CN107287882A - Lightening fire resistant thermally protective materials and preparation method thereof - Google Patents
Lightening fire resistant thermally protective materials and preparation method thereof Download PDFInfo
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- CN107287882A CN107287882A CN201710312315.3A CN201710312315A CN107287882A CN 107287882 A CN107287882 A CN 107287882A CN 201710312315 A CN201710312315 A CN 201710312315A CN 107287882 A CN107287882 A CN 107287882A
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- protective materials
- bonded fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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 preparation method of lightening fire resistant thermally protective materials provided in an embodiment of the present invention forms the carbon fibre fabric of thickness direction density gradient distribution by carrying out acupuncture to carbon cloth and net tire gradient cross-bedding stack；Fiber lap-joint forms matrix carbon, and the protective layer of fiber surface formation internally in carbon fibre fabric, realizes that fabric is shaped；Densification is oriented to high-density region using orientation densifying method, top layer densification, internal porous, the integrated material of intermediate configuration connection is formed；It is last to prepare oxidation protection coating in densified surface, form the anti-heat-barrier material of integral light.Efficiently solve prior art solar heat protection and the problem of insulating portion needs to mechanically connect, the complexity of thermal protection system can be greatly simplified, expand thermally protective materials has a wide range of application.
Description
Technical field
The present invention relates to anti-heat-barrier material of integral gradient structure light wt high temperature resistant and preparation method thereof, belong to inorganic functional
Material Field.
Background technology
Thermal protection system is to ensure the key that aerospace craft is depended on for existence when high speed is on active service in Aerodynamic Heating environment, with
Contemporary aircraft gradually to rapid, lightweight, it is long when, the direction such as reusableization develop, to solar heat protection/heat-insulated
High temperature resistant (more than 1600 DEG C) lightweight thermally protective materials of integrated function propose more and more urgent demand.
The heat insulation material formed using ceramic tile as the light heat-insulating material of representative and on surface after fine and close overcoat has existed
It is applied successfully in the thermal protection system of space shuttle, but because the temperature resistant grade of ceramic fibre is low, it is impossible to it is applied to height
In 1500 DEG C of occasion.The characteristics of lightweight carbon fiber heat insulation material (soft felt and hard felt) has high temperature resistant and high temperature insulating,
It is widely applied in the insulation system of high temperature furnace, but because itself easily oxidized ablation and surface are difficult to be directly realized by oxygen
The problems such as chemoprevention is protected and can not be applied in the thermal protection system of aerospace craft.
The U.S. proposes a kind of TUFROC composite construction in X37B aircraft development processes and prevents/heat-barrier material, wherein
Top layer uses the higher density protective materials with oxidation protection function of fibre reinforced, and inside then uses the ceramics of lightweight
Fibrous insulating material, two parts are mechanically attached.The lightweights of TUFROC composite constructions is anti-/ and heat-barrier material can be through
Prevent heat-insulated in short-term by more than 1600 DEG C, or even close to 1900 DEG C, and be verified in X37B flight test.This is combined
Structure light wt is anti-/ mode that is attached as a result of two class materials of heat-barrier material so that thermal protection system it is complicated,
Reliability is reduced.In addition, the skin-material in TUFROC materials is due to being loose structure before prepares coating, in densified carbon/carbon
The antioxidant coating preparation technology that composite material surface is obtained is not applied to, and the expansibility of thermally protective materials is poor.
The content of the invention
It is an object of the invention to protect material there is provided integral light high temperature heat-resistant for defect present in prior art
Material and preparation method thereof.
To achieve the above object, the present invention provides following technical scheme：
A kind of preparation method of lightening fire resistant thermally protective materials, comprises the following steps：
Step (1)：Through-thickness is prepared by carbon cloth and net tire from first surface to second surface density in gradient to subtract
Small carbon fibre fabric；
Step (2)：Matrix carbon is formed in the fiber lap-joint of the carbon fibre fabric, and is protected in fiber surface formation carbonaceous
Sheath, shapes to the carbon fibre fabric, obtains pattern bonded fabrics；
Step (3)：Densification is carried out to the corresponding high-density region of first surface of the pattern bonded fabrics, forms high
The integrated material of density area densification；
Step (4)：Oxidation protection is prepared on the first surface for the integrated material being densified in the high-density region to apply
Layer, forms the anti-heat-barrier material of lightening fire resistant.
