CN111331941A - Integrated density gradient thermal protection material and preparation method thereof - Google Patents

Integrated density gradient thermal protection material and preparation method thereof Download PDF

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CN111331941A
CN111331941A CN201811546459.6A CN201811546459A CN111331941A CN 111331941 A CN111331941 A CN 111331941A CN 201811546459 A CN201811546459 A CN 201811546459A CN 111331941 A CN111331941 A CN 111331941A
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fiber
reinforcement
resin
thermal protection
protection material
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CN111331941B (en
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许学伟
夏雨
谢永旺
许孔力
李永民
张苓涛
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Aerospace Research Institute of Materials and Processing Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/36—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and impregnating by casting, e.g. vacuum casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an integrated density gradient thermal protection material and a preparation method thereof, the thermal protection material comprises a substrate and a reinforcement, wherein the substrate is in a network-shaped porous resin structure, the reinforcement comprises a fiber reinforcement inner layer with a second volume density and a fiber reinforcement outer layer with a first volume density, which is arranged on the inner layer, the network-shaped porous structure is also dispersed and solidified in the fiber reinforcement outer layer and the fiber reinforcement inner layer, and the first volume density is 0.5-2.0g/cm3(ii) a The second bulk density is 0.05-0.4g/cm3. The method comprises the following steps: preparing a reinforcement; preparation ofA solution of a base material; injecting the solution into the reinforcement body to enable the reinforcement body to fully soak the solution; and then curing at the resin curing temperature to obtain the resin. The invention can solve the technical problems that the outer heat-proof layer of the existing heat protection material is easy to oxidize and cannot be used for a long time, the forming process period of the inner heat-proof layer is long, the cost is high, and the whole heat protection effect is poor due to the preparation method.

Description

Integrated density gradient thermal protection material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to an integrated density gradient thermal protection material and a preparation method thereof.
Background
The aircraft faces the development trend of high flying speed and long flying distance, and simultaneously needs to cope with the thermal environment with the characteristics of high heat flow, high enthalpy value, high stagnation pressure and the like, so that the outer heat-proof material of the aircraft needs to have the characteristics of low density, large specific heat capacity, low heat conductivity coefficient, ablation resistance, scouring resistance and the like.
The thermal protection material used in the aircraft at present comprises two parts, namely an outer thermal protection material and an inner thermal insulation material. The outer heat-proof material comprises carbon-carbon composite material, silicon carbide ceramic base and other reusable heat-proof materials and resin-based and rubber ablation heat-proof materials. The carbon-carbon and ceramic matrix composite material has excellent temperature resistance and anti-scouring performance, but the carbon material can generate oxidation reaction under the oxygen-rich environment, and the material performance can be rapidly reduced; resin-based and rubber thermal protection materials are large in material density and high in heat conductivity coefficient in order to ensure ablation resistance, erosion resistance and other performances, are often applied to a thermal protection system (100s) in a short time, cannot be applied to thermal protection of long-time aircrafts, and have certain limitations. The inner heat insulation material is an aerogel heat insulation material and mainly plays a role in heat insulation, but the supercritical drying method is required for drying, the forming process period is too long, and the manufacturing cost is too high.
In addition, the whole thermal protection system needs to be formed by bonding and fixing the outer heat-proof material and the inner heat-insulating material by using an adhesive after the outer heat-proof material and the inner heat-insulating material are respectively molded, and the temperature resistance and the reliability of the adhesive can seriously influence the whole protection effect of thermal protection.
Disclosure of Invention
The following presents a simplified summary of the invention in order to provide a basic understanding of some aspects of the invention. It should be understood that this summary is not an exhaustive overview of the invention. It is not intended to determine the key or critical elements of the present invention, nor is it intended to limit the scope of the present invention. Its sole purpose is to present some concepts in a simplified form as a prelude to the more detailed description that is discussed later.
The invention aims to overcome the defects in the prior art, provides an integrated density gradient thermal protection material and a preparation method thereof, and can solve the technical problems that an outer thermal protection layer of the existing thermal protection material is easy to oxidize and cannot be used for a long time, an inner thermal protection layer is long in forming process period and high in cost, and the whole thermal protection effect is poor due to the preparation method.
