CN117866380A - Fiber ceramic skeleton phenolic aerogel composite material and preparation method thereof - Google Patents
Fiber ceramic skeleton phenolic aerogel composite material and preparation method thereof Download PDFInfo
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- CN117866380A CN117866380A CN202410013637.8A CN202410013637A CN117866380A CN 117866380 A CN117866380 A CN 117866380A CN 202410013637 A CN202410013637 A CN 202410013637A CN 117866380 A CN117866380 A CN 117866380A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 163
- 239000000835 fiber Substances 0.000 title claims abstract description 141
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000004964 aerogel Substances 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 75
- 239000005011 phenolic resin Substances 0.000 claims description 74
- 229920001568 phenolic resin Polymers 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002679 ablation Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 238000005452 bending Methods 0.000 claims description 3
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- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The application relates to a fiber ceramic skeleton phenolic aerogel composite material and a preparation method thereof, wherein the fiber ceramic skeleton phenolic aerogel composite material comprises a fiber ceramic skeleton with a micropore structure and phenolic aerogel, and the inside of the fiber ceramic skeleton with the micropore structure is filled with the phenolic aerogel; the pore diameter of the fiber ceramic skeleton is 300 nm-600 nm, and the pore diameter of the phenolic aerogel is 30 nm-200 nm. The technical problem that the heat insulation effect of the existing phenolic aerogel is poor in the high-temperature environment is solved.
Description
Technical Field
The application relates to the technical field of composite materials, in particular to a fiber ceramic skeleton phenolic aerogel composite material and a preparation method thereof.
Background
With the development of phenolic resin matrix composite materials, the application range is wider and wider, and one important application direction is application in a high-temperature environment. However, the conventional phenolic resin-based composite material has relatively high density, relatively high thermal conductivity and relatively poor heat insulation effect. The phenolic aerogel is a lightweight quartz fabric reinforced by adopting a hybridized phenolic resin solution, is cured at high temperature to form a nanoscale phenolic resin network structure, and is dried at normal pressure to form the phenolic aerogel with a micropore shape, so that the phenolic aerogel has the high-temperature ablation resistance of the phenolic resin and the low heat conduction characteristic of an aerogel material.
However, under a high temperature environment, the organic phenolic resin forming the phenolic aerogel network is decomposed and carbonized, the phenolic network and micropores formed by the phenolic network are damaged, and the heat insulation effect inside the composite material is gradually lost, so that the heat conductivity of the composite material is basically equivalent to that of the traditional phenolic resin composite material at a high temperature, and the advantage of low heat conduction and heat insulation effects is lost.
Disclosure of Invention
The application provides a fiber ceramic skeleton phenolic aerogel composite material and a preparation method thereof, which are used for solving the technical problem that the heat insulation effect of the existing phenolic aerogel is poor in a high-temperature environment.
In a first aspect, the present application provides a fiber ceramic skeleton phenolic aerogel composite material, the fiber ceramic skeleton phenolic aerogel composite material includes a fiber ceramic skeleton with a microporous structure and phenolic aerogel, and the interior of the fiber ceramic skeleton with the microporous structure is filled with the phenolic aerogel;
the pore diameter of the fiber ceramic skeleton is 300 nm-600 nm, and the pore diameter of the phenolic aerogel is 30 nm-200 nm.
Optionally, the properties of the ceramic skeleton phenolic aerogel material include: density of 0.4g/cm 3 ～1.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending strength is greater than 50MPa; compressive strength greater than 10MPa; after passing through a typical thermal environment with a peak temperature of 1500 ℃, the compressive strength is greater than 8MPa; after passing through a typical thermal environment with a peak temperature of 1500 ℃, the size ablation is no greater than 1mm.
Optionally, the properties of the fibrous ceramic skeleton with microporous structure include: specific heat capacity not less than 1000J/(kg.K); the thermal conductivity is not more than 0.04W/(m.k); after passing through a typical thermal environment with a peak temperature of 1500 ℃, the thermal conductivity is not more than 0.07W/(m·k).
Optionally, the raw materials of the fibrous ceramic skeleton with the micropore structure comprise at least one of the following materials: quartz fibers, alumina fibers, silicon carbide fibers.
In a second aspect, the present application provides a method of preparing the fibrous ceramic matrix phenolic aerogel material of any one of the first aspects, the method comprising:
obtaining a fiber ceramic skeleton with a micropore structure;
injecting phenolic resin into the fiber ceramic skeleton with the micropore structure to obtain the fiber ceramic skeleton containing the phenolic resin;
and solidifying the fiber ceramic skeleton containing the phenolic resin, and drying to obtain the fiber ceramic skeleton phenolic aerogel material.
Alternatively, the phenolic resin has a solid content of 0.2 to 0.7 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure.
