CN113372682A - Light thermal protection composite material with capsule structure and preparation method thereof - Google Patents

Light thermal protection composite material with capsule structure and preparation method thereof Download PDF

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CN113372682A
CN113372682A CN202110661144.1A CN202110661144A CN113372682A CN 113372682 A CN113372682 A CN 113372682A CN 202110661144 A CN202110661144 A CN 202110661144A CN 113372682 A CN113372682 A CN 113372682A
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inorganic filler
fiber
resin
organic polymer
matrix
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CN113372682B (en
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彭志航
曹峰
向阳
陈莉
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National University of Defense Technology
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Abstract

The invention discloses a light thermal protection composite material with a capsule structure, which comprises a short fiber reinforcement, organic polymer resin and an inorganic filler, wherein the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and when the matrix is decomposed and ablated by heating, the inorganic filler is exposed and heated to be decomposed, softened, sintered and melted to cover the surface of the matrix. The invention also discloses a preparation method of the light thermal protection composite material with the capsule structure, and the preparation method has the advantages of simple process, short preparation period and capability of slowing down ablation of carbon fibers and a matrix.

Description

Light thermal protection composite material with capsule structure and preparation method thereof
Technical Field
The invention relates to the field of new materials, in particular to a light thermal protection composite material with a capsule structure and a preparation method thereof.
Background
When various returning spacecrafts return to the ground, the various returning spacecrafts enter the atmosphere at an extremely high speed, a large amount of pneumatic heat is generated through friction with the atmosphere, the surface temperature is up to 1500 ℃ or higher, if the pneumatic heat is not properly managed, a large amount of heat is transmitted into the spacecrafts, and internal goods, electromechanical equipment and passengers are damaged. There is therefore a need for highly effective thermal protection materials for protecting the safety of spacecraft. Commonly used thermal protective materials are rigid ceramic insulation tiles and ablative materials.
In the early days, the rigid ceramic heat insulation tile is important to be used as a heat protection material for American space shuttles, the material is obtained by sintering ceramic fibers and a high-temperature sintering aid at high temperature, and the technical difficulty is high. However, the materials have the defects of high brittleness, poor deformability, high assembly and maintenance cost, difficulty in preparing large-size components and the like. The ablation material takes away surface heat through the loss of the material quality and structure by utilizing the physical or chemical endothermic change or reaction of the heated material, such as evaporation, sublimation, chemical cracking and the like, and prevents the heat from being further transmitted into the interior to protect the aircraft. Compared to passive thermal protection materials, ablative materials do not have the limitation of maximum use temperature. Therefore, the heat-resistant material can resist the environment with extremely high heat flow, and is particularly suitable for the heat protection of the disposable recoverable spacecraft.
Ames research center of NASA, USA, using phenolic resin to impregnate rigid carbon fiber preform to obtainA low density (-0.3 g/cm)3) Low thermal conductivity phenolic impregnated carbon fiber ablative material (PICA), successfully used for the return task of the Stardust deep space probe. However, limited by the size limitations and manufacturing costs of rigid carbon fiber preforms, block designs have to be used in subsequent curio numbers of MSL and the european space, and Dragon cargo ships from SpaceX, inc, and the fiber reinforcement material replaced with less expensive carbon fiber needled felt. The successful completion of these spacecraft has returned the task that it has proven safe and feasible to use lightweight ablative materials for spacecraft thermal protection applications.
On the one hand, under the atmosphere of oxygen, the carbon fiber and the resin matrix thereof can accelerate oxidation and decomposition, so that the ablation amount is increased, and how to obstruct the oxygen from entering can slow down the oxidative decomposition of the ablation material and reduce the contribution of gas convection to heat transfer. In addition, the processing of fiber preforms is generally limited by the width and thickness, the fiber components are single, and it is difficult to prepare fiber preforms with specific sizes, large widths and mixed multiple fibers according to requirements.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a capsule-structured light thermal protection composite material which is simple in process, short in preparation period and capable of retarding ablation of carbon fibers and a matrix and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a light thermal protection composite material with a capsule structure comprises a short fiber reinforcement, organic polymer resin and inorganic filler, wherein the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and when the matrix is decomposed and ablated by heating, the inorganic filler is exposed to heat to be decomposed, softened, sintered and melted and covers the surface of the matrix.
