CN108585947A - A kind of lightening fire resistant thermally protective materials and preparation method thereof - Google Patents
A kind of lightening fire resistant thermally protective materials and preparation method thereof Download PDFInfo
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- CN108585947A CN108585947A CN201810684558.4A CN201810684558A CN108585947A CN 108585947 A CN108585947 A CN 108585947A CN 201810684558 A CN201810684558 A CN 201810684558A CN 108585947 A CN108585947 A CN 108585947A
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Abstract
The present invention relates to a kind of lightening fire resistant thermally protective materials and preparation method thereof, belong to inorganic functional material field.The method includes：Carbon fiber hard stephanoporate framework is prepared, the fiber lap-joint of the hard porous skeleton is connected by carbon, and fiber surface is covered with carbon-coating；Dipping sizing agent is prepared, includes boride ceramics powder, silicide ceramics powder and liquid phase Polycarbosilane in the dipping sizing agent；The surface layer of the hard porous skeleton is impregnated using the dipping sizing agent, the dipping sizing agent is made to fill the surface layer hole of the hard porous skeleton, then cures, be heat-treated, obtain lightening fire resistant thermally protective materials.Protective materials produced by the present invention has the performances such as high anti-oxidation, high temperature resistant and anti-high mechanical loading, the thermal shock that superhigh temperature ceramic material will not occur destroys problem, has the characteristics that high reliability, thermally protective materials can be applied in 2000 DEG C or more of oxidative environment without destroying.
Description
Technical field
The present invention relates to a kind of preparation methods of fibre reinforced surface layer ceramic lightening fire resistant thermally protective materials, belong to nothing
Machine field of functional materials.
Background technology
Hypersonicization of aircraft proposes higher heatproof requirement, special anti-hot spot (such as wing to thermal protection system
The positions such as leading edge, end, rudder leading edge and interference range) service temperature be up to 2000 DEG C or more, Antioxidated Carbon/carbon Composite Materials,
The thermally protective materials such as carbon/composite material of silicon carbide are limited to by heatproof and can not be used.Superhigh temperature ceramic material and low fever lose carbon/carbon
Composite material has superhigh temperature resistant characteristic, is the optional material of hypersonic aerospace craft thermal protection system high temperature position.
Superhigh temperature ceramic material superhigh temperature resistant and oxidation resistance are superior, but its thermal shock resistance is very poor, large-size structure
It is easy to that catastrophic failure occurs when part heated fast.Toughening for superhigh temperature ceramics is an important directions, but at present still
It does not solve well.It is to introduce a large amount of anti-yaw dampers in the fibre-reinforced skeleton of high density carbon that low fever, which loses carbon/carbon compound material,
Ceramic constituent element forms high density solid material, by preventing the too fast consumption of quality, reduces the ablation speed of carbon/carbon compound material
Rate, this material can well solve the problem of thermal shock destroys, can realize the application under superhigh temperature, but the material is being taken
Still there is ablation in the process, when heat shield member different zones thermal environment has differences, there will be ablation not during military service
Uniform phenomenon, to cause the variation of aircraft shape, the flight track of aircraft will change when larger profile variation；Together
When, since the density of material is high, thermal conductivity is high, almost without heat-insulating capability.
Thus, there is an urgent need for a kind of lightening fire resistant thermally protective materials with heat-insulating capability, thermal shock resistance.
Invention content
To solve problems of the prior art, the present invention provides a kind of lightening fire resistant thermally protective materials and its systems
Preparation Method, protective materials obtained have the performances such as high anti-oxidation, high temperature resistant and anti-high mechanical loading, and superhigh temperature pottery will not occur
The thermal shock of ceramic material destroys problem, has the characteristics that high reliability, thermally protective materials can be applied to 2000 DEG C or more of oxidation
Property environment in without destroy.