In an alternative embodiment, step (1) includes：
Multiple carbon fiber layers being made up of carbon cloth and net tire are stacked, layered product is formed, each institute of the layered product is formed
The density for stating carbon fiber layer is different；
By needling process, density through-thickness is made from first surface to second surface in gradient in the layered product
The carbon fibre fabric of reduction.
In an alternative embodiment, in step (3), the thickness of the high-density region is the pattern bonded fabrics gross thickness
5-15%.
In an alternative embodiment, the carbon fiber described in step (1) is viscose base carbon fibre or polyacrylonitrile-based carbon fibre.
In an alternative embodiment, by chemical vapor infiltration or liquid impregnation/carbonizatin method in step (2), described
The fiber lap-joint of carbon fibre fabric forms matrix carbon or in fiber surface formation carbonaceous protective layer.
In an alternative embodiment, the corresponding high density area of the first surface to the pattern bonded fabrics described in step (3)
Domain carries out densification, including：
Flow through the first surface of carbon-source gas from the pattern bonded fabrics is parallel, other surfaces are protected, and pass through institute
Stating the free diffusing and deposition of carbon-source gas makes the corresponding high-density region densification of the first surface of the pattern bonded fabrics.
In an alternative embodiment, the corresponding high density area of the first surface to the pattern bonded fabrics described in step (3)
Domain carries out densification, including：
By in the first surface immersion liquid phase presoma of the pattern bonded fabrics, acted on or combined by capillary siphoning and take out true
Sky reinforcing siphon makes the liquid phase presoma be spread to the corresponding high-density region of the first surface；
The corresponding high-density region of the first surface of the pattern bonded fabrics is densified by heat treatment.
In an alternative embodiment, the corresponding high density area of the first surface to the pattern bonded fabrics described in step (3)
Domain carries out densification, including：
Liquid phase presoma is coated to the first surface of the pattern bonded fabrics, by capillary action by before the liquid phase
Body is driven to be impregnated into the corresponding high-density region of the first surface of the pattern bonded fabrics；
It is subsequently heat-treated to make the corresponding high-density region densification of first surface of the pattern bonded fabrics.
In an alternative embodiment, the oxidation protection coating described in step (4) applies for the ceramics of resistance to 1500 DEG C of high temperature above
Layer.
Lightening fire resistant thermally protective materials prepared by the above method.
The advantage of the present invention compared with prior art：
(1) compared with the anti-heat-insulation integrative material of existing split interconnection system, the thermally protective materials that the present invention is provided have
Real integral feature, solar heat protection and it is heat-insulated be all to be realized by material different zones itself.Prior art is efficiently solved to prevent
The problem of heat and insulating portion need to mechanically connect, can greatly simplify the complexity of thermal protection system.
(2) the integral light high temperature heat-resistant protective materials that the present invention is provided may apply to more than 1500 DEG C of military service ring
In border, the not applicable high-temperature field of existing ceramic tile material may apply to.
(3) the integral light high temperature heat-resistant protective materials top layer that the present invention is provided is the region of higher carbon fiber content,
Surface region has the high many mechanical properties of heat-barrier material more anti-than existing lightweight after orientation densification.
(4) the integral light high temperature heat-resistant protective materials that the present invention is provided is densification table before oxidation protection layer is prepared
Layer, the high-temperature oxidation resistant coating system and preparation method applied in carbon/carbon compound material can be applied directly to this surface, greatly
The big application for having expanded the anti-heat-barrier material of lightweight.
Brief description of the drawings
Fig. 1 is a kind of carbon fibre fabric structural representation provided in an embodiment of the present invention.
Embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The embodiments of the invention provide a kind of preparation method of lightening fire resistant thermally protective materials, comprise the following steps：
Step (1)：Through-thickness is prepared by carbon cloth and net tire from first surface to second surface density in gradient to subtract
Small carbon fibre fabric；
Specifically, in the embodiment of the present invention, the viscose base carbon fibre carbon cloth or polyacrylonitrile-radical of the preferred lower thermal conductivity of carbon cloth
Carbon fiber carbon cloth, the viscose base carbon fibre net tire or polyacrylonitrile-based carbon fibre net tire of the preferred lower thermal conductivity of net tire, in order to enter one
Step reduction thermal conductivity, can carry out lower thermal conductivity processing to carbon fiber；
The layered product that carbon fibre fabric is formed by carbon cloth and net tire intersecting is made by fabric processing technology, such as Fig. 1
Shown, so that carbon fibre fabric is flat rectangular body structure as an example, upper surface is described first surface in figure, and lower surface is described
Second surface, the density of the carbon fibre fabric direction of arrow along along Fig. 1 reduces in gradient；
Specifically, multiple carbon fiber layers being made up of carbon cloth and net tire are stacked in the embodiment of the present invention, form layered product,
The density for forming each carbon fiber layer of the layered product is different；By needling process, edge is made in the layered product
The carbon fibre fabric that thickness direction reduces in gradient from first surface to second surface density.In an alternative embodiment, carbon is fine
The thickness for tieing up carbon cloth in layer is identical, and the thickness of net tire is different, thus forms the different carbon fiber layer of density；For example, layered product is by 3
Layer carbon fiber layer is stacked to be formed, and wherein first layer carbon fiber layer is made up of one layer of carbon cloth and one layer of net tire, second layer carbon fiber layer
It is made up of one layer of carbon cloth two layers of mesh tire, third layer is made up of one layer of carbon cloth and three-layer network tire, the density of first layer is more than the second layer
Density be more than third layer density, first layer carbon cloth face correspondence shaping after fabric first surface, third layer
The second surface of fabric after shaping corresponding with the net tyre surface that first surface is opposite；In another alternative embodiment, carbon is fine
The thickness for tieing up carbon cloth in layer is identical, and the thickness of net tire is also identical, but the density of carbon cloth is different in different carbon fiber layers, thus makes
The density of carbon fiber layer is also differed；
Specifically, the thickness of carbon fibre fabric is preferably 20~60mm in the embodiment of the present invention, and density is preferably 0.8~
0.1g/cm3, high density area density gradient is preferably 0.3~0.5 (g/cm3)/cm, low density area density gradient is preferably 0~0.3
(g/cm3)/cm。
Step (2)：Matrix carbon is formed in the fiber lap-joint of the carbon fibre fabric, and is protected in fiber surface formation carbonaceous
Sheath, shapes to the carbon fibre fabric, obtains pattern bonded fabrics；
In the embodiment of the present invention, described matrix carbon is the material such as gas phase or liquid phase hydro carbons, resinae, pitch through chemical gaseous phase
Chemical gaseous phase pyrolytic carbon, resin carbon or bitumencarb that the method such as osmosis or liquid impregnation/carbonizatin method is obtained, the carbonaceous protection
Layer can be above-mentioned matrix carbon coating, can also be carbide ceramics coating；It can be soaked by chemical vapor infiltration or liquid phase
Stain/carbonizatin method, matrix carbon is formed or in fiber surface formation carbonaceous protective layer in the fiber lap-joint of the carbon fibre fabric,
The carbon fibre fabric is shaped；Chemical vapor infiltration or liquid impregnation/carbonizatin method presoma use can form richness
The materials such as the gas phase or liquid phase hydro carbons, resinae, pitch of carbonizable substance, wherein liquid impregnation/carbonizatin method are used as leaching using weak solution
Stain liquid, to ensure that the matrix carbon to be formed is predominantly located at carbon fiber lapped point and fiber surface, rather than filling pore；Pass through sizing
Carbon fiber forms carbonaceous protective layer in surface simultaneously.
Step (3)：Densification is carried out to the corresponding high-density region of first surface of the pattern bonded fabrics, forms high
The integrated material of density area densification；
Specifically, the first surface of the pattern bonded fabrics is the density highest surface of pattern bonded fabrics, the first surface
Corresponding high-density region is the region for extending certain depth to pattern bonded fabrics thickness direction since first surface.With Fig. 1
Exemplified by shown pattern bonded fabrics, first surface is upper surface, and the corresponding high-density region of first surface is the edge since upper surface
The direction of arrow is to the region for extending certain depth inside pattern bonded fabrics in Fig. 1, and specific depth is that the thickness of high-density region can be with
According to use it needs to be determined that；The thickness of high-density region described in the embodiment of the present invention is the 5%- of the pattern bonded fabrics gross thickness
15%.High-density region plays a part of integral material carrying, and the antibody Monoclonal ability of lightweight thermally protective materials is substantially improved；With height
The opposite density regions of density area serve heat-insulated effect, are the main area of insulation of material；Intermediate density gradient mistake
Cross region and then connect high-density region and density regions, the thermal stress during sustained release high-temperature service ensures that material will not be
Transition region cracking destruction.