Optionally, the injecting phenolic resin into the fiber ceramic skeleton with the micropore structure to obtain the fiber ceramic skeleton containing phenolic resin comprises the following steps:
placing the fibrous ceramic skeleton with the micropore structure in a mould, and injecting nitrogen with the pressure of 0.1-0.5 MPa into the mould, wherein the pressure drop value of the mould within 10min is not more than 0.005MPa;
and vacuumizing the die containing nitrogen to enable the inside of the die and the inside of the fiber ceramic skeleton to reach a vacuum state, then injecting phenolic resin into the die, and enabling the phenolic resin to be filled in the inside of the fiber ceramic skeleton in the vacuum state to obtain the fiber ceramic skeleton containing the phenolic resin.
Optionally, the fiber ceramic skeleton with the micropore structure is obtained, which comprises the following steps:
mixing and stirring the fiber dispersion liquid and the binder slurry, and then performing filter pressing to obtain a mixed material filter cake;
performing first solidification and sintering on the mixed material filter cake to obtain a fiber ceramic framework with a micropore structure; wherein,
the temperature of the first solidification is 80-140 ℃, and the temperature of the sintering is 1200-1600 ℃.
Optionally, the raw material components of the binder slurry include at least one of: boron nitride, silicon nitride, zirconium boride.
Optionally, the step of curing the fiber ceramic skeleton containing the phenolic resin and then drying to obtain the fiber ceramic skeleton phenolic aerogel material comprises the following steps:
performing second curing on the fiber ceramic skeleton containing the phenolic resin, and performing two-stage normal-pressure drying to obtain a fiber ceramic skeleton phenolic aerogel material; wherein,
the temperature of the second solidification is 80-130 ℃; the temperature of the first-stage normal-pressure drying is 40-60 ℃; the temperature of the second-stage normal-pressure drying is 70-100 ℃.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the fiber ceramic skeleton phenolic aerogel composite material provided by the embodiment of the application simultaneously has two composite materials with microporous structures: the fiber ceramic skeleton with the micropore structure and the phenolic aerogel are filled with the phenolic aerogel, the ceramic skeleton forms a hard structure with micropores and low density and low heat conduction in the sintering process, and then the hard structure is combined with phenolic resin to form the phenolic aerogel in the ceramic skeleton, so that the fiber ceramic skeleton reinforced phenolic aerogel composite material is formed. Under a high-temperature environment, the surface phenolic resin is decomposed and carbonized, the phenolic aerogel structure is destroyed, but the microporous structure formed by the fiber ceramics still exists, and the fiber ceramics still has a low heat conduction structure at high temperature and plays a role in high-temperature heat insulation, so that the heat insulation stability of the composite material at high temperature is improved, the cold surface temperature of the composite material is reduced, and the reliability of a heat protection structure is improved; and the brittleness of the ceramic skeleton can be improved by the phenolic aerogel, so that a large-size component can be prepared, and the defect that the ceramic heat-insulating tile can only be spliced in small blocks is overcome. In conclusion, the technical problem that the heat insulation effect of the existing phenolic aerogel in a high-temperature environment is poor is solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application.
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a morphology diagram of a fiber ceramic framework phenolic aerogel composite material provided in an embodiment of the present application;
fig. 2 is a schematic flow chart of a method for preparing a fiber ceramic skeleton phenolic aerogel composite according to an embodiment of the present disclosure.
Detailed Description
For the purposes of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present application based on the embodiments herein.
Various embodiments of the present application may exist in a range format; it should be understood that the description in a range format is merely for convenience and brevity and should not be interpreted as a rigid limitation on the scope of the application. It is therefore to be understood that the range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that a description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, wherever applicable. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In this application, the terms "include," "include," and the like mean "including but not limited to. Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
Unless specifically indicated otherwise, the various raw materials, reagents, instruments, equipment, and the like used in this application are commercially available or may be prepared by existing methods.
FIG. 1 is a morphology diagram of a fiber ceramic framework phenolic aerogel composite material provided in an embodiment of the present application; referring to fig. 1, the present application provides a fiber ceramic skeleton phenolic aerogel composite material, which includes a fiber ceramic skeleton with a microporous structure and phenolic aerogel, wherein the inside of the fiber ceramic skeleton with the microporous structure is filled with the phenolic aerogel; it is apparent from FIG. 1 that the fiber ceramic skeleton is filled with small bubbles formed by phenolic resin;
the pore diameter of the fiber ceramic skeleton is 300 nm-600 nm, and the pore diameter of the phenolic aerogel is 30 nm-200 nm.