As a further improvement to the above technical solution:
the density of the light thermal protection composite material with the capsule structure is 0.15-1.8 g/cm3The compressive strength is 0.2-20 MPa, the mass ablation rate is within 15s under the ablation conditions of 2000 ℃ and 15s0.030 to 0.12g/s, and the wire ablation rate is 0.0602 to 0.415 mm/s.
As a general inventive concept, the present invention provides a method for preparing a lightweight thermal protective composite material for a capsule structure, comprising the steps of:
s1, weighing the raw materials of the inorganic filler according to a preset proportion, adding a dispersion medium, mixing, performing ball milling, and drying the slurry after ball milling to obtain the inorganic filler with the granularity no more than 200 nm;
s2, heating and stirring the short fiber reinforcement, the organic polymer resin, the organic solvent, the tackifier and the inorganic filler according to preset requirements, so that the organic polymer resin is completely dissolved, and the short fiber reinforcement and the inorganic filler are uniformly dispersed in a liquid phase to obtain injection molding slurry;
s3, injecting the injection molding slurry into a forming mold, and heating to promote the organic polymer resin to react and solidify to obtain wet gel;
and S4, drying the wet gel to obtain the light thermal protection composite material with the capsule structure.
As a further improvement to the above technical solution:
in step S1, the inorganic filler is one or more of silica, alumina, zirconia, boron oxide, hafnium oxide, tantalum pentoxide, niobium pentoxide, titanium dioxide, silicon carbide, boron carbide, hafnium carbide, vermiculite, glass, and calcium silicate;
the dispersion medium is one or more of ethanol, isopropanol or acetone.
In the step S2, the short fiber reinforcement is one or more of carbon fiber, alumina fiber, zirconia fiber, alumina silicate fiber, mullite fiber, quartz fiber, basalt fiber, high silica fiber, aramid fiber, and polyimide fiber.
The organic polymer resin is one or more of phenolic resin, epoxy resin, bismaleimide resin, cyanate resin and organic silicon resin.
The organic solvent is one or more of ethanol, isopropanol, ethylene glycol, dimethylformamide and toluene.
In step S2, a tackifier is further included in the liquid phase.
The tackifier is one or more of ethyl cellulose, polyethylene glycol and polyvinyl butyral.
In the step S2, the injection molding slurry comprises the following raw materials in parts by mass: 1-20 wt% of inorganic filler, 1-20 wt% of short fiber reinforcement, 5-50 wt% of organic polymer resin, 30-85 wt% of organic solvent and 0-10 wt% of tackifier.
In the step S2, the heating and stirring temperature is 50-150 ℃; the short fiber reinforcement has a length of no greater than 5 mm.
The step S3 specifically includes the following steps:
injecting the injection molding slurry into a forming mold, heating to 90-160 ℃, preserving heat for 24-72 h, cooling to 60-90 ℃, preserving heat for 12-48 h, solidifying the resin, cooling and opening the mold to obtain wet gel.
In the step S3, before the injection molding slurry is injected into the forming mold, the injection molding slurry and the forming mold are preheated to 30-80 ℃; the injection mode is compressed gas injection, and the pressure of the compressed gas is 1.05-3 bar.
Preferably, in the step S4, the drying temperature is 40-70 ℃, the vacuum degree is-0.4 to-0.7 bar, and the drying time is 6-72 h.
Preferably, in the step S1, the dispersion medium is 20 to 50% of the total mass of the inorganic filler; the ball milling speed is 300-; the drying temperature is 50-90 ℃, and the drying time is 1-12 h.
