Lightweight high-temperature-resistant heat-proof and heat-insulating integrated composite material and preparation method thereof

Abstract

The application discloses a kind of light high-temperature-resistant heat-proof and insulation integrated composite materials and preparation method, the preparation method of the light high-temperature-resistant heat-proof and insulation integrated composite material described in the application, light low-cost heat-proof and insulation integrated ceramic composite material only needs a set of mould to carry out thickness and shape control in the process of compounding, reduces production cost.Effectively shorten the preparation period, improve the preparation efficiency, simple operation, become the prospect of large-scale production preparation ceramic matrix composite in the industrial field.

Description

Technical Field

[0001] This invention belongs to the field of ceramic composite material technology, specifically relating to a lightweight, high-temperature resistant, heat-insulating integrated composite material and its preparation method. Background Technology

[0002] High-speed spacecraft such as space shuttles and recoverable satellites travel at high speeds for extended periods in the atmosphere, where temperatures over large areas exceed 600°C, and in some areas reach 1400°C. To prevent damage to internal equipment from these high temperatures, highly efficient heat-insulating materials must be used. Ceramic heat-insulating tiles played a crucial role in the US space shuttle program and are a well-developed technology, but they possess inherent brittleness (their toughness is generally 1-5 MPa·m). 1 / 2 Problems such as low strength (bending strength is generally less than 5MPa), high thermal conductivity (generally greater than 0.06W / m·k), and small single-piece area (generally 200×200mm) make it unsuitable for the high reliability and high efficiency requirements of large-area heat insulation in high-speed aircraft.

[0003] There are already relevant studies. For example, Chinese patent application number 202011290333.4 proposed a high-temperature resistant and heat-insulating sandwich structure ceramic matrix composite material. This composite material has the significant advantages of good toughness, high strength and good overall molding performance. It can be used for short-term high-temperature heat protection at 1500℃. However, in a one-hour single-sided radiant heating test at 1500℃, the material failed, mainly due to the oxidation and fracture of the sutures, which led to the destruction of the overall structure of the material.

[0004] Chinese patent application No. 202210736953.9 proposes an integrated composite ceramic structure that is resistant to 1500℃ and has heat insulation properties, as well as a preparation method. This composite material uses a porous ceramic structure with high-temperature resistant modified aluminum fiber-reinforced Al2O3 aerogel composite material as the core layer to obtain better heat insulation performance. However, the technology is relatively complex. The aerogel composite material is manually sewn with fiber cloth, which has process risks such as loose sewing and broken sewing lines. The low sewing efficiency leads to a long preparation cycle and low production efficiency. At the same time, the mold sizes involved in the preparation of aerogel composite material and sandwich structure ceramic composite material are different. It takes two sets of molds of different sizes to prepare one product, resulting in high production costs.

[0005] Therefore, it is necessary to strengthen research on lightweight, high-temperature resistant, heat-insulating integrated composite materials. Summary of the Invention

[0006] To address the shortcomings of existing heat-insulating composite materials, such as long preparation time and high production costs, this invention provides a lightweight, high-temperature resistant, heat-insulating integrated composite material and its preparation method. Specifically, it is a lightweight, high-temperature resistant, heat-insulating integrated ceramic composite material and its preparation method. Compared to previous processes, this invention uses prefabricated components for overall preparation. Previously, the aerogel composite core layer was made separately, then the fiber cloth was sewn together, and densification was then implemented. The previous process required two sets of molds, while this invention only requires one mold, reducing costs and shortening the cycle time. The preparation cycle is reduced from 8-12 steps in existing technologies to 3-5 steps in this invention, effectively shortening the preparation cycle.

[0007] The technical solution of the present invention is as follows:

[0008] A lightweight, high-temperature resistant, heat-insulating integrated composite material:

[0009] First, a ceramic composite preform is designed, which has a sandwich structure, including a core layer, an upper surface layer, and a lower surface layer; the core layer, the upper surface layer, and the lower surface layer are connected by fiber bundle puncture lines; the core layer is alumina fiber cotton felt, and the upper surface layer and the lower surface layer are both carbon fiber cloth; the thickness of the upper surface layer is greater than the thickness of the lower surface layer.

[0010] Secondly, aerogel composite materials were prepared. The core layer material was prepared using a supercritical drying method. The specific preparation method was carried out in accordance with the methods disclosed in Chinese Patent Application Nos. 200510031952.0, 200710034510.0, 201110110844.8, 201110110947.4, 201110110946.X, 201010300112.0, or 201010148105.3.

