7) supercritical fluid drying is handled
The Al that will contain reinforcing fiber
2O
3-SiO
2Wet gel is handled through supercritical fluid drying;
The condition of described supercritical fluid drying does, is drying medium with ethanol or isopropanol, will contain the Al of fiber
2O
3-SiO
2Wet gel is put into supercritical fluid drying equipment, and the nitrogen of preliminary filling 0.5 ~ 2 MPa is heated to more than the super critical point of alcoholic solvent with 1 ~ 2 ℃/min speed again, is incubated 1 ~ 2 hour, again with the slow release pressure of 50 ~ 100kPa/min speed, at last with N
2Gas dashes and swept 15 ~ 60 minutes, promptly obtains the aluminium oxide-silicon oxide aerogel heat-proof composite material.
2. the preparation method of heat-resisting alumina-silox aerogel thermal-protective composite material as claimed in claim 1; It is characterized in that; Said reinforcing fiber mats or fiber preform are made up of the good alumina silicate of resistance to high temperature, mullite, quartz fibre, Zirconium oxide fibre, alumina fibre, graphite fiber or silicon carbide fiber; Fiber diameter is 3 ~ 10mm, fiber volume fraction 3% ~ 10%, length of staple 0.5 ~ 10cm.
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