CN113788684B - Gradient density carbon-ceramic composite material and preparation method thereof - Google Patents

Gradient density carbon-ceramic composite material and preparation method thereof Download PDF

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CN113788684B
CN113788684B CN202111109336.8A CN202111109336A CN113788684B CN 113788684 B CN113788684 B CN 113788684B CN 202111109336 A CN202111109336 A CN 202111109336A CN 113788684 B CN113788684 B CN 113788684B
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李健
王孟
高宇智
刘晓波
张恩爽
张杨
孙阔
苏立军
李文静
赵英民
张昊
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Aerospace Research Institute of Materials and Processing Technology
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Abstract

The invention provides a gradient density carbon-ceramic composite material and a preparation method thereof, wherein the method comprises the following steps: preparing a porous carbon fiber matrix; preparing a carbon-ceramic panel with uniform density by using a porous carbon fiber substrate; determining a threshold value of the preparation times of the carbon-ceramic panel with the gradient density obtained by the carbon-ceramic panel with the uniform density; determining the volume of precursor solution required for each impregnation of a carbon-ceramic panel of uniform density; pouring the precursor solution into a pressure container containing the carbon-ceramic panel with uniform density according to the volume required by each impregnation, sequentially carrying out vacuum impregnation, curing and sintering to complete one-time preparation until the preparation times reach a preparation time threshold value to obtain the carbon-ceramic panel with gradient density; and compounding a high-emissivity coating on the surface of the carbon-ceramic panel with the gradient density to obtain the carbon-ceramic composite material with the gradient density. The gradient density carbon-ceramic composite material prepared by the invention has light weight, excellent temperature resistance and heat insulation performance.

Description

Gradient density carbon-ceramic composite material and preparation method thereof
Technical Field
The invention relates to the technical field of thermal protection materials, in particular to a gradient density carbon-ceramic composite material and a preparation method thereof.
Background
The traditional C/C and C/SiC reinforced composite thermal protection material has the defects of heavy weight of components, long manufacturing period, high manufacturing cost and the like, and the reliability of the thermal protection material applied for a long time in a high-temperature environment is also limited by the characteristic that the carbon-based material is easy to oxidize. Therefore, the overspeed aircrafts in the United states mostly adopt light rigid heat insulation tiles mainly made of quartz and alumina fibers as heat insulation structures in large areas, but the ceramic fibers have poor temperature resistance, so that the mechanical properties of the materials are remarkably poor in a high-temperature environment, and even a composite high-temperature coating is difficult to use in an environment with the temperature of above 1400 ℃ for a long time.
The invention patent US7314648B1 discloses a TUFROC toughening integral fiber reinforced oxidation resistant component, which utilizes a carbon fiber/ceramic composite panel coated with a coating as a main high temperature resistant and dimensional bearing structure to ensure that the ultimate high temperature resistant temperature of the component reaches 1700 ℃. The TUFROC serving as a thermal protection component at the position of an end head, a wing front edge and a rudder shaft is successfully applied to the American X-37B aircraft, and the great potential of the high-temperature-resistant panel material in solving the thermal protection requirement of the ultra-high-speed aircraft at the extreme position is verified.
According to the above patent, the refractory panel material of the TUFROC member contains a stoichiometric ratio of Si-O-C ceramic phase, but the structure of the refractory panel material becomes unstable due to carbothermic reduction reaction of oxygen element with the carbon fiber matrix in a high temperature environment exceeding 1500 ℃; furthermore, since the high density refractory panels have a high thermal conductivity, it is necessary to increase the thickness of the refractory panel material to match the temperature resistance of the insulation material to which the low temperature section is attached, but this increases the weight of the overall component. In view of the above problems, it is necessary to develop a heat protective material having excellent thermal stability under a high temperature environment (> 1500 ℃), light weight, and heat insulating properties.
Disclosure of Invention
The invention provides a gradient density carbon-ceramic composite material and a preparation method thereof, and the prepared gradient density carbon-ceramic composite material has the characteristics of light weight, excellent temperature resistance and excellent heat insulation performance.
In a first aspect, the present invention provides a method for preparing a gradient density carbon-ceramic composite material, comprising the steps of:
(1) Preparing a porous carbon fiber matrix;
(2) Dipping the porous carbon fiber matrix in a precursor solution to prepare a carbon-ceramic panel with uniform density;
(3) Determining a threshold value of the preparation times of the carbon-ceramic panel with the gradient density obtained by the carbon-ceramic panel with the uniform density;
(4) Determining the volume of precursor solution required for each impregnation of a carbon-ceramic panel of uniform density;
(5) Pouring the precursor solution into a pressure container containing the carbon-ceramic panel with uniform density according to the volume required by each impregnation, sequentially carrying out vacuum impregnation, curing and sintering to complete one-time preparation until the preparation times reach the preparation time threshold value, and obtaining the carbon-ceramic panel with gradient density;
(6) And compounding a high-emissivity coating on the surface of the carbon-ceramic panel with the gradient density to obtain the carbon-ceramic composite material with the gradient density.
Preferably, in the step (1), the porous carbon fiber matrix is prepared by curing and sintering chopped carbon fibers and phenolic resin; wherein the diameter of the chopped carbon fiber is 8-12 mu m, and the length of the chopped carbon fiber is 0.5-5 mm.