[0011] Finally, the upper and lower surface layers are composited to obtain a lightweight, high-temperature resistant, heat-insulating integrated ceramic composite material.

[0012] The objective of this invention is achieved through the following technical solution:

[0013] A method for preparing a lightweight, high-temperature resistant, heat-insulating integrated composite material includes the following steps:

[0014] S1: Design the thickness and material system of the core layer, upper surface layer and lower surface layer to prepare ceramic composite preforms with controllable thickness and adjustable system;

[0015] The ceramic composite preform has a sandwich structure, including a core layer, an upper surface layer, and a lower surface layer; the core layer, upper surface layer, and lower surface layer are connected by fiber bundle puncture lines; the core layer is alumina fiber felt, and the upper and lower surface layers are both carbon fiber cloth; the thickness of the upper surface layer is greater than the thickness of the lower surface layer.

[0016] S2: Preparation of aerogel composite material: The above-mentioned ceramic composite material preform was prepared by supercritical drying method;

[0017] S3: Clamp the ceramic composite preform prepared in S2 with a mold, immerse it in a polycarbosilane solution, and then cure it. Repeat the immersion and curing process 3-5 times.

[0018] S4: Under vacuum conditions, the ceramic composite preform treated by S3 is pyrolyzed and sintered, then cooled to room temperature to obtain an integrated heat-insulating ceramic composite material.

[0019] In this invention:

[0020] Furthermore, the thickness of the core layer in S1 is 20-300mm; the thickness of the upper surface layer is 1.0-3.0mm; and the thickness of the lower surface layer is 0.3-1.0mm.

[0021] Furthermore, the supercritical drying method described in S2 is specifically prepared using the methods disclosed in Chinese Patent Application Nos. 200510031952.0, 200710034510.0, 201110110844.8, 201110110947.4, 201110110946.X, 201010300112.0, or 201010148105.3.

[0022] Furthermore, in S3, the impregnation is atmospheric pressure impregnation, the predetermined curing temperature is 100-300℃, and the curing time is 30-120min.

[0023] Furthermore, in S4, the pyrolysis firing temperature is 900-1200℃ and the time is 30-120min.

[0024] This invention also relates to a lightweight, high-temperature resistant, and heat-insulating integrated composite material prepared by the above-mentioned method, specifically a lightweight, high-temperature resistant, and heat-insulating integrated ceramic composite material with the following technical indicators: the ceramic composite material has a thickness of 20-25 mm and a density of 0.60 g / cm³. 3The room temperature fracture compressive strain is 3600-4000με, the panel tensile strength is 100-200MPa, and the panel flexural strength is 150-300MPa; the typical ballistic heating environment heat resistance temperature is above 1500℃.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] 1. The lightweight, high-temperature resistant, and heat-insulating integrated composite material of the present invention adopts a sandwich structure. It utilizes a porous ceramic alumina aerogel composite material as the core layer to obtain better heat insulation performance, and a carbon fiber ceramic matrix composite material as the hot surface (upper surface layer) and cold surface (lower surface layer). The thickness of the upper surface layer is greater than that of the lower surface layer because thickness affects the heat insulation performance of the material. The upper surface layer is designed to be thicker to undertake the heat insulation task and withstand continuous high-temperature environments. The combination of the core layer and the hot surface layer has excellent heat resistance and insulation effects. Heat and temperature are significantly reduced by the time they reach the cold surface layer, improving the overall heat insulation performance. Simultaneously, the lower surface layer can be bonded to the cabin during product application. In summary, the structure significantly improves the long-term high-temperature resistance of the lightweight, high-temperature resistant, and heat-insulating integrated ceramic composite material of the present invention, significantly enhancing the heat insulation effect of the ceramic composite material and improving the safety performance of the aircraft.

[0027] 2. The lightweight, high-temperature resistant, heat-insulating integrated composite material of the present invention provides a ceramic composite preform with controllable thickness and adjustable system, which effectively improves the bonding strength between layers. Machine sewing can be used instead of manual sewing, which effectively improves sewing efficiency and avoids the disadvantages of low sewing efficiency leading to long preparation cycle and low production efficiency.

