CN117819999A - Heat-proof, heat-insulating and bearing integrated light carbon-ceramic composite material and preparation and application thereof - Google Patents
Heat-proof, heat-insulating and bearing integrated light carbon-ceramic composite material and preparation and application thereof Download PDFInfo
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- 229910052582 BN Inorganic materials 0.000 claims description 2
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Abstract
The invention discloses a heat-proof, heat-insulation and bearing integrated light carbon-ceramic composite material and preparation and application thereof, and belongs to the technical field of ultra-temperature heat protection materials. The invention adopts the organic aerogel-fiber synergic carbonization technology under the leading of ceramic powder and the porous carbon aerogel network matrix deep ceramization technology, thereby realizing the multi-scale synergic strengthening and toughening and antioxidation modification of the light carbon-based composite material. Fiber reinforced gradient SiC or ZrB with 200-2000 mu m surface layer of obtained material 2 -SiC ceramic layer with oxidation, ablation and erosion resistanceUsing; the bottom layer is a fiber reinforced carbon aerogel-ceramic particle double-network matrix, plays roles of ultrahigh temperature bearing, heat insulation and oxidation resistance, and further realizes the integration of reusable ultrahigh temperature non-ablative heat insulation bearing.
Description
Technical Field
The invention relates to the technical field of ultra-temperature heat protection materials, in particular to a heat-proof, heat-insulation and bearing integrated light carbon-ceramic composite material and a preparation method thereof.
Background
The light carbon aerogel composite material is a novel nano porous carbon material formed by stacking high-strength and high-toughness fibers and nano carbon particles, has excellent performances of light porosity of the aerogel, high-temperature stability of the carbon material, high toughness of the composite material and the like, is an ideal ultrahigh-temperature heat insulation-bearing composite material, and has an application prospect in the field of thermal protection of aerospace vehicles, power systems of aerospace vehicles and the like. However, the nano carbon matrix is extremely easy to oxidize at a temperature above 400 ℃, the structural strength of the material is destroyed, and the performance requirement of a new generation of aircraft heat protection system cannot be met. Therefore, the introduction of the antioxidant component into the porous carbon material is an effective way, so that the temperature sensitivity characteristic of the porous carbon material is improved, and the multifunctional integrated requirement of a heat protection system is met.
The precursor soaking and cracking process is widely applied to the modification and oxidation resistance of the carbon material matrix due to the characteristics of strong designability of components, low heat treatment temperature, simple process and the like. However, for carbon aerogel materials, the process is limited to a certain extent, and the cracking process releases small molecules to cause volume shrinkage, and the process is mismatched with the expansion of matrix carbon to generate stress, so that the contact neck among matrix particles is broken to generate defects, the structural integrity of the matrix is damaged, the mechanical properties of the matrix are influenced, and the application requirements of heat prevention-heat insulation-bearing integration cannot be met. Meanwhile, the precursor dipping and cracking process has certain limitation in the aspects of antioxidation modification due to the problems of limited precursor yield, limited single-introduced component types, long preparation period and the like.
Therefore, the invention provides an organic aerogel-fiber synergistic carbonization technology under the leading of ceramic powder, which is realized by doping one or more functional ceramic powderAdding the mixture into phenolic resin reaction solution, introducing the mixture into fiber reinforcement along with the phenolic resin reaction solution, obtaining a multi-scale double-network structure powder doped carbon aerogel composite material formed by a micron-sized carbon-ceramic framework and a nano-sized porous carbon framework through the processes of crosslinking, curing, normal-pressure drying, carbonization and the like, and preparing fiber reinforcement gradient SiC or ZrB on the basis of the matrix by adopting a deep ceramization technology 2 The SiC ceramic surface layer, thereby obtaining the light carbon-ceramic composite material with the heat-proof, heat-insulating and bearing integrated function.
Disclosure of Invention
The invention aims to provide a heat-proof heat-insulation-bearing integrated light carbon-ceramic composite material and a preparation method thereof, so as to meet the heat protection requirement under the conditions of ultrahigh temperature and oxygen and high bearing.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a heat-proof heat-insulation-bearing integrated light carbon-ceramic composite material comprises the following steps:
(1) Mixing phenolic resin, a pore-forming agent, a curing agent, deionized water, ceramic powder and a silane coupling agent according to a certain proportion, and uniformly stirring to obtain a powder doped phenolic resin reaction solution; wherein the phenolic resin is novolac resin, the pore-forming agent is one or more of ethanol, glycol and isopropanol, and the curing agent is one or more of benzenesulfonyl chloride, hexamethylenetetramine and p-toluenesulfonic acid.
(2) Introducing the reaction solution obtained in the step (1) into a die provided with the fiber mat, fully immersing the fiber mat by the solution, and realizing good infiltration effect by one or more methods of vacuum impregnation, mechanical vibration impregnation or ultrasonic vibration impregnation.