The technical solution of the invention is as follows:
according to one aspect, there is provided a unitary density gradient thermal protective material comprising a matrix and a reinforcement, wherein the matrix is a network-like porous resin structure, the reinforcement comprises an inner fiber reinforcement layer having a second bulk density and an outer fiber reinforcement layer having a first bulk density disposed on the inner layer, the network-like porous structure is further dispersion cured in the outer fiber reinforcement layer and the inner fiber reinforcement layer, and the first bulk density is 0.5-2.0g/cm3(ii) a The second bulk density is 0.05-0.4g/cm3。
Further, the volume of the reinforcement body accounts for 10-60% of the thermal protection material.
Further, the diameter of pores in the network-like porous resin structure is 10 nanometers to 100 micrometers.
Further, the reinforcement also includes a fiber reinforcement intermediate layer having a third bulk density, the fiber reinforcement intermediate layer being disposed between the fiber reinforcement outer layer and the fiber reinforcement inner layer, the third bulk density being greater than the second bulk density and less than the first bulk density.
Further, the matrix adopts the following raw materials: the polymeric monomer or low molecular weight polymer of the ablative resin is mixed with a proper amount of solvent to prepare a solution.
Further, the carbon residue rate of the ablative resin is higher than 50%, and the ablative resin is selected from at least one of phenolic resin, bismaleimide resin, polyimide resin, aryl acetylene resin, vinyl resin, benzoxazine resin, polyurethane resin and organic silicon modified phenolic resin.
Further, the outer layer of the fiber reinforcement is made of 2.5D braided fabric or coarse fiber fabric; the fiber reinforcement inner layer is made of chopped fiber net tires.
Further, the type of the fiber used for the reinforcement is at least one selected from aramid fiber, boron fiber, quartz fiber, carbon fiber, high silica fiber, glass fiber, phenolic resin fiber, silicon carbide fiber, silicon nitride fiber, woven fabric of a plurality of fibers, and mixed woven fabric of a plurality of fibers.
According to another aspect, there is provided a method for preparing the above one-piece density gradient thermal protection material, comprising the following steps:
preparing a reinforcement comprising:
laying a set number of layers of chopped fiber net tires in a mould and needling to obtain a fiber reinforcement inner layer; continuously laying a set number of layers of 2.5D braided fabrics or coarse fiber fabrics on the inner layer of the fiber reinforcement body for needling to obtain the outer layer of the fiber reinforcement body;
preparing a base material, comprising:
preparing a solution from a polymer elastomer or a low-molecular-weight polymer of ablative resin and a proper amount of solvent mixture;
forming a thermal protective material comprising:
injecting the solution into the reinforcement member to fully infiltrate the reinforcement member with the solution; and then curing at the resin curing temperature to obtain the resin.
By applying the technical scheme, the thermal protection material and the preparation method thereof are provided, through designing the reinforcement of the thermal protection material to comprise the outer layer and the inner layer of the fiber reinforcement with the first and second volume densities, and designing the specific range of the first and second volume densities, and the matrix of the thermal protection material is also distributed in the reinforcement, through the design, the integrated design of the network-shaped porous resin structure and the fiber reinforcement has the following advantages on the basis of ensuring the strength of the material: on one hand, the heat insulation effect of the material is ensured by the network-shaped porous resin structure; on the other hand, the designed volume density with gradient change sets the outer layer as a high-density fiber reinforced layer, so that the anti-scouring strength of the outer layer is improved, and the long-term use effect is ensured; meanwhile, the inner layer is designed into a low-density fiber reinforced layer to play a transition role and further ensure the heat insulation effect; in addition, the substrate and the reinforcement do not need to be formed separately, the substrate and the reinforcement are formed integrally, the forming period is greatly shortened, the cost is reduced, the risk of layering is reduced due to the integral forming mode, and the integral consistency of materials is guaranteed. In conclusion, the thermal protection material provided by the embodiment of the invention has the advantages of ablation resistance, scouring resistance, difficulty in oxidation and the like, has excellent heat insulation performance, is not easy to layer, and has good overall performance. In addition, the preparation process is simple, the molding period is short, the cost is low, and the large-scale application is facilitated.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
Fig. 1 is a schematic structural diagram of an integrated density gradient thermal protection material provided in embodiment 1 of the present invention.