[0028] 3. The method for preparing a lightweight, high-temperature resistant, heat-insulating integrated composite material according to the present invention requires only one mold for thickness and shape control during the composite process, thus reducing production costs. It effectively shortens the preparation cycle, improves preparation efficiency, and is simple to operate, making it a promising candidate for large-scale production of ceramic matrix composite materials in the industrial field. Attached Figure Description

[0029] These and / or other aspects and advantages of the present invention will become clearer and more readily understood from the following detailed description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:

[0030] Figure 1 This is a diagram of the preform of the lightweight, high-temperature resistant, heat-insulating integrated composite material provided in Experimental Example 1 of the present invention. Figure 1 The above is a cross-sectional view of the precast structure. Figure 1 Below is a surface view of the precast structure;

[0031] Figure 2 Figure 1 shows the lightweight, high-temperature resistant, heat-insulating integrated composite material prepared in Experimental Example 1 of this invention (A is a schematic diagram of the surface morphology of the lightweight, high-temperature resistant, heat-insulating integrated composite material; B is a schematic diagram of the cross-sectional morphology of the lightweight, high-temperature resistant, heat-insulating integrated composite material).

[0032] Figure 3 This is a flowchart of the preparation method of the lightweight, high-temperature resistant, heat-insulating integrated composite material provided in Embodiment 1 of the present invention;

[0033] Figure 4 shows the 1500℃ quartz lamp heating test of the lightweight high-temperature resistant and heat-insulating integrated composite material prepared in Example 1 of the present invention (A is a schematic diagram of the 1500℃ quartz lamp heating test of the lightweight high-temperature resistant and heat-insulating integrated composite material; B is a schematic diagram of the surface of the lightweight high-temperature resistant and heat-insulating integrated composite material after the 1500℃ quartz lamp heating test). Detailed Implementation

[0034] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0035] Example 1:

[0036] A method for preparing a lightweight, high-temperature resistant, heat-insulating integrated composite material includes the following steps:

[0037] First, a ceramic composite preform is designed. The preform has a sandwich structure, including a core layer, an upper surface layer, and a lower surface layer, which are connected by carbon fiber bundle puncture wires. The core layer is made of alumina fiber felt, and the upper and lower surface layers are both made of carbon fiber cloth. The thickness of the core layer is 20 mm, the thickness of the upper surface layer is 2.0 mm, and the thickness of the lower surface layer is 1 mm.

[0038] The ceramic composite preform was prepared by supercritical drying (the specific preparation method is as disclosed in Chinese Patent Application No. 200510031952.0, Chinese Patent Application No. 200710034510.0, Chinese Patent Application No. 201110110844.8, Chinese Patent Application No. 201110110947.4, Chinese Patent Application No. 201110110946.X, Chinese Patent Application No. 201010300112.0 or Chinese Patent Application No. 201010148105.3).

[0039] The preform was clamped in a mold, immersed in a polycarbosilane solution, and then cured. The immersion and curing were repeated three times at a curing temperature of 300°C. Under vacuum conditions, the preform was pyrolyzed and sintered, cooled to room temperature at a pyrolyzing temperature of 1200°C for 10 minutes to obtain an integrated heat-insulating ceramic composite material.

[0040] The basic properties of the lightweight, high-temperature resistant, heat-insulating integrated composite material in Example 1 are as follows:

[0041] (1) The ceramic composite material has a thickness of 20 mm and a density of 0.60 g / cm³. 3 ;

[0042] (2) The room temperature fracture compressive strain of the ceramic composite material is 4000με, the tensile strength of the panel is 200MPa, and the bending strength of the panel is 300MPa.

[0043] (3) The heat insulation and heat protection integrated composite material prepared in this embodiment was subjected to quartz lamp single-sided radiation heating tests at 1400℃ for 1 hour and 1500℃ for 1 hour. After the test, the surface structure of the material was intact and there was no obvious damage, indicating that the material system can be used normally for a long time at 1500℃ and the back temperature is 400℃.

[0044] Compared with the high-temperature resistant and heat-insulating sandwich-structured ceramic matrix composite material obtained after the implementation of Chinese Patent Publication No. CN112094130A, the preparation method of a lightweight high-temperature resistant and heat-insulating integrated composite material provided in Example 1 has a shorter preparation cycle (impregnation and curing only 3 times). The room temperature fracture compressive strain (3600με to 4000με), tensile strength (100MPa to 200MPa), and flexural strength (150MPa to 300MPa) of this material are significantly improved; the heat resistance temperature in a typical ballistic heating environment is increased from 1000℃ to 1500℃.

