High temperature resistant plugging insulation material and preparation method and application thereof

Abstract

The present invention relates to a high-temperature resistant plugging and heat-insulating material, and a preparation method and application thereof. The high-temperature resistant plugging and heat-insulating material comprises: a porous composite material body; a carbon aerogel layer with a glass carbonized surface, which is arranged on the surface of the porous composite material body; the carbon aerogel layer with a glass carbonized surface, one side of which is a carbon aerogel layer, and the other side of which is a glass carbonized layer; the carbon aerogel layer is arranged in the direction of the porous composite material body; a low-density heat-insulating material layer is arranged on the surface of the glass carbonized layer. The technical problem solved by the present invention is how to reduce the gas permeability of the high-temperature resistant porous composite material, so as to avoid or slow down the large pores and high porosity of the high-temperature resistant porous composite material, which may cause gas leakage in ultra-high temperature equipment and high-speed aircraft and affect the operation of its external system, thereby making it more suitable for practical use.

Description

Technical Field

[0001] The present invention belongs to the technical field of high-temperature resistant and heat-insulating materials, and particularly relates to a high-temperature resistant plugging and heat-insulating material, a preparation method thereof, and an application thereof. Background Art

[0002] For some ultra-high temperature equipment and high-speed aircraft, in order to meet their performance requirements such as high temperature resistance and high strength, the matrix materials of these ultra-high temperature equipment and high-speed aircraft are mostly prepared from porous composites based on carbon or silicon carbide. Due to the limitations of current preparation processes, these porous composites have relatively large defects in terms of pore size and porosity, often having large pores and high porosity, which can easily cause serious gas leakage in the ultra-high temperature equipment and high-speed aircraft under the action of high-speed airflows, seriously affecting systems with strict environmental requirements such as the electronic components of the ultra-high temperature equipment and high-speed aircraft. Therefore, it is necessary to design a material in the thermal protection material that can block the gas inside to avoid or mitigate the impact of gas leakage.

[0003] Currently, for the problems of large pores and high porosity in high-temperature resistant porous composites, the following methods are mainly used to solve them: First, by improving the preparation process of the porous composite or adopting a new process to reduce the pore size and porosity; however, due to the limitations of the preparation process of high-temperature resistant porous composites, the current process cannot effectively solve the problems of pore size and porosity; Second, methods such as plasma spraying and CVD are used to form a certain coating on the porous composite body or plug the pores to achieve a reduction in pore size and porosity; however, since the processes of plasma spraying and CVD both require the substrate to be a material with a dense surface, it is impossible to perform coating treatment on the surface of the porous composite. Summary of the Invention

[0004] The main purpose of the present invention is to provide a high-temperature resistant plugging and heat-insulating material, a preparation method thereof, and an application thereof, and the technical problem to be solved is how to reduce the gas permeability of high-temperature resistant porous composites to avoid or mitigate the phenomenon of gas leakage in ultra-high temperature equipment and high-speed aircraft caused by large pores and high porosity of the high-temperature resistant porous composites, thereby being more suitable for practical use.

[0005] The object of the present invention and the solution to its technical problem are achieved by the following technical solutions. A high-temperature resistant plugging and heat-insulating material according to the present invention includes:

[0006] A porous composite body;

[0007] A carbon aerogel layer with surface glass carbonization is disposed on the surface of the porous composite material body; one side surface of the carbon aerogel layer with surface glass carbonization is a carbon aerogel layer, and the other side surface is a glass carbonization layer; the carbon aerogel layer is disposed towards the porous composite material body.

[0008] A low-density heat insulation material layer is disposed on the surface of the glass carbonization layer.

[0009] The object of the present invention and the technical problems to be solved can be further realized by the following technical measures.

[0010] Preferably, in the aforementioned high-temperature resistant plugging and heat insulation material, a high-temperature resistant dense coating is further disposed between the glass carbonization layer and the low-density heat insulation material layer; the gas permeability of the high-temperature resistant plugging and heat insulation material is 30 - 200 cm 3 / (m -2 ×d -1 ×Pa -1 ).

[0011] Preferably, in the aforementioned high-temperature resistant plugging and heat insulation material, the porous composite material body and the carbon aerogel layer with surface glass carbonization are bonded by an adhesive; the high-temperature resistant dense coating and the low-density heat insulation material layer are bonded by an adhesive.

[0012] Preferably, in the aforementioned high-temperature resistant plugging and heat insulation material, the thickness of the carbon aerogel layer is 1 - 20 mm, and its density is 0.3 - 1.0 g / cm 3 ; the thickness of the glass carbonization layer is 0.1 - 3 mm, and its density is 0.8 - 1.5 g / cm 3 .

[0013] Preferably, in the aforementioned high-temperature resistant plugging and heat insulation material, the high-temperature resistant dense coating is selected from at least one of silicon carbide, zirconia, and zirconium carbide, and its thickness is 0.5 - 5 mm.

[0014] Preferably, in the aforementioned high-temperature resistant plugging and heat insulation material, the low-density heat insulation material layer includes a plurality of heat insulation prefabricated layers; an infrared shielding layer is disposed between adjacent heat insulation prefabricated layers; the heat insulation prefabricated layer and the infrared shielding layer are bonded together by a high-temperature adhesive; by mass percentage, the low-density heat insulation material layer includes 70 - 90% of heat insulation material, 5 - 15% of infrared shielding layer, and 5 - 20% of high-temperature adhesive; the heat insulation material is selected from at least two of aluminum silicate fiber, alumina fiber, silica fiber, basalt fiber, zirconia fiber, silica aerogel, and carbon aerogel; the infrared shielding layer is selected from graphite paper, metal foil, or polyimide film; the high-temperature adhesive is selected from aluminum dihydrogen phosphate, silica sol, zirconium sol, or yttrium sol.