The forming die is a metal die capable of realizing the air sealing function, and the die is made of No. 45 carbon steel or 304 stainless steel.
Compared with the prior art, the invention has the advantages that:
1. the capsule structure light thermal protection composite material comprises a short fiber reinforcement, organic polymer resin and an inorganic filler, wherein the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and a network structure formed by the structural matrix has holes with the sizes from nanometer to submicron holes, so that the contribution of internal convection to heat conduction can be effectively prevented, and the capsule structure is integrally represented. In the invention, the inorganic filler is an oxide with a high melting point, is used for improving the temperature resistance of the composite material, plays a role in supporting the macroscopic size of the material after high-temperature ablation and resin decomposition, prevents air flow from entering the interior of the composite material, reduces the heat conductivity of the composite material and improves the heat insulation performance; the short fiber reinforcement can improve the tensile strength of the composite material and prevent the material from shrinkage cracking, and meanwhile, different types of short fibers can be used for reinforcing the strength of the resin composite material according to different use temperatures; the organic polymer resin is high-temperature resistant synthetic resin; when the surface of the light thermal protection material is subjected to high temperature, the organic polymer resin matrix is decomposed and ablated, so that the internal inorganic filler is gradually exposed, and the inorganic filler is decomposed, softened, sintered, melted and the like after being heated, so that the light thermal protection material can absorb external heat to reduce the temperature rise of the body, and can cover the surface of the organic polymer resin matrix network under the action of surface tension/gas diffusion mass transfer, the skeleton strength of the composite material is enhanced, the further entry of gas is blocked, the oxidation reaction of the resin matrix is effectively delayed, the ablation rate of the composite material is reduced, and the high-temperature oxidative decomposition of the carbon-containing polymer matrix is prevented.
2. According to the preparation method of the capsule-structure light thermal protection composite material, the raw materials of the inorganic filler are ball-milled, so that the raw materials of the inorganic filler are uniformly mixed, and more importantly: the particle size of the final inorganic filler reaches the nanometer size level (no more than 200 nm), the inorganic filler is conveniently dispersed and suspended in the slurry prepared in the subsequent step, no obvious sedimentation occurs, when the injection molding slurry is prepared, the short fiber reinforcement, the inorganic filler, the organic polymer resin and the organic solvent are mixed, the tackifier is added to adjust the viscosity of the mixed solution (under the premise that the tackifier is in a small doping amount (0-10 wt%), the viscosity of the slurry can be obviously improved, the insoluble substances such as the short fiber and the inorganic filler are prevented from sedimentating in the processes of slurry preparation, resin curing and the like to cause uneven performance, when the content (concentration ratio) of the organic polymer resin is high enough (the viscosity is more than 500 cp), the prepared liquid viscosity is enough, the tackifier can not be used), the injection molding slurry for injection is obtained, the injection molding slurry is directly injected into a forming mold through the injection molding process, the wet gel can be obtained, the method does not need to prepare a fiber reinforced prefabricated body (ceramic heat insulation tile) in advance, is not limited by the size of the fiber prefabricated body, can prepare a homogeneous thermal protection composite material with a large size and a complex profile, and has a simple process.
3. The preparation method of the capsule-structured light heat protection composite material has mild preparation conditions and simple method, the highest temperature in the preparation process is not more than 160 ℃, sintering at high temperature (not less than 1000 ℃) is not needed, the capsule-structured light heat protection composite material can be formed through one-time crosslinking and solidification, and finally drying only needs normal pressure drying, so that the high-temperature-resistant light heat protection composite material is obtained at the temperature close to room temperature, and the energy-saving cost is lower. The invention has the characteristics of low preparation cost, short period, no high temperature and high pressure, good material designability and the like, and can meet the use requirements of heat preservation of various types of pipelines and heat protection of the recoverable spacecraft.
