CN116396093B - Melt siliconizing method of large-size complex-shape MI-SiC-SiC component - Google Patents

Melt siliconizing method of large-size complex-shape MI-SiC-SiC component Download PDF

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CN116396093B
CN116396093B CN202310040485.6A CN202310040485A CN116396093B CN 116396093 B CN116396093 B CN 116396093B CN 202310040485 A CN202310040485 A CN 202310040485A CN 116396093 B CN116396093 B CN 116396093B
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马付根
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Hefei Fuweikang New Material Technology Co ltd
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Abstract

The invention discloses a melt-siliconizing method of a large-size complex-shape MI-SiC component, which aims at solving the technical problem that the molten silicon of the large-size complex-shape component cannot completely fill a preform, and adopts the technical scheme that: the preparation method comprises the steps of preparing SiC fiber prepreg tape or cloth, laminating with a thin carbon fiber felt to form a preform, solidifying to form a solidified preform, performing heat treatment to form a carbonized preform, and performing melt siliconizing to form the MI-SiC-SiC composite material. According to the invention, the thin carbon fiber felt is added into the fiber prepreg tape or the prepreg cloth to serve as a rapid channel, so that the permeation speed of liquid silicon in the preform is remarkably increased, the difficult problems of high permeation resistance and short permeation distance of the liquid silicon in the SiC prepreg are overcome, and rapid and uniform siliconizing is realized.

Description

Melt siliconizing method of large-size complex-shape MI-SiC-SiC component
Technical Field
The invention belongs to the technical field of preparation of ceramic matrix composite materials, and particularly relates to a melt siliconizing method of a MI-SiC-SiC component with a large size and a complex shape.
Background
The continuous fiber reinforced ceramic matrix composite has the outstanding advantages of high temperature resistance, high specific strength and high specific modulus, has fracture characteristics similar to metal, and has high reliability, so that the continuous fiber reinforced ceramic matrix composite becomes a novel aerospace hot junction component and a nuclear industry radiation resistant component.
The continuous fiber reinforced ceramic matrix composite comprises three key components of fiber, matrix and interface layer. The fiber is a framework of the composite material and is a bearing main body; the matrix provides protection to the fibers and bonds the fibers together as a unit; the interface layer is positioned between the fiber and the matrix, and is mainly used for transmitting load, preventing crack propagation, protecting fiber, interface heat conduction and other functions, and plays an important role in the performances of the composite material such as strength, fracture toughness, oxidation resistance, heat conductivity and the like.
At present, the continuous silicon carbide fiber reinforced silicon carbide ceramic matrix composite (SiC/SiC) is one of the structural materials with the most excellent high temperature resistance. The preparation method of the material mainly comprises the following steps: chemical vapor infiltration (ChemicalVaporInfiltration, CVI), melt infiltration (MeltInfiltration, MI), nano-infiltration transient eutectic (Nano-InfiltrationandTransientEutectic, NITE), sol-Gel (Sol-Gel), precursor impregnation cracking (PrecursorImpregnationandPyrolysis, PIP), CVI+PIP and NITE+PIP.
Among these technologies, the SiC/SiC composite material (MI-SiC/SiC) prepared by the MI process has the performance advantages of low porosity, high thermal conductivity, high interlaminar shear strength, etc., and the process has the outstanding advantages of short preparation period and low cost, so that it has been applied to manufacture of aero-engines and industrial gas turbine hot end components abroad.