Detailed Description
The following provides a detailed description of specific embodiments of the present invention. In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the device structures and/or processing steps that are closely related to the scheme according to the present invention are shown in the drawings, and other details that are not so relevant to the present invention are omitted.
As mentioned in the background art, the outer layer of the existing thermal protection material is easily oxidized, so that the existing thermal protection material cannot be used for a long time; the aerogel material of the inner layer has excellent heat insulation effect, but the forming process is overlong and the manufacturing cost is high; in addition, during preparation, the outer layer and the inner layer are mostly formed respectively and then bonded, so that the material is easy to delaminate at high temperature, and the integrity is poor.
In view of the above technical problems, as shown in fig. 1, an embodiment of the present invention provides, in one aspect, an integrated density gradient thermal protection material, which includes a matrix and a reinforcement, wherein the matrix is a network-shaped porous resin structure, the reinforcement includes a fiber reinforcement inner layer having a second bulk density and a fiber reinforcement outer layer having a first bulk density, which is disposed on the inner layer, the network-shaped porous structure is further dispersedly cured in the fiber reinforcement outer layer and the fiber reinforcement inner layer, and the first bulk density is 0.5-2.0g/cm 3; the second bulk density is 0.05-0.4g/cm 3.
The outer layer of the fiber reinforcement is the layer facing the hot environment.
Preferably, the first bulk density may be 0.8 to 2.0g/cm3(ii) a The second bulk density is 0.1-0.3g/cm3。
The integral thermal protection material provided by the embodiment of the invention is called integral, because the matrix is dispersedly cured in the reinforcement in the thermal protection material provided by the embodiment of the invention, and by adopting the mode, the risk of delamination is reduced. For the thermal protection material provided by the embodiment of the invention, the heat insulation effect of the material is ensured by adopting a network-shaped porous resin structure; the volume density of gradient change is designed, and the outer layer is set as a high-density fiber reinforced layer, so that the anti-scouring strength of the outer layer is improved, and the long-term use effect is ensured; meanwhile, the inner layer is designed into the low-density fiber reinforced layer to play a transition role, so that the heat insulation effect is further ensured (because if transition is not performed, the fiber layer with high density fills the gaps of the matrix, so that the heat insulation effect is reduced), and the integral composition of the thermal protection material in the embodiment of the invention ensures the integral consistency of the material. Namely, the thermal protection material provided by the embodiment of the invention has the advantages of ablation resistance, scouring resistance, difficulty in oxidation and the like, and also has excellent heat insulation performance, and the material is not easy to delaminate and has good overall performance.
As an embodiment of the invention, the volume of the reinforcement body is 10-60% of the thermal protection material. By limiting the volume of the reinforcement in a specific range, if the reinforcement is too small, the properties of the material, such as scour resistance, material strength and the like, cannot be ensured, and if the reinforcement is too large, the heat insulation effect and the dimensional effect of the heat protection material are not good.
Preferably, the volume of the reinforcement body accounts for 30-60% of the thermal protection material; more preferably, the volume of the reinforcement body is 50-60% of the thermal protection material.
As an embodiment of the invention, the diameter of the pores in the network-like porous resin structure is 10 nm to 100 μm. By limiting the pore diameter of the porous resin structure to a specific range, if the pore diameter is too small, the thermal insulation performance of the material is lowered, and if the pore diameter is too large, the dimensional effect of the entire material is affected.
In the invention, in order to obtain the substrate with the structure, the substrate adopts the following raw materials: the polymeric monomer or low molecular weight polymer of the ablative resin is mixed with a proper amount of solvent to prepare a solution.
The solvent may be a solvent for dispersing the monomer or low-molecular weight polymer of the ablative resin, and may be selected according to the kind of the monomer or low-molecular weight polymer.