In the embodiment of the application, the fiber ceramic skeleton phenolic aerogel composite material is a composite material with two micropore structures: the fiber ceramic skeleton with the micropore structure and the phenolic aerogel are filled with the phenolic aerogel, the ceramic skeleton forms a hard structure with micropores and low density and low heat conduction in the sintering process, and then the hard structure is combined with phenolic resin to form the phenolic aerogel in the ceramic skeleton, so that the fiber ceramic skeleton reinforced phenolic aerogel composite material is formed. Under a high-temperature environment, the surface phenolic resin is decomposed and carbonized, the phenolic aerogel structure is destroyed, but the microporous structure formed by the fiber ceramics still exists, and the fiber ceramics still has a low heat conduction structure at high temperature and plays a role in high-temperature heat insulation, so that the heat insulation stability of the composite material at high temperature is improved, the cold surface temperature of the composite material is reduced, and the reliability of a heat protection structure is improved; and the brittleness of the ceramic skeleton can be improved by the phenolic aerogel, so that a large-size component can be prepared, and the defect that the ceramic heat-insulating tile can only be spliced in small blocks is overcome.
In the pore diameter range of the fiber ceramic skeleton, the fiber ceramic skeleton can obtain better density, mechanical property and thermal conductivity. If the pore diameter of the fiber ceramic skeleton is too large, the density and mechanical property of the material can be reduced to a certain extent; if the pore diameter of the fiber ceramic skeleton is too small, the thermal conductivity is larger to a certain extent, and the heat insulation effect is reduced. In the pore diameter range of the phenolic aerogel, the phenolic aerogel can obtain better ablation performance and heat insulation performance; if the pore diameter of the phenolic aerogel is too large, the ablation resistance can be weakened to a certain extent; if the pore size of the phenolic aerogel is too small, this will result in some increase in thermal conductivity. Illustratively, the pore diameter of the fiber ceramic skeleton may be 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, etc., and the pore diameter of the phenolic aerogel may be 30nm, 50nm, 80nm, 100nm, 120nm, 150nm, 180nm, 200nm, etc.
In some embodiments, the properties of the ceramic matrix phenolic aerogel material include: density of 0.4g/cm 3 ～1.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending strength is greater than 50MPa; compressive strength greater than 10MPa; after passing through a typical thermal environment with a peak temperature of 1500 c,compressive strength greater than 8MPa; after passing through a typical thermal environment with a peak temperature of 1500 ℃, the size ablation is no greater than 1mm.
In some embodiments, the properties of the fibrous ceramic skeleton having a microporous structure include: specific heat capacity not less than 1000J/(kg.K); the thermal conductivity is not more than 0.04W/(m.k); after passing through a typical thermal environment with a peak temperature of 1500 ℃, the thermal conductivity is not more than 0.07W/(m·k).
In some embodiments, the properties of the phenolic aerogel include: in the embodiment of the application, the fiber ceramic skeleton phenolic aerogel composite material has low linear ablation rate, so that the brittleness of the fiber ceramic skeleton is compensated; the thermal conductivity of the fiber ceramic skeleton is not greatly changed in a high-temperature environment, the thermal insulation performance is excellent, the defect that the thermal insulation effect of the phenolic aerogel in the high-temperature environment is poor is overcome, and the ceramic skeleton phenolic aerogel material formed by compounding the phenolic aerogel and the fiber ceramic skeleton has excellent thermal insulation performance and excellent mechanical property.
In some embodiments, the starting material of the fibrous ceramic skeleton having a microporous structure comprises at least one of the following: quartz fibers, alumina fibers, silicon carbide fibers.
In the embodiment of the application, quartz fibers, alumina fibers and silicon carbide fibers are selected as raw materials of the fiber ceramic skeleton with the micropore structure, and are all high-temperature resistant fibers.
FIG. 2 is a schematic flow chart of a method for preparing a fiber ceramic skeleton phenolic aerogel composite according to an embodiment of the present disclosure; referring to fig. 2, the present application provides a method for preparing the fiber ceramic skeletal phenolic aerogel material of any one of the first aspect, the method comprising:
s1, obtaining a fiber ceramic skeleton with a micropore structure;
in some embodiments, the resulting fibrous ceramic scaffold having a microporous structure comprises:
mixing and stirring the fiber dispersion liquid and the binder slurry, and then performing filter pressing to obtain a mixed material filter cake;
performing first solidification and sintering on the mixed material filter cake to obtain a fiber ceramic framework with a micropore structure; wherein,
the temperature of the first solidification is 80-140 ℃, and the temperature of the sintering is 1200-1600 ℃.
In some embodiments, the raw material components of the binder slurry include at least one of: boron nitride, silicon nitride, zirconium boride.