(3) Heating and curing the impregnated fiber mat obtained in the step (2), wherein the curing temperature is (120-200) DEG C, and the curing time is (8-20) h; and then placing the mixture into an oven for normal pressure drying, wherein the drying temperature is 100-150 ℃ and the drying time is 24-48 h, and obtaining the powder doped fiber reinforced phenolic xerogel.
(4) Carbonizing and cracking the xerogel obtained in the step (3) under inert atmosphere or vacuum condition to obtain a powder doped carbon aerogel composite material; and processing the material into a required shape, and then cleaning and drying the material.
(5) Preparing slurry by blending one or more than two of ceramic particles such as silicon carbide, zirconium diboride, aluminum oxide, boron trioxide and the like, and applying the slurry to the surface of the composite material obtained in the step (4); and (3) carrying out heat treatment at the temperature of (1400-1600) DEGC/(1-5) h through a silicon powder embedding process, and finally obtaining the SiC or modified SiC ceramic layer on the surface layer of the powder doped carbon aerogel composite material in situ to obtain the heat-resistant, heat-insulating and bearing integrated light carbon-ceramic composite material.
In the step (1), the powder is one or more of micron-sized and nano-sized ceramic powder silicon carbide, silicon dioxide, boron nitride, boron trioxide, aluminum trioxide, zirconium carbide, zirconium dioxide, zirconium diboride, hafnium carbide or hafnium diboride, the particle size range is (0.03-10) mu m, and the silane coupling agent is one or more of vinyl triethoxysilane (A151), vinyl trichlorosilane (A150), gamma-aminopropyl trimethoxysilane (KH-540), gamma-aminopropyl triethoxysilane (KH-550), gamma-methacryloxypropyl trimethoxysilane (KH-570) and the like.
In the step (1), the types and contents of the doped ceramic powder (the mass percentage of the powder doped phenolic resin reaction solution) include, but are not limited to, one of the following 10 types:
(1) 5-40% of silicon carbide with a particle size of 1 μm;
(2) 5-20% of silicon carbide with the particle size of 0.03 mu m;
(3) 5-30% of silicon carbide with a particle size of 1 mu m, and 5-20% of silicon carbide with a particle size of 0.03 mu m;
(4) 5-30% of silicon carbide with a particle size of 1 μm, and 5-30% of silicon dioxide with a particle size of 1 μm;
(5) 5-15% of zirconium carbide with a particle size of 1 mu m, and 5-20% of silicon carbide with a particle size of 0.03 mu m;
(6) 5-15% of zirconium diboride with the particle size of 1 mu m, and 5-15% of silicon carbide with the particle size of 1 mu m;
(7) 5-20% of silicon dioxide with the particle size of 1 mu m, and 3-10% of diboron trioxide with the particle size of 1 mu m;
(8) 5-10% of silicon dioxide with the particle size of 1 mu m, and 5-15% of aluminum oxide with the particle size of 1 mu m;
(9) 3-10% of hafnium diboride with the particle size of 1 mu m, 3-10% of zirconium diboride with the particle size of 1 mu m, and 3-15% of silicon carbide with the particle size of 3 mu m;
(10) 3-10% of zirconium carbide with a particle size of 0.05 mu m, 3-5% of diboron trioxide with a particle size of 1 mu m, 3-15% of silicon carbide with a particle size of 0.5 mu m, and 3-15% of silicon dioxide with a particle size of 1 mu m.
In the step (1), the mass ratio of the phenolic resin, the pore-forming agent, the curing agent and the deionized water is (2-10), 1 (0.1-1), preferably (6-10), 15-25, 1 (0.5-1), the mass ratio of the reaction solution to the ceramic powder is (1.5-19), preferably (1.5-10), 1 (1.01-0.1), preferably 1 (0.01-0.05).
In the step (2), the fiber felt is a pre-oxidized fiber needled felt, and the bulk density of the felt body is (0.1-0.5) g/cm 3 Preferably (0.1 to 0.3) g/cm 3 。
In the step (2), the vacuum impregnation process has the vacuum degree of less than or equal to-0.1 MPa and the dwell time of (1-48) h, preferably (24-36) h; the mechanical vibration impregnation process is characterized in that the vibration frequency of a vibration testing machine is (30-60) Hz, preferably (30-50) Hz, the amplitude is (0-3.5) mm, preferably (1-2.5) mm, and the vibration time is (1-5) h, preferably (1.5-4) h; the ultrasonic vibration impregnation process has ultrasonic time of (0.5-3) h, preferably (1-2) h. In the step (3), the normal pressure drying temperature is 100-150 ℃ and the time is 24-48 hours.