In the invention, the ablation-type resin has a carbon residue rate higher than 50%, and is selected from at least one of phenolic resin, bismaleimide resin, polyimide resin, aryl acetylene resin, vinyl resin, benzoxazine resin, polyurethane resin and organic silicon modified phenolic resin.
It will be understood by those skilled in the art that the kind of resin listed should not limit the scope of the present invention.
In the embodiment of the invention, the carbon residue rate of the ablative resin is higher than 50%, which means that the resin can keep more than 50% of the weight of the ablative resin in an inert atmosphere at the ambient temperature of 800 ℃, the ablative resin with higher carbon residue rate is adopted in the embodiment of the invention, the polymer monomer or low molecular weight polymer of the high molecular resin is mixed with a proper solvent to prepare a solution, and a porous material with nano-micron scale pores is formed through sol-gel reaction in the curing process, so that the porous material has the characteristics of low density, low thermal conductivity and the like, is an effective heat insulation material, and further the heat insulation effect of the material is ensured.
In the embodiment of the invention, the different materials can be selected as the substrate according to different use thermal environments.
As an example of the present invention, to achieve the preparation of a fiber-reinforced outer layer having a first bulk density, the fiber-reinforced outer layer is made of a 2.5D braid or coarse fiber fabric; to achieve the preparation of the fiber-reinforced inner layer having the second bulk density, the fiber-reinforced inner layer is made using a chopped strand batt.
In the embodiment of the invention, the reinforcement is a fiber fabric with gradient density change and consists of a plurality of layers of reinforcements, and the outermost side of the reinforcement is formed by a 2.5D braided fabric or a coarse fiber fabric, so that the effects of density increase, ablation resistance and scouring resistance are mainly achieved; the innermost layer of the reinforcement body is composed of chopped fiber net tires and mainly plays a role in reducing density and isolating heat from being transmitted to the inside. The two are cooperated, so that the anti-scouring and anti-ablation properties of the material are ensured, and the heat-insulating property of the material is ensured.
In an embodiment of the present invention, the type of the fiber used in the 2.5D woven fabric, the coarse fiber fabric, or the chopped fiber mat is at least one selected from the group consisting of aramid fiber, boron fiber, quartz fiber, carbon fiber, high silica fiber, glass fiber, phenol resin fiber, silicon carbide fiber, a plurality of types of silicon nitride fiber, a woven fabric of a plurality of types of fibers, and a mixed woven fabric of a plurality of types of fibers.
Wherein, according to the difference of thermal environment, different materials can be selected correspondingly as the reinforcement. When facing a low enthalpy value and a high stagnation pressure thermal environment, the fiber fabric material of the thermal protection material is preferably quartz fiber; when facing a high enthalpy and high heat flow thermal environment, the fiber fabric material of the thermal protection material is preferably silicon carbide fiber; the fibrous fabric material of the thermal protective material is preferably carbon fiber when exposed to low enthalpy, low heat flow environments.
As an embodiment of the invention, in order to ensure a transition between the gradient reinforcement layers, better preventing delamination phenomena, the reinforcement further comprises a fiber-reinforcement intermediate layer having a third bulk density, the fiber-reinforcement intermediate layer being interposed between the fiber-reinforcement outer layer and the fiber-reinforcement inner layer, the third bulk density being greater than the second bulk density and less than the first bulk density.
In summary, the structural form of the density gradient integrated thermal protection material not only ensures ablation heat dissipation and anti-scouring dimensional capability of the thermal protection material in a pneumatic heating environment in a high-speed flight process, but also ensures excellent heat insulation effect of the thermal protection material and low density of the whole material, realizes comprehensive benefits of ablation resistance, anti-scouring, long-term heat insulation, substantial weight reduction and the like, and provides technical support for further improving the flight speed and the flight distance of an aircraft.