In the embodiment of the present invention, surface parallel flow field chemical vapor infiltration, the reverse siphon/heat treatment in surface can be passed through
The method such as method and surface coating dipping/heat treating process is oriented densification to high-density region, obtains top layer fine and close, interior
Portion is porous, the integrated material of Middle-gradient transition structure connection.
Specifically, parallel flow field chemical vapor infiltration in surface includes：By carbon-source gas from the first of the pattern bonded fabrics
Surface is parallel to be flowed through, and other surfaces are protected, and prevents vapour-phase pyrolysis carbon from entering pattern bonded fabrics from other surfaces, by described
The free diffusing and deposition of carbon-source gas make the corresponding high-density region of the first surface of the pattern bonded fabrics turn into densification
Change layer；
Reverse siphon/the heat treating process in surface, including：The first surface of the pattern bonded fabrics is reversely immersed into liquid phase presoma
Middle certain depth (depth is determined by the thickness of high-density region), is acted on by capillary siphoning or combines and vacuumize reinforcing rainbow
Suction makes the liquid phase presoma be spread to the corresponding high-density region of the first surface；The pattern bonded fabrics are made by heat treatment
The corresponding high-density region of first surface turn into densified layer；
Surface coats dipping/heat treating process, including：Liquid phase presoma is coated to by the method brushed or sprayed described
The liquid phase presoma, the first table of the pattern bonded fabrics is impregnated into by capillary action by the first surface of pattern bonded fabrics
In the corresponding high-density region in face；It is subsequently heat-treated to make the corresponding high-density region of first surface of the pattern bonded fabrics is interior to be formed
Filler, as densified layer.
Step (4)：Oxidation protection is prepared on the first surface for the integrated material being densified in the high-density region to apply
Layer, forms the anti-heat-barrier material of lightening fire resistant.
Specifically, in the embodiment of the present invention, described oxidation protection coating is temperature in use more than 1500 DEG C, Ke Yi
Any ceramic coating system of surface of carbon/carbon composite application, preparation method mainly includes coating sintering method, plasma spraying
Method, one side solid phase investment and sol-gel process.
The preparation method of lightening fire resistant thermally protective materials provided in an embodiment of the present invention passes through to carbon cloth and net tire gradient
Cross-bedding stack carries out acupuncture, forms the carbon fibre fabric of thickness direction density gradient distribution；Fiber is taken in carbon fibre fabric
The place of connecing forms matrix carbon, and the protective layer of fiber surface formation internally, realizes that fabric is shaped；Using orientation densifying method to height
Density area is oriented densification, forms top layer densification, internal porous, the integrated material of intermediate configuration connection；Most
Oxidation protection coating is prepared in densified surface afterwards, the anti-heat-barrier material of integral light is formed.
The embodiment of the present invention additionally provides lightening fire resistant thermally protective materials prepared by a kind of above-mentioned preparation method.
The preparation method and lightening fire resistant thermal protection material of lightening fire resistant thermally protective materials provided in an embodiment of the present invention
Material possesses advantages below：
(1) compared with the anti-heat-insulation integrative material of existing split interconnection system, the thermally protective materials that the present invention is provided have
Real integral feature, solar heat protection and it is heat-insulated be all to be realized by material different zones itself.Prior art is efficiently solved to prevent
The problem of heat and insulating portion need to mechanically connect, can greatly simplify the complexity of thermal protection system.
(2) the integral light high temperature heat-resistant protective materials that the present invention is provided may apply to more than 1500 DEG C of military service ring
In border, the not applicable high-temperature field of existing ceramic tile material may apply to.
(3) the integral light high temperature heat-resistant protective materials top layer that the present invention is provided is the region of higher carbon fiber content,
Surface region has the high many mechanical properties of heat-barrier material more anti-than existing lightweight after orientation densification.
(4) the integral light high temperature heat-resistant protective materials that the present invention is provided is densification table before oxidation protection layer is prepared
Layer, the high-temperature oxidation resistant coating system and preparation method applied in carbon/carbon compound material can be applied directly to this surface, greatly
The big application for having expanded the anti-heat-barrier material of lightweight.