Preferably, in the step (1), the porosity of the porous carbon fiber matrix is 75-90%;
the density of the porous carbon fiber matrix is 0.1-0.3 g/cm 3 。
Preferably, the precursor solution comprises a solute and a solvent; wherein the solute is polycarbosilane or vinyl polycarbosilane, and the solvent is at least one of divinylbenzene, toluene, xylene, n-hexane and tetrahydrofuran.
Preferably, the content of the solute in the precursor solution is 20% -50%.
Preferably, in step (3), the threshold number of preparation times is 1 to 3.
Preferably, in step (4), the volume of the precursor solution required for each impregnation of the carbon-ceramic panel having a uniform density is determined by the following formula:
Figure BDA0003273511860000031
wherein A is i The volume of the precursor solution required in the i-th impregnation is represented by V, the apparent volume of the carbon-ceramic panel with uniform density is represented by V, and the number of density areas of the carbon-ceramic panel with gradient density is represented by N; wherein i is more than or equal to 1 and less than or equal to N-1, and i is an integer;
wherein the carbon-ceramic panel having a gradient density has a number of density zones of 2 to 4.
Preferably, in the step (5), the vacuum impregnation time is 5 to 30min;
the curing temperature of the curing is 150-240 ℃, and the curing time is 4-8 h;
the sintering temperature of the sintering is 1200-1400 ℃, and the sintering time is 1-4 h.
Preferably, in the step (5), the bottom area of the pressure vessel is 1.5 to 2 times the planar area of the carbon-ceramic panel having uniform density.
Preferably, in step (5), the precursor solution is poured in portions and along the edge of the pressure vessel.
Preferably, in the step (5), the carbon-ceramic panel having a gradient density has a density of 0.5 to 1.0g/cm 3 。
Preferably, in step (6), the high emissivity coating is prepared by sintering a coating mixture; wherein the coating mixture comprises 30-50 wt% of high-activity borosilicate glass, 5-10 wt% of zirconium boride, 10-30 wt% of tantalum disilicide, 30-60 wt% of molybdenum disilicide and 3-5 wt% of silicon carbide whiskers; wherein the particle size of the coating mixture is 0.5-5 μm.
In a second aspect, the present invention provides a gradient density carbon-ceramic composite material prepared by the preparation method of any one of the first aspect.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) According to the invention, the density of the carbon-ceramic panel is changed in a stepwise manner along the thickness direction by controlling the content of the ceramic phase in different areas of the carbon-ceramic panel, so that the carbon-ceramic panel has high temperature resistance and heat insulation capability, wherein the high-density area has excellent temperature resistance and faces the incoming flow direction, and the application reliability of the composite material in a severe thermal environment is improved; in the end region of the incoming flow, because the thermal environment is relatively mild, the density of the region is reduced, the heat conduction coefficient of the region is reduced, and the region has excellent heat insulation performance; meanwhile, a medium-density transition area is arranged between the high-density area and the low-density area, so that the mechanical property of the carbon-ceramic composite material is effectively prevented from being reduced due to internal stress mutation;
(2) The invention provides a preparation method of a gradient density carbon-ceramic composite material, which is simple and convenient and has short preparation period, and the preparation method can accurately control the density area of each layer of a carbon-ceramic panel, so that the gradient density area of the prepared carbon-ceramic composite material is well defined, different areas are applied to different thermal environments, and the problem that the weight of a high-temperature-resistant panel material needs to be increased to match the temperature resistance of a heat insulating material connected with the low-temperature section of the high-temperature-resistant panel material in the prior art is solved; therefore, the gradient density carbon-ceramic composite material prepared by the invention has the advantages of excellent heat insulation and temperature resistance and light weight;
(3) The high-emissivity coating is compounded on the surface of the gradient density carbon-ceramic panel, so that the temperature resistance and the heat insulation performance of the carbon-ceramic composite material are further improved, the carbon-ceramic composite material has the scouring resistance, and the reliability of the composite material applied to the extreme thermal environment part of the high-speed aerospace craft is greatly improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic representation of a gradient density carbon-ceramic composite material provided in example 2 of the present invention;
FIG. 2 is a tomographic image of a gradient density carbon-ceramic composite material provided in example 2 of the present invention;
FIG. 3 is a tomographic scan of a gradient density carbon-ceramic composite provided in comparative example 3 of the present invention;
FIG. 4 is a tomographic scan of one of the gradient density carbon-ceramic composites provided in comparative example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention, and based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts belong to the scope of the present invention.
The invention provides a preparation method of a gradient density carbon-ceramic composite material, which comprises the following steps:
(1) Preparing a porous carbon fiber substrate;
(2) Dipping the porous carbon fiber matrix in a precursor solution to prepare a carbon-ceramic panel with uniform density;
(3) Determining a threshold value of the preparation times of the carbon-ceramic panel with the gradient density obtained by the carbon-ceramic panel with the uniform density;
(4) Determining the volume of precursor solution required for each impregnation of a carbon-ceramic panel of uniform density;
(5) Pouring the precursor solution into a pressure container containing the carbon-ceramic panel with uniform density according to the volume required by each impregnation, and sequentially carrying out vacuum impregnation, curing and sintering to complete one-time preparation until the preparation times reach the preparation time threshold value to obtain the carbon-ceramic panel with gradient density;
(6) And compounding a high-emissivity coating on the surface of the carbon-ceramic panel with the gradient density to obtain the carbon-ceramic composite material with the gradient density.