[0015] Preferably, for the above-mentioned high-temperature resistant plugging and heat insulation material, the thickness of the low-density heat insulation material layer is 5-50 mm, and the density is 0.10-0.50 g / cm 3 , and its thermal conductivity at 1600 °C is ≤0.2 W / m·K, and its thermal conductivity at 200 °C is ≤0.05 W / m·K.

[0016] The object of the present invention and the technical problems to be solved are also achieved by the following technical solutions. A preparation method of a high-temperature resistant plugging and heat insulation material according to the above-mentioned one is proposed according to the present invention, which includes the following steps:

[0017] 1) Bond the carbon aerogel layer with surface glass carbonization on the surface of the porous composite material body; for the carbon aerogel layer with surface glass carbonization, one side surface is the carbon aerogel layer, and the other side surface is the glass carbonization layer; the carbon aerogel layer is arranged towards the porous composite material body;

[0018] 2) Bond the low-density heat insulation material layer on the surface of the glass carbonization layer to obtain the high-temperature resistant plugging and heat insulation material.

[0019] The object of the present invention and the technical problems to be solved can also be further achieved by the following technical measures.

[0020] Preferably, for the above-mentioned preparation method, a high-temperature resistant dense coating is also included on the surface of the glass carbonization layer between step 1) and step 2);

[0021] The high-temperature resistant dense coating is selected from at least one of silicon carbide, zirconia and zirconium carbide;

[0022] The method of setting the high-temperature resistant dense coating on the surface of the glass carbonization layer is to deposit the high-temperature resistant dense coating by chemical vapor deposition method, or spray the high-temperature resistant dense coating by plasma spraying method, or brush the high-temperature resistant dense coating by brushing method.

[0023] Preferably, for the above-mentioned preparation method, the preparation steps of the carbon aerogel layer with surface glass carbonization are as follows:

[0024] A. Mix resorcinol, formaldehyde, water and sodium carbonate in proportion to obtain a carbon aerogel precursor solution;

[0025] B. Let the carbon aerogel precursor solution stand to obtain a wet gel; the standing process is as follows: stand at room temperature for 12-24 h, stand at 60 °C for 12-24 h, and stand at 70-90 °C for 72-84 h;

[0026] C. Dry the wet gel to obtain a dry gel; the drying process is as follows: dry at 50-80 °C for 24-48 h;

[0027] D. Carbonize the xerogel and cool it down to obtain a carbon aerogel. The carbonization process is as follows: Under a nitrogen atmosphere, heat it up at a heating rate of 5 - 15 °C / min to 800 - 1000 °C and carbonize for 1 - 2 h.

[0028] E. Attach one side of the carbon aerogel to a glassware with a smooth surface and pyrolyze it locally in a nitrogen atmosphere. The pyrolysis process is as follows: Heat it up at a heating rate of 50 - 60 °C / h to 1000 °C to obtain a carbon aerogel with the surface glass carbonized.

[0029] Preferably, for the aforementioned preparation method, the preparation steps of the low - density heat - insulating material layer are as follows:

[0030] A. Process the heat - insulating material into a heat - insulating pre - formed body layer. The heat - insulating material is selected from at least two of aluminosilicate fiber, alumina fiber, silica fiber, basalt fiber, zirconia fiber, silica aerogel, and carbon aerogel.

[0031] B. Lay an infrared shielding layer between two adjacent heat - insulating pre - formed body layers. The infrared shielding layer is selected from graphite paper, metal foil, or polyimide film.

[0032] C. Bond the heat - insulating pre - formed body layer and the infrared shielding layer together with a high - temperature binder. The high - temperature adhesive is selected from aluminum dihydrogen phosphate, silica sol, zirconia sol, or yttrium sol. The mass percentage ratio of the heat - insulating material, infrared shielding layer, and high - temperature adhesive is 70 - 90%: 5 - 15%: 5 - 20%, and the sum of the three is 100%.

[0033] Preferably, for the aforementioned preparation method, when the heat - insulating pre - formed body layer and the infrared shielding layer are bonded, the pressure is 1 - 10 MPa, the temperature is 80 - 200 °C, and the time is 8 - 24 h.

[0034] The object of the present invention and the solution to its technical problems are also achieved by the following technical solutions. An application of the aforementioned high - temperature - resistant plugging and heat - insulating material in the technical fields of ultra - high - temperature equipment or high - speed aircrafts according to the present invention is proposed.

[0035] By means of the above - mentioned technical solutions, a high - temperature - resistant plugging and heat - insulating material, its preparation method, and application proposed by the present invention have at least the following advantages:

[0036] The high-temperature resistant plugging and heat-insulating material proposed by the present invention, its preparation method and application. Through the optimized design of the high-temperature resistant plugging and heat-insulating material, a carbon aerogel layer including a glass carbonization layer is provided on the porous composite material body; the carbon aerogel layer is arranged towards the direction of the porous composite material body to endow the high-temperature resistant plugging and heat-insulating material with heat insulation; the glass carbonization layer is arranged towards the other side, which has high heat resistance, extremely high chemical stability, low density, good compactness and great airtightness; when the thickness of the glass carbonization layer is 0.1-3 mm, its density is 0.8-1.5 g / cm 3 , the porosity is 10-40%, and the gas permeability is 30-200 cm 3 /