In the embodiment of the application, the fiber ceramic skeleton with the micropore structure is obtained, which specifically comprises the following steps: crushing; the high temperature resistant fiber is crushed to form short fiber with the length of about 2-5 mm, and the short fiber is stirred in 50% +/-25% water solution for at least 2h to be fully dispersed. Mixing; mixing the short fiber solution and the binder slurry according to the proportion of (50-150) to obtain a mixed solution; the binder slurry can be one or more of boron nitride, silicon nitride, zirconium boride and the like, can sinter the high-temperature resistant fibers together, and the reaction product has a higher melting point and can resist higher temperature. Stirring; stirring the mixed solution in a stirrer for at least 1h to make the components of the mixed solution uniform. Press filtration; placing the mixed solution into a container with holes, pressurizing the surface by a pressing block, and extruding excessive water by a filter pressing method to form a blank block. The water content before and after the pressing flow is determined by a weighing method, and the water content of the material returning block after the pressing flow is required to be not more than 30 percent. Curing; and (3) placing the blank block into an oven, curing at 80-140 ℃ for at least 2 hours, and further evaporating water and volatile matters to ensure that the water content is not more than 5%. Sintering; and placing the blank block into a muffle furnace, and sintering at 1200-1600 ℃ for at least 8 hours to obtain the fiber ceramic skeleton with the micropore structure. Defining a first curing temperature such that the feedstock is sufficiently cured, reducing moisture and volatiles in the billet, enhancing internal interactions of the billet; the sintering temperature is limited, so that a hard structure with micropores, low density and low heat conduction is formed in the sintering process. Illustratively, the temperature of the first curing may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, etc., and the temperature of the sintering may be 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, etc.
S2, injecting phenolic resin into the fiber ceramic skeleton with the micropore structure to obtain the fiber ceramic skeleton containing the phenolic resin;
in some embodiments, the phenolic resin has a solids content of 0.2 to 0.7 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure.
In the embodiment of the application, the proportion of the fiber ceramic skeleton to the phenolic resin is limited, so that the heat insulation performance of the material in a high-temperature environment is effectively controlled, and the brittleness of the ceramic heat insulation tile is improved. If the phenolic resin is used in an excessive amount, the heat insulation effect of the material is dominant to a certain extent, and when the phenolic resin is decomposed at a high temperature, the heat conductivity of the material is greatly improved, and the heat insulation effect of the material in a high-temperature environment is reduced. If the amount of the phenolic resin is too small, it is difficult to effectively improve the brittleness of the ceramic heat insulating tile to some extent, and thus it is difficult to prepare a large-sized product. For example, the solid content of the above phenolic resin may be 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, and the like.
In some embodiments, the injecting phenolic resin into the fiber ceramic skeleton with the micropore structure to obtain the fiber ceramic skeleton containing phenolic resin comprises:
placing the fibrous ceramic skeleton with the micropore structure in a mould, and injecting nitrogen with the pressure of 0.1-0.5 MPa into the mould, wherein the pressure drop value of the mould within 10min is not more than 0.005MPa;
and vacuumizing the die containing nitrogen to enable the inside of the die and the inside of the fiber ceramic skeleton to reach a vacuum state, then injecting phenolic resin into the die, and enabling the phenolic resin to be filled in the inside of the fiber ceramic skeleton in the vacuum state to obtain the fiber ceramic skeleton containing the phenolic resin.
In an embodiment of the present application, the implantation process includes: taking out the sintered blank block, polishing and cleaning the surface of the blank block, then loading the blank block into a metal steel closed mold, wherein a metal mold cavity is required to be plated with polytetrafluoroethylene or a polytetrafluoroethylene pressure-sensitive adhesive tape is adhered to the metal mold cavity, so that the mold cavity is not directly contacted with a product; the mold is required to be capable of maintaining airtightness at 0.3MPa, namely, nitrogen of 0.1MPa to 0.5MPa is injected into the mold, and the pressure drop value within 10min is required to be not more than 0.005MPa, so that the mold is stable in the detection process and does not cause unexpected chemical reactions, explosions and the like. And the density is relatively low, so that the glue is conveniently discharged from the upper part during the subsequent glue injection from bottom to top. And then the glue injection port of the die is connected with RTM glue injection equipment, and the glue outlet is connected with a transparent polyethylene pipe. The mould may be provided with one or more glue outlets depending on the size of the blank, in principle with the glue outlet above and the glue inlet below, wherein a glue outlet must be connected to the vacuum device. Starting the vacuum equipment, vacuumizing the mold for at least 0.5h, and enabling the mold cavity and the inside of the ceramic skeleton to be in a vacuum state. Then, the RTM glue injection apparatus was started in a state of maintaining vacuum, and a phenolic resin (HP-4 series resin or the like) was injected into the mold under a low pressure condition (the pressure was set according to the size of the mold, and typically 0.05 MPa) and the inside of the ceramic skeleton was filled with the resin under vacuum.