In the step (4), the carbonization process is different according to the addition conditions of the ceramic powder, including but not limited to the following 10 types (the listed 10 types of doped ceramic powder addition conditions listed in the step (1) correspond to each other in sequence by serial number):
(1) Raising the temperature to (800-1000) DEG C at the speed of (1-5) DEG C/min, and preserving the temperature for (1-2) h;
(2) Raising the temperature to (800-1000) DEG C at the speed of (5-10) DEG C/min, and preserving the temperature for (1-4) h;
(3) Raising the temperature to (600-1000) DEG C at the speed of (4-8) DEG C/min, and preserving the temperature for (1-5) h;
(4) Heating to (600-900) DEG C at the speed of (5-10) DEG C/min, and preserving heat for (1-2) h;
(5) Raising the temperature to (1200-1500) DEG C at the speed of (1-5) DEG C/min, and preserving the temperature for (2-4) h;
(6) Raising the temperature to (800-1200) DEG C at the speed of (5-8) DEG C/min, and preserving the temperature for (1-2) h;
(7) Raising the temperature to (600-800) DEG C at the speed of (5-10) DEG C/min, and preserving the temperature for (2-3) h;
(8) Heating to (600-800) DEG C at the speed of (2-4) DEG C/min, and preserving heat for (1-2) h;
(9) Raising the temperature to (800-1200) DEG C at the speed of (5-10) DEG C/min, and preserving the temperature for (2-4) h;
(10) Raising the temperature to (800-1000) DEG C at the speed of (5-10) DEG C/min, and preserving the temperature for (1-2) h;
wherein the density of the obtained powder doped carbon aerogel composite material is (0.4-1.0) g/cm 3 The carbonization shrinkage is 5-20%, the compression strength is (5-60) MPa, and the bending strength is (3-35) MPa.
In the step (5), the thickness of the surface layer of the obtained ceramic is (200-2000) mu m, the ceramic and the powder doped carbon aerogel composite material form gradient transition, no obvious coating/matrix interface exists, and the ceramic is well combined and has no cracking.
The heat-proof heat-insulation-bearing integrated light carbon-ceramic composite material prepared by the invention is prepared from 200-2000 mu m fiber reinforced gradient SiC or ZrB 2 The SiC ceramic surface layer and the fiber reinforced carbon aerogel-ceramic particle double-network matrix bottom layer are formed by adopting an organic aerogel-fiber synergistic carbonization technology under the dominant of ceramic powder and a porous carbon aerogel network matrix deep ceramization technology. The ceramic particles are uniformly dispersed and distributed in the carbon aerogel three-dimensional nano-network structure in the matrix to form a multi-scale double-network structure consisting of a micron-sized carbon-ceramic framework and a nano-sized porous carbon framework. The material realizes the repeatable use non-ablative heat prevention under the ultra-high temperature aerobic environment by the ceramic powder distributed in the whole material and the ceramic layer on the surface layer by the ceramicsThe ceramic powder modified carbon aerogel composite substrate realizes ultrahigh temperature heat insulation and bearing, and finally achieves the aim of heat prevention-heat insulation-bearing integration.
The design mechanism of the invention is as follows:
according to the invention, by utilizing the liquidity, the antioxidation ceramic powder is introduced into the fiber felt along with the phenolic resin reaction solution and uniformly dispersed, and the novel composite material with a multi-scale double-network structure formed by a micron-sized carbon-ceramic framework and a nano-sized porous carbon framework is obtained through the processes of crosslinking, solidifying, drying, carbonizing and the like, so that the antioxidation ablative performance of the composite material in a high-temperature aerobic environment is remarkably improved. And meanwhile, phenolic aldehyde gel particles are nucleated and grown on ceramic particles, and in the subsequent carbonization process, the shrinkage behavior of the phenolic aldehyde gel particles is acted on the ceramic particles, so that the overall shrinkage rate of a matrix is obviously reduced, and shrinkage deformation cracking is effectively relieved. In addition, due to poor compatibility of the phenolic aldehyde organic solution and the inorganic ceramic powder, the doping of the powder is extremely easy to cause the destruction of a matrix network structure, thereby influencing the mechanical property of the powder. Therefore, the invention modifies the inorganic powder by adding the silane coupling agent, wherein the silane coupling agent contains organic functional groups and siloxy groups, and can be respectively combined with phenolic resin and ceramic powder to form a combined layer of phenolic-silane coupling agent-ceramic powder, so that the two are connected through chemical bonds, the compatibility is obviously improved, and the matrix skeleton strength is improved; by combining with the organic fiber with excellent performance, the toughness of the matrix is further improved, so that the high-toughness composite material is obtained. Therefore, when the powder doped carbon aerogel composite material is used as a matrix, 2000 mu m crack-free deep ceramization can be realized by a surface limited domain ceramization in-situ reaction technology. In a high-temperature aerobic environment, the surface ceramic layer of the integrated light carbon-ceramic composite material is used as a main oxygen barrier to resist ablation and scouring, and the internal ceramic particles of the integrated light carbon-ceramic composite material oxidize and consume and block oxygen to be used as an auxiliary barrier to resist oxidation and erosion, so that the high-temperature service reliability of the material is effectively improved.