[0037] (m -2 ×d -1 ×Pa -1 ). Therefore, the glass carbonization layer can greatly improve the gas blocking performance of the high-temperature resistant plugging and heat-insulating material; the carbon aerogel layer including the glass carbonization layer is to attach one side of the carbon aerogel layer in a glass appliance with a smooth surface and locally pyrolyze it in a nitrogen atmosphere. The heating rate during pyrolysis is 50-60 °C / h, and the pyrolysis temperature is 1000 °C, so that a layered material including both a glass carbonization layer and a carbon aerogel layer can be obtained only through one process step, and the process steps are simple; then, a high-temperature resistant dense coating is provided on the surface of the glass carbonization layer, which can further enhance its efficiency and further improve the gas blocking performance of the high-temperature resistant plugging and heat-insulating material; finally, a low-density heat-insulating material layer is bonded on the surface of the high-temperature resistant dense coating to form a complete integrated high-temperature resistant plugging and heat-insulating material. The technical solution of the present invention, through the overall design of the above materials, makes it have good heat insulation performance, and at the same time can solve the problem of gas leakage in ultra-high temperature equipment and high-speed aircraft caused by large pores and high porosity of the porous composite material. Its gas permeability is 30-200 cm 3 / (m -2 ×d -1 ×Pa -1 ), thus providing a strong guarantee for the operation of the external system in ultra-high temperature equipment and high-speed aircraft.

[0038] The above description is only an overview of the technical solution of the present invention. In order to be able to understand the technical means of the present invention more clearly and implement it according to the content of the specification, the following takes the preferred embodiments of the present invention as detailed examples as follows. Detailed implementation manners

[0039] To further elaborate on the technical means and effects adopted by the present invention to achieve the intended invention purpose, the following will, in combination with preferred embodiments, detail the specific implementation manners, structures, features, and effects of a high-temperature resistant plugging and heat-insulating material, its preparation method, and its application proposed according to the present invention, as follows.

[0040] The present invention provides a high-temperature resistant plugging and heat-insulating material, which includes a porous composite material body, a carbon aerogel layer with surface glass carbonization, and a low-density heat-insulating material layer arranged in sequence, and can withstand high temperatures of 2000 °C and above.

[0041] The present invention also provides a preparation method for the high-temperature resistant plugging and heat-insulating material, which includes the following steps: bonding the carbon aerogel layer with surface glass carbonization on the surface of the porous composite material body; and then bonding the low-density heat-insulating material layer on the surface of the glass carbonization layer to obtain the high-temperature resistant plugging and heat-insulating material.

[0042] The porous composite material body can adopt the porous composite materials commonly used in the prior art, and the present invention does not make specific limitations on it.

[0043] To ensure the overall heat-insulating property and gas-blocking performance of the material, the present invention also provides a carbon aerogel layer with surface glass carbonization on the surface of the porous composite material body; preferably, the carbon aerogel layer with surface glass carbonization is adhesively connected to the porous composite material body; for the carbon aerogel layer with surface glass carbonization, one side surface is a carbon aerogel layer, and the other side surface is a glass carbonization layer; the carbon aerogel layer is arranged towards the porous composite material body to endow the high-temperature resistant plugging and heat-insulating material with heat insulation; the glass carbonization layer is arranged towards the low-density heat-insulating material layer, which can endow the high-temperature resistant plugging and heat-insulating material with gas-blocking performance.

[0044] The carbon aerogel layer with surface glass carbonization is prepared by locally pyrolyzing carbon aerogel. Among them, the preparation of carbon aerogel can be carried out by using the preparation method of carbon aerogel in the prior art, and the specific steps are as follows: First, resorcinol, formaldehyde, water and sodium carbonate are mixed evenly in proportion to obtain a carbon aerogel precursor solution; preferably, the molar ratio of resorcinol, formaldehyde, water and sodium carbonate is m:2m:50m-300m:1, where m is 50-2000; Second, the carbon aerogel precursor solution is allowed to stand to obtain a wet gel; the standing process is as follows: stand at room temperature for 12-24h, stand at 60°C for 12-24h, and stand at 70-90°C for 72-84h; Third, the wet gel is dried to obtain a dry gel; the drying process is as follows: dry at 50-80°C for 24-48h; Fourth, the dry gel is carbonized and cooled to obtain carbon aerogel; the carbonization process is as follows: under a nitrogen atmosphere, heat up to 800-1000°C at a heating rate of 5-15°C / min, and carry out carbonization at this temperature for 1-2h; The last step is the most critical step of the present invention, locally pyrolyzing the carbon aerogel to form a carbon aerogel with only one surface being a glass carbonization layer; during the pyrolysis operation, one surface of the carbon aerogel needs to be tightly attached to the inner surface of a glassware with a smooth surface, and then the whole is placed in a nitrogen atmosphere furnace for local pyrolysis, strictly controlling the heating rate to rise to 1000°C at a rate of 50-60°C / h, and then pyrolyzing at this temperature for 10-30min to obtain a carbon aerogel with surface glass carbonization.

[0045] When carbonizing the dry gel, its heating rate (5-15°C / min) is relatively fast, and the reason is to reach the carbonization temperature as soon as possible for carbonization to improve production efficiency.