In step (4), the volume of the precursor solution required for each impregnation is different.
According to some preferred embodiments, in the step (1), the porous carbon fiber matrix is prepared by curing and sintering chopped carbon fibers and phenolic resin; the chopped carbon fibers may have a diameter of 8 to 12 μm (for example, 8 μm, 9 μm, 10 μm, 11 μm or 12 μm) and a length of 0.5 to 5mm (for example, 0.5mm, 1mm, 1.5mm, 2mm, 2.5mm, 3mm, 3.5mm, 4mm, 4.5mm or 5 mm).
First, in the present invention, the diameter of the chopped carbon fiber is 8 to 12 μm, and when the diameter of the fiber is less than the above range, the mechanical properties of the fiber are deteriorated and the toughening effect is not obtained, and when the diameter of the fiber is more than the above range, the thermal conductivity is increased and the heat insulation effect is deteriorated, so that the heat insulation property can be enhanced while the toughening effect of the fiber is ensured within the scope of the present invention; next, in order to ensure that the chopped carbon fibers can be bonded to each other to form a fiber matrix and can be uniformly dispersed during pretreatment, the length of the chopped carbon fibers is 0.5 to 5mm, more preferably 1 to 3mm.
According to some preferred embodiments, in step (1), the porosity of the porous carbon fiber matrix is 75% to 90% (e.g., may be 75%, 78%, 80%, 83%, 85%, 88%, or 90%);
the density of the porous carbon fiber matrix is 0.1-0.3 g/cm 3 (for example, it may be 0.1g/cm 3 、0.2g/cm 3 Or 0.3g/cm 3 )。
It should be noted that, experiments prove that, when the porosity and density of the porous carbon fiber substrate are lower than the above ranges, on one hand, the precursor solution cannot be completely immersed into the porous carbon fiber substrate when preparing the carbon-ceramic panel with gradient density, so that the density of the high-density region cannot be ensured, and on the other hand, too low porosity of the low-density region causes poor heat insulation performance of the low-density region; when the porosity and density of the porous carbon fiber matrix are higher than the above ranges, the weight of the finally prepared gradient density carbon-ceramic composite material is increased; therefore, within the range defined by the present invention, the weight reduction of the gradient density carbon-ceramic composite material can be ensured, and the excellent heat insulating performance can be ensured, and in the present invention, the density of the porous carbon fiber matrix is more preferably 0.15 to 0.25g/cm 3 。
According to some preferred embodiments, the precursor solution comprises a solute and a solvent; wherein the solute is polycarbosilane or vinyl polycarbosilane, and the solvent is at least one of divinylbenzene, toluene, xylene, n-hexane and tetrahydrofuran.
At least one of them is a mixture of any one or more of them mixed in any ratio.
According to some preferred embodiments, the solute content of the precursor solution is 20% to 50% (e.g., it may be 20%, 25%, 30%, 35%, 40%, 45%, or 50%).
It should be noted that, in the present invention, the content of the solute in the precursor solution is 20% to 50%, and if the content of the solute in the precursor solution is less than 20%, multiple times of dipping are required when preparing the gradient density carbon-ceramic panel, which increases the whole process time; when the solute content in the precursor solution is higher than 50%, density controllability of each density region is poor in the process of preparing the carbon-ceramic panel with gradient density; therefore, within the concentration range specified by the invention, the process time can be shortened, and the density controllability in the preparation process of the density region can be improved.
According to some preferred embodiments, in step (3), the preparation number threshold is 1 to 3 (e.g., may be 1, 2, or 3).
According to some preferred embodiments, in step (4), the volume of the precursor solution required for each impregnation of the carbon-ceramic panel with uniform density is determined by the following formula:
Figure BDA0003273511860000061
wherein, A i For representing the volume of precursor solution required at the i-th impregnation, V for representing the apparent volume of the carbon-ceramic panel with uniform density, and N for representing the number of density zones of the carbon-ceramic panel with gradient density; wherein i is more than or equal to 1 and less than or equal to N-1, and i is an integer;
wherein the carbon-ceramic panel having a gradient density has a density area number of 2 to 4 (e.g., 2, 3, or 4).
It should be noted that, according to the above formula, the threshold value of the preparation times in step (3) can be represented as N-1.
According to the invention, the density of the carbon-ceramic panel is in stepped distribution along the thickness direction by controlling the content of the precursor solution in different areas of the carbon-ceramic panel, and the density of each area is adjustable. The invention overcomes the problem that the weight of the whole component is overlarge due to the improvement of the temperature resistance of the prior gradient density carbon-ceramic composite material, and the density of different areas can be controlled according to the requirements of the application environment of the gradient density carbon-ceramic composite material so that the density of the gradient density carbon-ceramic composite material is changed in a step manner along the incoming flow direction; the high-density area faces to the incoming flow direction, and the temperature resistance, the oxidation resistance and the mechanical property of the high-density area are excellent, so that the application reliability of the composite material in a severe thermal environment is improved; in the end region of the incoming flow, the density of the region is reduced due to the relatively mild thermal environment, so that the heat conduction of the region can be effectively reduced; meanwhile, a medium-density transition area is arranged between the high-density area and the low-density area, so that the mechanical property reduction caused by the internal stress mutation of the carbon-ceramic composite material can be effectively avoided.