And S3, solidifying the fiber ceramic skeleton containing the phenolic resin, and drying to obtain the fiber ceramic skeleton phenolic aerogel material.
In some embodiments, the curing of the fibrous ceramic skeleton containing phenolic resin followed by drying results in a fibrous ceramic skeleton phenolic aerogel material comprising:
solidifying the fiber ceramic skeleton containing the phenolic resin, and then drying at normal pressure in two stages to obtain a fiber ceramic skeleton phenolic aerogel material; wherein,
the temperature of the second solidification is 80-130 ℃; the temperature of the first-stage normal-pressure drying is 40-60 ℃; the temperature of the second-stage normal-pressure drying is 70-100 ℃.
In the embodiment of the application, the second curing temperature is limited, so that the fiber ceramic skeleton phenolic aerogel material can obtain higher curing degree, and the cured phenolic resin forms a phenolic resin crosslinked network and nano micropores formed by the resin network in micropores of the ceramic skeleton. Specific second curing includes: and closing the glue injection port and the glue outlet of the die after glue injection is completed, so that the die cavity is in a closed state. And then putting the mould into an oven, slowly heating to 80-130 ℃ and preserving heat for at least 12 hours to solidify the phenolic resin.
The drying under normal pressure can avoid dependence on supercritical drying equipment, prevent forming equipment bottleneck, be favorable to mass production organization of products, use air to replace the organic solvent in the micropore of the phenolic aldehyde slowly, form the phenolic aldehyde aerogel structure. The two-stage drying enables slow and controlled drying, so that air gradually replaces the internal organic solvent, and the phenomenon that the phenolic network collapses and contracts due to the fact that the organic solvent volatilizes too fast is prevented, and therefore the density and the heat conductivity of the phenolic aerogel are affected; the first stage of normal pressure low temperature drying, slow heating at a temperature far lower than the boiling point, so that the composite material is slowly and controllably dried, the air gradually replaces the internal organic solvent, and the collapse and shrinkage of the phenolic network caused by the too fast volatilization of the organic solvent are prevented; the second stage of drying at normal pressure and high temperature is heating in the vicinity of or above the boiling point, so that the organic solvent which has not been completely removed by displacement can be completely displaced and discharged after the first stage. Illustratively, the second cure temperature may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃; the temperature of the first stage normal pressure drying is 40 ℃, 45 ℃, 50 ℃, 55 ℃ and 60 ℃; the temperature of the second stage of normal pressure drying is 70deg.C, 75deg.C, 80deg.C, 85deg.C, 90deg.C, 95deg.C, 100deg.C, etc. The specific normal pressure drying comprises the following steps: and opening the cured mould, demoulding the blank block, namely firstly standing the blank block at normal temperature for at least 24 hours, then putting the blank block into an oven for heating, heating at normal pressure, respectively preserving heat at the temperature of the first-stage normal pressure drying and the temperature of the second-stage normal pressure drying for at least 12 hours, and slowly replacing the organic solvent in the phenolic micropores by using air to form the phenolic aerogel structure. The volume density of the phenolic resin solution is about 0.9, the density of the sintered fiber ceramic skeleton is about 0.3, the weight ratio of the solution to the skeleton before drying is about 1:3, the solvent in the phenolic resin solution volatilizes in the drying process, and the final phenolic resin content is the product of the phenolic resin solution amount and the solid content in the solution. The phenolic resin content is 0.6 to 2.1 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton with the micropore structure. The fiber ceramic skeleton phenolic aerogel material can be processed to form a final product.
The present application is further illustrated below in conjunction with specific examples. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Example 1
1. Crushing
The quartz fibers were pulverized to form short fibers having a fiber length of about 2mm, and stirred in a 30% aqueous solution for 2 hours.
2. Mixing
According to the boron oxide: boron nitride: binder slurry was formulated in a ratio of water=1:1:3. The quartz staple fiber solution was mixed with the binder slurry in a ratio of 100:75.
3. Stirring
The mixed solution was stirred in a stirrer for 1h.
4. Pressure filtration
Placing the mixed solution into a container with holes, pressing the surface of the container through a pressing block to form a blank block, and keeping the water content of the pressed blank block to be 25%.
8. Curing
The blank block was placed in an oven and cured at 100 ℃ for 4 hours with a moisture content of 2%.
6. Sintering
And (3) placing the blank block into a muffle furnace, and sintering for 16h at 1100 ℃ to form the fiber ceramic skeleton structure with the micropore structure.