The invention has the following beneficial effects:
1. the invention realizes multi-scale collaborative strengthening and toughening and antioxidation modification of the light carbon-based composite material by adopting an organic aerogel-fiber collaborative carbonization technology under the leading of ceramic powder and a porous carbon aerogel network matrix deep ceramization technology. The heat protection, heat insulation and bearing integration is realized by means of the heat insulation, bearing and oxidation resistance of the carbon aerogel-ceramic particle matrix and the oxidation resistance, ablation resistance and anti-scouring effects of the surface gradient ceramic layer.
2. According to the method, the density, carbonization shrinkage, thermal conductivity, mechanical property and the like of the composite material can be regulated and controlled by changing the types and the content of ceramic powder, so that the multifunctional requirements of the material under different service environments are further realized. Meanwhile, the method disclosed by the invention is simple to operate and low in cost, and the ceramic phase can be introduced without an additional heat treatment process, so that the damage to the three-dimensional structure of the matrix fiber and the porous carbon can be reduced.
Drawings
FIG. 1 is a microstructure topography of a powder doped carbon aerogel composite; wherein (a) a carbon-ceramic nanonetwork structure; (b) a micron-sized carbon-ceramic backbone; (c) a nanoscale porous carbon skeleton;
FIG. 2 is a graph of the mechanical properties of a powder doped carbon aerogel composite; wherein (a) a bending strength curve; (b) a compressive strength profile;
FIG. 3 is a topography of a ceramic layer obtained by a deep ceramming technique;
FIG. 4 is a graph showing the ablation rate of an oxyacetylene ablation line at 1800 ℃ as a function of the number of ablations;
FIG. 5 is a graph of oxyacetylene ablation back temperature for carbon-ceramic-1 and carbon-ceramic-2 composites;
FIG. 6 is a graph of macroscopic and microscopic tissue morphologies of the powder doped carbon aerogel composite of the comparative example; wherein (a) the SiC powder is distributed in the material; (b) agglomerated SiC morphology;
FIG. 7 is a graph of the mechanical properties of the powder doped carbon aerogel composite of the comparative example; wherein (a) a bending strength curve; (b) a compressive strength profile.
Detailed Description
For a further understanding of the present invention, the present invention is described below with reference to the examples, which are only illustrative of the features and advantages of the present invention and are not intended to limit the scope of the claims of the present invention.
Since SiC ceramics have excellent properties such as high temperature resistance, corrosion resistance, oxidation resistance and high surface radiation, the invention is further illustrated by the following examples in which SiC ceramic powder is used as an oxidation-resistant doping component to prepare a lightweight carbon-ceramic composite material having excellent comprehensive properties, but the scope of the invention is not limited to the examples.
Example 1
The embodiment is the preparation of the integrated light carbon-ceramic composite material, and the specific process is as follows:
(1) Phenolic novolac resin, ethylene glycol, hexamethylenetetramine and deionized water according to the proportion of 7.5:17.5:1:1, and then adding silicon carbide powder (particle size of 1 μm) with a final concentration of 20. 20 wt percent and a silane coupling agent KH-550 accounting for 5. 5wt percent of the powder mass in sequence, and mechanically stirring for 2 hours to uniformly mix the powder to obtain a powder doped phenolic resin reaction solution.
(2) Introducing the above reaction solution into a reactor having a bulk density of 0.2g/cm 3 The pre-oxidized fiber needled felt (produced by Jiangsu Tianguan Gao new technology Co., ltd.) is placed in a vacuum pressure tank (vacuum degree is less than or equal to-0.1 MPa), and the pressure is maintained for 24 hours, so that the solution and the fiber are fully soaked by using the atmospheric pressure.
(3) Crosslinking, curing and preserving heat for 10 hours at the temperature of 180 ℃ on the impregnated fiber felt; and demolding, and drying in an oven at 120 ℃ and normal pressure for 24 hours to obtain the powder doped pre-oxidized fiber reinforced phenolic xerogel.
(4) And (3) putting the powder doped organic xerogel into a carbonization furnace, introducing protective atmosphere argon, heating to 1000 ℃ from room temperature at a speed of 5 ℃/min, preserving heat for 1h, and carbonizing to obtain the powder doped carbon aerogel composite material. It is processed into a desired shape (rectangle, width×length×height=20×30×10 mm) 3 ) And (5) cleaning and drying by using alcohol.