It should be noted that, in the present invention, the number of the density regions of the carbon-ceramic panel with gradient density is 2 to 4, and the inventor finds that when the number of the density regions of the carbon-ceramic panel reaches two, the carbon-ceramic composite material with gradient density can meet the protection requirements in different application environments, and when the number of the density regions of the carbon-ceramic panel increases, the heat insulation performance and the temperature resistance performance of the carbon-ceramic panel are improved successively, but when the number of the density regions exceeds the above range of the density regions, the improvement amount of the temperature resistance and the heat insulation performance is reduced, and the weight of the finally prepared carbon-ceramic composite material with gradient density is increased, so that within the scope of the present invention, the light weight of the carbon-ceramic composite material with gradient density can be ensured, and the temperature resistance performance of the carbon-ceramic composite material with gradient density cannot be reduced.
According to some preferred embodiments, in step (5), the vacuum impregnation time is 5 to 30min (for example, may be 5min, 10min, 15min, 20min, 25min or 30 min);
the curing temperature of the curing is 150-240 ℃ (for example, 150 ℃, 180 ℃, 200 ℃, 220 ℃ or 240 ℃), and the curing time is 4-8 h (4 h, 5h, 6h, 7h or 8 h);
the sintering temperature of the sintering is 1200-1400 ℃ (for example, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ or 1400 ℃), and the sintering time is 1-4 h (for example, 1h, 2h, 3h or 4 h).
According to some preferred embodiments, in step (5), the bottom area of the pressure vessel is 1.5 to 2 times (e.g., may be 1.5 times, 1.6 times, 1.7 times, 1.8 times, 1.9 times, or 2 times) the planar area of the carbon-ceramic panel having uniform density.
According to some preferred embodiments, in step (5), the precursor solution is poured in portions and along the edges of the pressure vessel.
It should be noted that, in the present invention, when preparing a carbon-ceramic panel having a gradient density, the precursor solution is poured in several times along the edge gap of the pressure vessel, and one-time pouring of the precursor solution may make the boundary of each density region unclear, and even may form a crescent shape as shown in fig. 4, and pouring of the precursor solution in several times may avoid affecting the density of other regions, so that the density of each region is more controllable; meanwhile, the precursor solution is poured along the edge of the pressure container, so that the situation is avoided.
According to some preferred embodiments, in step (5), the gradient density carbon-ceramic panel has a density of 0.5 to 1.0g/cm 3 (for example, it may be 0.5g/cm 3 、0.6g/cm 3 、0.7g/cm 3 、0.8g/cm 3 、0.9g/cm 3 Or 1.0g/cm 3 )。
In the present invention, the density of the gradient density carbon-ceramic panel is 0.5 to 1.0g/cm 3 If the density is lower than the above range, the heat insulation effect of the material is deteriorated, and if the density is higher than the above range, the heat resistance effect is not remarkably increased even if the density is increased, and the weight of the entire material is increased; therefore, the carbon-ceramic panel with gradient density can be lightened as much as possible on the basis of ensuring the temperature-resistant and heat-insulating effects of different areas of the material.
According to some preferred embodiments, in step (6), the high emissivity coating is prepared by sintering a coating mixture; wherein the coating mixture comprises 30 to 50wt% of high-activity borosilicate glass (for example, 30wt%, 35wt%, 40wt%, 45wt%, or 50wt% may be used), 5 to 10wt% of zirconium boride (for example, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt% may be used), 10 to 30wt% of tantalum disilicide (for example, 10wt%, 15wt%, 20wt%, 25wt%, or 30wt% may be used), 30 to 60wt% of molybdenum disilicide (for example, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, or 60wt% may be used), and 3 to 5wt% of silicon carbide whisker (for example, 3wt%, 4wt%, or 5 wt%); wherein the particle size of the coating mixture is 0.5 to 5 μm (for example, it may be 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, or 5 μm).
In the present invention, the high-activity borosilicate glass has a core-shell structure of a boron oxide-coated borosilicate glass, wherein the content of boron oxide in the high-activity borosilicate glass is 5% by weight or more and 20% by weight or less.
It should be noted that, in the present invention, on the basis of ensuring that the carbon-ceramic panel with gradient density satisfies the requirement of light weight, the high emissivity coating is compounded on the surface of the carbon-ceramic panel, which not only can further improve the temperature resistance and heat insulation performance of the carbon-ceramic composite material with gradient density, but also can enhance the oxidation resistance and the scouring resistance of the composite material in a high-temperature aerobic environment, reduce the problem that the surface of the composite material is damaged and loses efficacy in the high-temperature aerobic environment, and further improve the reliability of the application of the composite material in a severe environment.