For achieving the above object, the present invention provides the following technical solutions：
A kind of preparation method of lightening fire resistant thermally protective materials, includes the following steps：
(1) carbon fiber hard stephanoporate framework and dipping sizing agent are prepared, the fiber lap-joint of the hard porous skeleton is by carbon
Connection, fiber surface are covered with carbon-coating, gather comprising boride ceramics powder, silicide ceramics powder and liquid phase in the dipping sizing agent
Carbon silane；
(2) surface layer of the hard porous skeleton is impregnated using the dipping sizing agent, the dipping sizing agent is made to fill out
The surface layer hole of the hard porous skeleton is filled, then cures, be heat-treated, obtain lightening fire resistant thermally protective materials.
In an alternative embodiment, the carbon fiber hard stephanoporate framework described in step (1) is existed by chemical vapor infiltration
The fiber lap-joint of carbon fiber intertexture porous structure forms connection carbon, and the method for forming carbon-coating in fiber surface is made.
In an alternative embodiment, step (before (2), further includes：
Oxidation protection layer is formed in the inside hole wall surface of the hard porous skeleton.
In an alternative embodiment, boride ceramics powder described in the dipping sizing agent described in step (1) and silicide pottery
The volume ratio of porcelain powder is 1：The total volume of (0.2~1.5), the boride ceramics powder and silicide ceramics powder with it is described
The volume ratio of liquid phase Polycarbosilane is 1：(0.5~2).
In an alternative embodiment, the solvent of liquid phase Polycarbosilane is also included in the dipping sizing agent described in step (1).
In an alternative embodiment, the volume ratio of the liquid phase Polycarbosilane and the solvent is 1：(0.1~2).
In an alternative embodiment, described in step (2) using the dipping sizing agent to the table of the hard porous skeleton
Face is impregnated, including：
Each surface of the hard porous skeleton is coated using solvent, makes each surface layer of the hard porous skeleton
Wetting forms liquid phase guide layer；
Then, the dipping sizing agent is coated in each continuous surface immediately, until the slurry of coating reaches expected penetration depth,
Wherein, the solvent is the solvent of the liquid phase Polycarbosilane.
In an alternative embodiment, the dipping described in step (2), including：
Unilateral impregnating depth of the dipping sizing agent on the hard porous skeleton surface layer is the hard porous skeleton
The 5~30% of overall thickness,
In an alternative embodiment, the solidification temperature described in step (2) is 150~200 DEG C, time 0.5-3h；It is described
Heat treatment carries out under inert gas protection, and temperature is 1100 DEG C~1600 DEG C, time 1-5h.
In an alternative embodiment, after the heat treatment described in step (2), further include：Ceramic protection is prepared on surface to apply
Layer.
In an alternative embodiment, ceramic protection coating is prepared on surface described in step (2), including：
Each surface of the carbon fibre reinforcement after heat treatment is coated using the dipping sizing agent, solidification and heat
After processing, ceramic protection coating is formed on surface.
The lightening fire resistant thermally protective materials prepared by the above method.
The present invention compared with prior art the advantages of：
(1) preparation method of lightening fire resistant thermally protective materials provided in an embodiment of the present invention, by using the poly- carbon of liquid phase
The surface layer of silane and superhigh temperature ceramics powder mixed slurry dipping, solidification and heat treatment method prepare lightening fire resistant thermal protection material
Material, since carbon fiber and superhigh temperature ceramics act synergistically in surface layer, make protective materials obtained have high anti-oxidation, high temperature resistant and
The performances such as anti-high mechanical loading, the thermal shock that superhigh temperature ceramic material will not occur destroy problem, have the characteristics that high reliability, heat
Protective materials can be applied in 2000 DEG C or more of oxidative environment without destroying；
(2) simultaneously, which has fibre reinforced superhigh temperature ceramics layer surface layer and low density porous carbon fiber skeleton core
Portion has the density more much lower than fiber reinforcement ultrahigh temperature ceramic composite, while internal porous core can also play
Heat-insulated effect can provide heat safe lightweight anti-heat-insulation integrative thermally protective materials for aerospace craft；
(3) this method have preparation process it is simple, to superhigh-temperature and-pressure equipment rely on it is small, be easily achieved shaped piece and prepare etc.
