CN112094130A - High-temperature-resistant heat-insulation sandwich-structure ceramic matrix composite and preparation method thereof - Google Patents
High-temperature-resistant heat-insulation sandwich-structure ceramic matrix composite and preparation method thereof Download PDFInfo
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Abstract
Hair brushThe composite material adopts a sandwich structure, the thickness of an upper surface layer is greater than that of a lower surface layer, and Al reinforced by high-temperature resistant modified aluminum fibers2O3The aerogel composite material is used as a core layer to obtain better heat insulation performance, the carbon fiber fabric reinforced silicon carbide ceramic matrix composite material is used as a hot surface to bear a heat-proof task and resist a continuous high-temperature environment, the combination of the core layer and the hot surface layer has good heat-resistant and heat-insulation effects, and the heat and the temperature are obviously reduced when reaching a cold surface, so that the high-temperature resistance of the high-temperature-resistant heat-insulation sandwich structure ceramic matrix composite material is obviously improved, the heat-resistant and heat-insulation effect of the ceramic composite material can be obviously improved, and the safety performance of an aircraft is improved; the preparation method has the advantages of mature preparation process, high production efficiency and simple operation, and has wide prospect for large-scale production and preparation of the ceramic matrix composite material in the industrial field.
Description
Technical Field
The invention relates to the technical field of ceramic matrix composite materials, in particular to a high-temperature-resistant heat-insulating sandwich-structure ceramic matrix composite material and a preparation method thereof.
Background
The high supersonic speed aircraft such as a space shuttle or a recoverable satellite flies in the atmosphere for a long time at a high supersonic speed, the temperature of a large area exceeds 800 ℃, and the temperature of a part reaches 1800 ℃. In order to prevent the damage of the internal equipment caused by high temperature, the high-efficiency heat-proof material must be adopted. The ceramic heat-insulating tile plays an important role in American space shuttles, but has inherent brittleness (the toughness is generally 1-5 MPa x m)1/2) Low strength (bending strength is generally less than 5MPa), high thermal conductivity (generally more than 0.06W/m multiplied by k), small single-piece area (generally 200 multiplied by 200 mm) and the like, and can not well meet the requirements of high reliability and high efficiency of large-area heat insulation of a high-speed aircraft. Based on the above, heat-proof and heat-insulation integrated composite materials have been proposed, which have the remarkable advantages of good toughness, high strength and good integral forming performance, but are limited to heat-proof at high temperature not exceeding 1100 ℃.
Disclosure of Invention
The invention provides a high-temperature-resistant heat-insulation sandwich-structure ceramic matrix composite and a preparation method thereof, which are used for overcoming the defects of limited high-temperature resistance of a heat-insulation composite in the prior art and the like.
In order to achieve the purpose, the invention provides a high-temperature-resistant heat-insulation sandwich-structure ceramic matrix composite material which is in a sandwich structure and comprises a core layer, an upper surface layer and a lower surface layerThe core layer, the upper surface layer and the lower surface layer are connected through fiber puncture lines; the core layer is Al enhanced by modified aluminum fiber2O3The upper surface layer is a carbon fiber fabric reinforced silicon carbide ceramic matrix composite, and the lower surface layer is a silicon oxide fiber fabric reinforced silicon oxide ceramic panel; the upper surface layer has a thickness greater than a thickness of the lower surface layer.
In order to achieve the above object, the present invention further provides a preparation method of the high temperature resistant heat insulation sandwich structure ceramic matrix composite material, comprising:
s1: al reinforced with modified aluminum fibers2O3The aerogel layer is used as a core layer, the silicon oxide fiber fabric is flatly laid on the lower surface of the core layer, and then needling, puncturing or sewing treatment is carried out to combine the silicon oxide fiber fabric with the core layer to form a first fabric skin;
s2: clamping the first fabric skin by using a mold, and soaking the first fabric skin in SiO2Gelling in the sol at a preset temperature, and repeatedly soaking and gelling for 3-10 times;
s3: carrying out heat treatment on the first fabric skin treated in the step S2, and then cooling to room temperature;
s4: c, laying a carbon fiber fabric on the upper surface of the core layer processed in the step S3, and then carrying out needling, puncturing or sewing treatment to form a fabric skin;
s5: dipping the fabric skin into a polycarbosilane precursor solution, then curing, and repeatedly dipping and curing for 8-12 times;
s6: and (4) carrying out pyrolysis firing on the fabric skin treated in the step S5 under a vacuum condition, and cooling to room temperature to obtain the ceramic matrix composite.