The universal electric (GE) company in the United states developed a unidirectional prepreg tape-infiltration (Prepreg-MI) process and developed toThe composite material is a brand MI-SiC/SiC composite material product, and is successfully applied to hot junction components (Dong Shaoming, hu Jianbao, zhang Xiangyu, MI process preparation technology of SiC/SiC composite materials, aviation manufacturing technology and 2014,6) of turbine outer rings, combustion chambers and the like of aeroengines and industrial gas turbines. The unidirectional prepreg tape-MI process mainly comprises the following steps: (1) Firstly, preparing an interface layer on the surface of SiC fiber by adopting a Chemical Vapor Deposition (CVD) technology; (2) Mixing SiC powder, carbon powder, a resin binder, a surfactant and a solvent to prepare ceramic slurry, immersing the slurry into a fiber bundle with a coating, and winding the fiber bundle by a wet method to form a SiC fiber unidirectional prepreg tape; (3) Forming a composite material preform after the unidirectional prepreg layers are stacked, and then curing to realize shaping; (4) Carbonizing the resin by pyrolysis, and discharging other organic components in a gaseous state to form a preform with a large number of micropores, so as to provide a channel for subsequent siliconizing; (5) And finally, heating the silicon powder or the silicon block to a molten state (higher than 1410 ℃), and allowing liquid silicon to infiltrate into the porous fiber preform under the action of capillary force, so that silicon carbide is generated by the reaction of silicon and carbon, and the compact MI-SiC/SiC composite material is prepared.
NASA developed a slurry cast-infiltration (SlurryCast-MI) process and formed a number of brands of ceramic matrix composite products such as N22, N24, etc. (Dong Shaoming, hu Jianbao, zhang Xiangyu, siC/SiC composite MI process fabrication techniques, aerospace manufacturing techniques, 2014,6). The slurry casting-infiltration process comprises the following steps: (1) Firstly, laminating and forming SiC fiber cloth to obtain a composite material preform; (2) adopting CVI technology to prepare an interface layer on the surface of the fiber; (3) Depositing a SiC protective layer on the surface of the interface layer by adopting a CVI technology so as to reduce corrosion of molten silicon to SiC fibers and fiber surface coatings in the subsequent infiltration process; (4) Mixing SiC powder, a resin binder, a surfactant and a solvent to prepare ceramic slurry, immersing the slurry into the preform, then carbonizing the resin by pyrolysis, and discharging other organic components in a gaseous state to form a preform with a large number of micropores, so as to provide a channel for subsequent siliconizing; (5) And finally, heating the silicon powder or the silicon block to a molten state (higher than 1410 ℃), and allowing liquid silicon to infiltrate into the porous fiber preform under the action of capillary force, so that silicon carbide is generated by the reaction of silicon and carbon, and the compact MI-SiC/SiC composite material is prepared.
In the MI process, molten silicon enters the preform under the action of capillary force, and as the molten silicon has strong corrosiveness to SiC fibers and SiC fiber surface coatings, the siliconizing conditions need to be strictly controlled to reduce the corrosion damage of liquid silicon to the fibers and coatings. Therefore, the temperature and time of the melt-siliconizing are strictly limited, and are generally 1410-1450 ℃ for 10-120 min. At this temperature, the silicon has a high viscosity and a high surface tension, which results in a limited penetration distance (typically within 50 mm) in the preform. In the MI process, liquid silicon reacts with carbon in the matrix to generate SiC, and the reaction formula is as follows:
Si(l)+C(s)＝SiC(s)
the generated SiC product can further obstruct the penetration of liquid silicon, so that the effective distance of siliconizing is further reduced. Therefore, how to adapt the melt-siliconizing technology to the preparation of large-size and complex-shape MI-SiC/SiC components is one of the core problems of engineering applications of the technology.
At present, the research of MI-SiC/SiC composite materials is less related to how to solve the engineering technical problem of siliconizing large-size components. As disclosed in patent CN112457027a,2020 (Wang Peng, zhao Bingbing, zhang Qian, zhang Haisheng, zhang Xi, wang Yan, li Jianzhang, tool and method for siliconizing large-sized circular-section ceramic matrix composite members by melting) a large-sized cylindrical member, the method adopts a method of stacking a plurality of graphite crucibles in the longitudinal direction of the cylindrical member, and connecting a silicon source with a preform by using graphite paper, so that a plurality of siliconizing points with equal intervals exist in the longitudinal direction of the preform, thereby solving the problem that molten silicon cannot permeate for a long distance. In the technology, the quality of siliconizing is affected by manual operation factors, such as the contact tightness of graphite paper and components, the filling density of silicon materials and the like, and a graphite crucible with complex shape is required to be processed aiming at different components, so that the process reliability is affected, and the cost is high; in addition, in order to ensure the sufficient penetration of silicon, the siliconizing temperature of the technology reaches 1650 ℃ and the time is as long as a plurality of hours, so that obvious corrosion damage and heat damage are generated on the coating and the SiC fiber, and the mechanical property of the composite material is obviously reduced.