(5) Silicon carbide (25 wt percent), zirconium diboride (35 wt percent), aluminum oxide (10 wt percent) and boron trioxide (30 wt percent) powder are mixed with alcohol according to a proportion to prepare slurry, and the slurry is applied to the surface of the composite material and embedded by silicon powderThe process comprises the steps of carrying out heat treatment at 1600 ℃ for 1h, and finally obtaining gradient ZrB on the surface layer of the powder doped carbon aerogel composite material 2 -a SiC ceramic layer, obtaining said heat-insulating-bearing integrated light carbon-ceramic composite (carbon-ceramic-1).
The heat-proof heat-insulation-bearing integrated light carbon-ceramic composite material matrix obtained by the steps is still in a porous structure (shown in figure 1), siC ceramic powder is uniformly distributed in the matrix, particles are connected through a carbon aerogel network to form a micro-nano multi-scale double-network structure consisting of a micron-sized carbon-ceramic particle network framework and a nano-sized porous carbon three-dimensional network framework, and the density is 0.65g/cm 3 The thermal conductivity was 0.32W/(m.K), the flexural strength was 28MPa, and the compressive strength was 47MPa (the mechanical properties were shown in FIG. 2). Surface layer ZrB 2 The SiC content distribution between the SiC ceramic layer and the matrix is in a gradient transition structure, the thickness is 1600 mu m, the ceramic layer is well combined with the matrix, and no cracking is seen (as shown in figure 3). Oxyacetylene is ablated for 5 times at 1800 ℃ and 600s once, and the linear ablation rate is 2.9x10 -4 The back temperature of a 10mm thick sample is only about 900 ℃ (as shown in carbon-ceramic-1 in fig. 4 and 5), and the material has excellent ultra-high temperature repeatable non-ablative heat-proof, heat-insulating and bearing performances.
Example 2
The procedure and conditions were the same as in example 1, except that the doping powder type, content and impregnation process were different from example 1. The technological parameters affecting the heat-proof and heat-insulating properties of the light carbon-based composite material are mainly the types and the contents of doped powder, the concentration of phenolic reaction solution and the like, and in the embodiment 2, two kinds of powder co-doping are mainly adopted to further explain the invention, and the method specifically comprises the following steps:
(1) Phenolic novolac resin, ethylene glycol, hexamethylenetetramine and deionized water according to the proportion of 7.5:22.5:1:1, then adding silicon carbide powder (particle size of 1 μm) with final concentration of 10. 10wt percent, silicon dioxide powder (particle size of 1 μm) with final concentration of 5. 5wt percent and silane coupling agent KH-570 with powder mass of 7. 7 wt percent in sequence, and mechanically stirring for 2 hours to uniformly mix the materials, thus obtaining the powder doped phenolic resin reaction solution.
(2) Introducing the reaction solution into a deviceHas a density of 0.15g/cm 3 In a mould of a pre-oxidized fiber needled felt (manufactured by Jiangsu Tianguan Gao New technology Co., ltd.), immersing the fiber felt in the solution, carrying out auxiliary impregnation for 2 hours at a frequency of 45Hz and an amplitude of 2mm by using a vibration tester, then placing the fiber felt into a vacuum pressure tank (the vacuum degree is less than or equal to-0.1 MPa), maintaining the pressure for 30 hours, and further fully impregnating the solution and the fiber by using the atmospheric pressure.
(3) Crosslinking, curing and preserving heat for 15 hours at the temperature of 120 ℃ of the impregnated fiber felt; and demolding, and drying in an oven at 120 ℃ and normal pressure for 36 hours to obtain the powder doped pre-oxidized fiber reinforced phenolic xerogel.
(4) And (3) putting the organic xerogel into a carbonization furnace, introducing protective atmosphere argon, heating to 800 ℃ from room temperature at a speed of 10 ℃/min, and then preserving heat for 1h, and carbonizing to obtain the powder doped carbon aerogel composite material. It is processed into a desired shape (rectangle, width×length×height=20×30×10 mm) 3 ) And (5) cleaning and drying by using alcohol.
(5) Mixing silicon carbide (35 wt.%), silicon dioxide (25 wt.%), aluminium oxide (10 wt.%) and diboron trioxide (30 wt.%) with alcohol according to a certain proportion to obtain slurry, applying the slurry on the surface of the above-mentioned powder doped carbon aerogel composite material, and making heat treatment for 1.5 hr at 1600 deg.C by means of silicon powder embedding process so as to obtain SiC gradient ceramic layer on the surface layer of the powder doped carbon aerogel composite material so as to obtain the invented heat-resisting heat-insulating-bearing integrated light carbon-ceramic composite material (carbon-ceramic-2).