[0045] Figure 1 A diagram of the preform of the lightweight, high-temperature resistant, heat-insulating integrated composite material provided in Experimental Example 1. Figure 1 The above is a cross-sectional view of the precast structure. Figure 1 Below is a surface view of the precast structure;

[0046] Figure 2 Figure 1 shows the lightweight, high-temperature resistant, heat-insulating integrated composite material prepared in Experiment Example 1 (A is a schematic diagram of the surface morphology of the lightweight, high-temperature resistant, heat-insulating integrated composite material; B is a schematic diagram of the cross-sectional morphology of the lightweight, high-temperature resistant, heat-insulating integrated composite material).

[0047] Figure 3 This is a flowchart illustrating the preparation method of the lightweight, high-temperature resistant, heat-insulating integrated composite material provided in Example 1.

[0048] Figure 4 shows the 1500℃ quartz lamp heating test of the lightweight high-temperature resistant and heat-insulating integrated composite material prepared in Example 1 (A is a schematic diagram of the 1500℃ quartz lamp heating test of the lightweight high-temperature resistant and heat-insulating integrated composite material; B is a schematic diagram of the surface of the lightweight high-temperature resistant and heat-insulating integrated composite material after the 1500℃ quartz lamp heating test).

[0049] Example 2:

[0050] A method for preparing a lightweight, high-temperature resistant, heat-insulating integrated composite material includes the following steps:

[0051] First, a ceramic composite preform is designed. The preform has a sandwich structure, including a core layer, an upper surface layer, and a lower surface layer. The core layer, upper surface layer, and lower surface layer are connected by carbon fiber bundle puncture wires. The core layer is made of alumina fiber felt, and the upper and lower surface layers are both made of carbon fiber cloth. The thickness of the core layer is 24 mm; the thickness of the upper surface layer is 3.0 mm; and the thickness of the lower surface layer is 1 mm.

[0052] The ceramic composite preform was prepared by supercritical drying (the specific preparation method is as disclosed in Chinese Patent Application No. 200510031952.0, Chinese Patent Application No. 200710034510.0, Chinese Patent Application No. 201110110844.8, Chinese Patent Application No. 201110110947.4, Chinese Patent Application No. 201110110946.X, Chinese Patent Application No. 201010300112.0 or Chinese Patent Application No. 201010148105.3).

[0053] The preform was clamped in a mold, immersed in a polycarbosilane solution, and then cured. The immersion and curing were repeated 5 times at a curing temperature of 100°C. Under vacuum conditions, the preform was pyrolyzed and sintered, cooled to room temperature at a pyrolyzing temperature of 1000°C for 30 minutes to obtain an integrated heat-insulating ceramic composite material.

[0054] The basic properties of the lightweight, high-temperature resistant, heat-insulating integrated composite material in Example 2 are as follows:

[0055] (1) The ceramic composite material has a thickness of 25 mm and a density of 0.60 g / cm³. 3 ;

[0056] (2) The room temperature fracture compressive strain of the ceramic composite material is 4000με, the tensile strength of the panel is 200MPa, and the bending strength of the panel is 300MPa.

[0057] (3) The heat insulation and heat protection integrated composite material prepared in this embodiment was subjected to quartz lamp single-sided radiation heating tests at 1400℃ for 1 hour and 1500℃ for 1 hour. After the test, the surface structure of the material was intact and there was no obvious damage, indicating that the material system can be used normally for a long time at 1500℃ and the back temperature is 340℃.

[0058] Compared with the high-temperature resistant and heat-insulating sandwich structure ceramic matrix composite material obtained after the implementation of Chinese Patent Publication No. CN112094130A, the preparation method of a lightweight high-temperature resistant and heat-insulating integrated composite material provided in Example 2 has a shorter preparation cycle (impregnation and curing only 4 times). The room temperature fracture compressive strain (3600με to 4000με), tensile strength (100MPa to 200MPa), and flexural strength (150MPa to 300MPa) of this material are significantly improved; the heat resistance temperature in a typical ballistic heating environment is increased from 1000℃ to 1500℃.

[0059] Example 3:

[0060] A method for preparing a lightweight, high-temperature resistant, heat-insulating integrated composite material includes the following steps:

[0061] First, a ceramic composite preform is designed. The preform has a sandwich structure, including a core layer, an upper surface layer, and a lower surface layer. The core layer, upper surface layer, and lower surface layer are connected by carbon fiber bundle puncture wires. The core layer is made of alumina fiber felt, and the upper and lower surface layers are both made of carbon fiber cloth. The thickness of the core layer is 26 mm. The thickness of the upper surface layer is 3.0 mm. The thickness of the lower surface layer is 1 mm.