7. Glue injection
Taking out the sintered blank block, polishing and cleaning the surface of the blank block, then loading the blank block into a metal steel closed mold, wherein a metal mold cavity is required to be plated with polytetrafluoroethylene or a polytetrafluoroethylene pressure-sensitive adhesive tape is adhered to the metal mold cavity, so that the mold cavity is not directly contacted with a product; nitrogen of 0.3MPa is injected into the die, and the pressure drop value of the die is 0.004MPa within 10 min. And then the glue injection port of the die is connected with RTM glue injection equipment, and the glue outlet is connected with a transparent polyethylene pipe. The mould may be provided with one or more glue outlets depending on the size of the blank, in principle with the glue outlet above and the glue inlet below, wherein a glue outlet must be connected to the vacuum device. Starting the vacuum equipment, vacuumizing the mold for 0.5h, and enabling the mold cavity and the inside of the ceramic framework to be in a vacuum state. And then starting RTM glue injection equipment under the state of maintaining vacuum, and injecting the hybridized phenolic resin into the mould under the low pressure condition (the pressure is set according to the size of the mould and is generally 0.05 MPa), so as to obtain the fiber ceramic skeleton containing the phenolic resin. Wherein, relative to 1 part by weight of fibrous ceramic skeleton with micropore structure, the solid content of the hybridized phenolic resin solution is 0.2 part by weight; the content of the hybrid phenolic resin solution was 3 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure.
8. Curing
And closing the glue injection port and the glue outlet of the die after glue injection is completed, so that the die cavity is in a closed state. The mold was then placed in an oven, slowly heated to 90 ℃ and incubated for 36h.
9. Drying under normal pressure
Opening the cured mould, demoulding the blank block, firstly standing the blank block at normal temperature for 48 hours, then placing the blank block into an oven for heating, heating the blank block at normal pressure, and respectively preserving heat at 50 ℃ for 24 hours and 80 ℃ for 24 hours to obtain the fiber ceramic skeleton phenolic aerogel material; wherein the content of the phenolic resin is 0.6 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure. Processing the blank as required by the article to form the final article.
Example 2
1. Crushing
The quartz fibers were pulverized to form short fibers having a fiber length of about 3mm, and stirred in a 50% aqueous solution for 3 hours.
2. Mixing
According to the boron oxide: boron nitride: binder slurry was formulated in a ratio of water=1:1:3. The quartz staple fiber solution was mixed with the binder slurry at a ratio of 100:100.
3. Stirring
The mixed solution was stirred in a stirrer for 2h.
4. Pressure filtration
And (3) placing the mixed solution into a container with holes, pressurizing the surface of the container through a pressing block to form a blank block, and keeping the water content of the pressed blank block to be 20%.
8. Curing
The blank block was placed in an oven and cured at 100 ℃ for 3 hours with a moisture content of 2.0%.
6. Sintering
And placing the blank block into a muffle furnace, and sintering for 14h at 1200 ℃ to form the fiber ceramic skeleton structure with the micropore structure.
7. Glue injection
Taking out the sintered blank block, polishing and cleaning the surface of the blank block, then loading the blank block into a metal steel closed mold, wherein a metal mold cavity is required to be plated with polytetrafluoroethylene or a polytetrafluoroethylene pressure-sensitive adhesive tape is adhered to the metal mold cavity, so that the mold cavity is not directly contacted with a product; nitrogen of 0.4MPa is injected into the die, and the pressure drop value of the die is 0.003MPa within 10 min. And then the glue injection port of the die is connected with RTM glue injection equipment, and the glue outlet is connected with a transparent polyethylene pipe. The mould may be provided with one or more glue outlets depending on the size of the blank, in principle with the glue outlet above and the glue inlet below, wherein a glue outlet must be connected to the vacuum device. Starting the vacuum equipment, vacuumizing the mold for 1h, and enabling the mold cavity and the inside of the ceramic framework to be in a vacuum state. And then starting RTM glue injection equipment under the state of maintaining vacuum, and injecting the hybridized phenolic resin into the mould under the low pressure condition (the pressure is set according to the size of the mould and is generally 0.05 MPa), so as to obtain the fiber ceramic skeleton containing the phenolic resin. Wherein, relative to 1 part by weight of the fibrous ceramic skeleton with the micropore structure, the solid content of the hybridized phenolic resin solution is 0.33 part by weight; the content of the hybrid phenolic resin solution was 3 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure.
8. Curing
And closing the glue injection port and the glue outlet of the die after glue injection is completed, so that the die cavity is in a closed state. The mold was then placed in an oven, slowly heated to 100 ℃ and incubated for 24 hours.
9. Drying under normal pressure
And opening the cured mould, demoulding the blank block, firstly standing the blank block at normal temperature for 36h, then placing the blank block into an oven for heating, heating at normal pressure, and respectively preserving heat at 40 ℃ for 48h and 70 ℃ for 48h to obtain the fiber ceramic skeleton phenolic aerogel material. The phenolic resin content was 0.99 parts by weight based on 1 part by weight of the fibrous ceramic skeleton having a microporous structure after drying. Processing the blank as required by the article to form the final article.
