CN104261798B - A kind of high temperature resistant SiCOB aerogel heat-proof composite material and preparation method thereof - Google Patents
A kind of high temperature resistant SiCOB aerogel heat-proof composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high temperature resistant SiCOB aerogel heat-proof composite material and preparation method thereof.High temperature resistant SiCOB aerogel heat-proof composite material is made up of with SiCOB aeroges high temperature resistant inorganic ceramic fibre；High temperature resistant inorganic ceramic fibre, SiCOB aeroges volumn concentration are respectively 20～70%, 30 80%.Preparation method is：SiCOB organic precursor colloidal sols are prepared, fiber preform is prepared, fiber preform is mixed with colloidal sol, after body gel to be mixed, SiCOB aerogel composite presomas are obtained after aging, supercritical drying, aerogel heat-proof composite material presoma is carried out Pintsch process again, high temperature resistant, anti-oxidant SiCOB aerogel heat-proof composite materials is obtained.Thermal conductivity of composite materials of the present invention is low, and high temperature insulating performance is good, and heat resistance and pyro-oxidation resistance are significantly improved, and maximum operation (service) temperature is up to 1500 DEG C；Preparation method low cost, non-environmental-pollution.
Description
Technical field
The invention belongs to heat-barrier material technical field, is related to a kind of heat-insulation composite material and preparation method thereof, more particularly to
A kind of high temperature resistant, anti-oxidant SiCOB aerogel heat-proof composite materials and preparation method thereof.
Background technology
As new aerospace craft flying speed is improved constantly, the flight time constantly extends, and it is pneumatic that aircraft stands
Heating environment very severe, the accumulative Aerodynamic Heating in surface are extremely serious, and the thermal protection system of aircraft is to excellent in mechanical performance, light
Matter, high temperature resistant, the anti-heat-barrier material of effectively insulating propose urgent demand.
Aerogel heat-proof composite material is as a kind of novel heat insulation material, each because being subject to the features such as its lightweight, effectively insulating
The favor of state aeronautical field investigation of materials person, especially siloxy aerogel material have obtained extensive research and application.?
In siloxy aerogel material, SiCO aeroges are the more important aerogel materials of a class, and the Si atoms in its structure are while and C
Atom is connected with O atom, relative to SiO2For aeroge, the part divalence O atom in silica network structure is by tetravalence C atom
Firm tetrahedron molecular structure is formed after replacement, can strengthen aeroge network structure, improve calorifics and the power of aerogel material
Learn performance.But SiCO aeroges are at 1000 DEG C or so, start generation carbothermic reduction reaction in the environment that oxygen is present and cause airsetting
The decomposition of plastic structure, have impact on its effect of heat insulation, Zhao Nan【Zhao Nan. silicate journal, 2012,40 (10), 1473-1477】、
Manuel W【Manuel W.Chemistry of.Materials,2010,22,1509-1520】And Chinese patent
【ZL201110110947.4】SiCO aerogel block body materials Deng report are oxidized in 1000 DEG C of aerobic environments.Temperature tolerance
The poor application for limiting SiCO aerogel materials of not high, high temperature oxidation resistance.
How to improve the temperature tolerance of aerogel heat-proof composite material, high temperature oxidation resistance is this to improve high temperature insulating effect
The technical problem that art personnel extremely pay close attention to.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of high temperature resistant SiCOB aerogel heat-proof composite material and its system
Preparation Method.The heat-insulation composite material matrix be SiCOB aeroges, reinforcement be high temperature resistant inorganic ceramic fibre, with high temperature resistant,
The features such as lightweight, lower thermal conductivity, resistance to high temperature oxidation, maximum operation (service) temperature, can meet new aerospace craft heat up to 1500 DEG C
The requirements at the higher level that guard system is proposed.
The technical scheme is that：
High temperature resistant SiCOB aerogel heat-proof composite material of the present invention is by high temperature resistant inorganic ceramic fibre and SiCOB aeroges
Composition.The heat resistance of wherein high temperature resistant inorganic ceramic fibre requires to reach more than 1500 DEG C, SiCOB aeroges be a kind of by
The solid material with three-dimensional net structure that tetra- kinds of elements of Si, C, O, B are constituted with any component, with lightweight, high temperature resistant, low
The characteristics of thermal conductivity.SiCOB aeroges are uniformly filled in the space of inorganic ceramic fiber, and both intact combinations are one
Rise.The volumn concentration of high temperature resistant inorganic ceramic fibre accounts for the 20～70% of high temperature resistant SiCOB aerogel heat-proof composite material
(including end points), the volumn concentration of SiCOB aeroges account for high temperature resistant SiCOB aerogel heat-proof composite material 30-80% (bags
Include end points).Both organically combine, it is ensured that SiCOB aerogel heat-proof composite materials have good high temperature insulating
Energy and mechanical property.