For small-sized, simple-shaped components (e.g., planar dimensions less than 100mm x 100 mm), the molten silicon can uniformly infiltrate the preform by capillary forces, resulting in a high quality, microstructure-uniform MI-SiC/SiC composite. However, for large-size and complex-shape components, the preform cannot be completely filled with molten silicon, the porosity of MI-SiC/SiC products is increased, the performance is reduced, and the MI-SiC/SiC products become key factors for limiting the quality and quality consistency of the products.
Disclosure of Invention
The invention aims to provide a melt siliconizing method of a large-size and complex-shape MI-SiC component, which aims to solve the technical problems.
The invention aims to solve the technical problems, and is realized by adopting the following technical scheme:
a method for melt siliconizing a large-size complex-shape MI-SiC member, comprising the steps of:
1) The continuous SiC fibers are made into any one of unidirectional prepreg tapes or prepregs, and the specific steps are as follows:
When preparing the unidirectional prepreg tape, firstly preparing a surface coating on the surface of SiC fiber bundle filaments, then enabling the fiber bundle filaments to continuously pass through a ceramic slurry pool, and then winding the fiber bundle filaments on a roller in a single layer along different directions to form the unidirectional prepreg tape;
When preparing the prepreg cloth, firstly weaving SiC fibers to obtain the fiber cloth; preparing a surface coating on the surface of the fiber cloth; soaking SiC fiber cloth with a fiber surface coating in ceramic slurry, taking out after full soaking, and drying to obtain prepreg cloth;
2) Laminating the unidirectional prepreg tape or the prepreg cloth obtained in the step 1) with a thin carbon fiber felt to form a preform;
3) Sealing the preform obtained in the step 2) by using a vacuum bag, continuously vacuumizing the interior, and curing in an autoclave to obtain a cured preform;
4) Performing heat treatment on the solidified preform obtained in the step 3) in an inert atmosphere to carbonize organic matters in the preform, thereby obtaining a carbonized preform;
5) Heating, melting and siliconizing the carbonized preform obtained in the step 4) in a vacuum atmosphere, preserving heat, and then cooling to room temperature along with a furnace to obtain the MI-SiC/SiC composite material.
Preferably, the surface coating prepared on the surface of the SiC fiber bundle filaments or the fiber cloth in the step 1) comprises a BN coating, a Si 3N4 coating and a C coating, and the thickness of the single prepreg tape is between 0.2mm and 0.6 mm; the thickness of the single prepreg cloth is between 0.3mm and 0.8mm, and the ceramic slurry contains silicon carbide powder, carbon powder, resin binder, dispersing agent and solvent.
Preferably, the granularity of the silicon carbide powder is 0.5-5 μm, the granularity of the carbon powder is 0.1-5 μm, and the resin binder is any one of epoxy resin, phenolic resin or furfural resin.
Preferably, the unidirectional prepreg tape, the prepreg cloth and the thin carbon fiber felt in the step 2) are all sheets, the thickness of the thin carbon fiber felt is 0.1mm-1mm, adjacent interlaminar fibers are overlapped at any angle, and a layer of thin carbon fiber felt is arranged between each layer of prepreg tape/prepreg cloth or between every other plurality of layers of prepreg tape/prepreg cloth.
Preferably, the curing pressure of the autoclave in the step 3) is 0.5MPa-2MPa, the temperature is 80-150 ℃, and the heat preservation time is 0.5-10 h.
Preferably, the inert atmosphere in the step 4) is any one of nitrogen and argon, the heat treatment temperature is 900-1300 ℃, and the heat preservation time is 0.5-5 h.