The manufacturing cost of high temperature heat-resistant protective materials can be greatly reduced in feature；
(4) fibre reinforced surface layer ceramic lightening fire resistant thermally protective materials surface forms superhigh temperature ceramics protection
Layer, the thermally protective materials of formation have the characteristics that non-ablative, and be on active service may be implemented the shape of heat shield member and do not change in the process.
Specific implementation mode
The specific implementation mode of the present invention is described further below in conjunction with specific embodiment.
An embodiment of the present invention provides a kind of preparation methods of lightening fire resistant thermally protective materials, include the following steps：
(1) carbon fiber hard stephanoporate framework is prepared, the fiber lap-joint of the hard porous skeleton is connected by carbon, fiber table
Face is covered with carbon-coating；
Specifically, in the embodiment of the present invention, connection carbon is to be formed after the organic substances high temperature such as resin, pitch, sucrose
The carbon materials such as resin carbon, bitumencarb；
Specifically, the present invention it is real one it is optional apply in example, the carbon fiber hard stephanoporate framework can pass through chemical gas
Phase osmosis forms connection carbon in the fiber lap-joint of carbon fiber intertexture porous structure, and forms carbon-coating in fiber surface and obtain；
Connection carbon may be implemented using chemical vapor infiltration and carbon-coating while is formed, and can effectively control carbon-coating uniformity and
Thickness is rear continued to ensure in carbon fiber hard stephanoporate framework forming process that hole is not filled and keeps effectively being connected to
Layer liquid impregnation prepares ceramic layer and provides condition；
In another alternative embodiment, the carbon fiber hard stephanoporate framework can also use carbon containing precursor (as set
Fat, pitch, sucrose etc.) techniques such as carbon fiber intertexture porous structure progress liquid impregnation, carbonization are obtained；
In a further alternative embodiment, the carbon fiber hard stephanoporate framework can also be by chopped carbon fiber with connect
Carbon matrix precursor (such as resin, pitch, sucrose) enhances hard skeleton by the carbon for filtering, curing, high-temperature heat treatment is formed；Its
In, the carbon fiber intertexture porous structure described in each embodiment can pass through volume by carbon fiber, carbon cloth and/or carbon fibre web tire
It knits, needle pierces or the techniques such as suture are made；
Further, the embodiment of the present invention preferably forms oxidation protection in the inside hole wall surface of the hard porous skeleton
Layer, for example, forming silicon carbide ceramics layer by chemical vapor infiltration.
(2) dipping sizing agent is prepared, includes boride ceramics powder, silicide ceramics powder and liquid phase in the dipping sizing agent
Polycarbosilane；
Specifically, in the embodiment of the present invention, the granularity of boride ceramics powder and silicide ceramics powder is respectively less than carbon fiber
Tie up the size of hard porous matrix porosity；Boride ceramics powder described in the dipping sizing agent and silicide ceramics powder
Volume ratio preferably 1：The total volume of (0.2~1.5), the boride ceramics powder and silicide ceramics powder is poly- with the liquid phase
The volume ratio of carbon silane preferably 1：(0.5~2)；
Further, also include liquid phase Polycarbosilane in the dipping sizing agent in order to adjust the mobility of dipping sizing agent
Solvent.The volume ratio preferably 1 of the liquid phase Polycarbosilane and the solvent：(0.1~2)；The preferred toluene of the solvent and/or
N-hexane；
(3) surface layer of the hard porous skeleton is impregnated using the dipping sizing agent, the dipping sizing agent is made to fill out
The surface layer hole of the hard porous skeleton is filled, then cures, be heat-treated, obtain lightening fire resistant thermally protective materials.