[0062] The ceramic composite preform was prepared by supercritical drying (the specific preparation method is as disclosed in Chinese Patent Application No. 200510031952.0, Chinese Patent Application No. 200710034510.0, Chinese Patent Application No. 201110110844.8, Chinese Patent Application No. 201110110947.4, Chinese Patent Application No. 201110110946.X, Chinese Patent Application No. 201010300112.0 or Chinese Patent Application No. 201010148105.3).

[0063] The preform was clamped in a mold, immersed in a polycarbosilane solution, and then cured. The immersion and curing were repeated 5 times at a curing temperature of 100°C. Under vacuum conditions, the preform was pyrolyzed and sintered, cooled to room temperature, and pyrolyzed at a temperature of 900°C for 30 minutes to obtain an integrated heat-insulating ceramic composite material.

[0064] The basic properties of the lightweight, high-temperature resistant, heat-insulating integrated composite material in Example 3 are as follows:

[0065] (1) The ceramic composite material has a thickness of 25 mm and a density of 0.60 g / cm³. 3 ;

[0066] (2) The room temperature fracture compressive strain of the ceramic composite material is 4000με, the tensile strength of the panel is 180MPa, and the bending strength of the panel is 260MPa.

[0067] (3) The heat insulation and heat protection integrated composite material prepared in this embodiment was subjected to quartz lamp single-sided radiation heating tests at 1400℃ for 1 hour and 1500℃ for 1 hour. After the test, the surface structure of the material was intact and there was no obvious damage, indicating that the material system can be used normally for a long time at 1500℃ and the back temperature is 450℃.

[0068] Compared to the high-temperature resistant, heat-insulating sandwich-structure ceramic matrix composite material obtained after implementing Chinese Patent Publication No. CN112094130A, the preparation method of the lightweight, high-temperature resistant, heat-insulating integrated composite material provided in Example 3 has a shorter preparation cycle (impregnation and curing only 3 times). The room temperature fracture compressive strain (3600με to 4000με), tensile strength (100MPa to 180MPa), and flexural strength (150MPa to 260MPa) of this material are all significantly improved. The heat resistance temperature in a typical ballistic heating environment is increased from 1000℃ to 1500℃, indicating that the material system can be used normally for a long time at 1500℃.

[0069] result:

[0070] As can be seen from the examples, the lightweight, high-temperature resistant, heat-insulating integrated ceramic composite material of the present invention has a high heat resistance temperature and significantly shortens the material preparation cycle from the initial 8-12 times to 3-5 times. This effectively shortens the preparation cycle, improves the preparation efficiency, and is simple to operate. It has broad prospects for large-scale production of ceramic matrix composite materials in the industrial field.

[0071] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a lightweight high-temperature resistant heat shield integrated composite material, characterized in that: The method comprises the following steps: S1: designing the thickness and material system of the core layer, upper surface layer and lower surface layer, and preparing a ceramic composite preform with controllable thickness and adjustable system; the ceramic composite preform is a sandwich structure comprising a core layer, an upper surface layer and a lower surface layer; the core layer, the upper surface layer and the lower surface layer are connected by fiber bundle puncture lines; the core layer is an alumina fiber felt, and the upper surface layer and the lower surface layer are both carbon fiber cloth; the thickness of the upper surface layer is greater than that of the lower surface layer; S2: aerogel composite material preparation, treating the above ceramic composite preform by a supercritical drying method; S3: clamping the ceramic composite preform prepared in S2 by a mold, immersing it in a polycarbosilane solution at normal pressure, then curing it at 100-300 DEG C for 30-120 min, and repeating the immersion and curing for 3-5 times; S4: pyrolysis sintering of the ceramic composite preform treated in S3 under vacuum, the pyrolysis sintering temperature is 900-1200 DEG C, the time is 30-120 min, and the ceramic composite material is obtained after cooling to room temperature.

2. The method of claim 1, wherein the method further comprises: The thickness of the core layer in S1 is 20-300 mm; the thickness of the upper surface layer is 1.0-3.0 mm; and the thickness of the lower surface layer is 0.3-1.0 mm. ​ 3. A lightweight, high temperature resistant, heat shield integrated composite material, characterized by: The light-weight high-temperature-resistant heat-proof and insulation integrated ceramic composite material is prepared by the method of any one of claims 1-2, and has the following technical indexes: the ceramic composite material has a thickness of 20-25 mm, a density of 0.60 g / cm 3 , a room-temperature compressive strain of 3600-4000 με, a panel tensile strength of 100-200 MPa, a panel bending strength of 150-300 MPa, and a typical ballistic heating environment heat-resistant temperature of above 1500 ℃.

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