4. The capsule-structure light thermal protection composite material has low thermal conductivity, light weight and high strength, and the density is 0.15-1.2 g/cm3The compressive strength is 0.2-20 MPa, the mass ablation rate is 0.030-0.12 g/s under the ablation conditions of 2000 ℃ and 15s, and the line ablation rate is 0.0602-0.415 mm/s.
Drawings
FIG. 1 is SEM images of the capsule structure light weight thermal protective composite of example 1 of the present invention before and after ablation.
Detailed Description
The invention will be described in further detail below with reference to the drawings and specific examples. Unless otherwise specified, the instruments or materials employed in the present invention are commercially available.
Example 1:
the capsule-structured light thermal protection composite material comprises a short fiber reinforcement, organic polymer resin and an inorganic filler, wherein the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and when the matrix is decomposed and ablated by heating, the inorganic filler is exposed and heated to be decomposed, softened, sintered and melted to cover the surface of the matrix.
In this embodiment, the organic polymer resin is a phenolic resin, the inorganic filler is silica, and the short fiber reinforcement is carbon fiber.
The preparation method of the capsule structure lightweight thermal protection composite material comprises the following steps:
(1) ball milling of inorganic filler: weighing a certain amount of silicon dioxide as an inorganic filler, putting into a ball milling tank, and adding absolute ethyl alcohol accounting for 20% of the mass of the silicon dioxide. Setting the ball milling rotation speed to 380 r/min, ball milling time to 72 h, heating the ball milled slurry in an oven at 50 ℃, and keeping the temperature for 10 h until the absolute ethyl alcohol is completely volatilized for later use.
In the present embodiment, the inorganic filler is silica, the dispersion medium is absolute ethyl alcohol, in other embodiments, the inorganic filler is one or more of silica, alumina, zirconia, boron oxide, hafnium oxide, tantalum pentoxide, niobium pentoxide, titanium dioxide, silicon carbide, boron carbide, hafnium carbide, vermiculite, glass, and calcium silicate, and the dispersion medium is one or more of ethyl alcohol, isopropyl alcohol, and acetone, all of which can achieve the same or similar technical effects.
The median particle size of the inorganic filler after ball milling is not more than 200nm, preferably 20-200 nm. If the particle size of the inorganic filler is too large, the inorganic filler can be settled under the action of gravity during the preparation of the slurry and the curing process, so that the prepared composite material has uneven density and performance.
(2) Preparing slurry: weighing the silicon dioxide, the carbon fiber with the fiber length of 0.5mm, the phenolic resin, the isopropanol and the polyethylene glycol which are subjected to ball milling in the step (1) according to the proportion of 5wt% of ball-milled silicon dioxide, 10 wt% of carbon fiber, 20 wt% of phenolic resin, 60 wt% of isopropanol and 5wt% of polyethylene glycol, putting the mixture into a reaction tank, heating the mixture to 60 ℃, and mechanically mixing the mixture for 4 hours to completely dissolve the phenolic resin and uniformly disperse the carbon fiber and the silicon dioxide in the isopropanol.
In the invention, the length of the short fiber reinforcement is not more than 5mm, and preferably 0.05-0.5 mm. In the present invention, the length of the short fiber reinforcement is limited because: long fibers outside the length range of the invention are not easy to disperse, and the doping amount ratio is small, and then the long fibers are easy to agglomerate and settle, so that the material and the performance thereof are not uniform.
In another embodiment, the short fiber reinforcement is one or more of carbon fiber, alumina fiber, zirconia fiber, alumina silicate fiber, mullite fiber, quartz fiber, basalt fiber, high silica fiber, aramid fiber and polyimide fiber, the organic polymer resin is one or more of phenolic resin, epoxy resin, bismaleimide resin, cyanate ester resin and silicone resin, the organic solvent is one or more of ethanol, isopropanol, ethylene glycol, dimethylformamide and toluene, and the tackifier is one or more of ethyl cellulose, polyethylene glycol and polyvinyl butyral.