Preferably, the melt siliconizing temperature in the step 5) is 1410-1450 ℃ and the siliconizing time is 1-60 min.
The beneficial effects of the invention are as follows:
1. According to the invention, the thin carbon fiber felt is introduced between the SiC fiber prepregs, so that a rapid infiltration channel with small liquid silicon resistance is provided, the flow speed and distance of molten silicon are accelerated, the problem of incomplete molten silicon infiltration of large-size and complex-shape components is effectively solved, and the MI-SiC/SiC composite material with low porosity, uniform microstructure and excellent mechanical property is obtained;
2. according to the invention, the siliconizing speed and the volume fraction of SiC fibers in the composite material can be adjusted by adjusting the thickness and the layer number of the carbon felt, so that the performance of the MI-SiC/SiC composite material is adjusted;
3. the invention has simple process, is suitable for mass production of large-size complex components, and has the value of engineering application.
Drawings
FIG. 1 is a schematic illustration of a carbon-containing felt preform stack according to example 1 of the present invention;
FIG. 2 is a schematic flow chart of the present invention;
wherein: 1. 0-degree unidirectional prepreg tape; 2. a thin carbon fiber mat; 3. 90-degree unidirectional prepreg tape.
Detailed Description
In order that the manner in which the above recited features, objects and advantages of the present invention are obtained, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the invention.
Specific embodiments of the present invention are described below with reference to the accompanying drawings.
Example 1
As shown in fig. 1, a method for melt-siliconizing a large-size complex-shape MI-SiC member includes the steps of:
1) The continuous SiC fibers are made into a fiber unidirectional prepreg tape, which is specifically as follows:
when preparing a unidirectional prepreg tape, firstly preparing a BN coating with the thickness of 500nm, a Si 3N4 coating with the thickness of 300nm and a C coating with the thickness of 30nm on the surface of SiC fiber bundle filaments by utilizing a Chemical Vapor Deposition (CVD) technology, then enabling the fiber bundle filaments to continuously pass through a ceramic slurry tank containing silicon carbide powder with the granularity of 2 mu m, carbon powder with the granularity of 1 mu m, epoxy resin, dispersing agent and solvent, then winding the fiber bundle filaments on a roller with the diameter of 600mm along the directions of 0 DEG and 90 DEG in a single layer, taking off the roller after the winding width reaches 400mm, and forming a 0 DEG unidirectional prepreg tape 1 with the width of 400mm, the length of 1884mm and the thickness of 0.4mm and a 90 DEG unidirectional prepreg tape 3;
2) Cutting the 0-degree unidirectional prepreg tape 1 and the 90-degree unidirectional prepreg tape 3 into 200mm multiplied by 200mm sheets, cutting the 0.12mm thin carbon fiber felt 2 into 200mm multiplied by 205mm sheets, and sequentially and alternately laminating seven layers of 0-degree unidirectional prepreg tapes 1, six layers of thin carbon fiber felts 2 and seven layers of 90-degree unidirectional prepreg tapes 3 to form a prefabricated body, wherein the thin carbon fiber felts are introduced between the SiC fiber unidirectional prepreg tapes or SiC fiber prepreg cloths, the thin carbon fiber felts provide quick infiltration channels with small liquid silicon resistance, the flow speed and the distance of molten silicon are accelerated, the problem that large-size and complex-shape components are incomplete in molten silicon infiltration is effectively solved, MI-SiC/SiC composite materials with low porosity, uniform microstructure and excellent mechanical property are obtained, the higher the volume fraction occupied by the thin carbon fiber felts 2 is, the subsequent silicon infiltration speed is higher, but simultaneously, the strength of the composite materials is reduced, the volume fraction of the carbon felts can be adjusted by adjusting the thickness and the number of layers of the thin carbon fiber felts, and the speed and the distance of the silicon infiltration are further adjusted, and the composite materials are suitable for different in size and structure.