It is below several specific embodiments of the present invention：
Embodiment 1：
(1) multiple carbon fiber layers being made up of carbon cloth and net tire are stacked, forms layered product, the density of each carbon fiber layer is not
Together, by needling process, the carbon fibre fabric that through-thickness reduces in gradient is made in the layered product；The carbon cloth is glutinous
The carbon cloth of matrix carbon fiber formation, the density of individual layer carbon cloth is about 1g/cm3, thickness is 0.16mm, and the net tire is viscose base carbon
Fibroplastic net tire, the density of monolayer net tire is 0.03g/cm3, thickness is about 5mm, the first surface of the carbon fibre fabric
Essentially carbon cloth, second surface is essentially net tire, and the carbon fibre fabric gross thickness is 60mm, and through-thickness is from first surface
Start to second surface, density is from 0.5g/cm3(averag density in 5mm thickness) is reduced to 0.1g/cm in gradient3(5mm thickness
Interior averag density).
(2) using propane as presoma, carbon fibre fabric global density increase about 0.02g/ is made using chemical vapor infiltration
cm3；Then by precursor of chlorosilane by chemical vapor infiltration on the fiber surface inside fabric deposit thickness
About 0.5 μm of coat of silicon carbide, forms the fabric stabilized.
(3) surface parallel flow field chemical vapor infiltration is used, is first table of the precursor in pattern bonded fabrics using propane
Face is oriented densification, and the filling of vapour-phase pyrolysis carbon is formed during down depth is the hole in the range of 5mm or so in first surface
Thing, so that the top layer density that thickness is 5mm or so reaches about 1.55g/cm3, the least density area density that thickness is 30mm is
0.25g/cm3, other regions fall between.
(4) carbonization of about 100 μm of thickness is prepared on the first surface of densification high-density region using coating sintering method
Silicon coating, then using sol-gel process formation silica packing layer, forms the anti-heat-barrier material of lightening fire resistant.
After tested, the averag density of the anti-heat-barrier material of integral light high temperature resistant provided in an embodiment of the present invention is about
0.8g/cm3, densification high-density region (about 5mm) compressive strength be not less than 20MPa.By 1600 DEG C of surface, 600s height
Warm single-side heating examination, back temperature is no more than 100 DEG C, and material is complete after examination, and delamination does not occur or mechanical property is bright
Aobvious reduction.
Embodiment 2：
(1) multiple carbon fiber layers being made up of carbon cloth and net tire are stacked, forms layered product, the density of each carbon fiber layer is not
Together, by needling process, the carbon fibre fabric that through-thickness reduces in gradient is made in the layered product；The carbon cloth is
The carbon cloth of T300 polyacrylonitrile-based carbon fibres formation, the density of individual layer carbon cloth is about 1.1g/cm3, thickness is 0.16mm, the net
Tire is the net tire of T300 polyacrylonitrile-based carbon fibres formation, and the density of monolayer net tire is 0.04g/cm3, thickness is about 4mm, described
The first surface of carbon fibre fabric is essentially carbon cloth, and second surface is essentially net tire, and the carbon fibre fabric gross thickness is 55mm,
Through-thickness is to second surface since first surface, and density is from 0.55g/cm3(averag density in 5mm thickness) in gradient
It is reduced to 0.12g/cm3(averag density in 5mm thickness).Then the fabric is aoxidized in 300 DEG C of oxidizing atmosphere 30min with
Reduce the thermal conductivity of carbon fiber.
(2) using phenolic resin alcohol dilute solution (mass concentration about 20%) liquid impregnation/carbonizatin method in above-mentioned carbon fiber
The fiber lap-joint of fabric forms resin carbon, makes carbon fibre fabric global density increase about 0.05g/cm3；Then using propane before
Body by the coat of silicon carbide of chemical vapor infiltration about 0.5 μm of deposit thickness on the fiber surface inside fabric,
Form the fabric stabilized.
(3) the reverse siphon/heat treating process in surface is used, the top layer by precursor of phenolic resin in pattern bonded fabrics is determined
To densification, fat carbon filler is formed in the hole in first surface down 4mm or so depth boundses, promotes first surface pair
The thickness answered is that the density of 4mm or so high-density region reaches about 1.6g/cm3, thickness is 30mm or so least density area
Density is 0.3g/cm3, other regions fall between.
(4) about 100 μm of thickness is first prepared on the first surface of densification high-density region using one side solid phase investment
Coat of silicon carbide, then prepares the MoSi of about 150 μm of thickness using plasma spraying method2-ZrB2Coating.