Compared with the prior art, the invention has the beneficial effects that:
1. the high-temperature-resistant heat-insulating sandwich-structure ceramic matrix composite material provided by the invention adopts a sandwich structure, the thickness of the upper surface layer is greater than that of the lower surface layer, and Al reinforced by high-temperature-resistant modified aluminum fibers2O3Aerogel composite as core layer to obtainThe heat-resistant heat-insulating sandwich structure ceramic-based composite material has the advantages that the heat-insulating property is better, the silicon carbide ceramic-based composite material reinforced by the carbon fiber fabric is used as a hot surface (upper surface layer) to undertake a heat-insulating task and resist a continuous high-temperature environment, the combination of the core layer and the hot surface layer has good heat-resistant and heat-insulating effects, and the heat and the temperature are obviously reduced when reaching a cold surface (lower surface layer), so that the high-temperature resistance of the high-temperature-resistant heat-insulating sandwich structure ceramic-based composite material is obviously improved, the heat-insulating effect of the ceramic composite material can be obviously improved, and.
2. The preparation method of the high-temperature-resistant heat-insulating sandwich structure ceramic matrix composite material provided by the invention has the advantages of mature preparation process, high production efficiency and simplicity in operation, and has a wide prospect of being used for preparing the ceramic matrix composite material in a large-scale production manner in the industrial field.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a diagram of an embodiment of a high temperature resistant, heat insulating sandwich ceramic matrix composite provided in example 1 of the present invention;
FIG. 2 is a cross-sectional view of a high temperature resistant heat insulating sandwich ceramic matrix composite provided in example 1 of the present invention;
FIG. 3 is a flowchart of a method for preparing a high temperature resistant heat insulating sandwich ceramic matrix composite according to example 1 of the present invention;
FIG. 4 is a physical diagram of the high temperature resistant heat insulating sandwich structure ceramic matrix composite material provided in embodiment 1 of the present invention after being examined in a 1500 ℃ wind tunnel test;
FIG. 5 is a cross-sectional view of the high temperature resistant heat insulating sandwich ceramic matrix composite material provided in embodiment 1 of the present invention after 1500 ℃ wind tunnel test examination.
The reference numbers illustrate: 1: an upper surface layer; 2: a core layer; 3: a lower surface layer.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a high-temperature-resistant heat-insulating sandwich-structure ceramic matrix composite, which is of a sandwich structure and comprises a core layer, an upper surface layer and a lower surface layer, wherein the core layer, the upper surface layer and the lower surface layer are connected through fiber puncture lines; the core layer is Al enhanced by modified aluminum fiber2O3The upper surface layer is a carbon fiber fabric reinforced silicon carbide ceramic matrix composite, and the lower surface layer is a silicon oxide fiber fabric reinforced silicon oxide ceramic panel; the upper surface layer has a thickness greater than a thickness of the lower surface layer.
Preferably, the thickness of the core layer is 2-300 mm; the thickness of the upper surface layer is 0.3-5.0 mm; the thickness of the lower surface layer is 0.3-5.0 mm. The thicknesses of the core layer, the upper surface layer and the lower surface layer are too thick, so that connection is not facilitated, and the whole sandwich structure is easy to damage; too thin, the heat-proof and heat-insulating effect is not good.
Preferably, the thickness of the core layer is more than or equal to 20 mm; the thickness of the upper surface layer is 0.5-3 mm (preferably 1.0-3.0 mm, and more preferably 2.0-2.5 mm); the thickness of the lower surface layer is 0.5-3 mm.
Preferably, the density of the core layer material is 0.15-0.40 g/cm3The heat conductivity is less than or equal to 0.03W/mxK, and a proper core layer material is selected to enable the core layer to have better heat insulation performance.