[0046] At present, when pyrolyzing carbon aerogel, it is generally overall pyrolysis. The key control point is to slowly heat up the carbon aerogel, and generally control its heating rate to be 10 - 20 °C / h; due to the cross-linked nature of the carbon aerogel itself and the slow heating rate, heat can slowly accumulate inside the carbon aerogel; since the polymer is difficult to move very freely, the formation of carbon atoms is blocked and amorphous carbon is formed; because this amorphous carbon has a glassy appearance, it is called a glassy carbonized layer. The technical solution of the present invention is completely different from the carbon aerogel pyrolysis process in the prior art. On the one hand, by accelerating the heating rate of the carbon aerogel (only relative to the conventional heating rate of the carbon aerogel), controlling its heating rate ≥50 °C, the time to reach the pyrolysis target temperature is greatly shortened, and the pyrolysis time is only controlled to be 10 - 30 min, so that insufficient heat can accumulate inside the carbon aerogel, and it is difficult to form a glassy carbonized layer on the surface of the carbon aerogel; on the other hand, by tightly attaching one surface of the carbon aerogel to a glass utensil with a smooth surface, due to the heat conductivity of the glass itself, the heat at the attachment surface of the carbon aerogel can be fully accumulated. By controlling the appropriate heating rate and the pyrolysis process time, a layer of glassy carbonized layer is formed on this side surface of the carbon aerogel. By controlling the heating rate and pyrolysis time during the pyrolysis of the carbon aerogel, and combined with the special process control of the surface to be glassy carbonized, a carbon aerogel layer with only one surface glassy carbonized can be obtained, that is, the surface glassy carbonized carbon aerogel layer described in the present invention.

[0047] The thickness of the carbon aerogel layer not glassy carbonized is 1 - 20 mm, and its density is 0.3 - 1.0 g / cm 3 。

[0048] The thickness of the glassy carbonized layer is 0.1 - 3 mm, and its density is 0.8 - 1.5 g / cm 3 。

[0049] Through the above technical solution, the present invention can realize that the layered material includes both a carbon aerogel layer with good heat insulation performance and a glassy carbonized layer with good gas blocking performance only through one-step process, that is, a layered material can simultaneously achieve two functions without the need to set up a process for later compounding the two, so the operation steps are simple.

[0050] To ensure the heat insulation of the high-temperature plugging and heat insulation material, a low-density heat insulation material layer is also provided on the side of the glassy carbonized layer of the surface glassy carbonized carbon aerogel layer; preferably, the low-density heat insulation material layer is adhesively connected to the surface glassy carbonized carbon aerogel layer.

[0051] The low-density heat insulation material layer includes several heat insulation prefabricated layers; an infrared shielding layer is provided between adjacent heat insulation prefabricated layers; the heat insulation prefabricated layer and the infrared shielding layer are bonded together by a high-temperature adhesive; the preparation steps of the low-density heat insulation material layer are as follows: First, process the heat insulation material into a heat insulation prefabricated layer; second, lay an infrared shielding layer between two adjacent heat insulation prefabricated layers; finally, bond the heat insulation prefabricated layer and the infrared shielding layer together by a high-temperature adhesive.

[0052] The bonding of the heat insulation prefabricated layer and the infrared shielding layer is hot-pressed and dried, and its process parameters are as follows: the pressure is 1 to 10 MPa, the temperature is 80 to 200 °C, and the time is 8 to 24 h.

[0053] By mass percentage, the low-density heat insulation material layer includes 70 to 90% of heat insulation material, 5 to 15% of infrared shielding layer, and 5 to 20% of high-temperature adhesive.

[0054] The heat insulation material is selected from at least two of aluminosilicate fiber, alumina fiber, silica fiber, basalt fiber, zirconia fiber, silica aerogel, and carbon aerogel.

[0055] The infrared shielding layer is selected from graphite paper, metal foil, or polyimide film.

[0056] The high-temperature adhesive is selected from aluminum dihydrogen phosphate, silica sol, zirconia sol, or yttrium sol.

[0057] The thickness of the low-density heat insulation material layer is 5 to 50 mm, and the density is 0.10 to 0.50 g / cm 3 , and its thermal conductivity at 1600 °C is ≤0.2 W / m·K, and its thermal conductivity at 200 °C is ≤0.05 W / m·K.

[0058] Preferably, a high-temperature resistant dense coating is further provided between the glass carbonized layer and the low-density heat insulation material layer; the high-temperature resistant dense coating can further improve the gas blocking performance of the high-temperature resistant plugging and heat insulation material.

[0059] The high-temperature resistant dense coating is selected from at least one of silicon carbide, zirconia, and zirconium carbide; the thickness of the high-temperature resistant dense coating is 0.5 to 5 mm.

[0060] The method of setting the high-temperature resistant dense coating on the surface of the glass carbonized layer is to deposit the high-temperature resistant dense coating by chemical vapor deposition method, or spray the high-temperature resistant dense coating by plasma spraying method, or brush the high-temperature resistant dense coating by brushing method; the high-temperature resistant dense coating can only be set on a dense surface and cannot be directly set on the surface of a porous material.

[0061] The low-density heat-insulating material layer and the high-temperature resistant dense coating are bonded by an adhesive.

[0062] The gas permeability of the high-temperature resistant plugging and heat-insulating material is 30-200 cm 3 / (m -2 ×d -1 ×Pa -1 ).

[0063] The present invention also provides an application of the foregoing high-temperature resistant plugging and heat-insulating material in the technical fields of ultra-high temperature equipment or high-speed aircraft.

[0064] The present invention will be further described below in conjunction with specific embodiments, but it should not be construed as a limitation to the protection scope of the present invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the above content of the present invention still fall within the protection scope of the present invention.

[0065] Unless otherwise specified, the materials, reagents, etc. involved below are all commercially available products well-known to those skilled in the art; unless otherwise specified, the methods are all well-known methods in the art. Unless otherwise defined, the technical terms or scientific terms used should have the ordinary meaning understood by those of ordinary skill in the art to which the present invention belongs.

