CN102276236A - High temperature resistant Si-C-O aerogel thermal insulation composite material and preparation method thereof - Google Patents
High temperature resistant Si-C-O aerogel thermal insulation composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high temperature resistant Si-C-O aerogel thermal insulation composite material and a preparation method thereof. The preparation method comprises the following steps: mixing an Si source and a C source, and carrying out hydrolysis and condensation polymerization to form a sol which has a nanometer porous three-dimensional network skeleton structure and contains three elements of Si, C, and O in the network structure; compositing the sol with a high temperature resistant inorganic ceramic fiber to form a fiber-gel mixture; carrying out supercutical fluid drying to obtain an Si-C-O aerogel precursor composite material with the nanometer porous structure; and cracking the Si-C-O aerogel precursor composite material in high temperature inert atmosphere to form the Si-C-O aerogel thermal insulation composite material with an Si-O bond and an Si-C bond coexisting. The thermal conductivities of the Si-C-O aerogel thermal insulation composite material prepared in the invention at 800DEG C, 1000DEG C, and 1200DEG C are low to 0.32W/m.K, 0.043 W/m.K, and 0.051 W/m.K respectively, and the bending strength of the Si-C-O aerogel thermal insulation composite material is 2.6MPa, so the Si-C-O aerogel thermal insulation composite material can satisfy stringent thermal insulation requirements by aerospace fields, military fields and civil fields.
Description
Technical field
The present invention relates to a kind of preparation method of aerogel heat-proof composite material, especially relate to a kind of preparation method of the aerogel heat-proof composite material that high temperature resistant Si-C-O aerogel and inorganic ceramic fiber composite are obtained.
Background technology
When following aerospacecraft direction such as to high Mach number, long boat the time developed, the pneumatic heat that adds that the aircraft outside surface is afforded was big, and the surface temperature height is harsh more to the requirement of anti-heat insulation structural.Aspect civilian, global energy is in short supply day by day, and some high temperature fields such as aircraft engine, petroleum pipe line, stove and other Thermal Equipment etc. also propose requirements at the higher level to lagging material.Cotton felt of traditional lagging material such as ceramic fiber and ceramic insulation watt etc. have been difficult to satisfy the requirements at the higher level that practical application proposes.Therefore, the high efficiency heat insulation material of developing a kind of anti-higher temperature, lightweight, excellent mechanical performances is to satisfying domestic energy-saving and reduce discharging and the demand of aerospacecraft thermal protection system having important practical significance.
Aerogel material is a kind of novel lagging material, and it has low density (the minimum 0.003g/cm of reaching
3), high porosity (reaching as high as 99.8%), high-specific surface area (200-1000m
2/ g) and characteristics such as very thin skeleton particle and nano-porous structure, can at utmost suppress solid, gas thermal conduction, be that the minimum solid material of present known thermal conductivity is (as SiO
2Thermal conductivity is about 0.015W/mK under the aerogel normal temperature).At present, aerogel system commonly used mainly contains SiO
2, Al
2O
3And carbon aerogels etc., and obtained application in some fields, demonstrated good heat insulation and preservation effect.For example, the SiO of U.S. ASPEN company preparation
2The aerogel composite product is respectively 0.013-0.016W/m.K and 0.033W/m.K at normal temperature and 500 ℃ of following thermal conductivities.U.S. Pat 6620458B2 discloses the Al of a kind of low density, high porosity
2O
3The aerogel preparation method, its can be anti-950 ℃ of sintering not, 800 ℃ of thermal conductivities are 0.098W/m.K, the disclosed Al of patent application CN101041770A that the applicant proposed in 2007
2O
3The thermal conductivity of aerogel heat-proof composite material in the time of 1000 ℃ is 0.063-0.069W/m.K.The disclosed a kind of fiber composite carbon aerogel lagging material of Chinese patent CN101698591A, the normal temperature thermal conductivity is 0.03-0.05W/m.K, 1000 ℃ of thermal conductivities are 0.05-0.09W/m.K.