3) Sealing the preform obtained in the step 2) by using a vacuum bag, continuously vacuumizing the interior, and placing the preform in an autoclave for curing, wherein the curing pressure is 1.2MPa, the curing temperature is 130 ℃, and the curing time is 2 hours, so as to obtain a cured preform; in the process, the resin is solidified, the porosity in the prefabricated body is reduced, and the structural uniformity and strength are greatly improved;
4) Placing the solidified preform obtained in the step 3) in N 2 atmosphere, and performing heat treatment at 1100 ℃ for 1h to obtain a carbonized preform, wherein in the process, carbon-based resin in the preform is carbonized, gas byproducts are removed, a large number of holes are introduced into a matrix, and a passage is provided for subsequent melt siliconizing;
5) Heating, melting and siliconizing the carbonized preform obtained in the step 4), heating to 1440 ℃ under 10Pa vacuum, preserving heat for 30min, and then cooling to room temperature along with a furnace to obtain the MI-SiC/SiC composite material.
Enters from the prepreg and the thin carbon fiber felt simultaneously under the action of capillary force, and the thin carbon fiber felt has high porosity and small channel resistance, so that the molten silicon can quickly permeate in the layer. Although the thin carbon fiber felt 2 reacts with the liquid silicon to generate silicon carbide so as to narrow the channel, the developed and unobstructed pore structure can still ensure the rapid transmission of the liquid silicon. The liquid silicon is transmitted in the plane direction of the thin carbon fiber felt 2 and is permeated into the SiC fiber prepreg layers on the upper layer and the lower layer by the layer, so that the permeation distance of the liquid silicon in the SiC fiber prepreg layers is shortened, after the siliconizing is finished, the carbon fibers in the thin carbon fiber felt 2 are completely converted into SiC, and carbon in the SiC prepreg layers and the liquid silicon react to be converted into SiC, so that the SiC fiber felt becomes a part of a matrix, and the MI-SiC/SiC performance is not adversely affected.
The thickness of the single prepreg tape in the step 1) can be any value between 0.2mm and 0.6 mm; the granularity of the silicon carbide powder can be any value between 0.5 and 5 mu m, and the granularity of the carbon powder can be any value between 0.1 and 5 mu m; the resin binder may be any one of a phenolic resin or a furfural resin.
The thickness of the thin carbon fiber mat 2 may also be any value between 0.1mm and 1 mm.
The curing pressure of the autoclave in the step 3) can be any value between 0.5MPa and 2MPa, the temperature can be any value between 80 ℃ and 150 ℃, and the heat preservation time can be any value between 0.5h and 10 h.
The inert atmosphere in the step 4) can be argon, the heat treatment temperature can be any value between 900 ℃ and 1300 ℃, and the heat preservation time can be any value between 0.5h and 5 h.
The temperature of the melt siliconizing in the step 5) can be any value between 1410 ℃ and 1450 ℃, and the siliconizing time can be any value between 1min and 60 min.
The test results show that the MI-SiC/SiC composite material obtained in the example 1 has the porosity of 2.5%, the volume fraction of the SiC fibers of 16%, the tensile strength of 215MPa and the fracture strain of 0.45%, and has excellent mechanical properties.
Example 2
1) Step 1) as in example 1;
2) Cutting the 0-degree unidirectional prepreg tape 1 and the 90-degree unidirectional prepreg tape 3 into sheets with the thickness of 200mm multiplied by 200mm, cutting the 0.12-mm thin carbon fiber felt 2 into sheets with the thickness of 200mm multiplied by 205mm, and stacking the three layers of the 0-degree unidirectional prepreg tape 1, the one layer of the thin carbon fiber felt 2 and the three layers of the 90-degree unidirectional prepreg tape 3 together to form a prefabricated body, wherein the thin carbon fiber felt 2 is positioned in the middle, namely, three layers of the unidirectional prepreg tapes are respectively arranged on the upper surface and the lower surface. The volume fraction of the thin carbon fiber mat 2 in the preform was significantly reduced compared to example 1;
3) Step 3) of example 1;
4) Step 4) of example 1;
5) As in step 5 of example 1).