[0066] Example 1:

[0067] In this example, a high-temperature resistant plugging and heat-insulating material is prepared. The specific steps are as follows:

[0068] 1) Prepare a carbon aerogel layer with surface glass carbonization:

[0069] ①. Resorcinol, formaldehyde, water and sodium carbonate are fully mixed evenly in proportion to obtain a carbon aerogel precursor solution; among them, the molar ratio of each raw material is: resorcinol: formaldehyde = 1:2; resorcinol: sodium carbonate = 500:1; water: resorcinol = 100:1;

[0070] ②. The carbon aerogel precursor solution of this example is sequentially allowed to stand at room temperature for 15 h, at 60 °C for 15 h, and at 85 °C for 76 h to obtain a wet gel;

[0071] ③. The wet gel of this example is dried at a temperature of 70 °C for 24 h to obtain a dry gel;

[0072] ④. The dry gel of this example is placed in a nitrogen atmosphere furnace for carbonization, the heating rate is 10 °C / min, the carbonization temperature is 800 °C, the carbonization time is 1 h, and it is cooled to room temperature to obtain a carbon aerogel;

[0073] ⑤. Closely attach one surface of the carbon aerogel described in this embodiment to the smooth inner surface of a glassware, and place the whole into a nitrogen atmosphere furnace for local pyrolysis. The heating rate is 60 °C / h, the pyrolysis temperature is 1000 °C, and the pyrolysis time is 20 min, obtaining a carbon aerogel with one surface carbonized by glass.

[0074] After testing, in the carbon aerogel layer with the surface carbonized by glass described in this embodiment, the thickness of the carbon gel layer not carbonized by glass is 5 mm, and the density is 0.562 g / cm 3 ; the thickness of the glass carbonized layer is 1 mm, and the density is 1.221 g / cm 3 .

[0075] 2) Prepare a low-density thermal insulation material layer:

[0076] Using alumina fiber, zirconia fiber, and silica aerogel as the matrix materials of the thermal insulation layer, prepare a preform with a thickness of 1 mm. Use graphite paper and aluminum foil as the infrared shielding layer, place one layer of infrared shielding layer on every 2-mm-thick preform, and alternate the placement of graphite paper and aluminum foil. Use aluminum dihydrogen phosphate and zirconium sol as high-temperature adhesives to bond the preform and the infrared shielding layer. Among them, the total amount of matrix materials is 500 g, with 100 g, 200 g, and 100 g of alumina fiber, zirconia fiber, and silica aerogel respectively; the infrared shielding layer is 30 g, and the high-temperature adhesive is 50 g, with 40 g and 10 g of aluminum dihydrogen phosphate and zirconium sol respectively. Carry out pressing and drying. The pressing pressure is 5 MPa, and the pressing time is 12 h; the drying temperature is 120 °C, and the drying time is 12 h. After drying, a low-density thermal insulation material is obtained.

[0077] After testing, the overall thickness of the low-density thermal insulation material layer prepared in this embodiment is 20 mm, and the density is 0.337 g / cm 3 , and its thermal conductivity at 1600 °C is 0.178 W / (m·K), and the thermal conductivity at 200 °C is 0.046 W / (m·K).

[0078] 3) Prepare a high-temperature resistant sealing and thermal insulation material:

[0079] ①. Bond the carbon aerogel layer with the surface carbonized by glass prepared in this embodiment to the surface of the porous composite material body with an adhesive; the side not carbonized on the surface, that is, the carbon aerogel side, is adjacent to the porous composite material body;

[0080] ②. Adopt the chemical vapor deposition method to deposit a SiC high-temperature resistant dense coating with a thickness of 2 mm on the glass carbonized layer surface of the carbon aerogel layer with the surface carbonized by glass;

[0081] ③. Bond the low-density thermal insulation material prepared in this embodiment to the SiC high-temperature resistant dense coating with an adhesive;

[0082] ④ Dry at 120 °C for 12 h to obtain a high-temperature resistant plugging and heat-insulating material.

[0083] After testing, the gas permeability of the high-temperature resistant plugging and heat-insulating material prepared in this example is 58.6 cm 3 / (m -2 × d -1 × Pa -1 ).

[0084] Example 2:

[0085] A high-temperature resistant plugging and heat-insulating material is prepared in this example. The specific steps are as follows:

[0086] 1) Prepare a carbon aerogel layer with surface glass carbonization:

[0087] ①. Mix resorcinol, formaldehyde, water and sodium carbonate evenly in proportion to obtain a carbon aerogel precursor solution; among them, the molar ratio of each raw material is: resorcinol:formaldehyde = 1:2; resorcinol:sodium carbonate = 1000:1; water:resorcinol = 50:1;

[0088] ②. Let the carbon aerogel precursor solution of this example stand at room temperature for 12 h, at 60 °C for 13 h, and at 80 °C for 80 h to obtain a wet gel;

[0089] ③. Dry the wet gel of this example at 80 °C for 30 h to obtain a dry gel;

[0090] ④. Put the dry gel of this example into a nitrogen atmosphere furnace for carbonization, with a heating rate of 8 °C / min, a carbonization temperature of 900 °C, a carbonization time of 1.5 h, and cool down to room temperature to obtain a carbon aerogel;

[0091] ⑤. Closely attach one surface of the carbon aerogel of this example to the inside of a glassware with a smooth surface, and put the whole into a nitrogen atmosphere furnace for local pyrolysis, with a heating rate of 50 °C / h, a pyrolysis temperature of 1000, and a pyrolysis time of 30 min to obtain a carbon aerogel with one surface carbonized by glass.

[0092] After testing, in the carbon aerogel layer with surface glass carbonization of this example, the thickness of the carbon gel layer not carbonized by glass is 10 mm, and the density is 0.724 g / cm 3 ; the thickness of the glass carbonization layer is 1.5 mm, and the density is 1.386 g / cm 3 .