But, existing aerogel heat-insulating material still exists following problem to have much room for improvement: (1) is because infrared radiation heat transfer is directly proportional with 3 powers of temperature, and radiative transfer will occupy the dominant position of heat transfer under the high temperature, and simple SiO
2, Al
2O
3Aerogel has stronger perviousness at the near infrared of 3-8mm, and it is relatively poor that high temp, infrared radiation blocks ability, has limited its application in heat insulation field.At present, many scholars adopt modes such as adding opalizer or fiber surface modification to improve SiO more
2, Al
2O
3The high temp, infrared radiation of aerogel composite blocks ability.Opalizer commonly used has carbon black, mineral compound (TiO
2, Fe
3O
4, B
4C), potassium titanate crystal whisker, Nano semiconductor etc.These modes are not that the angle from aerogel itself improves its ir radiation and blocks ability.Simultaneously, it is compound that most opalizer adopts in the colloidal sol preparation process through mechanical stirring or ultrasonic wave effect and aerogel more, the dispersing uniformity of opalizer is had relatively high expectations, if disperse inhomogeneous or reunite, can reduce the heat-proof quality and the mechanical property of material sometimes on the contrary; (2) owing to the natural characteristics of material own, along with the rising of use temperature, the aerogel vesicular structure can cave in gradually, and particle is grown up, and causes the reduction of its specific surface area and porosity, thereby influences the use properties of aerogel material.Generally speaking, SiO
2Aerogel, Al
2O
3The use temperature of aerogel is no more than 800 ℃ and 1000 ℃ respectively.Carbon aerogels can bear higher temperature under nonoxidizing atmosphere or vacuum, but next easily oxidized at aerobic conditions, use temperature is not high.Thereby, be badly in need of seeking a kind of anti-higher temperature, itself have the aerogel material system of necessarily blocking the ir radiation ability simultaneously.
Reach higher use temperature because simple oxide silica aerogel is difficult, and pass through at oxide compound such as SiO
2Introduce carbon on the basis of system to improve its composition and valence bond structure, the Si-C-O pottery that then obtains compares SiO
2To have anti-higher temperature and reach heat-proof quality preferably.This is because in the Si-C-O material, has formed Si-C tetrahedral structure and the free carbon more firm than Si-O tetrahedral structure, and viscosity is than SiO
2Non-crystalline material also increased by two orders of magnitude above (Rouxel T. J. Sol-Gel Sci. Techn., 1999,14:87-94), having of these components is beneficial to the high temperature sintering that suppresses the Si-C-O pottery.
At present, the Si-C-O material is generally by the preparation of precursor cracking conversion method, because violent chemical reaction and contraction in the cracking process, the Si-C-O material that obtains mostly is fine and close glass greatly at present.Weinberger M etc. has reported the preparation method of high-specific surface area Si-C-O bulk material, and this material has the hierarchical porous structure of macropore (greater than 50nm), mesoporous, micropore, density 0.4g/cm
3, its aperture is bigger, be unfavorable for realizing low gaseous state thermal conduction (Weinberger M. Chem. Mater., 2010,22:1509-1520).U.S. Pat 6620749B2 discloses a kind of black lightweight Si-C-O porous ceramics lagging material, with the organo-siloxane is raw material, prepared Si-C-O black refractory ceramics by sol-gel, constant pressure and dry and Pintsch process, it has high temperature resistant (use temperature can reach 1700 ℃), and (density is 0.12-0.6g/cm to lightweight
3) etc. characteristics, but simple Si-C-O porous ceramics fragility is bigger, has limited its application in the high temperature insulating field.
Summary of the invention
For overcoming problems such as existing Si-C-O aerogel mechanical strength is low, the invention provides a kind of both high temperature resistantly, have the preparation method of the Si-C-O aerogel heat-proof composite material of good heat-proof quality and mechanical property again.
Technical scheme of the present invention is, silicon source and carbon source are mixed, through hydrolysis and polycondensation, formation has the three-dimensional network skeleton structure of nanoporous and contain Si in network structure, C, the colloidal sol of three kinds of elements of O, then that described colloidal sol and fibrefelt or prefabricated component is compound, form fiber and gel mixture, pass through supercritical fluid drying then, obtain having the Si-C-O aerogel precursor composite material of nano-porous structure, again Si-C-O aerogel precursor composite material is carried out the cracking of high temperature inert atmosphere, the final Si-C-O aerogel heat-proof composite material that forms with Si-O key and Si-C key.