Specifically, the methods of dipping, vacuum or impregnating by pressure can be coated by surface in the embodiment of the present invention and realizes table
Layer dipping, wherein dipping sizing agent is impregnated into surface layer hole by coating impregnation method using capillary force；Vacuum or impregnating by pressure side
Method is：The placement of carbon fiber hard stephanoporate framework is vacuumized in a reservoir, dipping sizing agent is then injected into, dipping sizing agent is impregnated into
In the bone porous surface layer hole of carbon fiber hard.It can be added after evacuation to increase impregnating depth in dipping process
Pressure (being not higher than 5MPa) processing.After the completion of dipping, sample is taken out from liquid phase, is dried after removing excess surface material；
It is described that the surface of the hard porous skeleton is soaked using the dipping sizing agent in an alternative embodiment
Stain, including：Each surface of the hard porous skeleton is coated using solvent, makes each surface layer of the hard porous skeleton
Wetting forms liquid phase guide layer；Then, the dipping sizing agent is coated in each continuous surface immediately, until the slurry of coating reaches
It is expected that penetration depth；Wherein, the solvent be the liquid phase Polycarbosilane solvent, described refer to immediately exist naked eyes can
In a period of the liquid phase guide layer seen；The dipping method by solvent by being first coated in hard porous skeleton surface, immediately after
Dipping sizing agent is coated, dipping sizing agent is impregnated into the certain depth of surface layer using the guide functions to be formed are oozed in solvent, can avoid
The formation of filter cake, it is ensured that solid-phase component impregnating depth and impregnation increment are controllable；
In the embodiment of the present invention, preferably 150~200 DEG C of solidification temperature, time preferably 0.5~3h；The heat treatment is lazy
It is carried out under property gas shield, preferably 1100 DEG C~1600 DEG C of temperature, time preferably 1~5h.Surface layer dipping material may be implemented to burn
While knot forms complex phase ceramic, the heat-proof quality of internal porous region material is not reduced, realizes superficial oxidation protection and inside
Heat-insulated collaboration.
In the embodiment of the present invention, above-mentioned dipping, solidification, heat treatment process can be repeated, to realize that carbon fiber hard is more
The maximum filling on hole on framework surface layer；
Further, after the heat treatment, further include：Ceramic protection coating is prepared on surface, in the present embodiment, institute
State the coating that the preferred heatproof of ceramic protection coating is more than 1800 DEG C.
It is described to prepare ceramic protection coating on surface in an alternative embodiment, including：
Each surface of the carbon fibre reinforcement after heat treatment is coated using the dipping sizing agent, solidification and heat
After processing, ceramic protection coating is formed on surface.
The preparation method of lightening fire resistant thermally protective materials provided in an embodiment of the present invention, by using liquid phase Polycarbosilane
Lightening fire resistant thermally protective materials are prepared with surface layer dipping, solidification and the heat treatment method of superhigh temperature ceramics slurry material, due to table
Carbon fiber acts synergistically with superhigh temperature ceramics in layer, and protective materials obtained is made to have high anti-oxidation, high temperature resistant and anti-high mechanics
The performances such as load, the thermal shock that superhigh temperature ceramic material will not occur destroy problem, have the characteristics that high reliability, thermally protective materials
It can be applied in 2000 DEG C or more of oxidative environment without destroying；Meanwhile the material is made pottery with fibre reinforced superhigh temperature
Enamel coating surface layer and low density porous carbon fiber skeletal core have more much lower than fiber reinforcement ultrahigh temperature ceramic composite close
Degree, while internal porous core can also play heat-insulated effect, can be provided for aerospace craft heat safe lightweight prevent every
Heating integrated thermally protective materials；This method have preparation process it is simple, to superhigh-temperature and-pressure equipment rely on it is small, be easily achieved abnormity
The features such as prepared by part, can be greatly reduced the manufacturing cost of high temperature heat-resistant protective materials；Fibre reinforced surface layer ceramic lightweight is resistance to
High-temperature hot protection material surface forms superhigh temperature ceramics protective layer, and the thermally protective materials of formation have the characteristics that non-ablative, military service
The shape that heat shield member may be implemented in the process does not change.