Preferably, graphite paper is flatly laid between the core layer and the upper surface layer, and the thickness of the graphite paper is 0.5 mm. Graphite paper is flatly laid between the core layer and the hot surface (namely the upper surface layer), polycarbosilane precursor solution is effectively prevented from entering the core layer, the polycarbosilane precursor solution does not enter the core layer material on the basis of ensuring that the polycarbosilane precursor solution fully impregnates the panel material, selective impregnation compounding of a ceramic fiber fabric region is formed, and the ceramic matrix composite material capable of being designed at fixed points is prepared.
Preferably, the fiber-piercing line is one or more of carbon fiber and alumina fiber.
The invention also provides a preparation method of the high-temperature-resistant heat-insulation sandwich structure ceramic matrix composite material, which comprises the following steps:
s1: al reinforced with modified aluminum fibers2O3The aerogel layer is used as a core layer, the silicon oxide fiber fabric is flatly laid on the lower surface of the core layer, and then needling, puncturing or sewing treatment is carried out to combine the silicon oxide fiber fabric with the core layer to form a first fabric skin;
s2: clamping the first fabric skin by using a mold, and soaking the first fabric skin in SiO2Gelling in the sol at a preset temperature, and repeatedly soaking and gelling for 3-10 times;
s3: carrying out heat treatment on the first fabric skin treated in the step S2, and then cooling to room temperature;
s4: c, laying a carbon fiber fabric on the upper surface of the core layer processed in the step S3, and then carrying out needling, puncturing or sewing treatment to form a fabric skin;
s5: dipping the fabric skin into a polycarbosilane precursor solution, then curing, and repeatedly dipping and curing for 8-12 times;
s6: and (4) carrying out pyrolysis firing on the fabric skin treated in the step S5 under a vacuum condition, and cooling to room temperature to obtain the ceramic matrix composite.
Preferably, in step S2, the impregnation is normal pressure impregnation, and the normal pressure impregnation replaces a vacuum impregnation manner, so that the preparation cost can be effectively reduced;
the preset temperature is 50-200 ℃, the gelation temperature is low, so that the sol is not easy to gel, the gelation time is too long, the production efficiency is reduced, the gelation temperature is high, the sol is rapidly gelled, the gel impregnation effect is poor, and the preferable temperature is 100-150 ℃;
in step S3, the heat treatment is performed to chemically react the gel to form SiO2The temperature of the heat treatment of the ceramic is 300-800 ℃ (preferably 500-700 ℃), and the time is 10-30 min (preferably 15-20 min);
in step S4, graphite paper is further laid flat between the upper surface of the core layer and the carbon fiber fabric;
in step S5, the impregnation is atmospheric impregnation; the curing temperature is 100-400 ℃ (preferably 200-300 ℃);
in step S6, the temperature of the pyrolysis firing is 700 to 1200 ℃ (preferably 800 to 1000 ℃), and the time is 10 to 40min (preferably 20 to 30 min).
Preferably, the thickness of the core layer is 2-300 mm; the thickness of the silicon oxide fiber fabric is 0.3-5.0 mm; the thickness of the carbon fiber fabric is 0.3-5.0 mm.
Preferably, the needling, piercing or sewing pitch in steps S1 and S4 is 3 to 30mm (preferably 5 to 10 mm).
Example 1
The embodiment provides a high-temperature-resistant heat-insulating sandwich-structure ceramic matrix composite material, which is a sandwich structure and comprises a core layer 2, an upper surface layer 1 and a lower surface layer 3, as shown in fig. 1 and 2, wherein the core layer 2, the upper surface layer 1 and the lower surface layer 3 are connected and reinforced into a whole through alumina fiber sewing; the core layer 2 is Al reinforced by modified aluminum fiber2O3Aerogel layer, core layer2 is 27.5mm thick; the density of the core layer material is 0.30g/cm3The thermal conductivity is 0.025W/m multiplied by K; the upper surface layer 1 is a carbon fiber fabric reinforced silicon carbide ceramic matrix composite, and the lower surface layer 3 is a silicon oxide fiber fabric reinforced silicon oxide ceramic panel; graphite paper with the thickness of 0.5mm is further tiled between the upper surface layer 1 and the core layer 2, the thickness of the upper surface layer is 2mm, and the thickness of the lower surface layer is 0.5 mm.