The present invention specifically may further comprise the steps:
(1) preparation of Si-C-O aerogel precursor body colloidal sol
Silicon source, carbon source are mixed stirring with solvent and water, successively add bronsted lowry acids and bases bronsted lowry catalysis again, make silicon source and carbon source issue at acid and alkaline condition respectively that unboiled water is separated and polycondensation, obtain containing in the network structure Si-C-O aerogel precursor body colloidal sol of Si, C, three kinds of elements of O, the mol ratio of described silicon source, carbon source, solvent, water, acid catalyst and alkaline catalysts is 1: 0.1-10: 2-30: 2-12: 1.0 * 10
-3-8.0 * 10
-3: 1.0 * 10
-2-6 * 10
-2
Described silicon source can be a kind of tetraalkoxysilane Si (OR
1)
4, R wherein
1Be the group of the saturated or unsaturated 1-12 of comprising carbon atom, as methyl silicate or tetraethoxy;
Described carbon source can be a kind of dialkoxy silicane (R
2O)
2-Si-R
4R
3, R wherein
2Be the group of the saturated or unsaturated 1-12 of comprising carbon atom, R
4, R
3Be the similar or different group of the saturated or unsaturated 1-12 of comprising carbon atom, comprise alkyl, haloalkene alkyl, aryl, alkaryl, aralkyl; R
3, R
4In one also can be hydrogen atom, the mixture that dissolves each other with any ratio as dimethyldiethoxysilane, methyldiethoxysilane, methyl dimethoxysilane, dimethyldimethoxysil,ne, diethyl dibutoxy silane, dihexyl dimethoxy silane, dialkylene methyldiethoxysilane or above each material;
Described alcoholic solvent can be one or more the arbitrary proportion mixture in methyl alcohol, ethanol, propyl alcohol, Virahol, the butanols;
Described acid catalyst can be hydrochloric acid, nitric acid, sulfuric acid, oxalic acid or acetate;
Described alkaline catalysts can be ammoniacal liquor, sodium hydroxide, potassium hydroxide or urea;
(2) mix
Step (one) gained Si-C-O aerogel precursor body colloidal sol is added fibrefelt or prefabricated component, makes it to mix with fibrefelt or prefabricated component, at room temperature leave standstill 1-10 hour after, the formation gel obtains fiber and gel mixture;
Described fibrefelt or prefabricated component can be cellucotton, tapetum fibrosum, fiberboard or fiber preform, mainly be to constitute by fiber, the preferential good fiber of resistance to elevated temperatures of selecting, can be to be selected from two or more combination in a kind of or described fiber of carbon fiber, pre-oxygen silk, sapphire whisker, Zirconium oxide fibre, silica fiber, mullite fiber, aluminum silicate fiber, silicon carbide fiber, high silica fiber, Fibre diameter 3-10mm, the fiber volume fraction 2%-15% of fibrefelt or prefabricated component;
(3) aging
Step (two) gained fiber and gel mixture adding alcoholic solvent are worn out, as long as the alcoholic solvent add-on can cover fiber and gel mixture surface, the solvent evaporates that prevents gel inside gets final product, aging temperature 25-50 ℃, digestion time 1-3 days, described alcoholic solvent can be one or more the arbitrary proportion mixture that is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, the butanols;
(4) supercritical drying
To carry out supercritical fluid drying through step (three) aged fiber and gel mixture, the condition of described supercritical fluid drying is: with ethanol, propyl alcohol or Virahol is drying medium, preferred alcohol, fiber and gel mixture are put into supercritical fluid drying equipment, the nitrogen of preliminary filling 0.4-2.5MPa is heated to more than the super critical point of alcoholic solvent with 0.5-1.5 ℃/min speed again, is incubated 1-5 hour, again with the slow relief pressure of 40-100KPa/min speed, at last with N
2Gas dashes and swept 10-90 minute, obtains Si-C-O aerogel precursor composite material;
(5) Pintsch process
The Si-C-O aerogel precursor composite material that will obtain behind step (four) supercritical drying is under inert atmosphere protection, carry out Pintsch process, the rearrangement reaction of Si-C-O aerogel precursor body generation scission of link, the final Si-C-O aerogel heat-proof composite material that generates with the amorphous network structure of Si-C-O and uncombined carbon structure;
Described inert atmosphere can be N
2, Ar or He gas, cracking temperature is preferably 900 ℃-1500 ℃, the inert protective gas flow velocity is 100-600mL/min during cracking, soaking time is 1-4 hour.