The analysis of the results of example 2 shows that the MI-SiC/SiC composite material has the porosity of 3.8 percent, the volume fraction of SiC fibers in the composite material of 21 percent, the tensile strength of the composite material of 253MPa and the fracture strain of 0.48 percent, and has excellent mechanical properties.
Example 3
1) When preparing fiber prepreg cloth, firstly weaving SiC fibers to obtain plain fiber cloth; preparing a BN coating with the thickness of 500nm, a Si 3N4 coating with the thickness of 300nm and a C coating with the thickness of 30nm on the surface of the fiber cloth by utilizing a Chemical Vapor Deposition (CVD) technology, soaking the SiC fiber cloth with the coating into ceramic slurry, taking out after full soaking, and drying to obtain prepreg cloth;
2) Cutting prepreg cloth into sheets with the thickness of 200mm multiplied by 200mm, cutting 0.12mm thin carbon fiber felt 2 into sheets with the thickness of 200mm multiplied by 205mm, and then alternately laminating seven layers of prepreg cloth and six layers of thin carbon fiber felt 2 to form a prefabricated body;
3) Step 3) of example 1;
4) Step 4) of example 1;
5) As in step 5 of example 1).
Example 3 analysis of the results shows that the MI-SiC/SiC composite material has a porosity of 3.2%, a volume fraction of SiC fibers in the composite material of 18%, a tensile strength of 245MPa, a fracture strain of 0.42%, and excellent mechanical properties
In the present invention, unless expressly stated or limited otherwise, a first feature "above" or "below" a second feature may include both the first and second features being in direct contact, as well as the first and second features not being in direct contact but being in contact with each other through additional features therebetween. Moreover, a first feature being "above," "over" and "on" a second feature includes the first feature being directly above and obliquely above the second feature, or simply indicating that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature includes the first feature being directly under and obliquely below the second feature, or simply means that the first feature is less level than the second feature.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (7)

1. A method for melt siliconizing a large-size complex-shape MI-SiC member, characterized by comprising the steps of:
1) The continuous SiC fibers are made into any one of unidirectional prepreg tapes or prepregs, and the specific steps are as follows:
When preparing the unidirectional prepreg tape, firstly preparing a surface coating on the surface of SiC fiber bundle filaments, then enabling the fiber bundle filaments to continuously pass through a ceramic slurry pool, and then winding the fiber bundle filaments on a roller in a single layer along different directions to form the unidirectional prepreg tape;
When preparing the prepreg cloth, firstly weaving SiC fibers to obtain the fiber cloth; preparing a surface coating on the surface of the fiber cloth; soaking SiC fiber cloth with a fiber surface coating in ceramic slurry, taking out after full soaking, and drying to obtain prepreg cloth;
2) Laminating the unidirectional prepreg tape or the prepreg cloth obtained in the step 1) with a thin carbon fiber felt to form a preform;
3) Sealing the preform obtained in the step 2) by using a vacuum bag, continuously vacuumizing the interior, and curing in an autoclave to obtain a cured preform;
4) Performing heat treatment on the solidified preform obtained in the step 3) in an inert atmosphere to carbonize organic matters in the preform, thereby obtaining a carbonized preform;
5) Heating, melting and siliconizing the carbonized preform obtained in the step 4) in a vacuum atmosphere, preserving heat, and then cooling to room temperature along with a furnace to obtain the MI-SiC/SiC composite material.
2. The method for melt siliconizing large-size complex-shaped MI-SiC members according to claim 1, wherein the surface coating layer prepared on the surface of the SiC fiber bundle filaments or fiber cloth in the step 1) comprises a BN coating layer, a Si 3N4 coating layer and a C coating layer, the thickness of the single prepreg tape is between 0.2mm and 0.6mm, the thickness of the single prepreg cloth is between 0.3mm and 0.8mm, and the ceramic slurry contains silicon carbide powder, carbon powder, a resin binder, a dispersing agent and a solvent.
3. The method for melt-siliconizing a large-size complex-shape MI-SiC member according to claim 2, wherein the particle size of the silicon carbide powder is 0.5 μm to 5 μm, the particle size of the carbon powder is 0.1 μm to 5 μm, and the resin binder is any one of epoxy resin, phenolic resin or furfural resin.