High temperature resistant SiCOB aerogel heat-proof composite material preparation method of the present invention is：Prepare SiCOB organic precursors molten
Glue, prepare fiber preform, fiber preform is mixed with colloidal sol, after body gel to be mixed, through aging, supercritical drying
After obtain SiCOB aerogel composite presomas, then aerogel heat-proof composite material presoma is carried out Pintsch process, you can
Obtain high temperature resistant, anti-oxidant SiCOB aerogel heat-proof composite materials.Comprise the following steps that：
The first step, prepares SiCOB precursor sols
First silicon source, carbon source, acidic catalyst are mixed 1～6 hour under room temperature (10-30 DEG C) so as to fully
Hydrolysis；Add boron source to stir 2～8 hours so as to polycondensation reaction occurs, obtains SiCOB precursor sols, the silicon source, carbon
Source, boron source, the mol ratio of acidic catalyst are：1：0.1～10：0.05～2：0.0005～0.010；
Described silicon source is a kind of tetraalkoxysilane Si (OR1)4(wherein R1It is saturation or unsaturated comprising 1-12
The group of individual carbon atom), such as methyl silicate, tetraethyl orthosilicate；
It is R that described carbon source is a kind of structural formula2 nSi(OR3)4-nOrganosiloxane (wherein n=1,2 or 3, R2、R3
One or more different structure saturation or unsaturated group comprising 1-6 carbon atoms can be represented, including alkyl,
Haloalkene alkyl, aryl；R2、R3One of them can also be hydrogen atom), such as MTMS, dimethylformamide dimethyl epoxide
Silane, divinyl diethoxy silane, and the mixture that each material is dissolved each other with any ratio above；
It is B (OR that described boron source can be structural formula4)3Orthoboric acid ester (wherein R4One or more can be represented
Different structure saturation or unsaturated group comprising 1-12 carbon atoms) such as trimethylborate, triethyl borate；Also may be used
To be structural formula as R5 nB(OR6)3-nMetaboric acid ester (wherein n=1 or 2, R5、R6One or more can be represented
Different structure saturation or unsaturated group comprising 1-12 carbon atoms, including alkyl, haloalkene alkyl, aryl, alkaryl,
Aralkyl etc.), such as diethylmethoxyborane, vinyl diethoxy borine；
The silicon source, carbon source, the mol ratio preferably 1.0: 0.5～2 of boron source：0.5～1；
The acidic catalyst can be hydrochloric acid, nitric acid, sulfuric acid, oxalic acid or acetic acid, as the price of hydrochloric acid is relatively low, use
Get up comparatively safe, preferably hydrochloric acid, wherein, silicon source and acidic catalyst mol ratio preferably 1.0: 0.001～0.005；
Second step, prepares fiber preform
Design fiber preform apparent density scope is 0.05～0.40g/cm3, that is, the inorganic ceramic fiber that selects is apparent
Density range is 0.05～0.40g/cm3, using quality=density × volume, needed for calculating, inorganic ceramic fiber quality, prefabricated
The volume of part is determined by mould；Quality by gained is calculated weighs inorganic ceramic fiber, and the shape and specification according to mould is to fibre
Dimension is arranged, and makes fiber architecture direction perpendicular to direction of heat flow during heat-insulated use, then with mould by the fiber that arranges
Grip, obtain fiber preform；
Inorganic ceramic kinds of fibers in the above fiber preform can be carbon fiber, alumina fibre, zirconium oxide
One or two kinds of combination of the above in fiber, mullite fiber, silicon carbide fibre and above-mentioned fiber；
The apparent density preferably 0.15～0.25g/cm of the inorganic ceramic fiber3；
3rd step, prepares gel/fiber preform mixture
The fiber preform that second step is obtained is placed in the impregnating autoclave of sealing, is vacuumized, vacuum be 0.03～