The Si-C-O aerogel heat-proof composite material of the present invention's preparation has following excellent properties:
1. high temperature resistant, the present invention passes through dialkoxy silicane (R in (one) step
2O)
2-Si-R
4R
3For carbon source is introduced carbon, finally through having formed the Si-C-O aerogel with Si-C bond structure after (five) the step Pintsch process, wherein the existence of Si-C key has improved the resistance to elevated temperatures of aerogel, has overcome SiO
2, Al
2O
3Aerogel at high temperature pore structure collapses, therefore the Si-C-O aerogel that obtains at high temperature still has higher specific surface area and porosity, use temperature can reach 1200 ℃, and 1200 ℃ of thermal treatments of Si-C-O aerogel heat-proof composite material are after 2 hours, and the material contracts rate is no more than 5%.
2. the elevated temperature heat conductance is low, the high temperature insulating performance is good, the present invention's (one) step preparation colloidal sol, (2) step made its formation have the gel (being ethanol liquid in the gel pore) of nanometer skeleton and nanoporous, (3) step supercritical drying has been got rid of the ethanol in the gel pore, be replaced as air, and kept its nanometer skeleton and nano-pore structure, the Si-C-O aerogel that final (five) step Pintsch process forms has still kept nanometer skeleton and nano-pore structure, this helps reducing the gentle body heat conduction of solid, have free C and SiC nanometer crystalline phase in the Si-C-O aerogel that (five) step Pintsch process forms simultaneously, this helps improving aerogel high temperature and blocks the ir radiation ability; In addition, in (two) step, adopted ceramic fiber, these ceramic fibers have further strengthened under the material at high temperature absorption and the scattering power to ir radiation, reduce radiative transfer, effectively solve the relatively poor problem of aerogel high temperature retaining ir radiation effect in the past: the Si-C-O aerogel heat-proof composite material of the present invention's preparation at high temperature still has lower thermal conductivity, minimum 0.032W/mK, 0.043W/mK, the 0.051W/mK of reaching respectively of its 800 ℃, 1000 ℃, 1200 ℃ thermal conductivity.
3. good mechanical performance and processability, the present invention utilized the inorganic ceramic fiber to be wild phase in (two) step, by with of the compound use of one or more inorganic fibres with goods form (as cellucotton, tapetum fibrosum, fiberboard or fiber preform) and Si-C-O aerogel, solved the problem that pure Si-C-O aerogel intensity is low, fragility is big, improved the physical strength of itself, bending strength can reach 2.6MPa; Simultaneously material also has good moulding and processing characteristics, can prepare the heat insulating component of various large complicated shapes, and application performance further improves, and can satisfy aerospace, military affairs and the relatively heat-insulation and heat-preservation requirement of harshness of field such as civilian.
Embodiment
The invention will be further described by the following examples, but these embodiment must not be used to explain limiting the scope of the invention.
Embodiment 1
The present embodiment product is made of mullite fiber and Si-C-O aerogel, the silicon source is a tetraethoxy, carbon source is a dimethyldiethoxysilane, alcoholic solvent is a dehydrated alcohol, acid catalyst is a hydrochloric acid, alkaline catalysts is an ammoniacal liquor, and the material molar ratio of precursor colloidal sol is a tetraethoxy: dimethyldiethoxysilane: dehydrated alcohol: deionized water: hydrochloric acid: ammoniacal liquor=1: 1.5: 6: 6: 2 * 10
-3: 6 * 10
-2, preparation process is as follows: after 30 minutes leave standstill the meromict stirring of tetraethoxy, dimethyldiethoxysilane, hydrochloric acid, deionized water, required dehydrated alcohol amount 5 hours (1); (2) with continuing to stir 20 minutes in ammoniacal liquor and second half the dehydrated alcohol adding mixing solutions, obtain Si-C-O aerogel precursor body colloidal sol; (3) Si-C-O aerogel precursor body colloidal sol is added volume fraction is housed is that the Fibre diameter of mullite fiber is 7mm in 5% the mullite fiber felt mould, gel after 1 hour, and add dehydrated alcohol makes it to soak full sample, in 25 ℃ aging 2 days down; (4) above-mentioned sample is put into autoclave, preliminary filling N
2To 2.1MPa, be heated to 280 ℃ with the speed of 1.5 ℃/min, be incubated after 2 hours, keep temperature-resistant, with the slow relief pressure of speed of 50KPa/min, to normal pressure, with N
2Dash and swept autoclave 30 minutes, powered-down makes its naturally cooling, obtains Si-C-O aerogel precursor composite material; (5) Si-C-O aerogel precursor composite material is put into high-temperature cracking furnace, charge into N
2, being warming up to 1200 ℃ and constant temperature 1 hour with the speed of 5 ℃/min, powered-down is cooled to room temperature.Promptly obtain the Si-C-O aerogel heat-proof composite material.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 168m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.45g/cm
3, 800 ℃ of thermal conductivities are 0.032W/mK, and 1000 ℃ of thermal conductivities are 0.043W/mK, and bending strength is 2.6MPa, and tensile strength is 1.38MPa, ultimate compression strength 4.9MPa(deformation quantity is 50% o'clock).
