A method for preparing a low-cost ultra-high-temperature ceramic matrix composite large-size component
By depositing a pyrolytic carbon interface layer on the surface of carbon fiber preforms and combining PIP and RMI processes, large-size components of ultra-high temperature ceramic matrix composites with low cost and high density were prepared. This solved the problems of long preparation cycle, high cost and low density in the existing technology, and realized an efficient and low-cost preparation method.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- AEROSPACE INST OF ADVANCED MATERIALS & PROCESSING TECH
- Filing Date
- 2022-09-26
- Publication Date
- 2026-05-05
AI Technical Summary
Existing technologies for preparing large-size ultra-high temperature ceramic matrix composite components suffer from problems such as long production cycles, high costs, and low density. In particular, the RMI process has limitations in the preparation of large-size components, while the PIP process uses expensive raw materials.
A pyrolytic carbon interface layer was deposited on the surface of a carbon fiber preform using chemical vapor deposition, followed by impregnation and curing using the PIP process. Subsequently, reactive infiltration was carried out at the other end using the RMI process, and the preform was treated with phenolic resin and ultra-high temperature alloy powder to form an ultra-high temperature ceramic matrix composite material.
This technology enables the fabrication of large-size components from ultra-high temperature ceramic matrix composites with low cost and high density, improving production efficiency, reducing costs, and avoiding stress risks caused by compositional mutations in high-temperature applications.
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Figure CN117125989B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of ultra-high temperature ceramic matrix composites, and particularly relates to a low-cost method for preparing large-size ultra-high temperature ceramic matrix composite components. Background Technology
[0002] The main technologies for preparing ultra-high temperature ceramic matrix composites include chemical vapor deposition (CVI), precursor impregnation pyrolysis (PIP), and reactive infiltration (RMI). CVI and PIP processes have long production cycles and high costs, resulting in composites with low density; while RMI processes have the advantages of low cost, short cycle time, and high density of the composites.
[0003] The basic principle of RMI (Residual Infiltration) technology is to prepare composite materials by infiltrating molten metal into the interior of the composite material through capillary action inside the preform. Therefore, the infiltration depth is limited, which has certain limitations in the preparation of large-size components. PIP (Polypropylene Infiltration) technology for preparing large-size components is not only time-consuming, but also has high production costs due to the high price of polymer raw materials such as polyhafnium carbide, polyzirconium carbide, and polycarbosilane. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention provides a low-cost method for preparing large-size components made of ultra-high temperature ceramic matrix composites.
[0005] To achieve the above objectives, the present invention provides the following technical solution:
[0006] A low-cost method for preparing large-size components from ultra-high temperature ceramic matrix composites includes the following steps:
[0007] (1) Deposition of pyrolytic carbon interface layer on fiber surface of large-size carbon fiber preform: A pyrolytic carbon interface layer is deposited on fiber surface of large-size carbon fiber preform using chemical vapor deposition.
[0008] (2) PIP process for large-size components: one end of the large-size component is impregnated, cured and subjected to high-temperature pyrolysis using hafnium silicon integrated ceramic precursor solution or zirconium silicon integrated ceramic precursor solution;
[0009] (3) RMI process for large-size components: Based on the PIP process, the other end of the large-size component is impregnated with phenolic resin, then cured and pyrolyzed at high temperature, and this end is embedded with an ultra-high temperature alloy infiltrator for reaction melting and infiltration to obtain a large-size ceramic matrix composite component.
[0010] Preferably, a pyrolytic carbon interface layer is deposited on the fiber surface of a large-size carbon fiber preform using chemical vapor deposition. The carbon source is propylene, the carrier gas is nitrogen, the deposition temperature is 800-1100℃, and the deposition time depends on the density of the carbon fiber preform after pyrolytic carbon deposition.
[0011] Preferably, the density of the carbon fiber preform after pyrolytic carbon deposition is 0.9-1.1 g / cm³. 3 .
[0012] Preferably, the hafnium-silicon integrated ceramic precursor solution comprises polyhafnium carbide, polycarbosilane, and phenolic resin, wherein the molar ratio of polyhafnium carbide, polycarbosilane, and phenolic resin is 1:(0.25-4):(2-6); the zirconium-silicon integrated ceramic precursor solution comprises polyzirconium carbide, polycarbosilane, and phenolic resin, wherein the molar ratio of polyzirconium carbide, polycarbosilane, and phenolic resin is 1:(0.25-4):(2-6); and / or
[0013] The viscosity of the hafnium-silicon integrated ceramic precursor solution or zirconium-silicon integrated ceramic precursor solution is 50-500 mPa·s.