The invention also provides a gradient density carbon-ceramic composite material which is prepared by the preparation method of the gradient density carbon-ceramic composite material.
In order to more clearly illustrate the technical solution and advantages of the present invention, a gradient density carbon-ceramic composite material and a method for preparing the same are described in detail below by way of several examples.
Example 1:
(1) Preparing a porous carbon fiber matrix:
(11) Placing the chopped carbon fibers with the diameter of 8 mu m and the length of 1mm in an atmosphere sintering furnace protected by inert atmosphere, and carrying out heat treatment at 450 ℃ for 2h;
(12) Dispersing the chopped carbon fibers in an aqueous solution (the mass ratio of the chopped carbon fibers to water is 1: 300), and stirring at 2500rpm for 1h to obtain a fiber slurry;
(13) Transferring the fiber slurry into a square mold with a porous partition plate, and sequentially carrying out vacuum filtration and compression to obtain a wet blank;
(14) Drying the wet blank in a 120 ℃ drying oven for 24 hours to obtain a dry blank, transferring the dry blank into a closed steel container, filling a water-soluble phenolic resin solution into the container, then closing the container, and carrying out heat treatment in an 80 ℃ drying oven for 24 hours to solidify the phenolic resin and bond the phenolic resin with the carbon fibers;
(15) After the cover of the container in the step (14) is opened, drying the container in a 120 ℃ oven for 24 hours to obtain a carbon fiber matrix primary blank;
(16) Placing the carbon fiber substrate primary blank in an atmosphere sintering furnace, heating to 240 ℃ at a speed of 5 ℃/min under the protection of inert atmosphere, then heating to 1000 ℃ at a speed of 10 ℃/min, keeping for 2h, and naturally cooling to obtain a porous carbon fiber substrate; wherein the porosity of the porous carbon fiber matrix is 80%, and the density is 0.15g/cm 3 。
(2) Preparing a precursor solution with the concentration of 50% by taking polysilazane as a precursor solute and divinylbenzene as a solvent, soaking the porous carbon fiber substrate obtained in the step (1) in the precursor solution, then performing crosslinking curing for 8 hours at 180 ℃ to obtain a composite panel, then placing the composite panel in an atmosphere sintering furnace, heating to 1200 ℃ at the speed of 10 ℃/min under the protection of inert atmosphere, and preserving heat for 1 hour to obtain the Si-C ceramic phase composite carbon-ceramic panel with uniform density.
(3) Preparation of density gradient carbon-ceramic panels with 2 density zones:
(31) Determining that the threshold number of times of preparation of the carbon-ceramic panel with the gradient density from the carbon-ceramic panel with the uniform density is 1 (namely N-1=2-1= 1);
reconfiguring the precursor solution with the concentration of 50% according to the step (2), and determining the volume A of the precursor solution required for impregnation 1 Is 1/2 x V;
Figure BDA0003273511860000101
wherein V is used to represent the apparent volume of the carbon-ceramic panel of uniform density obtained in step (2), N =2;
(32) Placing the carbon-ceramic panel with uniform density in a pressure container with an opening on the surface, wherein the bottom area of the pressure container is 2 times of that of the carbon-ceramic panel with uniform density;
(33) Slowly pouring 1/3 of the precursor solution determined in the step (31) along the gap between the carbon-ceramic panel with uniform density and the side edge of the pressure container, then sealing the container and vacuumizing for 10min to enable the ceramic precursor solution to enter the gap inside the carbon-ceramic panel;
(34) Repeating the step (33) twice, and then sequentially carrying out curing and sintering according to the curing and sintering conditions in the step (2) to obtain a carbon-ceramic panel with 2 gradient density areas;
(4) The high emissivity coating is compounded on the surface of the carbon-ceramic panel with 2 gradient density areas:
(41) The coating mixture is prepared according to the following proportion: 30wt% of high-activity borosilicate glass, 5wt% of zirconium boride, 15wt% of tantalum disilicide, 45wt% of molybdenum disilicide and 5wt% of silicon carbide whiskers;
(42) Mixing the coating mixture with absolute ethyl alcohol, and performing ball milling assisted by zirconia balls by using a high-speed ball mill to obtain the coating mixture with the particle size of 1-3 mu m;
(43) And (3) uniformly spraying the ball-milled coating mixture on the surface of the carbon-ceramic panel with the gradient density by using a spray gun, drying the carbon-ceramic panel with the gradient density by using an oven at room temperature (25 ℃) and 120 ℃, and sintering the coating in an inert atmosphere furnace at 1100 ℃ to obtain the carbon-ceramic composite material with the gradient density.