It is several specific embodiments of the embodiment of the present invention below：
Embodiment 1
An embodiment of the present invention provides a kind of lightening fire resistant thermally protective materials, preparation method includes：
(1) using propane as carbon source, by chemical vapour deposition technique viscose base carbon fibre net plies fold needling shape at it is more
The fiber lap-joint of hole carbon fibre fabric forms connection carbon, while forming continuous carbon-coating in fiber surface, obtains with trepanning
The carbon of structure is bonded hard porous skeleton, wherein the viscose base carbon fibre needling shape at porous carbon fiber fabric density
For 0.16g/cm3, the average pore size of obtained hard porous skeleton is 50 μm, thickness 20mm, density 0.32g/cm3。
(2) hafnium boride powder for being 10 μm with granularity, the molybdenum silicide powder that granularity is 10 μm and silicon-carbon atomic ratio are 1：1、
Viscosity is that the liquid phase Polycarbosilane of 50cp is mixed with dipping sizing agent, wherein the volume ratio of hafnium boride powder and molybdenum silicide powder
It is 1：1, the total volume of two kinds of powders is 1 with the volume ratio of liquid phase Polycarbosilane：1.2, toluene solvant is added, after mixing
To dipping sizing agent, the volume ratio of the volume that toluene is added and liquid phase Polycarbosilane is 0.5：1.
(3) toluene is coated on each surface of the hard porous skeleton, each surface layer of the hard porous skeleton is made to soak,
Form the liquid phase guide layer of 2mm left and right thicknesses；Then, immediately in each continuous surface coating in each surface of the hard porous skeleton
The dipping sizing agent, until the penetration depth of the slurry of coating is about 5mm, then after 180 DEG C cure 1.5h, then in inertia
1.5h is heat-treated under gas shield at 1500 DEG C, forms the carbon fiber of hafnium boride-molybdenum silicide-carborundum composite-phase ceramic surface layer filling
Tie up reinforcing material.
(4) increased using the carbon fiber of above-mentioned dipping sizing agent coating hafnium boride-molybdenum silicide-carborundum composite-phase ceramic surface layer filling
Strong each surface of material forms continuous coating, and after 180 DEG C cure 1h, 1500 DEG C of heat treatment 1h, being formed has about 150 μ m thicks pottery
The lightening fire resistant thermally protective materials of porcelain protective coating.
The apparent bulk density of the lightening fire resistant thermally protective materials of acquisition is 1.6g/cm3, far below hafnium boride, silication
Density (the about 6.5g/cm of molybdenum and silicon carbide superhigh temperature ceramics3), there is lighting feature.Oxygen is carried out to the material sample of acquisition
Acetylene flame is heated at high temperature, and surface temperature is up to 2100 DEG C, and thermal shock destruction does not occur for material, and sample is intact, shows excellent
Non-ablative high temperature resistance and thermal shock resistance.
Embodiment 2
An embodiment of the present invention provides a kind of lightening fire resistant thermally protective materials, preparation method includes：
(1) with T700 polyacrylonitrile-based carbon fibres staple fiber, phenolic resin and ethyl alcohol according to mass ratio be 3：1：1 ratio
Mixing, obtains mixed slurry, filters, then cures 1h at 180 DEG C, high-temperature heat treatment 1h, phenolic resin exist at 1500 DEG C
Fiber lap-joint forms connection carbon, while forming continuous carbon-coating in fiber surface, obtains the carbon bonding carbon with open-celled structure
The hard porous skeleton of fiber, average pore size are about 60 μm, thickness 20mm, density 0.20g/cm3。
(2) zirconium boride powder for being 15 μm with granularity, the molybdenum silicide powder that granularity is 10 μm and silicon-carbon atomic ratio are 1：1、
Viscosity is that the liquid phase Polycarbosilane of 50cp is mixed with dipping sizing agent, wherein the volume ratio of zirconium boride powder and molybdenum silicide powder
It is 1：0.5, the total volume of two kinds of powders is 1 with the volume ratio of liquid phase Polycarbosilane：1, n-hexane solvent is added, after mixing
Dipping sizing agent is obtained, the volume ratio of the volume that n-hexane is added and liquid phase Polycarbosilane is 0.8：1.