0.005MPa, impregnates SiCOB precursor sols under vacuum conditions, is slowly added to SiCOB precursor sols, treats SiCOB forerunner
Body colloidal sol is completely immersed in fiber preform, opens valve and causes the pressure in container to be changed into normal pressure, quiet under room temperature (10-30 DEG C)
After putting 2～30 hours, the SiCOB precursor sols in fiber preform become gel, obtain gel/fiber preform mixing
Body；
4th step, gel/fiber preform mixture are aging：
Gel/fiber preform mixture is sealed, is stored at room temperature, reached aging purpose, ageing time is 0.5
～7 days；
5th step, supercritical drying treatment gel/fiber preform mixture：
The gel that 4th step is obtained/fiber preform mixture carries out supercritical fluid drying process, wherein shooting flow
Body dried medium is ethanol, propyl alcohol or isopropanol, and gel/fiber preform mixture is put into supercritical fluid by preferred alcohol
In drying equipment, the nitrogen of 0.3～2.2MPa of preliminary filling, then 240～260 DEG C are heated to 0.5～3 DEG C/min speed, insulation 0.5
～2 hours, then pressure is slowly discharged with 40～80kPa/min speed, finally with N2Punching is swept 30～90 minutes, and obtaining SiCOB has
Machine precursor gas gel complex material；
6th step, Pintsch process SiCOB organic precursor aerogel composites：
SiCOB organic precursor aerogel composites are put in pyrolysis furnace, is filled with the slumpability gas of certain flow rate
Body, under inert atmosphere protection, is warming up to cracking temperature, held for some time with certain heating rate so as to which cracking occurs
Scission of link rearrangement reaction, ultimately generates the fiber reinforcement with the amorphous network structure of Si-C-O, Si-O-B and free carbon structure
SiCOB aerogel heat-proof composite materials；
Wherein, the inert gas can be N2, Ar or He.Cracking temperature is 950 DEG C～1600 DEG C, indifferent gas during cracking
Rate of flow of fluid is 50～400mL/min, and heating rate is 2～10 DEG C/min, and temperature retention time is 0.5～3 hour.
Following beneficial effect can be reached using the present invention：
The present invention adopts sol-gel process, and silicon source, carbon source are fully hydrolyzed in sour environment, adds shape after boron source
Into the sol system containing tetra- kinds of elements of Si, C, O, B, then which is combined with high-temperature fibre, by gel, aging, overcritical
The techniques such as drying, Pintsch process obtain fiber reinforcement SiCOB aerogel heat-proof composite materials.
Therefore the fiber reinforcement SiCOB aerogel heat-proof composite materials that prepared by the present invention have the advantage that；
(1) heat resistance and pyro-oxidation resistance are significantly improved.In the preparation method first step of the present invention, by adding
Boron source introduces B atoms in SiCO structures, and sol phase forms the network structure of Si-O-B, by gel process, forms Si-C-
The three-dimensional net structure of O-B high molecular polymers, obtains the SiCOB aeroges of inorganic states after the 6th step Pintsch process,
The formation of Si-O-B bridging keys can effectively prevent SiO2Crystallization, overcome SiO2, collapse at high temperature by pore structure for SiCO aeroges
Fall into, complicated stable SiCOB three-dimensional net structures can improve the high-temperature oxidation resistance of material, materials'use temperature can reach
1500 DEG C, SiCOB aerogel heat-proof composite materials are heat-treated 1h in 1500 DEG C of aerobic environments, and the outward appearance of material is unchanged, put down
Face direction ungauged regions, thickness direction shrinkage factor are less than 3%.