Embodiment 2
The present embodiment product is made of carbon fiber and Si-C-O aerogel.
Fibrefelt is that volume fraction is 8% carbon fiber felt, and the carbon fiber diameter is 7mm, and in addition all the other processes are identical with embodiment 1.
The Si-C-O aerogel specific surface area of gained is 217m/g
2, the Si-C-O aerogel heat-proof composite material bending strength of gained is 2.4MPa, and 1200 ℃ of thermal conductivities are 0.051W/mK, and 1200 ℃ of thermal treatments are after 2 hours, and the material contracts rate is 4.8%.
Embodiment 3
The present embodiment product is made of aluminum silicate fiber and Si-C-O aerogel.
Fibrefelt is that volume fraction is 7% alumina silicate fiber felt, and the aluminum silicate fiber diameter is 10mm, and in addition all the other processes are identical with embodiment 1.
The Si-C-O aerogel heat-proof composite material tensile strength of gained is 1.45MPa, and 1000 ℃ of thermal conductivities are 0.044W/mK.
Embodiment 4
The present embodiment fibrefelt is that volume fraction is 8% mullite fiber felt, and in addition all the other processes are identical with embodiment 1.
The Si-C-O aerogel heat-proof composite material bending strength of gained is 2.18MPa, and 900 ℃ of thermal conductivities are 0.038W/mK, and 1200 ℃ of thermal conductivities are 0.055W/mK.
Embodiment 5
The present embodiment product is made of silicon carbide fiber and Si-C-O aerogel.
Fibrefelt is that volume fraction is 7.5% silicon carbide fiber felt, and the silicon carbide fiber diameter is 10mm, and in addition all the other processes are identical with embodiment 1.
The Si-C-O aerogel heat-proof composite material bending strength of gained is 2.36MPa, and ultimate compression strength 4.3MPa(deformation quantity is 50% o'clock), 1200 ℃ of thermal conductivities are 0.058W/mK, and 1200 ℃ of thermal treatments are after 2 hours, and the material contracts rate is 4.5%.
Embodiment 6
The present embodiment product is made of Zirconium oxide fibre and Si-C-O aerogel.
Fibrefelt is that volume fraction is 6.8% Zirconium oxide fibre, and the Zirconium oxide fibre diameter is 3mm, and in addition all the other processes are identical with embodiment 1.
The Si-C-O aerogel specific surface area of gained is 325m/g
2, the Si-C-O aerogel heat-proof composite material bending strength of gained is 1.75MPa, ultimate compression strength 3.9MPa(deformation quantity is 50% o'clock), 1200 ℃ of thermal conductivities are 0.053W/mK.
Embodiment 7
The present embodiment product is made of Zirconium oxide fibre and Si-C-O aerogel.
Fibrefelt is that volume fraction is 2% Zirconium oxide fibre, and the Zirconium oxide fibre diameter is 3mm, and in addition all the other processes are identical with embodiment 1.
The Si-C-O aerogel specific surface area of gained is 325m/g
2, the Si-C-O aerogel heat-proof composite material bending strength of gained is 1.35MPa, ultimate compression strength 2.0MPa(deformation quantity is 50% o'clock), 1200 ℃ of thermal conductivities are 0.051W/mK.