[0093] 2) Prepare a low-density heat-insulating material layer:

[0094] Using aluminosilicate fiber, zirconia fiber, and silica aerogel as the matrix materials for the thermal insulation layer, a 2-mm-thick preform is prepared. Graphite paper and polyimide film are used as the infrared shielding layer. One layer of the infrared shielding layer is placed on every 2-mm-thick preform. First, the graphite paper is placed, and then several layers of polyimide film are placed. The preform and the infrared shielding layer are bonded with silica sol and alumina sol as the high-temperature adhesives. Among them, the total amount of the matrix materials is 600 g, including 300 g of aluminosilicate fiber, 150 g of zirconia fiber, and 150 g of silica aerogel; the infrared shielding layer is 80 g, and the high-temperature adhesive is 100 g, including 70 g of silica sol and 30 g of alumina sol. Pressing and drying are carried out. The pressing pressure is 8 MPa, and the pressing time is 20 h; the drying temperature is 130 °C, and the drying time is 20 h. After drying, a low-density thermal insulation material is obtained.

[0095] After testing, the overall thickness of the low-density thermal insulation material layer prepared in this example is 35 mm, and the density is 0.345 g / cm 3 , and its thermal conductivity at 1600 °C is 0.185 W / (m·K), and the thermal conductivity at 200 °C is 0.048 W / (m·K).

[0096] 3) Preparation of a high-temperature resistant plugging and thermal insulation material:

[0097] ① Bond the carbon aerogel layer with surface glass carbonization prepared in this example to the surface of the porous composite material body with an adhesive; the uncarbonized side, that is, the carbon aerogel side, is adjacent to the porous composite material body;

[0098] ② Use the plasma spraying method to spray a ZrO 2 high-temperature resistant dense coating with a thickness of 1.5 mm on the glass carbonization layer of the carbon aerogel layer with surface glass carbonization;

[0099] ③ Bond the low-density thermal insulation material prepared in this example to the ZrO 2 high-temperature resistant dense coating with an adhesive;

[0100] ④ Dry at 130 °C for 10 h to obtain a high-temperature resistant plugging and thermal insulation material.

[0101] After testing, the gas permeability of the high-temperature resistant plugging and thermal insulation material prepared in this example is 105.4 cm 3 / (m -2 ×d -1 ×Pa -1 ).

[0102] Example 3:

[0103] This example prepares a high-temperature resistant plugging and thermal insulation material. The specific steps are as follows:

[0104] 1) Preparation of a carbon aerogel layer with surface glass carbonization:

[0105] ①. Resorcinol, formaldehyde, water, and sodium carbonate are fully mixed evenly in proportion to obtain a carbon aerogel precursor solution; among them, the molar ratio of each raw material is: resorcinol:formaldehyde = 1:2; resorcinol:sodium carbonate = 800:1; water:resorcinol = 150:1;

[0106] ②. The carbon aerogel precursor solution described in this example is successively left standing at room temperature for 20 h, at 60 °C for 20 h, and at 70 °C for 78 h to obtain a wet gel;

[0107] ③. The wet gel described in this example is placed in an oven at 70 °C for drying, and the drying time is 24 h to obtain a dry gel;

[0108] ④. The dry gel described in this example is placed in a nitrogen atmosphere furnace for carbonization, the heating rate is 12 °C / min, the carbonization temperature is 1000 °C, the carbonization time is 1 h, and it is cooled to room temperature to obtain a carbon aerogel;

[0109] ⑤. One surface of the carbon aerogel described in this example is tightly attached to a glassware with a smooth surface, and the whole is placed in a nitrogen atmosphere furnace for local pyrolysis. The heating rate is 55 °C / h, and the pyrolysis temperature is 1000 °C to obtain a carbon aerogel with one side surface carbonized by glass.

[0110] After testing, in the carbon aerogel layer with surface glass carbonization described in this example, the thickness of the carbon gel layer not carbonized by glass is 8 mm, and the density is 0.412 g / cm 3 ; the thickness of the glass carbonized layer is 1.5 mm, and the density is 0.974 g / cm 3 .

[0111] 2) Preparation of a low-density thermal insulation material layer:

[0112] Using basalt fiber and silica aerogel as the matrix materials of the thermal insulation layer, a preform with a thickness of 1 mm is prepared. Using graphite paper as the infrared shielding layer, one layer of infrared shielding layer is placed on every 2 mm thick preform, and the preform and the infrared shielding layer are bonded with yttrium sol and aluminum sol as high-temperature adhesives. Among them, the total amount of the matrix materials is 350 g, of which basalt fiber and silica aerogel are 225 g and 125 g respectively; the infrared shielding layer is 20 g, and the total amount of the high-temperature adhesive is 30 g, of which yttrium sol and aluminum sol are 20 g and 10 g respectively. Pressing and drying are carried out. The pressing pressure is 1 MPa, and the pressing time is 15 h; the drying temperature is 160 °C, and the drying time is 15 h. A low-density thermal insulation material is obtained after drying.

[0113] After testing, the overall thickness of the low-density thermal insulation material prepared in this example is 30 mm, the density is 0.385 g / cm3, the thermal conductivity at 1600 °C is 0.190 W / m·K, and the thermal conductivity at 200 °C is 0.046 W / m·K.