(3) Injection molding: preheating the mould and the slurry to 80 ℃, injecting the slurry into a forming mould by using compressed gas, wherein the pressure of the compressed gas is 1.5 bar, and closing a valve after injection moulding is finished.
(4) Curing the slurry gel: heating the mould filled with the slurry to 130 ℃, preserving heat for 48 h, cooling to 85 ℃, preserving heat for 36 h, closing and heating, cooling to room temperature along with the furnace, standing for 12 h, opening the mould, and taking out the wet gel.
(5) And (3) drying: and (3) putting the wet gel into a vacuum drying oven, controlling the vacuum degree to be-0.4 bar, heating to 50 ℃, and keeping the temperature for 8 hours until the solvent is completely volatilized, thereby obtaining the light thermal protection composite material with the capsule structure.
The capsule-structure light thermal protection composite material obtained by the preparation method of the embodiment has the following properties: the density was 0.45 g/cm3The compressive strength (5% strain condition) was 5.4 MPa, the mass ablation rate was 0.031 g/s under 15s ablation conditions at 2000 ℃ and the line ablation rate was 0.0642 mm/s.
Fig. 1 is SEM images of the composite of example 1 of the present invention before and after ablation, before ablation, the morphology is a network porous structure built by organic polymer resin matrix, whose pores are in the nanometer scale range, and after ablation, the organic polymer resin matrix decomposes and shrinks, exposing the nano inorganic particle filler inside, and these nano particles can continue to support the whole composite structure, preventing the material from shrinking in the macro scale (in case of high magnification, it is difficult to observe and record because the diameter of short fiber is too large).
Example 2
The capsule-structured light thermal protection composite material comprises a short fiber reinforcement, organic polymer resin and an inorganic filler, wherein the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and when the matrix is decomposed and ablated by heating, the inorganic filler is exposed and heated to be decomposed, softened, sintered and melted to cover the surface of the matrix.
In this example, the organic polymer resin is a mixture of phenol resin and epoxy resin at a mass ratio of 9:1, the inorganic filler is a mixture of silica, alumina, and calcium silicate at a mass ratio of 1:1:0.3, and the short fiber reinforcement is quartz fiber.
The preparation method of the capsule structure lightweight thermal protection composite material comprises the following steps:
(1) ball milling of inorganic filler: silica, alumina and calcium silicate are weighed as inorganic fillers according to the mass ratio of 1:1:0.3, and are put into a ball milling tank, and absolute ethyl alcohol accounting for 20% of the total mass of the inorganic fillers is added. Setting the ball milling rotation speed to 380 r/min, ball milling time to 72 h, heating the ball milled slurry in an oven at 50 ℃, and keeping the temperature for 10 h until the absolute ethyl alcohol is completely volatilized for later use.
(2) Preparing slurry: and (2) weighing the inorganic filler, the quartz fiber with the fiber length of 1 mm, the organic polymer resin, the isopropanol and the ethyl cellulose in proportion after ball milling in the step (1). Wherein the organic polymer resin is formed by mixing phenolic resin and epoxy resin in a mass ratio of 9: 1. The weighed proportions were 10 wt% of the inorganic filler, 8 wt% of the quartz fiber, 30 wt% of the organic polymer resin, 50.5 wt% of isopropyl alcohol, and 1.5 wt% of ethyl cellulose. Putting into a reaction tank, heating to 60 deg.C, and mechanically mixing for 4 hr to dissolve or uniformly disperse the raw materials in the solvent.
(3) Injection molding: preheating the mould and the slurry to 55 ℃, injecting the slurry into a forming mould by using compressed gas, wherein the pressure of the compressed gas is 2.5 bar, and closing a valve after injection molding is finished.
(4) Curing the slurry gel: heating the mould filled with the slurry to 110 ℃, preserving heat for 48 h, cooling to 80 ℃, preserving heat for 12 h, closing and heating, cooling to room temperature along with the furnace, standing for 12 h, opening the mould, and taking out the wet gel.