The embodiment also provides a preparation method of the ceramic matrix composite material with the high-temperature-resistant heat-insulating sandwich structure, the flow of which is shown in fig. 3, and the preparation method comprises the following steps:
(1) al reinforced with high temperature resistant modified aluminum fibers2O3The aerogel composite material is used as a core layer, the core layer material is prepared by a supercritical drying method (refer to methods disclosed by Chinese patents 200510031952.0, 200710034510.0, 201110110844.8, 201110110947.4, 201110110946.X, 201010300112.0 or 201010148105.3), and the thickness of the core layer is 27.5 mm;
spreading 1 layer of silicon oxide fiber fabric (which can expand after being soaked so that the thickness of the finally obtained lower surface layer is 0.5 mm) with the thickness of 0.38mm on the lower surface of the core layer, and then carrying out integral sewing treatment so that the silicon oxide fiber fabric is combined with the core layer to form a silicon oxide fiber fabric skin (a first fabric skin); the fibers adopted by the sewing are alumina fibers, and the distance between every two sewing threads is 20 mm;
(2) clamping the silica fiber fabric skin obtained in the step (1) by using a heat-resistant steel mould, placing the silica fiber fabric skin into a container, pouring SiO into the container2Sol, then gelatinizing at 150 ℃, repeatedly soaking and gelatinizing for 8 times;
(3) placing the silicon oxide fiber fabric skin treated in the step (2) in a high-temperature furnace for heat treatment at 750 ℃ for 20min, and then cooling to room temperature;
(4) sequentially arranging 1 layer of graphite paper and 10 layers of carbon fiber fabric on the upper surface of the core layer treated in the step S3, and then performing puncture treatment to form a fabric skin; wherein the thickness of the graphite paper is 0.5mm, and the total thickness of the carbon fiber fabric is 2 mm;
(5) dipping the fabric skin prepared in the step (4) into the polycarbosilane precursor solution at normal pressure, then curing at a preset temperature of 200 ℃, and repeatedly dipping and curing for 11 times;
(6) and (4) placing the fabric skin treated in the step (5) in a high-temperature furnace for pyrolysis firing at 800 ℃, preserving the heat for 30min, cooling to room temperature, and performing mechanical processing to reach the required size, thus obtaining the high-temperature-resistant heat-insulation sandwich structure ceramic matrix composite material.
The high-temperature-resistant heat-insulating sandwich structure ceramic matrix composite material prepared by the embodiment is subjected to 1500 ℃ wind tunnel test for 2000s, and the result is shown in fig. 4 and 5, after the material is subjected to the wind tunnel test, the surface structure of the material is finished, no obvious damage is caused, and the material system can be normally used at 1500 ℃.
The basic performance of the high-temperature-resistant heat-insulating sandwich structure ceramic matrix composite material provided by the embodiment is shown in table 1, the heat-resistant temperature of the material system is high (up to 1700 ℃), the normal-temperature tensile strength reaches 300MPa, the 1500 ℃ tensile strength is 220MPa, and the material system has excellent high-temperature resistance and successfully passes the 1500 ℃ wind tunnel test of 2000 s.
TABLE 1 basic Properties of the sandwich ceramic matrix composite of example 1
Composite material of upper surface layer | Core layer material | Composite material of lower surface layer | |
Density g/cm3 | 1.6 | 0.3 | 1.4 |
Average thermal conductivity W/m × K | 0.9 | 0.03 | 0.8 |
Short-time temperature resistance (1-3 min) | 1700℃ | 1600℃ | 1100℃ |
Long-term temperature resistance (20-30 min) | 1400℃ | 1300℃ | 900℃ |
Tensile strength at room temperature | 300MPa | 1MPa | 100 MPa |
Tensile modulus at room temperature | 9Gpa | 30MPa | 8GPa |
Elongation at break | 1.2% | 1.5% | 1.3% |
Toughness MPa m1/2 | 25 | 20 | 25 |
Tensile strength at 1500 DEG C | 220MPa | 0.5MPa | The facing away from the heat source need not be |
Tensile modulus at 1500 DEG C | 5Gpa | 10MPa | The facing away from the heat source need not be |
Example 2
In this embodiment, compared with embodiment 1, the thickness of the upper surface layer of the ceramic matrix composite material with a sandwich structure of the present invention is 1.5mm, and the rest is the same as embodiment 1.