The heat-proof heat-insulation-bearing integrated light carbon-ceramic composite material matrix obtained by the steps is still of a porous structure, and the density is 0.58g/cm 3 The thermal conductivity was 0.28W/(mK), the flexural strength was 20MPa, and the compressive strength was 30MPa. The thickness of the surface ceramic layer is 1800 mu m, and no cracking is seen. SiO (SiO) 2 Has low density and low thermal conductivity, and has fluidity at high temperature, and can cover the surface of the matrix carbon particles to isolate oxygen. In comparison with example 1, siC is used with SiO 2 By combining doping, the overall heat conduction of the material can be further reduced on the basis of guaranteeing the oxidation resistance function, the heat insulation performance is improved, and the ablation back temperature of a 10 mm-thick sample oxyacetylene at 1800 ℃ is reduced to 820 ℃ (as shown in the carbon-ceramic-2 in figure 5).
Example 3
(1) Phenolic novolac resin, ethylene glycol, hexamethylenetetramine and deionized water according to the proportion of 7.5:15:1:1, then adding zirconium diboride powder (particle size of 1 mu m) with the final concentration of 10. 10wt percent and silicon carbide powder (particle size of 1 mu m) with the final concentration of 10. 10wt percent, and silane coupling agent KH-550 accounting for 5. 5wt percent of the powder mass in sequence, and mechanically stirring for 3 hours to uniformly mix the powder materials, thus obtaining the powder doped phenolic resin reaction solution.
(2) Introducing the above reaction solution into a reactor having a bulk density of 0.15g/cm 3 In a mold of a pre-oxidized fiber needled felt (manufactured by Jiangsu Tianguan Gao New technology Co., ltd.), immersing the fiber felt in the solution, performing auxiliary impregnation for 1.5 hours at a frequency of 45Hz and an amplitude of 1.5mm by using a vibration tester, then placing the fiber felt in a vacuum pressure tank (the vacuum degree is less than or equal to-0.1 MPa), maintaining the pressure for 24 hours, and further performing full impregnation of the solution and the fiber by using the atmospheric pressure.
(3) Crosslinking, curing and preserving heat for 12 hours at the temperature of 120 ℃ for the impregnated fiber felt; and demolding, and drying in an oven at 120 ℃ and normal pressure for 30 hours to obtain the powder doped pre-oxidized fiber reinforced phenolic xerogel.
(4) And (3) putting the powder doped organic xerogel into a carbonization furnace, introducing protective atmosphere argon, heating to 1000 ℃ from room temperature at a speed of 5 ℃/min, preserving heat for 1.5 hours, and carbonizing to obtain the powder doped carbon aerogel composite material. It is processed into a desired shape (rectangle, width×length×height=20×30×10 mm) 3 ) And (5) cleaning and drying by using alcohol.
(5) Silicon carbide (25 wt percent), zirconium diboride (35 wt percent), aluminum oxide (10 wt percent) and boron trioxide (30 wt percent) powder are mixed with alcohol according to a proportion to prepare slurry, the slurry is applied to the surface of the composite material, and after the silicon powder embedding process and the heat treatment for 1h at 1600 ℃, the gradient ZrB is finally obtained on the surface layer of the powder doped carbon aerogel composite material 2 -a SiC ceramic layer, obtaining said heat-insulating-bearing integrated light carbon-ceramic composite (carbon-ceramic-3).
The heat-proof heat-insulation-bearing integrated light carbon-ceramic composite material matrix obtained by the stepsStill porous with a density of 0.68g/cm 3 The thermal conductivity was 0.38W/(mK), the flexural strength was 23MPa, and the compressive strength was 46MPa. The thickness of the surface ceramic layer is 1200 mu m, the bonding with the matrix is good, and no cracking is seen. ZrB 2 Has excellent performances of high melting point, high strength, high thermal stability, oxidation ablation resistance and the like, and can effectively improve the thermal protection performance of the matrix. Oxyacetylene is ablated for 5 times at 1800 ℃ and 600s once, and the linear ablation rate is 2.3 multiplied by 10 -4 mm/s. In comparison with example 1, siC and ZrB are used 2 The combination of doping can improve the oxidation and ablation resistance of the material in an ultra-high temperature environment, and further widen the thermal protection temperature range.
Comparative example 1
The comparative experiment of example 1 has the disadvantage that no silane coupling agent is added during the preparation of the powder doped phenolic resin reaction solution, and other process parameters remain unchanged. The method comprises the following specific steps:
(1) Phenolic novolac resin, ethylene glycol, hexamethylenetetramine and deionized water according to the proportion of 7.5:17.5:1:1, adding silicon carbide powder (with the grain diameter of 1 mu m) with the final concentration of 20. 20 wt percent, and mechanically stirring for 2 hours to uniformly mix the powder to obtain the powder doped phenolic resin reaction solution.
(2) Introducing the above reaction solution into a reactor having a bulk density of 0.2g/cm 3 The pre-oxidized fiber needled felt (produced by Jiangsu Tianguan Gao new technology Co., ltd.) is placed in a vacuum pressure tank (vacuum degree is less than or equal to-0.1 MPa), and the pressure is maintained for 24 hours, so that the solution and the fiber are fully soaked by using the atmospheric pressure.