(5) And (3) drying: and (3) putting the wet gel into a vacuum drying oven, controlling the vacuum degree to be-0.4 bar, heating to 50 ℃, and keeping the temperature for 8 hours until the solvent is completely volatilized, thereby obtaining the light thermal protection composite material with the capsule structure.
The capsule structure light thermal protection composite material obtained by the embodiment has the following properties: the density was 0.51 g/cm3The compressive strength (5% strain condition) was 8.2 MPa, and the mass ablation rate was 0.055 g/s and the thread ablation rate was 0.082 mm/s under the conditions of 2000 ℃ and 15s ablation.
Example 3
The capsule-structured light thermal protection composite material comprises a short fiber reinforcement, organic polymer resin and an inorganic filler, wherein the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and when the matrix is decomposed and ablated by heating, the inorganic filler is exposed and heated to be decomposed, softened, sintered and melted to cover the surface of the matrix.
In this example, the organic polymer resin is a mixture of phenol resin, epoxy resin, and silicone resin at a mass ratio of 10:2:1, the inorganic filler is a mixture of silica, zirconia, silicon carbide, boron carbide, and vermiculite at a mass ratio of 1:2:1:0.5:0.2, and the short fiber reinforcement is a mixture of carbon fiber and quartz fiber at a mass ratio of 1: 1.
The preparation method of the capsule structure lightweight thermal protection composite material comprises the following steps:
(1) ball milling of inorganic filler: respectively weighing silicon dioxide, zirconium oxide, silicon carbide, boron carbide and vermiculite as inorganic fillers according to the mass ratio of 1:2:1:0.5:0.2, putting the inorganic fillers into a ball milling tank, and then adding acetone accounting for 30% of the total mass of the inorganic fillers. Setting the ball milling rotation speed to be 330 r/min, setting the ball milling time to be 80 h, heating the ball milled slurry in an oven at the temperature of 55 ℃, and keeping the temperature for 8 h until the acetone is completely volatilized for later use.
(2) Preparing slurry: and (2) weighing the inorganic filler and the short fiber reinforcement body which are subjected to ball milling in the step (1) according to a mass ratio of 1:1, organic polymer resin, ethylene glycol and ethyl cellulose, wherein the carbon fiber with the length of 0.3mm and the quartz fiber with the length of 0.5 mm. Wherein the organic polymer resin is formed by mixing phenolic resin, epoxy resin and organic silicon resin in a mass ratio of 10:2: 1. The weighing proportions are 5wt% of inorganic filler, 15 wt% of short fiber reinforcement, 30 wt% of organic polymer resin, 48.5 wt% of ethylene glycol and 1.5 wt% of ethyl cellulose. Putting into a reaction tank, heating to 60 ℃, and mechanically mixing for 4h to completely dissolve the organic polymer resin and uniformly disperse the inorganic filler and the short fiber reinforcement in the solvent.
(3) Injection molding: preheating the mould and the slurry to 55 ℃, injecting the slurry into a forming mould by using compressed gas, wherein the pressure of the compressed gas is 2.5 bar, and closing a valve after injection molding is finished.
(4) Curing the slurry gel: heating the mould filled with the slurry to 130 ℃, preserving heat for 48 h, cooling to 90 ℃, preserving heat for 24 h, closing and heating, cooling to room temperature along with the furnace, standing for 8 h, opening the mould, and taking out the wet gel.
(5) And (3) drying: and (3) putting the wet gel into a vacuum drying oven, controlling the vacuum degree to be-0.5 bar, heating to 45 ℃, and keeping the temperature for 24 hours until the solvent is completely volatilized, thereby obtaining the light thermal protection composite material with the capsule structure.
The capsule structure light thermal protection composite material obtained by the embodiment has the following properties: the density was 0.65 g/cm3The compressive strength (5% strain condition) was 13.4 MPa, and the mass ablation rate was 0.067 g/s and the line ablation rate was 0.076 mm/s under the conditions of 2000 ℃ and 15s ablation.