The embodiment also provides a preparation method of the ceramic matrix composite material with the high-temperature-resistant heat-insulating sandwich structure, which is compared with the embodiment 1:
(1) the fibers adopted by the sewing are alumina fibers, and the distance between every two sewing threads is 30 mm;
(2) then gelatinizing at 200 deg.C, repeatedly soaking and gelatinizing for 10 times;
(3) the heat treatment temperature is 800 ℃, and the time is 30 min;
(4) sequentially arranging 1 layer of graphite paper and 5 layers of carbon fiber fabric on the upper surface of the core layer treated in the step S3, and then performing puncture treatment to form a fabric skin; wherein the thickness of the graphite paper is 0.5mm, and the total thickness of the carbon fiber fabric is 1 mm;
(5) then curing at a preset temperature of 400 ℃, repeatedly dipping and curing for 12 times;
(6) placing the fabric skin treated in the step (5) in a high-temperature furnace for pyrolysis firing at 1200 ℃, and keeping the temperature for 20 min;
the other procedures were the same as in example 1.
The basic performance of the high-temperature-resistant heat-insulating sandwich structure ceramic matrix composite material provided by the embodiment is shown in table 2, the heat-resistant temperature of the material system is high (up to 1700 ℃), the normal-temperature tensile strength reaches 280MPa, the 1500 ℃ tensile strength is 200MPa, and the high-temperature-resistant material has excellent high-temperature resistance.
TABLE 2 basic Properties of the sandwich ceramic matrix composite of example 2
Composite material of upper surface layer | Core layer material | Composite material of lower surface layer | |
Density g/cm3 | 1.6 | 0.3 | 1.4 |
Average thermal conductivity W/m × K | 0.9 | 0.03 | 0.8 |
Short-time temperature resistance (1-3 min) | 1700℃ | 1600℃ | 1100℃ |
Long-term temperature resistance (20-30 min) | 1400℃ | 1300℃ | 900℃ |
Tensile strength at room temperature | 280MPa | 1MPa | 90 MPa |
Tensile modulus at room temperature | 9Gpa | 30MPa | 8GPa |
Elongation at break | 1.5% | 1.5% | 1.5% |
Toughness MPa m1/2 | 25 | 20 | 25 |
Tensile strength at 1500 DEG C | 200MPa | 0.5MPa | The facing away from the heat source need not be |
Tensile modulus at 1500 DEG C | 5Gpa | 10MPa | The facing away from the heat source need not be |
Example 3
In this embodiment, compared with embodiment 1, the thickness of the upper surface layer of the ceramic matrix composite material with a sandwich structure of the present invention is 1.5mm, and the rest is the same as embodiment 1.
The embodiment also provides a preparation method of the ceramic matrix composite material with the high-temperature-resistant heat-insulating sandwich structure, which is compared with the embodiment 1:
(1) the fibers adopted by the sewing are alumina fibers, and the distance between every two sewing threads is 5 mm;
(2) then gelatinizing at 100 deg.C, repeatedly soaking and gelatinizing for 3 times;
(3) the heat treatment temperature is 300 ℃ and the time is 30 min;
(4) sequentially arranging 1 layer of graphite paper and 5 layers of carbon fiber fabric on the upper surface of the core layer treated in the step S3, and then performing puncture treatment to form a fabric skin; wherein the thickness of the graphite paper is 0.5mm, and the total thickness of the carbon fiber fabric is 1 mm;
(5) then curing at a preset temperature of 100 ℃, repeatedly soaking and curing for 8 times;
(6) placing the fabric skin treated in the step (5) in a high-temperature furnace for pyrolysis firing at 700 ℃, and keeping the temperature for 40 min;
the other procedures were the same as in example 1.
The basic properties of the high-temperature-resistant heat-insulation sandwich structure ceramic matrix composite material provided by the embodiment are shown in table 3, the heat-resistant temperature of the material system is high (up to 1600 ℃), the normal-temperature tensile strength reaches 200MPa, the 1500 ℃ tensile strength is 160MPa, and the material system has excellent high-temperature resistance, and compared with tables 1 and 2, the material system prepared by the preparation process adopted in table 1 has more excellent properties.