Example 3
1. Crushing
The quartz fibers were pulverized to form short fibers having a fiber length of about 5mm and stirred in a 70% aqueous solution for 4 hours.
2. Mixing
According to the boron oxide: boron nitride: binder slurry was formulated in a ratio of water=1:1:3. The quartz staple fiber solution was mixed with the binder slurry in a ratio of 100:125.
3. Stirring
The mixed solution was stirred 4.h in a stirrer.
4. Pressure filtration
And (3) placing the mixed solution into a container with holes, pressurizing the surface of the container through a pressing block to form a blank block, and keeping the water content of the pressed blank block to be 15%.
8. Curing
The blank block was placed in an oven and cured at 100 ℃ for 4 hours with a moisture content of 0.7%.
6. Sintering
And (3) placing the blank block into a muffle furnace, and sintering for 10 hours at 1400 ℃ to form the fiber ceramic skeleton structure with the micropore structure.
7. Glue injection
Taking out the sintered blank block, polishing and cleaning the surface of the blank block, then loading the blank block into a metal steel closed mold, wherein a metal mold cavity is required to be plated with polytetrafluoroethylene or a polytetrafluoroethylene pressure-sensitive adhesive tape is adhered to the metal mold cavity, so that the mold cavity is not directly contacted with a product; nitrogen of 0.3MPa is injected into the die, and the pressure drop value is 0.005MPa within 10 min. And then the glue injection port of the die is connected with RTM glue injection equipment, and the glue outlet is connected with a transparent polyethylene pipe. The mould may be provided with one or more glue outlets depending on the size of the blank, in principle with the glue outlet above and the glue inlet below, wherein a glue outlet must be connected to the vacuum device. Starting the vacuum equipment, vacuumizing the mold for 1.5 hours, and enabling the mold cavity and the inside of the ceramic framework to reach a vacuum state. And then starting RTM glue injection equipment under the state of maintaining vacuum, and injecting the hybridized phenolic resin into the mould under the low pressure condition (the pressure is set according to the size of the mould and is generally 0.05 MPa), so as to obtain the fiber ceramic skeleton containing the phenolic resin. Wherein the solid content of the hybrid phenolic resin solution is 0.7 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure; the content of the hybrid phenolic resin solution was 3 parts by weight with respect to 1 part by weight of the fibrous ceramic skeleton having a microporous structure.
8. Curing
And closing the glue injection port and the glue outlet of the die after glue injection is completed, so that the die cavity is in a closed state. The mold was then placed in an oven, slowly heated to 85 ℃ and incubated for 48h.
9. Drying under normal pressure
And opening the cured mould, demoulding the blank block, firstly standing the blank block at normal temperature for 24 hours, then placing the blank block into an oven for heating, heating at normal pressure, and respectively preserving heat at 60 ℃ for 16 hours and at 90 ℃ for 16 hours to obtain the fiber ceramic skeleton phenolic aerogel material. Wherein the content of the phenolic resin is 2.1 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure. Processing the blank as required by the article to form the final article.
Comparative example 1 (preparation of phenolic aerogel)
1. Die-filling
Assembling a metal steel closed mold, wherein a metal mold cavity is required to be plated with polytetrafluoroethylene or a polytetrafluoroethylene pressure-sensitive adhesive tape is adhered to the metal mold cavity, so that the metal mold cavity is not directly contacted with a product; nitrogen gas of 0.3MPa was injected into the mold, and a pressure drop of 0.005MPa was required within 10 minutes.
2. Glue injection
The glue injection port of the die is connected with RTM glue injection equipment, and the glue outlet is connected with a transparent polyethylene pipe. The mould may be provided with one or more glue outlets depending on the size of the blank, in principle with the glue outlet above and the glue inlet below, wherein a glue outlet must be connected to the vacuum device. Starting the vacuum equipment, and vacuumizing the die for 0.5h to enable the interior of the die cavity to reach a vacuum state. The RTM glue injection apparatus was then started while maintaining vacuum, and the hybrid phenolic resin was injected into the mold under low pressure conditions (pressure set according to the mold dimensions, typically 0.05 MPa).
3. Curing
And closing the glue injection port and the glue outlet of the die after glue injection is completed, so that the die cavity is in a closed state. The mold was then placed in an oven, slowly heated to 100 ℃ and incubated for 24 hours.
4. Drying under normal pressure
And opening the cured mould, demoulding the blank block, firstly standing the blank block at normal temperature for 48 hours, then placing the blank block into an oven for heating, heating at normal pressure, and respectively preserving heat at 50 ℃ for 24 hours and 80 ℃ for 24 hours to obtain the phenolic aerogel material. Processing the blank as required by the article to form the final article.