Example 4
The capsule-structured light thermal protection composite material comprises a short fiber reinforcement, organic polymer resin and an inorganic filler, wherein the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and when the matrix is decomposed and ablated by heating, the inorganic filler is exposed and heated to be decomposed, softened, sintered and melted to cover the surface of the matrix.
In this example, the organic polymer resin is a phenolic resin, the inorganic filler is a mixture of zirconia, alumina, hafnia, and glass in a mass ratio of 1:2:0.5:0.05, and the short fiber reinforcement is a mixture of carbon fibers and glass fibers in a mass ratio of 15: 1.
The preparation method of the capsule structure lightweight thermal protection composite material comprises the following steps:
(1) ball milling of inorganic filler: respectively weighing zirconium oxide, aluminum oxide, hafnium oxide and glass as inorganic fillers according to the mass ratio of 1:2:0.5:0.05, putting the inorganic fillers into a ball milling tank, and adding acetone accounting for 30% of the total mass of the inorganic fillers. Setting the ball milling rotation speed to 300 r/min, the ball milling time to 96 h, heating the ball milled slurry in an oven at the temperature of 55 ℃, and keeping the temperature for 8 h until the acetone is completely volatilized for later use.
(2) Preparing slurry: and (2) weighing the inorganic filler, the short fiber reinforcement, the organic polymer resin, the ethylene glycol and the polyvinyl butyral which are subjected to ball milling in the step (1) according to a proportion. Wherein the short fiber reinforcement body is composed of carbon fiber with the length of 0.3mm and glass fiber with the length of 0.1 mm according to the mass ratio of 15:1, and the organic polymer resin is phenolic resin. The weighed proportions are 10 wt% of inorganic filler, 15 wt% of short fiber reinforcement, 20 wt% of organic polymer resin, 50 wt% of ethylene glycol and 5wt% of polyvinyl butyral. Putting into a reaction tank, heating to 60 deg.C, and mechanically mixing for 4 hr to dissolve or uniformly disperse the raw materials in the solvent.
(3) Injection molding: preheating the mould and the slurry to 50 ℃, injecting the slurry into a forming mould by using compressed gas with the pressure of 2 bar, and closing the valve after injection moulding.
(4) Curing the slurry gel: heating the mold filled with the slurry to 135 deg.C, maintaining the temperature for 48 h, cooling to 90 deg.C, maintaining the temperature for 30 h, heating while closing, cooling to room temperature, standing for 12 h, opening the mold, and taking out the wet gel.
(5) And (3) drying: and (3) putting the wet gel into a vacuum drying oven, controlling the vacuum degree to be-0.7 bar, heating to 70 ℃, and keeping the temperature for 24 hours until the solvent is completely volatilized, thereby obtaining the light thermal protection composite material with the capsule structure.
The capsule structure light thermal protection composite material obtained by the embodiment has the following properties: the density was 0.88 g/cm3The compressive strength (5% strain condition) was 7.9 MPa, and the mass ablation rate was 0.042 g/s and the line ablation rate was 0.122 mm/s under the conditions of 2000 ℃ and 15s ablation.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments to equivalent variations, without departing from the scope of the invention, using the teachings disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention should fall within the protection scope of the technical scheme of the present invention, unless the technical spirit of the present invention departs from the content of the technical scheme of the present invention.

Claims (10)

1. The utility model provides a capsule structure light thermal protection combined material which characterized in that: the organic polymer resin is used as a matrix, the short fiber reinforcement and the inorganic filler are coated in the matrix, and when the matrix is decomposed and ablated by heating, the inorganic filler is exposed and heated to be decomposed, softened, sintered and melted to cover the surface of the matrix.