TABLE 3 basic Properties of the sandwich ceramic matrix composite of example 3
Composite material of upper surface layer | Core layer material | Composite material of lower surface layer | |
Density g/cm3 | 1.5 | 0.3 | 1.3 |
Average thermal conductivity W/m × K | 0.9 | 0.03 | 0.8 |
Short-time temperature resistance (1-3 min) | 1600℃ | 1600℃ | 1000℃ |
Long-term temperature resistance (20-30 min) | 1400℃ | 1300℃ | 800℃ |
Tensile strength at room temperature | 200MPa | 1MPa | 100 MPa |
Tensile modulus at room temperature | 9Gpa | 30MPa | 8GPa |
Elongation at break | 1.5% | 1.5% | 1.5% |
Toughness MPa m1/2 | 20 | 20 | 20 |
Tensile strength at 1500 DEG C | 160MPa | 0.5MPa | The facing away from the heat source need not be |
Tensile modulus at 1500 DEG C | 5Gpa | 10MPa | The facing away from the heat source need not be |
The embodiments 1-3 show that the high-temperature-resistant heat-insulating sandwich structure ceramic composite material has high heat-resistant temperature (not less than 1600 ℃), the preparation cost is further reduced by adopting a normal-pressure impregnation mode (the vacuum impregnation mode is adopted in the traditional mode), the production efficiency is high, and the rapid preparation is realized. The preparation method provided by the invention is expected to become an effective method for preparing the high-temperature-resistant heat-insulating sandwich structure ceramic composite material in a large-scale production manner in the industrial field, and the obtained product has a wide application prospect.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The high-temperature-resistant heat-insulation sandwich-structure ceramic matrix composite is characterized in that the composite is of a sandwich structure and comprises a core layer, an upper surface layer and a lower surface layer, wherein the core layer, the upper surface layer and the lower surface layer are connected through fiber puncture lines; the core layer is Al enhanced by modified aluminum fiber2O3The upper surface layer is a carbon fiber fabric reinforced silicon carbide ceramic matrix composite, and the lower surface layer is a silicon oxide fiber fabric reinforced silicon oxide ceramic panel; the upper surface layer has a thickness greater than a thickness of the lower surface layer.
2. The high-temperature-resistant heat-insulating sandwich structure ceramic matrix composite material according to claim 1, wherein the thickness of the core layer is 2-300 mm; the thickness of the upper surface layer is 0.3-5.0 mm; the thickness of the lower surface layer is 0.3-5.0 mm.
3. The high temperature resistant heat insulating sandwich ceramic matrix composite material according to claim 2, wherein the thickness of the core layer is not less than 20 mm; the thickness of the upper surface layer is 0.5-3 mm; the thickness of the lower surface layer is 0.5-3 mm.
4. The high temperature resistant, heat insulating proof sandwich ceramic matrix composite of claim 1, wherein the density of the core material is 0.15-0.40 g/cm3The thermal conductivity is less than or equal to 0.03W/m multiplied by K.
5. The high temperature resistant, heat insulating sandwich ceramic matrix composite of claim 1 wherein graphite paper is laid between the core layer and the top surface layer.
6. The refractory heat insulating sandwich ceramic matrix composite according to claim 1, wherein the fiber puncture lines are one or more of carbon fibers and alumina fibers.
7. A preparation method of a high-temperature-resistant heat-insulation sandwich-structure ceramic matrix composite is characterized by comprising the following steps:
s1: al reinforced with modified aluminum fibers2O3The aerogel layer is used as a core layer, the silicon oxide fiber fabric is flatly laid on the lower surface of the core layer, and then needling, puncturing or sewing treatment is carried out to combine the silicon oxide fiber fabric with the core layer to form a first fabric skin;
s2: clamping the first fabric skin by using a mold, and soaking the first fabric skin in SiO2Gelling in the sol at a preset temperature, and repeatedly soaking and gelling for 3-10 times;
s3: carrying out heat treatment on the first fabric skin treated in the step S2, and then cooling to room temperature;
s4: c, laying a carbon fiber fabric on the upper surface of the core layer processed in the step S3, and then carrying out needling, puncturing or sewing treatment to form a fabric skin;
s5: dipping the fabric skin into a polycarbosilane precursor solution, then curing, and repeatedly dipping and curing for 8-12 times;
s6: and (4) carrying out pyrolysis firing on the fabric skin treated in the step S5 under a vacuum condition, and cooling to room temperature to obtain the ceramic matrix composite.