(3) Crosslinking, curing and preserving heat for 10 hours at the temperature of 180 ℃ on the impregnated fiber felt; and demolding, and drying in an oven at 120 ℃ and normal pressure for 24 hours to obtain the powder doped pre-oxidized fiber reinforced phenolic xerogel.
(4) And (3) putting the powder doped organic xerogel into a carbonization furnace, introducing protective atmosphere argon, heating to 1000 ℃ from room temperature at a speed of 5 ℃/min, preserving heat for 1h, and carbonizing to obtain the powder doped carbon aerogel composite material. It is processed into a desired shape (rectangle, width×length×height=20×30×10 mm) 3 ) Post-alcohol cleanerWashing and drying.
(5) Silicon carbide (25 wt percent), zirconium diboride (35 wt percent), aluminum oxide (10 wt percent) and boron trioxide (30 wt percent) powder are mixed with alcohol according to a proportion to prepare slurry, the slurry is applied to the surface of the composite material, and after the silicon powder embedding process and the heat treatment for 1h at 1600 ℃, the gradient ZrB is finally obtained on the surface layer of the powder doped carbon aerogel composite material 2 -a SiC ceramic layer, obtaining said heat-insulating-bearing integrated light carbon-ceramic composite (carbon-ceramic-1-contrast).
The density of the matrix of the composite material prepared by the process is 0.67g/cm 3 The thermal conductivity is 0.31W/(m.K), and the inside of the material has defects such as cracking. The SiC powder is unevenly distributed, and local agglomeration phenomenon occurs (as shown in figure 6); the internal carbon particles were poorly bonded to the SiC particles, and the flexural strength was 11MPa and the compressive strength was 18MPa (see fig. 7). The thickness of the surface ceramic layer is 2000 mu m, the surface is loose and porous, and the ceramic layer is very easy to fall off. From this, the density of the matrix material in example 1 is similar to that of the comparative example, but the strength is significantly higher than that of the comparative example, and the internal powder is distributed more uniformly, and the performance improvement is mainly due to the silane coupling agent as the binder and the dispersant, so that the chemical combination between the ceramic particles and the phenolic resin is formed, and meanwhile, the dispersibility and the stability of the ceramic powder in the solution are improved.
Claims (9)
1. A preparation method of a heat-proof heat-insulation-bearing integrated light carbon-ceramic composite material is characterized by comprising the following steps of: mainly comprises the following steps:
(1) Mixing and uniformly stirring phenolic resin, a pore-forming agent, a curing agent, deionized water, ceramic powder and a silane coupling agent according to a required proportion to obtain a powder doped phenolic resin reaction solution;
(2) Introducing the reaction solution obtained in the step (1) into a die provided with a fiber mat, fully infiltrating the fiber mat by the reaction solution, and realizing good infiltration effect by one or more methods of vacuum impregnation, mechanical vibration impregnation or ultrasonic vibration impregnation;
(3) Carrying out high-temperature curing and normal-pressure drying on the impregnated fiber mat obtained in the step (2) to obtain powder doped fiber reinforced phenolic xerogel; wherein the curing temperature is 120-200 ℃ and the curing time is 8-20 h;
(4) Carbonizing and cracking the xerogel obtained in the step (3) under inert atmosphere or vacuum condition to obtain a powder doped carbon aerogel composite material; processing the raw materials into a required shape, and then cleaning and drying the raw materials;
(5) Preparing slurry by blending one or more than two of silicon carbide, zirconium diboride, aluminum oxide and boron trioxide ceramic particles, and applying the slurry to the surface of the composite material obtained in the step (4); and carrying out heat treatment at 1400-1600 ℃ for 1-5 h through a silicon powder embedding process, and finally obtaining the SiC or modified SiC ceramic layer on the surface layer of the powder doped carbon aerogel composite material in situ to obtain the heat-resistant, heat-insulating and bearing integrated light carbon-ceramic composite material.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the phenolic resin is novolac; the pore-forming agent is one or more of ethanol, glycol or isopropanol; the curing agent is one or more than two of benzenesulfonyl chloride, hexamethylenetetramine or p-toluenesulfonic acid;
the ceramic powder is one or more than two of micron-sized and nano-sized ceramic powder silicon carbide, silicon dioxide, boron nitride, boron trioxide, aluminum trioxide, zirconium carbide, zirconium dioxide, zirconium diboride, hafnium carbide or hafnium diboride, and the grain size range is 0.03-10 mu m;
the silane coupling agent is one or more than two of vinyl triethoxysilane, vinyl trichlorosilane, gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the type and content of the doped ceramic powder are one of the following 10 types:
(1) 5-40% of silicon carbide with a particle size of 1 μm;
(2) 5-20% of silicon carbide with the particle size of 0.03 mu m;
(3) 5-30% of silicon carbide with a particle size of 1 mu m, and 5-20% of silicon carbide with a particle size of 0.03 mu m;
(4) 5-30% of silicon carbide with a particle size of 1 μm, and 5-30% of silicon dioxide with a particle size of 1 μm;
(5) 5-15% of zirconium carbide with a particle size of 1 mu m, and 5-20% of silicon carbide with a particle size of 0.03 mu m;
(6) 5-15% of zirconium diboride with the particle size of 1 mu m, and 5-15% of silicon carbide with the particle size of 1 mu m;
(7) 5-20% of silicon dioxide with the particle size of 1 mu m, and 3-10% of diboron trioxide with the particle size of 1 mu m;
(8) 5-10% of silicon dioxide with the particle size of 1 mu m, and 5-15% of aluminum oxide with the particle size of 1 mu m;
(9) 3-10% of hafnium diboride with the particle size of 1 mu m, 3-10% of zirconium diboride with the particle size of 1 mu m, and 3-15% of silicon carbide with the particle size of 3 mu m;
(10) 3-10% of zirconium carbide with a particle size of 0.05 mu m, 3-5% of diboron trioxide with a particle size of 1 mu m, 3-15% of silicon carbide with a particle size of 0.5 mu m, and 3-15% of silicon dioxide with a particle size of 1 mu m.