Example 2
(1) Preparing a porous carbon fiber matrix:
(11) Placing the short carbon fiber with the diameter of 10 mu m and the length of 1mm in an atmosphere sintering furnace protected by inert atmosphere, and carrying out heat treatment for 2h at 550 ℃;
(12) Dispersing the chopped carbon fibers in an aqueous solution (the mass ratio of the chopped carbon fibers to water is 1: 250), and stirring at 3000rpm for 1.5h to obtain a fiber slurry;
(13) Transferring the fiber slurry into a square mold of a porous partition plate, and sequentially carrying out vacuum filtration and compression to obtain a wet blank;
(14) Drying the wet blank in a 120 ℃ drying oven for 24 hours to obtain a dry blank, transferring the dry blank into a closed steel container, filling a water-soluble phenolic resin solution into the container, then closing the container, and carrying out heat treatment on the container in an 80 ℃ drying oven for 24 hours to cure the phenolic resin and bond the phenolic resin with the carbon fibers;
(15) After the cover of the container in the step (14) is opened, drying the container in a 120 ℃ oven for 24 hours to obtain a carbon fiber matrix primary blank;
(16) Placing the carbon fiber substrate primary blank in an atmosphere sintering furnace, heating to 240 ℃ at a speed of 5 ℃/min under the protection of inert atmosphere, then heating to 1200 ℃ at a speed of 10 ℃/min, keeping for 2h, and naturally cooling to obtain a porous carbon fiber substrate; wherein the porous carbon fiber matrix has a porosity of 78% and a density of 0.15g/cm 3 。
(2) Preparing a precursor solution with the concentration of 40% by taking polysilazane as a precursor solute and xylene as a solvent, dipping the porous carbon fiber matrix obtained in the step (1) in the precursor solution, then crosslinking and curing for 8h at 200 ℃ to obtain a composite panel, then placing the composite panel in an atmosphere sintering furnace, heating to 1200 ℃ at the speed of 10 ℃/min under the protection of inert atmosphere, and keeping for 1h to obtain the Si-C ceramic phase composite carbon-ceramic panel with uniform density.
(3) Preparation of density gradient carbon-ceramic panels with 3 density zones:
(31) Determining that the threshold number of times of preparation of the carbon-ceramic panel with the gradient density from the carbon-ceramic panel with the uniform density is 2 (namely N-1=3-1= 2);
reconfiguring the precursor solution with the concentration of 40% according to the step (2), and determining the volume A of the precursor solution required by the first impregnation 1 2/3 x v;
Figure BDA0003273511860000111
wherein V is used to represent the apparent volume of the carbon-ceramic panel of uniform density obtained in step (2), N =3;
(32) Placing the carbon-ceramic panel with uniform density in a pressure container with an opening on the surface, wherein the bottom area of the pressure container is 2 times of that of the carbon-ceramic panel with uniform density;
(33) Slowly pouring 1/3 of the precursor solution determined in the step (31) along the gap between the carbon-ceramic panel with uniform density and the side edge of the pressure container, then sealing the container and vacuumizing for 20min to enable the ceramic precursor solution to enter the gap inside the carbon-ceramic panel;
(34) Repeating the step (33) twice, and then sequentially carrying out curing and sintering according to the curing and sintering conditions in the step (2);
(35) Reconfiguring the precursor solution with the concentration of 40% according to the step (2), and determining the volume A of the precursor solution required by the second impregnation 2 At 1/3 × v, and repeating steps (33) - (34) to obtain a carbon-ceramic panel having 3 regions of gradient density;
Figure BDA0003273511860000121
(4) The surface of the carbon-ceramic panel with 3 gradient density areas is compounded with a high emissivity coating:
(41) Preparing a coating mixture according to the following proportion: 25wt% of high-activity borosilicate glass, 5wt% of zirconium boride, 15wt% of tantalum disilicide, 52wt% of molybdenum disilicide and 3wt% of silicon carbide whiskers;
(42) Mixing the coating mixture with absolute ethyl alcohol, and performing ball milling assisted by zirconia balls by using a high-speed ball mill to obtain the coating mixture with the particle size of 1-3 mu m;
(43) And (3) uniformly spraying the ball-milled coating mixture on the surface of the carbon-ceramic panel with the gradient density by using a spray gun, drying the carbon-ceramic panel with the gradient density by using an oven at room temperature (25 ℃) and 120 ℃, and sintering the coating in an inert atmosphere furnace at 1150 ℃ to obtain the carbon-ceramic composite material with the gradient density.
Example 3
(1) Preparing a porous carbon fiber matrix:
(11) Placing short carbon fibers with the diameter of 9 mu m and the length of 2mm in an atmosphere sintering furnace protected by inert atmosphere, and carrying out heat treatment at 450 ℃ for 3h;
(12) Dispersing the chopped carbon fibers in an aqueous solution (the mass ratio of the chopped carbon fibers to water is 1: 250), and stirring at 4500rpm for 1.5h to obtain a fiber slurry;
(13) Transferring the fiber slurry into a square mold of a porous partition plate, and sequentially carrying out vacuum filtration and compression to obtain a wet blank;
(14) Drying the wet blank in a 120 ℃ drying oven for 24 hours to obtain a dry blank, transferring the dry blank into a closed steel container, filling a water-soluble phenolic resin solution into the container, then closing the container, and performing crosslinking curing at 80 ℃ for 24 hours to cure the phenolic resin and bond the phenolic resin with the carbon fibers;
(15) After the cover of the container in the step (14) is opened, drying the container in a 120 ℃ oven for 24 hours to obtain a carbon fiber matrix primary blank;
(16) Placing the carbon fiber substrate primary blank in an atmosphere sintering furnace, heating to 240 ℃ at a speed of 5 ℃/min under the protection of inert atmosphere, then heating to 1000 ℃ at a speed of 10 ℃/min, keeping for 2h, and naturally cooling to obtain a porous carbon fiber substrate; wherein the porosity of the porous carbon fiber matrix is 85%, and the density is 0.12g/cm 3 。
(2) Preparing a precursor solution with the concentration of 30% by taking vinyl polysilazane as a precursor solute and xylene as a solvent, dipping the porous carbon fiber matrix obtained in the step (1) in the precursor solution, then crosslinking and curing for 8 hours at 240 ℃ to obtain a composite panel, then placing the composite panel in an atmosphere sintering furnace, heating to 1300 ℃ at the speed of 10 ℃/min under the protection of inert atmosphere, and keeping for 2 hours to obtain the Si-C ceramic phase composite carbon-ceramic panel with uniform density.