According to another embodiment, a method for preparing the integrated density gradient thermal protection material is also provided, which comprises the following steps:
step 1, preparing a reinforcement, comprising:
laying a set number of layers of chopped fiber net tires in a mould and needling to obtain a fiber reinforcement inner layer; continuously laying a set number of layers of 2.5D braided fabrics or coarse fiber fabrics on the inner layer of the fiber reinforcement body for needling to obtain the outer layer of the fiber reinforcement body;
step 2, preparing a matrix raw material, comprising:
preparing a solution from a polymer elastomer or a low-molecular-weight polymer of ablative resin and a proper amount of solvent mixture;
and 3, forming the thermal protection material, comprising:
injecting the solution into the reinforcement member to fully infiltrate the reinforcement member with the solution; and then curing at the resin curing temperature to obtain the resin.
By the preparation method, the matrix and the reinforcement do not need to be formed separately, the prepared resin solution is only needed to be provided for the matrix, the prefabricated body is only needed to be provided for the reinforcement, and then the resin solution is fully impregnated in the prefabricated body and cured to obtain the integrated thermal protection material. The preparation method greatly shortens the molding period and reduces the cost, and the integrated molding mode also reduces the risk of layering and ensures the integral consistency of the material.
In the step 1, the knitting mode of the 2.5D knitted fabric or the coarse fiber fabric may be a shallow cross-straight connection mode, a shallow cross-curved connection mode or an angle interlock mode.
In the step 1, the fabrics with different densities can be connected by adopting a needling or sewing mode.
In the step 1, a fiber reinforcement intermediate layer may be added between the outer layer and the inner layer as required, and the specific preparation method refers to the preparation process of the outer layer and the inner layer.
In the step 1, the number of layers can be selected and set according to the requirement of the thermal environment.
In the step 3, a resin solution can be injected into the fiber reinforcement by using a commonly used RTM (resin transfer molding) process of the composite material such as dipping, pouring, injection, vacuum suction injection, pressure injection and the like, so that the fiber reinforcement is fully soaked in the resin. Then assembling and sealing the forming mold, placing the forming mold in a high-temperature oven, setting the temperature of the oven according to the curing temperature of the resin, and keeping the temperature in the high-temperature oven for a certain time to ensure that the resin is slowly polymerized in the mold to form a network-shaped porous structure; and after the resin is completely cured, disassembling the mold, and taking out the thermal protection material for drying.
Wherein the drying mode of the thermal protection material comprises normal pressure drying, freeze drying or supercritical drying.
According to the method provided by the embodiment of the invention, the reinforced fibers are woven and punctured to form the prefabricated body with high outer layer density and ultralow inner density, the ablation-resistant resin is infiltrated into the fiber prefabricated body by means of impregnation, glue injection and the like, and finally the fiber prefabricated body is solidified to form the integrated thermal protection material, so that the overall consistency of the thermal protection material is increased, the phenomenon of layered cracking caused by different thermal expansion coefficients of the material is effectively avoided, and the reliability of thermal protection is improved.
The present invention is described in further detail below with reference to specific examples, which are not to be construed as limiting the scope of the invention as claimed.
Example 1
A preferred range for determining the strength of the integral thermal protection composite reinforcement is a density of 3mm in thickness and a density of 1.0g/cm3The 2.5D quartz fiber fabric has a combined thickness of 12mm and a density of 0.12g/cm3The injected matrix resin is a matrix resin having a density of 0.3g/cm3The organic silicon modified phenolic resin is cured for 20 hours at 80 ℃ by adopting an RTM (resin transfer molding) liquid forming process to form the density gradient thermal protection material.
Example 2
The reinforcing body of the integrated density gradient thermal protection material has the thickness of 1mm and the density of 0.5g/cm3The high-density quartz fiber cloth with the thickness of 1mm and the density of 0.3g/cm3The quartz fiber cloth with the thickness of 13mm and the density of 0.12g/cm3The injected matrix resin is a matrix resin having a density of 0.2g/cm3The organic silicon modified phenolic resin is cured for 12 hours at 120 ℃ by adopting an RTM (resin transfer molding) liquid forming process to form the integrated density gradient thermal protection material.