4. The method of manufacturing according to claim 1, characterized in that: in the step (1), the mass ratio of phenolic resin to pore-forming agent to curing agent to deionized water is (2-10): (8-25): 1, (0.1-1), and the phenolic resin, pore-forming agent and the curing agent are mixed to form a reaction solution; the mass ratio of the reaction solution to the ceramic powder is (1.5-19): 1, and the mass ratio of the ceramic powder to the silane coupling agent is (0.01-0.1).
5. The method of manufacturing according to claim 1, characterized in that: in the step (2), the fiber felt is a pre-oxidized fiber needled felt, and the bulk density of the felt body is 0.1-0.5 g/cm 3 ；
The vacuum impregnation is carried out, the vacuum degree is less than or equal to-0.1 MPa, and the pressure maintaining time is 1-48 h;
the mechanical vibration impregnation is carried out, the vibration frequency of the vibration testing machine is 30-60 Hz, the amplitude is 0-3.5 mm, and the vibration time is 1-5 h;
the ultrasonic vibration impregnation is carried out for 0.5-3 hours;
in the step (3), the normal pressure drying temperature is 100-150 ℃ and the time is 24-48 h.
6. The method of manufacturing according to claim 1, characterized in that: in the step (4), the carbonization and pyrolysis are different according to the addition conditions of the ceramic powder, and the number of the carbonization and pyrolysis is 10, and the listed 10 powder addition conditions are sequentially corresponding to those listed in the claim 3 according to the sequence: heating the mixture from room temperature to carbonization temperature,
(1) Heating to 800-1000 ℃ at a speed of 1-5 ℃/min, and preserving heat for 1-2 h;
(2) Heating to 800-1000 ℃ at a speed of 5-10 ℃/min, and preserving heat for 1-4 h;
(3) Heating to 600-1000 ℃ at the speed of 4-8 ℃/min, and preserving heat for 1-5 h;
(4) Heating to 600-900 ℃ at a speed of 5-10 ℃/min, and preserving heat for 1-2 h;
(5) Heating to 1200-1500 ℃ at a speed of 1-5 ℃/min, and preserving heat for 2-4 h;
(6) Heating to 800-1200 ℃ at a speed of 5-8 ℃/min, and preserving heat for 1-2 h;
(7) Heating to 600-800 ℃ at a speed of 5-10 ℃/min, and preserving heat for 2-3 h;
(8) Heating to 600-800 ℃ at a speed of 2-4 ℃/min, and preserving heat for 1-2 h;
(9) Heating to 800-1200 ℃ at a speed of 5-10 ℃/min, and preserving heat for 2-4 h;
(10) Heating to 800-1000 ℃ at a speed of 5-10 ℃/min, and preserving heat for 1-2 h;
wherein the density of the obtained powder doped carbon aerogel composite material is 0.4-1.0 g/cm 3 The carbonization shrinkage rate is 5-20%, the compression strength is 5-60 MPa, and the bending strength is 3-35 MPa.
7. The method of manufacturing according to claim 1, characterized in that: in the step (5), the thickness of the surface layer of the obtained ceramic is 200-2000 mu m, the ceramic and the powder doped carbon aerogel composite material form gradient transition, no obvious coating or matrix interface exists, and the ceramic is well combined and has no cracking.
8. A heat-resistant, heat-insulating, load-bearing integrated light carbon-ceramic composite prepared by the method of any one of claims 1-7.
9. A heat-insulating-load-bearing integrated lightweight carbon-ceramic composite material as claimed in claim 8 for use in non-ablative ultra-high temperature thermal protection materials in aircraft thermal protection systems.
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