After tested, the averag density of the anti-heat-barrier material of integral light high temperature resistant provided in an embodiment of the present invention is about
0.9g/cm3, densification high-density region (about 5mm) compressive strength be not less than 20MPa.By 1700 DEG C of surface, 100s height
Warm single-side heating examination, back temperature is no more than 150 DEG C, and material is complete after examination, and delamination does not occur or mechanical property is bright
Aobvious reduction.
Embodiment 3：
(1) multiple carbon fiber layers being made up of carbon cloth and net tire are stacked, forms layered product, the density of each carbon fiber layer is not
Together, by needling process, the carbon fibre fabric that through-thickness reduces in gradient is made in the layered product；The carbon cloth is glutinous
The carbon cloth of matrix carbon fiber formation, the density of individual layer carbon cloth is about 1g/cm3, thickness is 0.16mm, and the net tire is viscose base carbon
Fibroplastic net tire, the density of monolayer net tire is 0.03g/cm3, thickness is about 5mm, the first surface of the carbon fibre fabric
Essentially carbon cloth, second surface is essentially net tire, and the carbon fibre fabric gross thickness is 60mm, and through-thickness is from first surface
Start to second surface, density is from 0.5g/cm3(averag density in 5mm thickness) is reduced to 0.1g/cm in gradient3(5mm thickness
Interior averag density).
(2) make carbon fibre fabric whole using dilute toluene solution (mass concentration about 25%) liquid impregnation/carbonizatin method of pitch
Volume density increase about 0.04g/cm3；Then by precursor of liquid phase Polycarbosilane by liquid impregnation/carbonization in fabric
The coat of silicon carbide of about 0.4 μm of thickness is formed on the fiber surface in portion, the fabric stabilized is formed.
(3) it is precursor using phenolic resin, first surface of the dipping/heat treating process in pattern bonded fabrics is coated using surface
Densification is oriented, resin carbon filler is formed during down depth is the hole in the range of 6mm or so in first surface, promotes
Thickness is that 6mm or so top layer density reaches about 1.56g/cm3, the least density area density that thickness is 30mm is 0.25g/cm3,
Other regions fall between.
(4) about 80 μm of coat of silicon carbide of thickness are first prepared in densified surface using coating sintering method, then utilizes coating
Sintering process prepares the MoSi of about 200 μm of thickness2-TaSi2- silicon boron glass high temperature coating, forms the anti-heat-barrier material of lightening fire resistant.
After tested, the averag density of the anti-heat-barrier material of integral light high temperature resistant provided in an embodiment of the present invention is about
0.83g/cm3, densification high-density region (about 5mm) compressive strength be not less than 20MPa.By 1650 DEG C of surface, 300s
High temperature single-side heating is examined, and back temperature is no more than 130 DEG C, and material is complete after examination, and delamination or mechanical property do not occur
Substantially reduction.
Embodiment 4：
(1) multiple carbon fiber layers being made up of carbon cloth and net tire are stacked, forms layered product, the density of each carbon fiber layer is not
Together, by needling process, the carbon fibre fabric that through-thickness reduces in gradient is made in the layered product；The carbon cloth is
The carbon cloth of T700 polyacrylonitrile-based carbon fibres formation, the density of individual layer carbon cloth is about 1.1g/cm3, thickness is 0.16mm, the net
Tire is the net tire of T700 polyacrylonitrile-based carbon fibres formation, and the density of monolayer net tire is 0.04g/cm3, thickness is about 5mm, described
The first surface of carbon fibre fabric is essentially carbon cloth, and second surface is essentially net tire, and the carbon fibre fabric gross thickness is 40mm,
Through-thickness since first surface to second surface, density from density be 0.6g/cm3(averag density in 5mm thickness)
0.15g/cm is reduced in gradient3(averag density in 5mm thickness).Then 30min is aoxidized in 300 DEG C of oxidizing atmosphere to drop
The thermal conductivity of low-carbon fiber.
(2) using phenol resin solution liquid impregnation/carbonizatin method, carbon fibre fabric global density increase about 0.05g/ is made
cm3；Then thickness is formed on the fiber surface inside fabric by Polycarbosilane weak solution liquid impregnation/high-temperature cracking method
The coat of silicon carbide of about 0.5 μm of degree, forms the fabric stabilized.