(2) thermal conductivity factor is low, and high temperature insulating performance is good.The SiCOB prepared by sol-gel, supercritical drying process
Aeroge has three-dimensional net structure, and density is low, aperture is little, has good iris action to solid heat transfer and gas heat-transfer, and B is former
Son is introduced into cause the atomic distance in aeroge nanometer skeleton diminishes, mean free path of phonons reduction, contribute to reduction solid-state
Thermal conductivity；The free C and SiC nanometers crystalline phase that SiCOB aeroges itself are present simultaneously is conducive to raising aeroge high temperature to block
Infra-red radiation ability, can effectively reduce high-temperature heat conductivity.In addition the high temperature resistant inorganic ceramic fibre reinforced material that the present invention is adopted
There is certain absorption and scattering power at high temperature to infra-red radiation, it is possible to decrease radiant heat transfer, further reduce the height of material
Warm conduction.The SiCOB aerogel composites that the present invention is obtained in 1000 DEG C, 1200 DEG C, 1500 DEG C of minimum thermal conductivity are
0.056W/m·K、0.089W/m·K、0.325W/m·K；
(3) low cost, non-environmental-pollution.The present invention is that acid is catalyst with organosiloxane and borate as raw material
SiCOB presomas are prepared, raw produce is cheap；The stage is prepared in the first step colloidal sol of technological approaches, it is not necessary to add and appoint
What solvent, raw material availability are high, can further reduce production cost, without waste liquid, therefore, not produce any environmental pollution；Additionally,
The byproduct emission of the equal nonpollution environment of technical process such as gel, aging, supercritical drying, Pintsch process, is suitable for industrial production.
Specific embodiment
Below for the invention will be further described in conjunction with the embodiments, but these embodiments must not be used for explaining to the present invention
The restriction of protection domain.
Embodiment 1
The present embodiment product is made up of with SiCOB aeroges carbon fiber.
(1) colloidal sol is prepared：It is 1: 1 in molar ratio by tetraethyl orthosilicate, dimethyldiethoxysilane, hydrochloric acid first:
0.0025；Mix 1 hour at room temperature, silicon source and carbon source is fully hydrolyzed in sour environment；It is subsequently adding orthoboric acid
Methyl esters, continues stirring 2 hours, obtains SiCOB precursor sols；
(2) prepared by fiber preform：Design fiber preform apparent density is 0.15g/cm3, according to quality=volume ×
Density, calculates fiber quality, weighs carbon fiber, make fiber architecture direction perpendicular to direction of heat flow during heat-insulated use, use mould
Fiber is gripped, carbon fiber preform is obtained；
(3) gel/fiber preform mixture is prepared：Fiber preform is placed in the impregnating autoclave of sealing, is vacuumized
It is 0.005Mpa to vacuum, is slowly added to SiCOB aerogel precursor body colloidal sols, makes colloidal sol be totally immersed in fiber preform
In, open valve and cause the pressure in container to be changed into normal pressure, after standing 2 hours at room temperature, the colloidal sol in fiber preform becomes
Into gel, gel/fiber preform mixture is obtained；
(4) gel/fiber preform mixture is aging：Gel/fiber preform mixture is sealed, aging at room temperature
0.5 day；
(5) supercritical fluid drying treatment gel/fiber preform mixture：With absolute ethyl alcohol or isopropanol as overcritical
Fluid drying medium, fibre reinforced SiCOB presoma wet gel complexs is put in supercritical fluid drying equipment, preliminary filling
The nitrogen of 0.3MPa, then 240 DEG C are heated to 0.5 DEG C/min speed, 0.5 hour is incubated, then is slowly released with 40kPa/min speed
Power is bled off pressure, finally with N2Punching is swept 30 minutes, obtains SiCOB organic precursor aerogel composites；
(6) SiCOB organic precursor aerogel composites are put in high-temperature cracking furnace, are filled with high-purity argon gas, air-flow
Speed be 50mL/min, 950 DEG C and constant temperature 3 hours are warming up to the speed of 2 DEG C/min, power supply are closed, is cooled to room temperature.I.e.
Obtain SiCOB aerogel heat-proof composite materials.The density of the carbon fiber reinforced SiCOB aerogel heat-proof composite materials of gained is
0.49g/cm3, 1h is heat-treated in 1500 DEG C of aerobic environments, the outward appearance of material is unchanged, parallel fibers direction ungauged regions, vertically
Machine direction shrinkage factor is 1.53%, and 1000 DEG C of thermal conductivities are 0.059W/m K, and 1200 DEG C of thermal conductivities are 0.092W/m K,
1500 DEG C of thermal conductivities are 0.331W/m K.
Embodiment 2
The present embodiment product is made up of with SiCOB aeroges mullite fiber.