(3) Preparation of density gradient carbon-ceramic panels with 4 density zones:
(31) Determining that the threshold number of times of preparation of the carbon-ceramic panel with the gradient density from the carbon-ceramic panel with the uniform density is 3 (namely N-1=4-1= 3);
reconfiguring the precursor solution with the concentration of 30% according to the step (2), and determining the volume A of the precursor solution required by the first impregnation 1 Is 3/4 x V;
Figure BDA0003273511860000131
wherein V is used to represent the apparent volume of the uniform density carbon-ceramic panel resulting from step (2), N =4;
(32) Placing the carbon-ceramic panel with uniform density in a pressure container with an opening on the surface, wherein the bottom area of the pressure container is 1.8 times that of the carbon-ceramic panel with uniform density;
(33) Slowly pouring 1/4 of the precursor solution determined in the step (31) along the gap between the carbon-ceramic panel with uniform density and the side edge of the pressure container, then sealing the container and vacuumizing for 30min to enable the ceramic precursor solution to enter the gap inside the carbon-ceramic panel;
(34) Repeating the step (33) for three times, and then sequentially carrying out curing and sintering according to the curing and sintering conditions in the step (2);
(35) Respectively reconfiguring precursor solutions with the concentration of 30% according to the step (2), and determining the volume A of the precursor solution required by the second impregnation 2 Volume A of precursor solution required for the third impregnation at 1/2 x V 3 At 1/4 × v and repeating steps (33) - (34) to obtain a carbon-ceramic panel having 4 regions of gradient density;
Figure BDA0003273511860000141
Figure BDA0003273511860000142
(4) The high emissivity coating is compounded on the surface of the carbon-ceramic panel with 4 gradient density areas:
(41) Preparing a coating mixture according to the following proportion: 35wt% of high-activity borosilicate glass, 5wt% of zirconium boride, 5wt% of tantalum disilicide, 55wt% of molybdenum disilicide and 5wt% of silicon carbide whiskers;
(42) Mixing the coating mixture with absolute ethyl alcohol, and performing ball milling assisted by zirconia balls by using a high-speed ball mill to obtain the coating mixture with the particle size of 2-4 microns;
(43) And (3) uniformly spraying the ball-milled coating on the surface of the carbon-ceramic panel with the gradient density by using a spray gun, drying the carbon-ceramic panel with the gradient density by using a drying oven at room temperature (25 ℃) and 120 ℃, and sintering the coating in an inert atmosphere furnace at 1200 ℃ to obtain the carbon-ceramic composite material with the gradient density.
Example 4
Example 4 is essentially the same as example 2, except that: the porous carbon fiber substrate prepared in step (1) had a porosity of 88% and a density of 0.10g/cm 3 。
Comparative example 1
Comparative example 1 is substantially the same as example 2 except that: the procedure for preparing a gradient density carbon-ceramic panel in example 2 was modified as follows:
(31) Completely immersing the carbon-ceramic panel with uniform density by adopting a precursor solution with the concentration of 40%, and curing and sintering after vacuum impregnation for 20min to obtain the carbon-ceramic panel with uniform density of the composite 2-time ceramic phase;
(32) And (5) repeating the step (31) to obtain the carbon-ceramic panel with uniform density of the composite ceramic phase for 3 times.
Comparative example 2
Comparative example 2 is substantially the same as comparative example 1 except that: in the step of preparing the carbon-ceramic panel with gradient density, the precursor solution with the concentration of 30% is adopted to impregnate the carbon-ceramic panel with uniform density.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that: in the preparation of carbon-ceramic panels with two gradient densities, the precursor solution was poured into a pressure vessel without evacuation.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that: in preparing carbon-ceramic panels with two gradient densities, the precursor solution was poured into the pressure vessel at once.
The composite materials prepared in examples 1 to 5 and comparative examples 1 to 4 were subjected to the performance test of the present invention, and the results of the performance test are shown in table 1. Wherein, the heat insulation performance is obtained by testing the back temperature of the composite material after heating for 500s by a quartz lamp at 1000 ℃.