(3) using phenolic resin as precursor, entered using the reverse siphon/heat treating process in surface in the first surface of pattern bonded fabrics
Row orientation densification, forms resin carbon filler during down depth is the hole in 5mm or so depth bounds in first surface, promotees
The density for entering the corresponding thickness of first surface for 5mm or so region reaches about 1.6g/cm3, thickness is 25mm least density area
Density is 0.3g/cm3, other regions fall between.
(4) coat of silicon carbide of about 80 μm of thickness is first prepared in densified surface using coating sintering method, is then utilized
Plasma spray method prepares the MoSi of about 200 μm of thickness2-HfB2High temperature coating, forms the anti-heat-barrier material of lightening fire resistant.
After tested, the averag density of the anti-heat-barrier material of integral light high temperature resistant provided in an embodiment of the present invention is about
0.86g/cm3, densification high-density region (about 5mm) compressive strength be not less than 20MPa.By 1700 DEG C of surface, 300s
High temperature single-side heating is examined, and back temperature is no more than 150 DEG C, and material is complete after examination, and delamination or mechanical property do not occur
Substantially reduction.
It is described above, it is only the optimal embodiment of the present invention, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
It should all be included within the scope of the present invention.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. a kind of preparation method of lightening fire resistant thermally protective materials, it is characterised in that comprise the following steps：
Step (1)：Prepare what through-thickness reduced in gradient from first surface to second surface density by carbon cloth and net tire
Carbon fibre fabric；
Step (2)：Matrix carbon is formed in the fiber lap-joint of the carbon fibre fabric, and in fiber surface formation carbonaceous protection
Layer, shapes to the carbon fibre fabric, obtains pattern bonded fabrics；
Step (3)：Densification is carried out to the corresponding high-density region of first surface of the pattern bonded fabrics, high density is formed
The integrated material of area densification；
Step (4)：Oxidation protection coating, shape are prepared on the first surface for the integrated material being densified in the high-density region
Into the anti-heat-barrier material of lightening fire resistant.
2. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that step (1) is wrapped
Include：
Multiple carbon fiber layers being made up of carbon cloth and net tire are stacked, layered product is formed, each carbon of the layered product is formed
The density of fibrous layer is different；
By needling process, density through-thickness is made in the layered product and is reduced in gradient from first surface to second surface
Carbon fibre fabric.
3. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that in step (3),
The thickness of the high-density region is the 5-15% of the pattern bonded fabrics gross thickness.
4. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step (1) institute
The carbon fiber stated is viscose base carbon fibre or polyacrylonitrile-based carbon fibre.
5. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that in step (2)
By chemical vapor infiltration or liquid impregnation/carbonizatin method, the fiber lap-joint of the carbon fibre fabric formed matrix carbon or
Person is in fiber surface formation carbonaceous protective layer.
6. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step (3) institute
The corresponding high-density region of the first surface to the pattern bonded fabrics stated carries out densification, including：
Flow through the first surface of carbon-source gas from the pattern bonded fabrics is parallel, other surfaces are protected, and pass through the carbon
The free diffusing and deposition of source gas make the corresponding high-density region densification of the first surface of the pattern bonded fabrics.
7. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step (3) institute
The corresponding high-density region of the first surface to the pattern bonded fabrics stated carries out densification, including：
Will in the first surface immersion liquid phase presoma of the pattern bonded fabrics, acted on by capillary siphoning or combine vacuumize it is strong
Changing siphon makes the liquid phase presoma be spread to the corresponding high-density region of the first surface；
The corresponding high-density region of the first surface of the pattern bonded fabrics is densified by heat treatment.
8. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that step (3) institute
The corresponding high-density region of the first surface to the pattern bonded fabrics stated carries out densification, including：
Liquid phase presoma is coated to the first surface of the pattern bonded fabrics, by capillary action by the liquid phase presoma
It is impregnated into the corresponding high-density region of the first surface of the pattern bonded fabrics；
It is subsequently heat-treated to make the corresponding high-density region densification of first surface of the pattern bonded fabrics.
9. the preparation method of lightening fire resistant thermally protective materials according to claim 1, it is characterised in that：Step (4) institute
The oxidation protection coating stated is the ceramic coating of resistance to 1500 DEG C of high temperature above.
10. the lightening fire resistant thermally protective materials prepared by any one of claim 1-9 methods provided.
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