(1) colloidal sol is prepared：It is 1: 1 in molar ratio by tetraethyl orthosilicate, dimethyldiethoxysilane, hydrochloric acid first:
0.0009；Mix 6 hours at room temperature, silicon source and carbon source is fully hydrolyzed in sour environment；It is subsequently adding orthoboric acid
Methyl esters, continues stirring 8 hours, obtains SiCOB precursor sols；
(2) prepared by fiber preform：Design fiber preform apparent density is 0.25g/cm3, according to quality=volume ×
Density, calculates fiber quality, weighs carbon fiber, make fiber architecture direction perpendicular to direction of heat flow during heat-insulated use, use mould
Fiber is gripped, carbon fiber preform is obtained；
(3) gel/fiber preform mixture is prepared：Fiber preform is placed in the impregnating autoclave of sealing, is vacuumized
It is 0.03MPa to vacuum, is slowly added to SiCOB aerogel precursor body colloidal sols, colloidal sol is totally immersed in fiber preform,
Opening valve causes the pressure in container to be changed into normal pressure, and after standing 30 hours at room temperature, the colloidal sol in fiber preform becomes
Gel, obtains gel/fiber preform mixture；
(4) gel/fiber preform mixture is aging：Gel/fiber preform mixture is sealed, aging at room temperature
7 days；
(5) supercritical fluid drying treatment gel/fiber preform mixture：With absolute ethyl alcohol or isopropanol as overcritical
Fluid drying medium, fibre reinforced SiCOB presoma wet gel complexs is put in supercritical fluid drying equipment, preliminary filling
The nitrogen of 2.2MPa, then 260 DEG C are heated to 3 DEG C/min speed, 2 hours are incubated, then pressure is slowly discharged with 80kPa/min speed
Power, finally with N2Punching is swept 90 minutes, obtains SiCOB organic precursor aerogel composites；
(6) SiCOB organic precursor aerogel composites are put in high-temperature cracking furnace, are filled with high-purity argon gas, air-flow
Speed be 400mL/min, 1600 DEG C and constant temperature 0.5 hours are warming up to the speed of 10 DEG C/min, power supply are closed, is cooled to room
Temperature.SiCOB aerogel heat-proof composite material is obtained.The carbon fiber reinforced SiCOB aerogel heat-proof composite materials of gained
Density is 0.47g/cm3, 1h is heat-treated in 1500 DEG C of aerobic environments, the outward appearance of material is unchanged, and parallel fibers direction is without receipts
Contracting, vertical fibers direction shrinkage factor are 1.49%, and 1000 DEG C of thermal conductivities are 0.054W/m K, and 1200 DEG C of thermal conductivities are 0.089W/
M K, 1500 DEG C of thermal conductivities are 0.329W/m K.
Embodiment 3
The present embodiment product is made up of with SiCOB aeroges Zirconium oxide fibre.
(1) colloidal sol is prepared：It is 1: 1 in molar ratio by tetraethyl orthosilicate, dimethyldiethoxysilane, hydrochloric acid first:
0.0075；Mix 3 hours at room temperature, silicon source and carbon source is fully hydrolyzed in sour environment；It is subsequently adding orthoboric acid
Methyl esters, continues stirring 4 hours, obtains SiCOB precursor sols；
(2) prepared by fiber preform：Design fiber preform apparent density is 0.15g/cm3, according to quality=volume ×
Density, calculates fiber quality, weighs Zirconium oxide fibre, makes fiber architecture direction perpendicular to direction of heat flow during heat-insulated use, uses
Fiber is gripped by mould, obtains carbon fiber preform；
(3) gel/fiber preform mixture is prepared：Fiber preform is placed in the impregnating autoclave of sealing, is vacuumized
It is 0.01Mpa to vacuum, is slowly added to SiCOB aerogel precursor body colloidal sols, colloidal sol is totally immersed in fiber preform,
Opening valve causes the pressure in container to be changed into normal pressure, and after standing 15 hours at room temperature, the colloidal sol in fiber preform becomes
Gel, obtains gel/fiber preform mixture；
(4) gel/fiber preform mixture is aging：Gel/fiber preform mixture is sealed, aging at room temperature
3 days；
(5) supercritical fluid drying treatment gel/fiber preform mixture：With absolute ethyl alcohol or isopropanol as overcritical
Fluid drying medium, fibre reinforced SiCOB presoma wet gel complexs is put in supercritical fluid drying equipment, preliminary filling
The nitrogen of 1.0MPa, then 255 DEG C are heated to 2 DEG C/min speed, 1.5 hours are incubated, then are slowly discharged with 60kPa/min speed
Pressure, finally with N2Punching is swept 60 minutes, obtains SiCOB organic precursor aerogel composites；
(6) SiCOB organic precursor aerogel composites are put in high-temperature cracking furnace, are filled with high-purity argon gas, air-flow
Speed be 200mL/min, 1200 DEG C and constant temperature 1 hours are warming up to the speed of 5 DEG C/min, power supply are closed, is cooled to room temperature.