8. The method for preparing a ceramic matrix composite material with a high temperature resistant, heat insulating proof sandwich structure according to claim 7, wherein in step S2, the impregnation is atmospheric impregnation; the preset temperature is 50-200 ℃;
in step S3, the temperature of the heat treatment is 300-800 ℃ and the time is 10-30 min;
in step S4, graphite paper is further laid flat between the upper surface of the core layer and the carbon fiber fabric;
in step S5, the impregnation is atmospheric impregnation; the curing temperature is 100-400 ℃;
in step S6, the temperature of the pyrolysis firing is 700-1200 ℃, and the time is 10-40 min.
9. The preparation method of the high-temperature-resistant heat-insulating sandwich structure ceramic matrix composite material according to claim 7, wherein the thickness of the core layer is 2-300 mm; the thickness of the silicon oxide fiber fabric is 0.3-5.0 mm; the thickness of the carbon fiber fabric is 0.3-5.0 mm.
10. The method for preparing the ceramic matrix composite material with the high-temperature-resistant, heat-insulating-proof sandwich structure according to claim 7, wherein the needling, puncturing or sewing intervals in the step S1 and the step S4 are 3-30 mm.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102642350A (en) * | 2012-04-24 | 2012-08-22 | 中国人民解放军国防科学技术大学 | Ceramic composite material of high temperature insulation sandwich structure and method for preparing ceramic composite material |
CN103922779A (en) * | 2014-04-10 | 2014-07-16 | 中国人民解放军国防科学技术大学 | Boundary phase-containing three-dimensional aluminum oxide fiber fabric-reinforced aluminosilicate ceramic and preparation method thereof |
CN106218061A (en) * | 2016-07-26 | 2016-12-14 | 中国人民解放军国防科学技术大学 | A kind of double-decker ceramic matric composite and preparation method thereof |
CN109824372A (en) * | 2019-02-25 | 2019-05-31 | 中国人民解放军国防科技大学 | Low-cost high-temperature-resistant ceramic composite material and rapid preparation method thereof |
-
2020
- 2020-11-18 CN CN202011290333.4A patent/CN112094130B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102642350A (en) * | 2012-04-24 | 2012-08-22 | 中国人民解放军国防科学技术大学 | Ceramic composite material of high temperature insulation sandwich structure and method for preparing ceramic composite material |
CN103922779A (en) * | 2014-04-10 | 2014-07-16 | 中国人民解放军国防科学技术大学 | Boundary phase-containing three-dimensional aluminum oxide fiber fabric-reinforced aluminosilicate ceramic and preparation method thereof |
CN106218061A (en) * | 2016-07-26 | 2016-12-14 | 中国人民解放军国防科学技术大学 | A kind of double-decker ceramic matric composite and preparation method thereof |
CN109824372A (en) * | 2019-02-25 | 2019-05-31 | 中国人民解放军国防科技大学 | Low-cost high-temperature-resistant ceramic composite material and rapid preparation method thereof |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112876271A (en) * | 2021-01-29 | 2021-06-01 | 中国人民解放军国防科技大学 | Wave-absorbing ceramic wing rudder type component based on lossy high-temperature electromagnetic periodic structure and preparation method thereof |
CN113669395A (en) * | 2021-08-18 | 2021-11-19 | 巩义市泛锐熠辉复合材料有限公司 | High-temperature-resistant brake system component and preparation method thereof |
CN114619719A (en) * | 2022-03-15 | 2022-06-14 | 江苏新扬新材料股份有限公司 | Heat-insulation high-pressure-resistance heat protection structure and preparation method thereof |
CN114619719B (en) * | 2022-03-15 | 2023-06-27 | 江苏新扬新材料股份有限公司 | Heat-insulating high-compression-resistance heat protection structure and preparation method thereof |
CN115057713A (en) * | 2022-06-27 | 2022-09-16 | 中国人民解放军国防科技大学 | 1500 ℃ resistant heat-insulation integrated composite structure ceramic and preparation method thereof |
CN117945711A (en) * | 2024-03-26 | 2024-04-30 | 中国人民解放军国防科技大学 | Low-cost non-ablative sandwich heat-resistant structural material and preparation method thereof |
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