Performance tests were conducted on the fiber ceramic skeleton phenolic aerogel materials obtained in examples 1 to 3 and the phenolic aerogel materials obtained in comparative example 1, see tables 1 to 2.
TABLE 1 Properties of fiber ceramic skeleton and phenolic aerogel in fiber ceramic skeleton phenolic aerogel Material
TABLE 2 fiber ceramic matrix phenolic aerogel materials obtained in examples 1-3 and phenolic aerogel material obtained in comparative example 1
The fiber ceramic skeleton phenolic aerogel material prepared by the embodiment of the application has excellent heat insulation performance and excellent mechanical performance on the basis of the phenolic aerogel material.
The foregoing is merely a specific embodiment of the application to enable one skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The fiber ceramic skeleton phenolic aerogel composite material is characterized by comprising a fiber ceramic skeleton with a micropore structure and phenolic aerogel, wherein the inside of the fiber ceramic skeleton with the micropore structure is filled with the phenolic aerogel;
the pore diameter of the fiber ceramic skeleton is 300 nm-600 nm, and the pore diameter of the phenolic aerogel is 30 nm-200 nm.
2. The fibrous ceramic matrix phenolic aerogel material of claim 1, wherein the properties of the ceramic matrix phenolic aerogel material include: density of 0.4g/cm 3 ～1.0g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending strength is greater than 50MPa; compressive strength greater than 10MPa; after passing through a typical thermal environment with a peak temperature of 1500 ℃, the compressive strength is greater than 8MPa; at the passing peak temperatureAfter a typical thermal environment of 1500 ℃, the size ablation is no greater than 1mm.
3. The fibrous ceramic matrix phenolic aerogel material of claim 1, wherein the properties of the fibrous ceramic matrix having a microporous structure comprise: specific heat capacity not less than 1000J/(kg.K); the thermal conductivity is not more than 0.04W/(m.k); after passing through a typical thermal environment with a peak temperature of 1500 ℃, the thermal conductivity is not more than 0.07W/(m·k).
4. The fibrous ceramic matrix phenolic aerogel material of claim 1, wherein the fibrous ceramic matrix having a microporous structure comprises at least one of the following raw materials: quartz fibers, alumina fibers, silicon carbide fibers.
5. A method of preparing the fibrous ceramic matrix phenolic aerogel material of any one of claims 1-4, comprising:
obtaining a fiber ceramic skeleton with a micropore structure;
injecting phenolic resin into the fiber ceramic skeleton with the micropore structure to obtain the fiber ceramic skeleton containing the phenolic resin;
and (3) carrying out first curing on the fiber ceramic skeleton containing the phenolic resin, and then drying to obtain the fiber ceramic skeleton phenolic aerogel material.
6. The method according to claim 5, wherein the phenolic resin has a solid content of 0.2 to 0.7 parts by weight relative to 1 part by weight of the fibrous ceramic skeleton having a microporous structure.
7. The method of claim 5, wherein said injecting a phenolic resin into said fibrous ceramic skeleton having a cellular structure to obtain said fibrous ceramic skeleton containing phenolic resin comprises:
placing the fibrous ceramic skeleton with the micropore structure in a mould, and injecting nitrogen with the pressure of 0.1-0.5 MPa into the mould, wherein the pressure drop value of the mould within 10min is not more than 0.005MPa;
and vacuumizing the die containing nitrogen to enable the inside of the die and the inside of the fiber ceramic skeleton to reach a vacuum state, then injecting phenolic resin into the die, and enabling the phenolic resin to be filled in the inside of the fiber ceramic skeleton in the vacuum state to obtain the fiber ceramic skeleton containing the phenolic resin.
8. The method of claim 5, wherein the obtaining a fibrous ceramic skeleton having a microporous structure comprises:
mixing and stirring the fiber dispersion liquid and the binder slurry, and then performing filter pressing to obtain a mixed material filter cake;
performing second solidification and sintering on the mixed material filter cake to obtain a fiber ceramic framework with a micropore structure; wherein the temperature of the first solidification is 80-140 ℃, and the temperature of the sintering is 1200-1600 ℃.
9. The method of claim 8, wherein the raw material components of the binder slurry comprise at least one of: boron nitride, silicon nitride, zirconium boride.
10. The method of claim 5, wherein said first curing and then drying said fibrous ceramic matrix containing phenolic resin to provide a fibrous ceramic matrix phenolic aerogel material comprising:
performing first curing on the fiber ceramic skeleton containing phenolic resin, and performing two-stage normal-pressure drying to obtain a fiber ceramic skeleton phenolic aerogel material; wherein,
the temperature of the second solidification is 80-130 ℃; the temperature of the first-stage normal-pressure drying is 40-60 ℃; the temperature of the second-stage normal-pressure drying is 70-100 ℃.
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