SiCOB aerogel heat-proof composite material is obtained.The density of the carbon fiber reinforced SiCOB aerogel heat-proof composite materials of gained
For 0.49g/cm3, 1h is heat-treated in 1500 DEG C of aerobic environments, the outward appearance of material is unchanged, and parallel fibers direction ungauged regions hang down
Fibers straight direction shrinkage factor is 1.61%, and 1000 DEG C of thermal conductivities are 0.052W/m K, and 1200 DEG C of thermal conductivities are 0.094W/m K,
1500 DEG C of thermal conductivities are 0.354W/m K.
Embodiment 4～648
Hydrochloric acid, nitric acid, sulfuric acid, oxalic acid or acetic acid can be added during first step colloidal sol is prepared, add acid main
Be control collosol PH value, acid species on the performance of material without impact, it is therefore an objective to make silicon source and carbon source abundant in acid condition
Hydrolysis, afterwards, adds silicon source and carbon source after boron source, with hydrolysis to crosslink polycondensation reaction, forms gel, and the time of gel takes
Certainly in the speed of three's cross-linked polymeric, gel time is 2-30 hours.During colloidal sol is prepared, mixing time only affects work
The skill time, material property is not affected.When second step prepares fiber preform, any one above-mentioned fiber can be selected, fine
The size of the species and apparent density of dimension is had an impact to composite materials property, to composite heat resistance, thermal conductivity and
The impact very little of material processability.To impregnating autoclave in the 3rd step fiber preform with SiCOB precursor sol recombination processes
In vacuumize be in order that colloidal sol and fiber preform fully, homogeneous immersion, as long as keeping certain vacuum just make colloidal sol
, homogeneous impregnation complete with fiber；4th step ageing process, is that crosslinking condensation degree of dissolved is completeer in order that gel is further stabilized
Entirely, keep enough Sealing period it is ensured that gel aging, ageing time to the temperature tolerance of material and thermal conductivity substantially without
Affect, have minor impact to the mechanical property of composite；Pre- inflated with nitrogen and intensification in the 5th step supercritical drying process
It is that and temperature retention time reach in kettle to be allowed in order to reach the above-critical state of absolute ethyl alcohol (6MPa, 248 DEG C) to 240～260 DEG C
Arrive overcritical balance.The speed for sweeping speed with nitrogen punching of finally deflating simply affects the process time, to composite property without bright
Development rings.During the 6th step Pintsch process, be filled with inert gas be in order to prevent cracking reset process there are other
Side reaction, it is heating rate and temperature retention time in order that organic precursor is sufficiently inorganization that temperature will reach more than 950 DEG C
Performance on material is substantially without impact.Therefore, above acidic catalyst species, the species of fiber and apparent density, dipping when
Vacuum and ageing time, supercritical drying condition are not produced to the temperature tolerance of SiCOB aerogel heat-proof composite materials and thermal conductivity
Raw decisive influence, as long as selecting in the scope described in content of the invention, can prepare the little SiCOB airsettings of performance difference
Glue heat-insulation composite material.SiCOB aerogel heat-proof composite materials performances is produced affect mainly have silicon source, carbon source, boron source
Species, and silicon source, carbon source, boron source, the mole of acid, the technological parameter adopted by embodiment 4～648 are as shown in table 1, wherein,
Example 4-280 is implemented according to the technological parameter of example 1, and example 281-469 is implemented according to the technological parameter of example 2, example 470-
648 implement according to the technological parameter of example 3, and due to sour species on the performance of material without impact, therefore embodiment 4～648 is equal
Using hydrochloric acid, in table, not listed experimental process parameters are same as Example 1.