2. The capsule structured light weight thermal protective composite of claim 1, wherein: the density of the light thermal protection composite material with the capsule structure is 0.15-1.8 g/cm3The compressive strength is 0.2-20 MPa, the mass ablation rate is 0.030-0.12 g/s under the ablation conditions of 2000 ℃ and 15s, and the line ablation rate is 0.0602-0.415 mm/s.
3. A preparation method of a light thermal protection composite material with a capsule structure is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing the raw materials of the inorganic filler according to a preset proportion, adding a dispersion medium, mixing, performing ball milling, and drying the slurry after ball milling to obtain the inorganic filler with the granularity no more than 200 nm;
s2, heating and stirring the short fiber reinforcement, the organic polymer resin, the organic solvent and the inorganic filler according to the preset requirement, so that the organic polymer resin is completely dissolved, and the short fiber reinforcement and the inorganic filler are uniformly dispersed in a liquid phase, thereby obtaining injection molding slurry;
s3, injecting the injection molding slurry into a forming mold, and heating to promote the organic polymer resin to react and solidify to obtain wet gel;
and S4, drying the wet gel to obtain the light thermal protection composite material with the capsule structure.
4. The production method according to claim 3, characterized in that: in step S1, the inorganic filler is one or more of silica, alumina, zirconia, boron oxide, hafnium oxide, tantalum pentoxide, niobium pentoxide, titanium dioxide, silicon carbide, boron carbide, hafnium carbide, vermiculite, glass, and calcium silicate;
the dispersion medium is one or more of ethanol, isopropanol or acetone.
5. The production method according to claim 3, characterized in that: in the step S2, the short fiber reinforcement is one or more of carbon fiber, alumina fiber, zirconia fiber, alumina silicate fiber, mullite fiber, quartz fiber, basalt fiber, high silica fiber, aramid fiber, and polyimide fiber;
the organic polymer resin is one or more of phenolic resin, epoxy resin, bismaleimide resin, cyanate resin and organic silicon resin;
the organic solvent is one or more of ethanol, isopropanol, ethylene glycol, dimethylformamide and toluene.
6. The production method according to claim 3, characterized in that: in step S2, a tackifier is further included in the liquid phase.
7. The method of claim 6, wherein: the tackifier is one or more of ethyl cellulose, polyethylene glycol and polyvinyl butyral.
8. The method of claim 7, wherein: in the step S2, the injection molding slurry comprises the following raw materials in parts by mass: 1-20 wt% of inorganic filler, 1-20 wt% of short fiber reinforcement, 5-50 wt% of organic polymer resin, 30-85 wt% of organic solvent and 0-10 wt% of tackifier.
9. The production method according to claim 3, characterized in that: in the step S2, the heating and stirring temperature is 50-150 ℃; the short fiber reinforcement has a length of no greater than 5 mm.
10. The production method according to any one of claims 3 to 9, characterized in that: the step S3 specifically includes the following steps:
injecting the injection molding slurry into a forming mold, heating to 90-160 ℃, preserving heat for 24-72 h, cooling to 60-90 ℃, preserving heat for 12-48 h, solidifying the resin, cooling and opening the mold to obtain wet gel.
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CN109968757A (en) * 2019-04-22 2019-07-05 中国人民解放军国防科技大学 Ablation-resistant light heat-proof heat-insulation integrated composite material and preparation method thereof
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CN110216930A (en) * 2019-04-22 2019-09-10 湖南远辉新材料研究院有限公司 A kind of high intensity can ceramic resin composite materials and preparation method thereof
CN112321894A (en) * 2020-11-02 2021-02-05 航天特种材料及工艺技术研究所 Non-coating light ablation-resistant heat-insulation composite material and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN109968757A (en) * 2019-04-22 2019-07-05 中国人民解放军国防科技大学 Ablation-resistant light heat-proof heat-insulation integrated composite material and preparation method thereof
CN110003658A (en) * 2019-04-22 2019-07-12 中国人民解放军国防科技大学 Ablation-resistant silicon-based resin/ceramic hybrid material and preparation method thereof
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