4. The method for melt siliconizing a large-size complex-shape MI-SiC member according to claim 1, wherein in the step 2), the unidirectional prepreg tape, the prepreg cloth and the thin carbon fiber felt are all sheets, the thickness of the thin carbon fiber felt is 0.1mm-1mm, adjacent interlaminar fibers are overlapped at any angle, and a layer of thin carbon fiber felt is arranged between each layer of prepreg tape/prepreg cloth or between every other layers of prepreg tape/prepreg cloth.
5. The method for melt-siliconizing a large-size complex-shape MI-SiC member according to claim 1, wherein the autoclave in step 3) has a solidification pressure of 0.5MPa to 2MPa, a temperature of 80 ℃ to 150 ℃ and a holding time of 0.5h to 10h.
6. The method for melt-siliconizing a large-size complex-shape MI-SiC member according to claim 1, wherein the inert atmosphere in the step 4) is any one of nitrogen and argon, the heat treatment temperature is 900 ℃ to 1300 ℃, and the holding time is 0.5h to 5h.
7. The method for melt-siliconizing a large-size complex-shape MI-SiC member according to claim 1, wherein the melt-siliconizing temperature in the step 5) is 1410 ℃ to 1450 ℃ and the siliconizing time is 1min to 60min.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1344205A (en) * 1999-03-30 2002-04-10 Cytec技术有限公司 Composite comprising structural and non structural fibers
CN1749217A (en) * 2004-08-11 2006-03-22 通用电气公司 CMC process using water-based prepreg slurry

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2724131C2 (en) * 1977-05-27 1982-06-09 C. Conradty Nürnberg GmbH & Co KG, 8505 Röthenbach Plate-shaped carbon body and method for its manufacture
AU649687B2 (en) * 1990-05-09 1994-06-02 Lanxide Corporation Thin metal matrix composites and production methods
WO1999019273A1 (en) * 1997-10-09 1999-04-22 Ngk Insulators, Ltd. Fibrous composite material and process for producing the same
JP3096716B1 (en) * 1999-03-01 2000-10-10 工業技術院長 Method for producing fiber-reinforced silicon carbide composite
JP4437617B2 (en) * 2001-01-31 2010-03-24 日本碍子株式会社 Method for producing carbon fiber reinforced SiC composite material
DE102005042870B3 (en) * 2005-09-08 2007-04-26 Astrium Gmbh Process for the preparation of siliconized molded bodies
US20080149255A1 (en) * 2006-12-20 2008-06-26 General Electric Company Ceramic composite article manufacture using thin plies
DE102011007815B4 (en) * 2011-04-20 2016-09-29 Sgl Carbon Se Method for producing a ceramic component assembled from several preforms
CN103342570B (en) * 2013-07-11 2014-08-20 山东宝纳新材料有限公司 Method for preparing C/SiC composite material through low-cost fused silicon impregnation method
US10794205B2 (en) * 2017-02-27 2020-10-06 Rolls-Royce North American Technologies Inc. Ceramic seal component for gas turbine engine and process of making the same
US10774008B2 (en) * 2017-09-21 2020-09-15 General Electric Company Ceramic matrix composite articles
CN109721377B (en) * 2019-01-30 2020-06-30 湖南兴晟新材料科技有限公司 Carbon fiber reinforced silicon carbide ceramic matrix composite and preparation method thereof
CN216001519U (en) * 2021-11-02 2022-03-11 常州市宏发纵横新材料科技股份有限公司 Reinforced fabric and multi-axial reinforced material
CN115368141B (en) * 2022-09-15 2023-07-14 湖南博云新材料股份有限公司 alpha-SiC and amorphous silicon nitride composite ceramic brake material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1344205A (en) * 1999-03-30 2002-04-10 Cytec技术有限公司 Composite comprising structural and non structural fibers
CN1749217A (en) * 2004-08-11 2006-03-22 通用电气公司 CMC process using water-based prepreg slurry

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