TABLE 1
Figure BDA0003273511860000151
As can be seen from table 1, the gradient density carbon-ceramic composite materials prepared in examples 1 to 4 have a low overall apparent density, a high density region having a high density, a long-term temperature resistance of 1400 ℃ or higher, an excellent temperature resistance, and a low density region having a low density, and after being heated by a 1000 ℃ quartz lamp for 500 seconds, the back temperature of the material is 257 ℃, which has an excellent heat insulation effect; meanwhile, as shown in fig. 1 and 2, each density region of the gradient density carbon-ceramic composite material prepared by the present invention is well-defined, and in fig. 2, the higher the brightness of the image represents the higher the density of the region; in comparative example 1, a composite material prepared by compounding carbon-ceramic panels having uniform density for 3 times was prepared, and although it could withstand 1400 ℃ for a long time, the overall density of the composite material was increased and the heat-insulating property thereof was poor; in comparative example 2, if the density of the material was reduced, the temperature resistance and heat insulation properties of the material were deteriorated, and a structural damage phenomenon caused by oxidation of carbon fibers in the surface carbon-ceramic panel occurred at 1200 ℃ of oxyacetylene flame test; in comparative example 3, although the density of the prepared composite material was low, the temperature of the back surface of the composite material was high after heating by a quartz lamp, because vacuum impregnation was not employed in the impregnation process, so that the carbon-ceramic panel was not uniformly impregnated in the precursor solution, and a large number of pores were present in the interior of the prepared composite material, thereby deteriorating the heat insulating property; in comparative example 4, the precursor solution was poured into the pressure vessel at one time, not separately, so that the edge region of the carbon-ceramic panel excessively absorbed the precursor solution, forming a crescent-shaped uneven state as in fig. 4, and further deteriorating the properties of the prepared gradient density carbon-ceramic composite.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention. The invention has not been described in detail and is in part known to those of skill in the art.

Claims (9)

1. A method of preparing a gradient density carbon-ceramic composite, comprising the steps of:
(1) Preparing a porous carbon fiber matrix; the porous carbon fiber matrix is prepared by curing and sintering chopped carbon fibers and phenolic resin;
(2) Dipping the porous carbon fiber matrix in a precursor solution to prepare a carbon-ceramic panel with uniform density; the solute in the precursor solution is polycarbosilane or vinyl polycarbosilane;
(3) Determining a threshold value of the preparation times of the carbon-ceramic panel with the gradient density obtained by the carbon-ceramic panel with the uniform density;
(4) Determining the volume of precursor solution required for each impregnation of a carbon-ceramic panel of uniform density;
the volume of precursor solution required for each impregnation of a carbon-ceramic panel of uniform density is determined by the following formula:
Figure 408642DEST_PATH_IMAGE001
wherein A is i The volume of the precursor solution required in the i-th impregnation is represented by V, the apparent volume of the carbon-ceramic panel with uniform density is represented by V, and the number of density areas of the carbon-ceramic panel with gradient density is represented by N; wherein i is more than or equal to 1 and less than or equal to N-1, and i is an integer;
(5) Pouring the precursor solution into a pressure container containing the carbon-ceramic panel with uniform density according to the volume required by each impregnation, sequentially carrying out vacuum impregnation, curing and sintering to complete one-time preparation until the preparation times reach the preparation time threshold value, and obtaining the carbon-ceramic panel with gradient density; the bottom area of the pressure container is 1.5 to 2 times of the plane area of the carbon-ceramic panel with uniform density; the precursor solution is poured in a plurality of times along the edge of the pressure container;
(6) Compounding a high-emissivity coating on the surface of the carbon-ceramic panel with the gradient density to obtain a carbon-ceramic composite material with the gradient density; the high-emissivity coating is prepared by sintering a coating mixture; the coating mixture comprises 30-50 wt% of high-activity borosilicate glass, 5-10 wt% of zirconium boride, 10-30 wt% of tantalum disilicide, 30-60 wt% of molybdenum disilicide and 3-5 wt% of silicon carbide whiskers, and the mass sum of all the substances in the coating mixture is one hundred percent.
2. The production method according to claim 1, wherein in step (1):
the diameter of the chopped carbon fiber is 8 to 12 mu m, and the length of the chopped carbon fiber is 0.5 to 5mm;
the porosity of the porous carbon fiber matrix is 75-90%;
the density of the porous carbon fiber matrix is 0.1 to 0.3g/cm 3 。
3. The production method according to claim 1, characterized in that:
the precursor solution comprises a solute and a solvent; the solvent is at least one of divinylbenzene, toluene, xylene, n-hexane and tetrahydrofuran;
the content of solute in the precursor solution is 20% -50%.
4. The method of claim 1, wherein:
in the step (3), the threshold value of the preparation times is 1 to 3.
5. The production method according to claim 1, wherein in step (4):
the number of density areas of the carbon-ceramic panel with the gradient density is 2 to 4.
6. The production method according to claim 1, wherein in step (5):
the vacuum impregnation time is 5 to 30min;
the curing temperature of the curing is 150 to 240 ℃, and the curing time is 4 to 8h;
the sintering temperature of the sintering is 1200 to 1400 ℃, and the sintering time is 1 to 4h.
7. The production method according to claim 1, wherein in step (5):
the density of the carbon-ceramic panel with the gradient density is 0.5 to 1.0g/cm 3 。
8. The production method according to any one of claims 1 to 7, characterized in that, in step (6):
the particle size of the coating mixture is 0.5 to 5 mu m.
9. A gradient density carbon-ceramic composite material prepared by the method of any one of claims 1 to 8.
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