[0114] 3) Prepare a high-temperature resistant plugging and thermal insulation material:

[0115] ① Bond the carbon aerogel layer with surface glass carbonization prepared in this example on the surface of the porous composite material body with an adhesive; the un-carbonized side, that is, the carbon aerogel side, is adjacent to the porous composite material body;

[0116] ② Use the direct brushing method to brush a ZrC high-temperature resistant dense coating on the glass carbonization layer surface of the carbon aerogel layer with surface glass carbonization, with a thickness of 3 mm;

[0117] ③ Bond the low-density thermal insulation material prepared in this example on the ZrC high-temperature resistant dense coating with an adhesive;

[0118] ④ Dry at 130 °C for 15 h to obtain a high-temperature resistant plugging and thermal insulation material.

[0119] After testing, the gas permeability of the high-temperature resistant plugging and thermal insulation material prepared in this example is 126.7 cm 3 / (m -2 ×d -1 ×Pa -1 ).

[0120] Example 4:

[0121] Same as Example 1, the difference is that it does not include depositing a SiC high-temperature resistant dense coating on the glass carbonization layer surface of the carbon aerogel layer with surface glass carbonization by chemical vapor deposition method, and directly bonding the low-density thermal insulation material prepared in this example on the glass carbonization layer with an adhesive.

[0122] After testing, the gas permeability of the high-temperature resistant plugging and thermal insulation material prepared in this example is 357.5 cm 3 / (m -2 ×d -1 ×Pa -1 ).

[0123] Comparative Example 1:

[0124] Same as Example 1, the difference is that it does not include the carbon aerogel layer with surface glass carbonization, and does not include depositing a SiC high-temperature resistant dense coating on the glass carbonization layer surface of the carbon aerogel layer with surface glass carbonization by chemical vapor deposition method, but directly bonds the low-density thermal insulation material prepared in this comparative example on the porous composite material body with an adhesive.

[0125] After testing, the gas permeability of the high-temperature resistant plugging and heat-insulating material prepared in this example is 1639.2 cm 3 / (m -2 ×d -1 ×Pa -1 ).

[0126] Comparative Example 2:

[0127] Same as Example 1, the difference is that when preparing the carbon aerogel layer with surface glass carbonization, instead of attaching one surface of the carbon aerogel to the smooth inner surface of a glass appliance, all six surfaces of it are directly exposed to a nitrogen atmosphere for pyrolysis, with a heating rate of 60 °C / h and a pyrolysis temperature of 1000 °C.

[0128] After testing, in the carbon aerogel layer with surface glass carbonization described in this example, no glass carbonization layer is formed. The thickness of the carbon gel layer is 11.5 mm and the density is 0.736 g / cm 3 . The gas permeability of the high-temperature resistant plugging and heat-insulating material is 1046.8 cm 3 / (m -2 ×d -1 ×Pa -1 ).

[0129] Comparative Example 3:

[0130] Same as Comparative Example 2, the difference is that the heating rate during pyrolysis is 15 °C / h and the pyrolysis temperature is 1000 °C.

[0131] After testing, in the carbon aerogel layer with surface glass carbonization described in this example, the carbon aerogel is entirely pyrolyzed into a glass carbonization layer. Although it has excellent gas blocking performance, it also loses the carbon aerogel layer with high-temperature heat-insulating performance and cannot be applied to the technical solution of the present invention.

[0132] From the test results of the above Examples 1 to 4 and Comparative Examples 1 to 3, it can be seen that when a carbon aerogel layer with surface glass carbonization is provided between the porous composite material body and the low-density heat-insulating material, it can greatly reduce its gas permeability and greatly improve its gas blocking performance, and its gas permeability is lower than 400 cm 3 / (m -2 ×d -1 ×Pa -1 ); further, when a high-temperature resistant dense coating is further provided on the surface of the glass carbonization layer, its gas blocking performance can be further improved, and its gas permeability is further reduced to 200 cm 3 / (m -2 ×d -1 ×Pa -1)Next; further, the placement method of the carbon aerogel in the atmosphere furnace during pyrolysis is crucial. When one surface of the carbon aerogel is tightly attached to a glass appliance with a smooth surface to make it in close contact with the glass surface, and by strictly controlling the heating rate of pyrolysis, the attached surface of the carbon aerogel can be carbonized by the glass, while the un-attached surface will not be carbonized by the glass. This makes the pyrolysis product include both a glass carbonized layer to endow it with excellent gas barrier performance and a carbon aerogel layer to endow it with excellent heat insulation performance.

[0133] The technical features in the claims and / or the specification of the present invention can be combined, and the combination method is not limited to the combination obtained through the citation relationship in the claims. The technical solution obtained by combining the technical features in the claims and / or the specification also falls within the protection scope of the present invention.

[0134] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A high temperature resistant plugging and heat insulating material, characterized in that: It includes: A porous composite body; A carbon aerogel layer with glass carbonization on the surface is arranged on the surface of the porous composite material body; the carbon aerogel layer with glass carbonization on the surface has a carbon aerogel layer on one side and a glass carbonization layer on the other side; the carbon aerogel layer is arranged toward the porous composite material body; the glass carbonization layer is prepared as follows: one side of the carbon aerogel is attached to a glass container with a smooth surface, and the temperature is raised to 1000°C at a heating rate of 50-60°C / h in a nitrogen atmosphere to locally pyrolyze the carbon aerogel; The low-density heat-insulating material layer is arranged on the surface of the glass carbonization layer.

2. The high temperature resistant plugging and heat insulating material according to claim 1, characterized in that: A high temperature resistant dense coating is also provided between the glass carbonization layer and the low density heat insulation material layer; the gas permeability of the high temperature resistant sealing heat insulation material is 30 to 200 cm 3 / (m -2 ×d -1 ×Pa -1 ).