(3) carbon is bonded hard porous skeleton placement to vacuumize in a reservoir, dipping sizing agent is then injected into, by dipping sizing agent
It is impregnated into carbon to be bonded in the surface layer hole of hard porous skeleton, then inflating pressure to 2MPa.After the completion of dipping, by sample from liquid
Taken out in phase, remove excess surface dipping sizing agent after dry, then in 200 DEG C cure 1h after, then under inert gas protection in
It is heat-treated 1h at 1600 DEG C.Repeated impregnations, solidification and heat treatment process are primary, form zirconium boride-molybdenum silicide-silicon carbide complex phase pottery
The carbon fibre reinforcement of porcelain surface layer filling.Wherein filling skin depth about 6mm.
(4) plasma spraying method is used to prepare zirconium boride-molybdenum silicide pottery of about 200 μm of thickness on each surface of above-mentioned material
Porcelain coating forms the lightening fire resistant thermally protective materials with ceramic protection coating.
The apparent bulk density of the lightening fire resistant thermally protective materials of acquisition is 1.5g/cm3, far below zirconium boride, silication
Density (the about 5.0g/cm of molybdenum and silicon carbide superhigh temperature ceramics3), there is lighting feature.Oxygen is carried out to the material sample of acquisition
Acetylene flame is heated at high temperature, and surface temperature is up to 1950 DEG C, and thermal shock destruction does not occur for material, and sample is intact, shows excellent
Non-ablative high temperature resistance and thermal shock resistance.
Embodiment 3
An embodiment of the present invention provides a kind of lightening fire resistant thermally protective materials, preparation method includes：
(1) using propane as carbon source, by chemical vapour deposition technique viscose base carbon fibre net plies fold needling shape at it is more
The fiber lap-joint of hole carbon fibre fabric forms connection carbon, while forming continuous carbon-coating in fiber surface, obtains with trepanning
The carbon of structure is bonded hard porous skeleton, wherein the viscose base carbon fibre needling shape at porous carbon fiber fabric density
For 0.16g/cm3, the average pore size of obtained hard porous skeleton is 50 μm, and material thickness 20mm, density are
0.32g/cm3。
(2) the titanium boride powder for being 10 μm with granularity, the zirconium silicide powder that granularity is 10 μm and silicon-carbon atomic ratio are 1：1、
Viscosity is that the liquid phase Polycarbosilane of 50cp is mixed with dipping sizing agent, and the wherein volume ratio of titanium boride powder and zirconium silicide powder is
1：0.5, the total volume of two kinds of powders is 1 with the volume ratio of liquid phase Polycarbosilane：0.8, toluene solvant is added, after mixing
To dipping sizing agent, the volume ratio of the volume that toluene is added and liquid phase Polycarbosilane is 1.2：1.
(3) dipping sizing agent is persistently coated to carbon and is bonded hard porous skeleton surface, will be impregnated using capillary action
Slurry penetration is bonded hard porous skeleton skin depth about 5mm to carbon, then after 180 DEG C cure 1.5h, then in inert gas
Under protection 1.5h is heat-treated at 1500 DEG C.Repetitive coatings infiltration, solidification and heat treatment are primary, form titanium boride-zirconium silicide-carbon
The carbon fibre reinforcement of SiClx complex phase ceramic surface layer filling.