Comparative example 1
The reinforcing body of the integrated density gradient thermal protection material has the thickness of 1mm and the density of 0.3g/cm3The high-density quartz fiber cloth with the thickness of 11mm and the density of 0.02g/cm3The injected matrix resin is a matrix resin having a density of 0.2g/cm3The organic silicon modified phenolic resin is cured for 12 hours at 120 ℃ by adopting an RTM (resin transfer molding) liquid forming process to form the integrated density gradient thermal protection material.
Comparative example 2
The reinforcing body of the integrated density gradient thermal protection material has the thickness of 3mm and the density of 0.3g/cm3The high-density quartz fiber cloth with the thickness of 12mm and the density of 0.3g/cm3The injected matrix resin is a matrix resin having a density of 0.2g/cm3The organic silicon modified phenolic resin is cured for 12 hours at 120 ℃ by adopting an RTM (resin transfer molding) liquid forming process to form the integrated density gradient thermal protection material.
Comparative example 3
The reinforcing body of the integrated density gradient thermal protection material has the thickness of 3mm and the density of 0.9g/cm3The 2.5D quartz fiber fabric with the thickness of 12mm and the density of 0.6g/cm3The injected matrix resin is a matrix resin having a density of 0.2g/cm3The organic silicon modified phenolic resin is cured for 12 hours at 120 ℃ by adopting an RTM (resin transfer molding) liquid forming process to form the integrated density gradient thermal protection material.
The properties of the materials obtained in the above examples and comparative examples are shown in Table 1.
TABLE 1 comparison of Material Properties
Figure BDA0001909422650000121
From the comparison results of the above tables, we can see that the density and thermal conductivity of the existing thermal protection material are both large, about 50s of effective protection can be realized, and when the flight time is long, the outer surface of the existing thermal protection material is peeled off in a large area, the aerodynamic shape is difficult to maintain, and the existing thermal protection material cannot effectively isolate heat from being transferred to the inside.
The materials prepared in the examples 1 and 2 can effectively reduce the density and the thermal conductivity of the materials, ensure that the outer surface of the aircraft is not ablated and stripped after the aircraft flies for a long time, and effectively isolate heat.
In comparative example 1, the density of the first volume is too low, and the density of the second volume is also too low, so that the ablation resistance of the outer layer of the material is reduced, and the mechanical strength of the whole material is also reduced; in comparative example 2, the first volume is too low in density and the second volume is moderate, which affects the ablation performance of the material; the density of the second volume in comparative example 3 was too high to effectively insulate heat because of its decreased insulating properties.
Features that are described and/or illustrated above with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein, is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
The many features and advantages of these embodiments are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of these embodiments which fall within the true spirit and scope thereof. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the embodiments of the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope thereof.
The invention has not been described in detail and is in part known to those of skill in the art.

Claims (10)

1. An integrated density gradient thermal protective material, comprising a substrate and a reinforcement, characterized in that the substrate is a network-like porous resin structure, the reinforcement comprises a fiber reinforcement inner layer with a second volume density and a fiber reinforcement outer layer with a first volume density arranged on the inner layer, the network-like porous structure is also dispersed and cured in the fiber reinforcement outer layer and the fiber reinforcement inner layer, and the first volume density is 0.5-2.0g/cm3(ii) a The second bulk density is 0.05-0.4g/cm3。
2. The integrated density gradient thermal protection material according to claim 1, wherein the volume of the reinforcement is 10-60% of the thermal protection material.
3. The integrated density gradient thermal protection material according to claim 1, wherein the diameter of pores in the network-like porous resin structure is 10 nm-100 μm.
4. An integrated density gradient thermal protection material according to claims 1-3, wherein the reinforcement further comprises a fiber reinforcement intermediate layer having a third bulk density, the fiber reinforcement intermediate layer being disposed between the fiber reinforcement outer layer and the fiber reinforcement inner layer, the third bulk density being greater than the second bulk density and less than the first bulk density.
5. The integrated density gradient thermal protection material according to claim 1, wherein the matrix is prepared from the following raw materials: the polymeric monomer or low molecular weight polymer of the ablative resin is mixed with a proper amount of solvent to prepare a solution.