Embodiment 8
Methyl silicate is adopted in present embodiment silicon source, and in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 166m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.43g/cm
3, 800 ℃ of thermal conductivities are 0.037W/mK, and 1000 ℃ of thermal conductivities are 0.047W/mK, and bending strength is 2.6MPa, and tensile strength is 1.39MPa.
Embodiment 9
The present embodiment carbon source adopts dimethyldimethoxysil,ne, and in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 188m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.40g/cm
3, 800 ℃ of thermal conductivities are 0.036W/mK, and 1000 ℃ of thermal conductivities are 0.045W/mK, and bending strength is 2.5MPa, and tensile strength is 1.33MPa.
Embodiment 10
The present embodiment alcoholic solvent adopts Virahol, and the mol ratio of silicon source and Virahol is 1:30, and in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 165m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.33g/cm
3, 800 ℃ of thermal conductivities are 0.045W/mK, and 1000 ℃ of thermal conductivities are 0.050W/mK, and bending strength is 1.02MPa, and tensile strength is 1.11MPa.
Embodiment 11
The present embodiment acid catalyst is selected nitric acid for use, and alkaline catalysts is selected urea for use, and the mol ratio of silicon source and nitric acid is 1:8 * 10
-3, the mol ratio of silicon source and urea is 1:6 * 10
-2, in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 188m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.43g/cm
3, 800 ℃ of thermal conductivities are 0.037W/mK, and 1000 ℃ of thermal conductivities are 0.046W/mK, and bending strength is 2.3MPa, and tensile strength is 1.25MPa.
Embodiment 12
Present embodiment silicon source and alcoholic acid mol ratio are 1:2, and in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 201m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.54g/cm
3, 800 ℃ of thermal conductivities are 0.065W/mK, and 1000 ℃ of thermal conductivities are 0.078W/mK, and bending strength is 4.3MPa, and tensile strength is 3.6MPa.
Embodiment 13
The mol ratio of present embodiment silicon source and carbon source is 1:2, and in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 176m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.32g/cm
3, 800 ℃ of thermal conductivities are 0.045W/mK, and 1000 ℃ of thermal conductivities are 0.056W/mK, and bending strength is 1.9MPa, and tensile strength is 2.1MPa.
Embodiment 14
The volume fraction of present embodiment mullite fiber is 15%, and in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 167m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.44g/cm
3, 800 ℃ of thermal conductivities are 0.049W/mK, and 1000 ℃ of thermal conductivities are 0.058W/mK, and bending strength is 2.9MPa, and tensile strength is 3.8MPa.
Embodiment 15
50 ℃ of present embodiment aging temperatures, digestion time 1 day, in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 171m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.43g/cm
3, 800 ℃ of thermal conductivities are 0.033W/mK, and 1000 ℃ of thermal conductivities are 0.045W/mK, and bending strength is 2.8MPa, and tensile strength is 1.4MPa.
Embodiment 16
The present embodiment cracking temperature is 900 ℃, cracking soaking time 4 hours, and in addition all the other processes are identical with embodiment 1.
The Si-C-O aerogel specific surface area of gained is 171m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.41g/cm
3, 800 ℃ of thermal conductivities are 0.031W/mK, and 1000 ℃ of thermal conductivities are 0.039W/mK, and bending strength is 2.1MPa, and tensile strength is 1.1MPa.
Embodiment 17
The present embodiment cracking temperature is 1500 ℃, cracking soaking time 1 hour, and in addition all the other processes are identical with embodiment 1.
1200 ℃ of thermal treatments of the Si-C-O aerogel of gained are after 2 hours, and specific surface area is 156m/g
2, the Si-C-O aerogel heat-proof composite material density of gained is 0.47g/cm
3, 800 ℃ of thermal conductivities are 0.040W/mK, and 1000 ℃ of thermal conductivities are 0.048W/mK, and bending strength is 2.5MPa, and tensile strength is 1.7MPa.