(4) plasma spraying method is used to prepare thickness in material surface as the ZrB of 200 μm of d2SiC ceramic coating is formed
Lightening fire resistant thermally protective materials with ceramic protection coating.
The apparent bulk density of the lightening fire resistant thermally protective materials of acquisition is 1.25g/cm3, far below titanium boride, silication
Density (the about 4.3g/cm of zirconium and silicon carbide superhigh temperature ceramics3), there is lighting feature.Oxygen is carried out to the material sample of acquisition
Acetylene flame is heated at high temperature, and surface temperature is up to 2000 DEG C, and thermal shock destruction does not occur for material, and sample is intact, shows excellent
Non-ablative high temperature resistance and thermal shock resistance.
The above, best specific implementation mode only of the invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.
The content that description in the present invention is not described in detail belongs to the known technology of professional and technical personnel in the field.
Claims (12)
1. a kind of preparation method of lightening fire resistant thermally protective materials, which is characterized in that include the following steps：
(1) carbon fiber hard stephanoporate framework and dipping sizing agent are prepared, the fiber lap-joint of the hard porous skeleton is connected by carbon,
Fiber surface is covered with carbon-coating, includes boride ceramics powder, silicide ceramics powder and the poly- carbon silicon of liquid phase in the dipping sizing agent
Alkane；
(2) surface layer of the hard porous skeleton is impregnated using the dipping sizing agent, makes dipping sizing agent filling institute
The surface layer hole of hard porous skeleton is stated, then cures, be heat-treated, obtain lightening fire resistant thermally protective materials.
2. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step
(1) carbon fiber hard stephanoporate framework described in by chemical vapor infiltration carbon fiber intertexture porous structure fiber lap-joint
Connection carbon is formed, and the method for forming carbon-coating in fiber surface is made.
3. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step
(2) before, further include：
Oxidation protection layer is formed in the inside hole wall surface of the hard porous skeleton.
4. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：
The volume ratio of boride ceramics powder and silicide ceramics powder described in dipping sizing agent described in step (1) is 1：(0.2
~1.5), the total volume of the boride ceramics powder and silicide ceramics powder and the volume ratio of the liquid phase Polycarbosilane are
1：(0.5~2).
5. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step
(1) also include the solvent of liquid phase Polycarbosilane in the dipping sizing agent described in.
6. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 5, it is characterised in that：The liquid
The volume ratio of phase Polycarbosilane and the solvent is 1：(0.1~2).
7. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step
(2) the surface of the hard porous skeleton is impregnated using the dipping sizing agent described in, including：
Each surface of the hard porous skeleton is coated using solvent, each surface layer of the hard porous skeleton is made to moisten
It is wet, form liquid phase guide layer；
Then, the dipping sizing agent is coated in each continuous surface immediately, until the slurry of coating reaches expected penetration depth,
In, the solvent is the solvent of the liquid phase Polycarbosilane.
8. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step
(2) dipping described in, including：
Unilateral impregnating depth of the dipping sizing agent on the hard porous skeleton surface layer is the hard porous skeleton total thickness
The 5~30 of degree.
9. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step
(2) solidification temperature described in is 150~200 DEG C, time 0.5-3h；The heat treatment carries out under inert gas protection, temperature
Degree is 1100 DEG C~1600 DEG C, time 1-5h.
10. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step
(2) after the heat treatment described in, further include：Ceramic protection coating is prepared on surface.
11. a kind of preparation method of lightening fire resistant thermally protective materials according to claim 10, it is characterised in that：Step
(2) ceramic protection coating is prepared on surface described in, including：
Each surface of the carbon fibre reinforcement after heat treatment is coated using the dipping sizing agent, cures and is heat-treated
Afterwards, ceramic protection coating is formed on surface.
12. the lightening fire resistant thermally protective materials prepared by any one of claim 1-11 the methods.
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