6. The integrated density gradient thermal protection material according to claim 5, wherein the ablation-based resin has a carbon residue rate higher than 50%, and is selected from at least one of phenolic resin, bismaleimide resin, polyimide resin, aryl acetylene resin, vinyl resin, benzoxazine resin, polyurethane resin and organic silicon modified phenolic resin.
7. The integrated density gradient thermal protection material according to claim 1, wherein the fiber reinforcement outer layer is made of 2.5D braided fabric or coarse fiber fabric; the fiber reinforcement inner layer is made of chopped fiber net tires.
8. The integrated density gradient thermal protection material of claim 7, wherein the type of the fiber used for the reinforcement is selected from at least one of aramid fiber, boron fiber, quartz fiber, carbon fiber, high silica fiber, glass fiber, phenolic resin fiber, silicon carbide fiber, silicon nitride fiber, woven fabric of fibers, and mixed woven fabric of fibers.
9. The method for preparing the integrated density gradient thermal protection material according to the claims 1 to 8, wherein the method comprises the following steps:
preparing a reinforcement comprising:
laying a set number of layers of chopped fiber net tires in a mould and needling to obtain a fiber reinforcement inner layer; continuously laying a set number of layers of 2.5D braided fabrics or coarse fiber fabrics on the inner layer of the fiber reinforcement body for needling to obtain the outer layer of the fiber reinforcement body;
preparing a base material, comprising:
preparing a solution from a polymer elastomer or a low-molecular-weight polymer of ablative resin and a proper amount of solvent mixture;
forming a thermal protective material comprising:
injecting the solution into the reinforcement member to fully infiltrate the reinforcement member with the solution; and then curing at the resin curing temperature to obtain the resin.
10. An integral density gradient thermal protective material made according to the method of claim 9.
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CN112659589A (en) * 2020-12-04 2021-04-16 湖北三江航天红阳机电有限公司 Preparation method of low-density heat-insulation integrated gradient material
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CN113997652A (en) * 2021-11-30 2022-02-01 北京理工大学 Continuous fiber reinforced thermal protection material and preparation method thereof
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CN111635614B (en) * 2020-05-19 2023-03-24 湖北航天技术研究院总体设计所 Light heat-proof composite material and preparation method thereof
CN111997781B (en) * 2020-07-17 2022-02-08 上海复合材料科技有限公司 Composite material diffusion section forming method based on RTM (resin transfer molding) process semi-cured surface
CN111997781A (en) * 2020-07-17 2020-11-27 上海复合材料科技有限公司 Composite material diffusion section forming method based on RTM (resin transfer molding) process semi-cured surface
CN112250418A (en) * 2020-10-22 2021-01-22 航天特种材料及工艺技术研究所 Lightweight toughened heat-insulation composite material member and preparation method and application thereof
CN112659589A (en) * 2020-12-04 2021-04-16 湖北三江航天红阳机电有限公司 Preparation method of low-density heat-insulation integrated gradient material
CN113580612A (en) * 2021-08-19 2021-11-02 湖北菲利华石英玻璃股份有限公司 Low-density near-zero ablation composite material forming method
CN113997652A (en) * 2021-11-30 2022-02-01 北京理工大学 Continuous fiber reinforced thermal protection material and preparation method thereof
CN113997652B (en) * 2021-11-30 2023-09-26 北京理工大学 Continuous fiber reinforced heat protection material and preparation method thereof
CN114031414A (en) * 2021-12-02 2022-02-11 内蒙古航天红岗机械有限公司 Carbon-based composite material with low expansion coefficient and low thermal conductivity and preparation method thereof
CN115257078A (en) * 2022-06-20 2022-11-01 航天材料及工艺研究所 Light heat-proof and heat-insulation integrated thermal protection material carbon fiber reinforcement and preparation method thereof
CN115257078B (en) * 2022-06-20 2024-03-15 航天材料及工艺研究所 Light heat-proof and heat-insulating integrated heat-proof material carbon fiber reinforcement and preparation method thereof
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