Claims (6)
1. the preparation method of a high temperature resistant Si-C-O aerogel heat-proof composite material is characterized in that, may further comprise the steps:
(1) preparation of Si-C-O aerogel precursor body colloidal sol
Silicon source, carbon source are mixed with alcoholic solvent and deionized water, stir, successively add bronsted lowry acids and bases bronsted lowry catalysis again, make silicon source and carbon source issue at acid and alkaline condition respectively that unboiled water is separated and polycondensation, obtain containing in the network structure Si-C-O aerogel precursor body colloidal sol of Si, C, three kinds of elements of O, the mol ratio of described silicon source, carbon source, alcoholic solvent, deionized water, acid catalyst and alkaline catalysts is 1: 0.1-10: 2-30: 2-12: 1.0 * 10
-3-8.0 * 10
-3: 1.0 * 10
-2-6 * 10
-2
(2) mix
Step (one) gained Si-C-O aerogel precursor body colloidal sol is added in fibrefelt or the prefabricated component, makes it to mix with fibrefelt or prefabricated component, at room temperature leave standstill 1-10 hour after, the formation gel obtains fiber and gel mixture;
(3) aging
Step (two) gained fiber and gel mixture adding alcoholic solvent are worn out, and the alcoholic solvent add-on is wanted to cover fiber and gel mixture surface, aging temperature 25-50 ℃, digestion time 1-3 days;
(4) supercritical drying
To carry out supercritical fluid drying through step (three) aged fiber and gel mixture, obtain Si-C-O aerogel precursor composite material;
(5) Pintsch process
The Si-C-O aerogel precursor composite material that will obtain behind step (four) supercritical drying is under inert atmosphere protection; carry out Pintsch process; the rearrangement reaction of Si-C-O aerogel precursor body generation scission of link, the final Si-C-O aerogel heat-proof composite material that generates with the amorphous network structure of Si-C-O and uncombined carbon structure.
2. the preparation method of high temperature resistant Si-C-O aerogel heat-proof composite material as claimed in claim 1 is characterized in that, described silicon source is a kind of tetraalkoxysilane Si (OR
1)
4, R wherein
1It is the group of the saturated or unsaturated 1-12 of comprising carbon atom;
Described carbon source is a kind of dialkoxy silicane (R
2O)
2-Si-R
4R
3, R wherein
2Be the group of the saturated or unsaturated 1-12 of comprising carbon atom, R
4, R
3Be similar or different group alkyl, haloalkene alkyl, aryl, alkaryl or the aralkyl of the saturated or unsaturated 1-12 of comprising carbon atom; Perhaps, R
3, R
4In one be hydrogen atom;
Described alcoholic solvent is one or more the arbitrary proportion mixture in methyl alcohol, ethanol, propyl alcohol, Virahol, the butanols;
Described acid catalyst is hydrochloric acid, nitric acid, sulfuric acid, oxalic acid or acetate;
Described alkaline catalysts is ammoniacal liquor, sodium hydroxide, potassium hydroxide or urea.
3. the preparation method of high temperature resistant Si-C-O aerogel heat-proof composite material as claimed in claim 1 or 2 is characterized in that, described tetraalkoxysilane Si (OR
1)
4Be methyl silicate or tetraethoxy; Described dialkoxy silicane (R
2O)
2-Si-R
4R
3It is the mixture of two or more arbitrary proportions in dimethyldiethoxysilane, methyldiethoxysilane, methyl dimethoxysilane, dimethyldimethoxysil,ne, diethyl dibutoxy silane, dihexyl dimethoxy silane, dialkylene methyldiethoxysilane or above each material.
4. the preparation method of high temperature resistant Si-C-O aerogel heat-proof composite material as claimed in claim 1 or 2, it is characterized in that, described fibrefelt of step (two) or prefabricated component are cellucotton, tapetum fibrosum, fiberboard or fiber preform, and the fiber volume fraction of fibrefelt or prefabricated component is 2%-15%.
5. the preparation method of high temperature resistant Si-C-O aerogel heat-proof composite material as claimed in claim 1 or 2, it is characterized in that, described fiber is to be selected from two or more combination in a kind of or above fiber of carbon fiber, pre-oxygen silk, sapphire whisker, Zirconium oxide fibre, silica fiber, mullite fiber, aluminum silicate fiber, silicon carbide fiber, high silica fiber, and the diameter of described fiber is 3-10 μ m.
6. the preparation method of high temperature resistant Si-C-O aerogel heat-proof composite material as claimed in claim 1 or 2 is characterized in that, the described inert atmosphere of step (five) is N
2, Ar or He gas, cracking temperature is 900 ℃-1500 ℃, the inert protective gas flow velocity is 100-600mL/min during cracking, soaking time is 1-4 hour.
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