3. The high temperature resistant plugging and heat insulating material according to claim 2, characterized in that: The porous composite material body and the carbon aerogel layer with glass carbonized on the surface are bonded by an adhesive; the high temperature resistant dense coating and the low density thermal insulation material layer are bonded by an adhesive.

4. The high temperature resistant plugging and insulating material according to claim 2, characterized in that: The thickness of the carbon aerogel layer is 1 to 20 mm, and its density is 0.3 to 1.0 g / cm 3 The thickness of the glass carbonization layer is 0.1 to 3 mm, and its density is 0.8 to 1.5 g / cm 3 .

5. The high temperature resistant plugging and insulating material according to claim 2, characterized in that: The high temperature resistant dense coating is selected from at least one of silicon carbide, zirconium oxide and zirconium carbide, and has a thickness of 0.5 to 5 mm.

6. The high temperature resistant plugging and insulating material according to claim 1 or 2, characterized in that: The low-density thermal insulation material layer comprises a plurality of thermal insulation preform layers; an infrared shielding layer is arranged between adjacent thermal insulation preform layers; the thermal insulation preform layer and the infrared shielding layer are bonded together by a high-temperature adhesive; in terms of mass percentage, the low-density thermal insulation material layer comprises 70-90% of thermal insulation material, 5-15% of infrared shielding layer and 5-20% of high-temperature adhesive; the thermal insulation material is selected from at least two of aluminum silicate fiber, aluminum oxide fiber, silicon oxide fiber, basalt fiber, zirconium oxide fiber, silicon oxide aerogel and carbon aerogel; the infrared shielding layer is selected from graphite paper, metal foil or polyimide film; the high-temperature adhesive is selected from aluminum dihydrogen phosphate, silica sol, zirconium sol or yttrium sol.

7. The high temperature resistant plugging and heat insulating material according to claim 1 or 2, characterized in that: The thickness of the low-density heat-insulating material layer is 5 to 50 mm, and the density is 0.10 to 0.50 g / cm 3 Its thermal conductivity at 1600℃ is ≤0.2W / m·K, and its thermal conductivity at 200℃ is ≤0.05W / m·K.

8. A method for preparing a high temperature resistant plugging and heat insulating material according to any one of claims 1 to 7, characterized in that: It includes the following steps: 1) bonding a carbon aerogel layer with a glassy carbonized surface to the surface of a porous composite material body; the carbon aerogel layer with a glassy carbonized surface has a carbon aerogel layer on one side and a glassy carbonized layer on the other side; the carbon aerogel layer is arranged toward the porous composite material body; 2) Bonding a low-density thermal insulation material layer onto the surface of the glass carbonization layer to obtain a high-temperature resistant sealing thermal insulation material.

9. The preparation method according to claim 8, characterized in that: Between step 1) and step 2), the method further includes providing a high temperature resistant dense coating on the surface of the glass carbonization layer; The high temperature resistant dense coating is selected from at least one of silicon carbide, zirconium oxide and zirconium carbide; The method for setting the high temperature resistant dense coating on the surface of the glass carbonization layer is to deposit the high temperature resistant dense coating by chemical vapor deposition, or to spray the high temperature resistant dense coating by plasma spraying, or to brush the high temperature resistant dense coating by brushing.

10. The preparation method according to claim 8, characterized in that: The preparation steps of the surface glass carbonized carbon aerogel layer are as follows: A. Mix resorcinol, formaldehyde, water and sodium carbonate in proportion to obtain a carbon aerogel precursor solution; B. The carbon aerogel precursor solution is allowed to stand to obtain a wet gel; the standing process is as follows: standing at room temperature for 12 to 24 hours, standing at 60°C for 12 to 24 hours, and standing at 70 to 90°C for 72 to 84 hours; C. Drying the wet gel to obtain a dry gel; the drying process is as follows: drying at 50-80°C for 24-48h; D. Carbonizing the dry gel and cooling it to obtain carbon aerogel; the carbonization process is as follows: in a nitrogen atmosphere, heating to 800-1000°C at a heating rate of 5-15°C / min, and carbonizing for 1-2h; E. Place one side of the carbon aerogel in a glass container with a smooth surface and perform local pyrolysis in a nitrogen atmosphere. The pyrolysis process is as follows: heat the aerogel to 1000° C. at a heating rate of 50 to 60° C. / h to obtain a carbon aerogel with carbonized surface glass.

11. The preparation method according to claim 8, characterized in that: The preparation steps of the low-density thermal insulation material layer are as follows: A. Processing a thermal insulation material into a thermal insulation preform layer; wherein the thermal insulation material is selected from at least two of aluminum silicate fiber, aluminum oxide fiber, silicon oxide fiber, basalt fiber, zirconium oxide fiber, silicon oxide aerogel and carbon aerogel; B. Laying an infrared shielding layer between two adjacent layers of heat-insulating preforms; the infrared shielding layer is selected from graphite paper, metal foil or polyimide film; C. Bonding the thermal insulation preform layer and the infrared shielding layer together by a high-temperature adhesive; the high-temperature adhesive is selected from aluminum dihydrogen phosphate, silica sol, zirconium sol or yttrium sol; the mass percentage ratio of the thermal insulation material, the infrared shielding layer and the high-temperature adhesive is 70-90%: 5-15%: 5-20%, and the sum of the three is 100%.

12. The preparation method according to claim 11, characterized in that: The pressure when the thermal insulation preform layer and the infrared shielding layer are bonded is 1-10 MPa, the temperature is 80-200° C., and the time is 8-24 hours.

13. Use of the high temperature resistant sealing and insulating material according to any one of claims 1 to 7 in the field of ultra-high temperature equipment or high-speed aircraft technology.