Table 1SiCOB aerogel heat-proof composite materials preparation technology parameter and material property parameter
Claims (11)
1. a kind of preparation method of high temperature resistant SiCOB aerogel heat-proof composite material, it is characterised in that comprise the following steps：
The first step, prepares SiCOB precursor sols：
Silicon source, carbon source, acidic catalyst are mixed 1～6 hour at 10-30 DEG C so as to be fully hydrolyzed；Add boron source
Stirring 2～8 hours so as to polycondensation reaction occurs, obtains SiCOB precursor sols, the silicon source, carbon source, boron source, acidic catalyst
The mol ratio of agent is：1：0.1～10：0.05～2：0.0005～0.010；
The silicon source is a kind of tetraalkoxysilane Si (OR1)4, wherein R1It is saturation or unsaturated former comprising 1-12 carbon
The group of son；
It is R that the carbon source is a kind of structural formula2 nSi(OR3)4-nOrganosiloxane, wherein n=1,2 or 3, R2、R3Represent one
Plant or two or more different structure saturations or unsaturated group comprising 1-6 carbon atom；Or R2、R3One of them is
Hydrogen atom；
It is B (OR that the boron source is structural formula4)3Orthoboric acid ester, wherein R4It is saturation or unsaturated comprising 1-12 carbon atoms
Group；Boron source or structural formula are R5 nB(OR6)3-nMetaboric acid ester, wherein n=1 or 2, R5、R6Represent one or two
Above different structure saturation or unsaturated group comprising 1-12 carbon atom；
The acidic catalyst is hydrochloric acid, nitric acid, sulfuric acid, oxalic acid or acetic acid；
Second step, prepares fiber preform：
Design fiber preform apparent density scope is 0.05～0.40g/cm3, that is, the inorganic ceramic fiber apparent density model selected
Enclose for 0.05～0.40g/cm3, inorganic ceramic fiber quality needed for being calculated using quality=density × volume, fiber preform
Volume is determined by mould；Quality by gained is calculated weighs inorganic ceramic fiber, fiber is entered according to the shape and specification of mould
Row is arranged, and is made fiber architecture direction perpendicular to direction of heat flow during heat-insulated use, is then clamped the fiber that arranges with mould
Fixed, obtain fiber preform；
The inorganic ceramic kinds of fibers is carbon fiber, alumina fibre, Zirconium oxide fibre, mullite fiber, silicon carbide fibre
In one or two kinds of combination of the above；3rd step, prepares gel/fiber preform mixture：
The fiber preform that second step is obtained is placed in the impregnating autoclave of sealing, is vacuumized, impregnate SiCOB under vacuum conditions
Precursor sol, is slowly added to SiCOB precursor sols, treats that SiCOB precursor sols are completely immersed in fiber preform, opens valve
Door causes the pressure in container to be changed into normal pressure, the SiCOB forerunner after standing 2～30 hours at 10-30 DEG C, in fiber preform
Body colloidal sol becomes gel, obtains gel/fiber preform mixture；
4th step, gel/fiber preform mixture are aging：
Gel/fiber preform mixture is sealed, is stored at room temperature, reached aging purpose, ageing time is 0.5～7
My god；
5th step, supercritical drying treatment gel/fiber preform mixture：
The gel that 4th step is obtained/fiber preform mixture carries out supercritical fluid drying process, wherein supercritical fluid
Dry medium is ethanol, propyl alcohol or isopropanol, and gel/fiber preform mixture is put in supercritical fluid drying equipment, in advance
Inflated with nitrogen, is again heated to 240～260 DEG C, insulation a period of time, then slowly discharges pressure, finally with N2Punching is swept, and obtains SiCOB
Organic precursor aerogel composite；
6th step, Pintsch process SiCOB organic precursor aerogel composites：
SiCOB organic precursor aerogel composites are put in pyrolysis furnace, is filled with the inert gas of flowing, in inert atmosphere
Under protection, cracking temperature, insulation a period of time so as to which cracking occurs scission of link rearrangement reaction, ultimately generates with Si-C- is warming up to
The amorphous network structure of O, Si-O-B and the SiCOB aerogel heat-proof composite materials of free carbon structure, wherein high temperature resistant inorganic are made pottery
The volumn concentration of porcelain fiber accounts for high temperature resistant SiCOB aerogel heat-proof composite material 20-70%, the volume of SiCOB aeroges
Percentage composition accounts for high temperature resistant SiCOB aerogel heat-proof composite material 30-80%.
2. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that the silicon
Criticize methyl silicate, tetraethyl orthosilicate in source.
3. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that the institute
State R2、R3When representing one or more different structure saturation or unsaturated group comprising 1-6 carbon atom, bag
Include alkyl, haloalkene alkyl, aryl.
4. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that the carbon
Source refers to MTMS, dimethyldimethoxysil,ne, divinyl diethoxy silane, and above each material with
Mixture arbitrarily than dissolving each other.
5. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that the boron
Orthoboric acid ester in source refers to trimethylborate, triethyl borate；Metaboric acid ester structure formula R in the boron source5 nB(OR6)3-n's
R5、R6Including alkyl, haloalkene alkyl, aryl, alkaryl, aralkyl.
6. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that the silicon
Source, carbon source, the mol ratio of boron source are 1.0: 0.5～2：0.5～1.
7. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that the acid
Property catalyst be hydrochloric acid, silicon source and acidic catalyst mol ratio are 1.0: 0.001～0.005.
8. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that the nothing
The apparent density of machine ceramic fibre is 0.15～0.25g/cm3.
9. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that described
When three steps prepare gel/fiber preform mixture, the vacuum for vacuumizing is 0.03～0.005MPa.
10. the preparation method of high temperature resistant SiCOB aerogel heat-proof composite material as claimed in claim 1, it is characterised in that described
During the 5th step supercritical drying treatment gel/fiber preform mixture, supercritical fluid drying medium be ethanol, the nitrogen of preliminary filling
Gas is 0.3～2.2MPa, and firing rate is 0.5～3 DEG C/min, and temperature retention time is 0.5～2 hour, and the speed for discharging pressure is
40～80kPa/min, N2Flyback time is rushed for 30～90 minutes.
The preparation method of 11. high temperature resistant SiCOB aerogel heat-proof composite materials as claimed in claim 1, it is characterised in that described
During the 6th step Pintsch process SiCOB organic precursor aerogel composites：Inert gas is N2, Ar or He, cracking temperature is
950 DEG C～1600 DEG C, during cracking, inert gas flow velocity is 50～400mL/min, and heating rate is 2～10 DEG C/min, during insulation
Between be 0.5～3 hour.
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| CN106608730A (en) * | 2015-10-26 | 2017-05-03 | 沈阳拓荆科技有限公司 | Carbon-based Si-C-O aerogel thermal insulation composite material and preparation method thereof |
| CN107473761B (en) * | 2016-06-08 | 2020-07-07 | 中国科学院金属研究所 | Heat-proof and load-bearing integrated carbon aerogel/ceramic layered composite material and preparation method and application thereof |
| CN106242642B (en) * | 2016-07-28 | 2019-01-25 | 航天材料及工艺研究所 | Resistance to 1700 DEG C of low density carbon watt surface oxidation-resistant coatings of one kind and preparation method thereof |
| CN106854086B (en) * | 2016-12-29 | 2021-11-19 | 北京华夏特材科技发展有限公司 | High-temperature-resistant mullite aerogel composite material and preparation method thereof |
| CN108929074B (en) * | 2018-08-07 | 2019-08-02 | 湖南荣岚智能科技有限公司 | A kind of silicon dioxide aerogel heat-insulating composite material plate and preparation method thereof |
| CN110436953B (en) * | 2019-09-16 | 2021-09-14 | 中国科学院兰州化学物理研究所 | High-temperature-resistant Al-Si-B-O ceramic aerogel material and synthesis method thereof |
| CN110898772B (en) * | 2019-11-13 | 2020-10-23 | 温州崎芳新能源有限公司 | Preparation method and application of composite organic aerogel |
| CN111302827A (en) * | 2020-04-10 | 2020-06-19 | 中国人民解放军国防科技大学 | Preparation method of high-temperature-resistant fiber-reinforced silica aerogel heat-insulation composite material |
| CN111517817A (en) * | 2020-05-20 | 2020-08-11 | 罗时举 | Antioxidant high-temperature-resistant carbon fiber composite material and preparation method thereof |
| CN114132937A (en) * | 2021-01-08 | 2022-03-04 | 上海联锴日用化工有限公司 | Preparation method of large-block silicon dioxide aerogel |
| CN112960987B (en) * | 2021-03-08 | 2022-07-29 | 烟台职业学院 | Preparation method of SiBOC/silicon dioxide/high silica fiber heat-insulation-prevention composite material |
| CN113831105B (en) * | 2021-10-14 | 2022-11-15 | 南京航空航天大学 | High-temperature heat-insulation noise-reduction irradiation-resistant superfine fiber reinforced aerogel composite material and preparation method thereof |
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