[0014] Preferably, the curing temperature of the hafnium-silicon integrated ceramic precursor solution or the zirconium-silicon integrated ceramic precursor solution is 200-300℃, and the time is 1-10h; and / or the high-temperature pyrolysis temperature is 1200-1800℃, and the time is 1-5h.
[0015] Preferably, the phenolic resin is vacuum impregnated for 1-3 hours under a vacuum of 5-100 kPa; the curing temperature is 100-350℃, the curing pressure is 3-10 MPa, and the curing time is 0.5-2 hours; the high-temperature pyrolysis temperature is 700-1000℃, and the pyrolysis time is 2-4 hours.
[0016] Preferably, the porous low-density C / C substrate obtained after impregnation with phenolic resin has a density of 1.2-1.4 g / cm³. 3 .
[0017] Preferably, the ultra-high temperature alloying agent is hafnium silicon alloy powder or zirconium silicon alloy powder, wherein the atomic weight ratio of hafnium or zirconium in the hafnium silicon alloy powder or zirconium silicon alloy powder is 10-39%.
[0018] Preferably, the reaction melting temperature is 1600-1800℃, and the holding time is 1-2h.
[0019] The present invention also provides a low-cost, ultra-high temperature ceramic matrix composite large-size component prepared by the above method.
[0020] Compared with the prior art, the present invention has at least the following beneficial effects:
[0021] This invention employs a combined reactive infiltration (RMI) and precursor impregnation pyrolysis (PIP) process to prepare large-size ultra-high temperature ceramic matrix composite components. The reactive infiltration process offers advantages such as high speed, low cost, and high density of the resulting composite material. The combined RMI and PIP process not only ensures the introduction of the ultra-high temperature ceramic matrix into the large-size components but also significantly improves production efficiency and reduces costs. The large-size ultra-high temperature ceramic matrix composite components prepared by this invention exhibit low cost, high density, and excellent resistance to oxidation and ablation. Attached Figure Description
[0022] Figure 1 This is a flowchart of the steps of the method of the present invention. Detailed Implementation
[0023] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.
[0024] This invention provides a low-cost method for preparing large-size components of ultra-high temperature ceramic matrix composites, the method comprising the following steps:
[0025] (1) Deposition of pyrolytic carbon interface layer on fiber surface of large-size carbon fiber preform: A pyrolytic carbon interface layer is deposited on fiber surface of large-size carbon fiber preform using chemical vapor deposition.
[0026] (2) PIP process for large-size components: one end of the large-size component is impregnated, cured and subjected to high-temperature pyrolysis using hafnium silicon integrated ceramic precursor solution or zirconium silicon integrated ceramic precursor solution;
[0027] (3) RMI process for large-size components: Based on the PIP process, the other end of the large-size component is impregnated with phenolic resin, then cured and pyrolyzed at high temperature, and this end is embedded with an ultra-high temperature alloy infiltrator for reaction melting and infiltration to obtain a large-size ceramic matrix composite component.
[0028] This invention first employs a PIP (Potential In-Place) process to impregnate, cure, and pyrolyze one end of a large-sized component using a hafnium-silicon integrated ceramic precursor solution or a zirconium-silicon integrated ceramic precursor solution. Then, the other end of the large-sized component is impregnated with phenolic resin, followed by curing and high-temperature pyrolysis. Hafnium-silicon alloy powder or zirconium-silicon alloy powder is then embedded in this other end for reactive infiltration. This invention discovers that hafnium-silicon alloy powder or zirconium-silicon alloy powder can introduce a large amount of ultra-high temperature ceramic matrix into large-sized components, thereby improving production efficiency and reducing production costs. This invention first employs a PIP process to deposit a pyrolytic carbon preform (density 0.9 g / cm³). 3 ~1.1g / cm 3 Based on this, an ultra-high temperature ceramic matrix is prepared at one end using a hafnium-silicon integrated ceramic precursor solution or a zirconium-silicon integrated ceramic precursor solution. Then, a porous low-density C / C substrate is prepared at the other end using phenolic resin, achieving a density of 1.2 g / cm³. 3 ~1.4g / cm 3 Then, hafnium silicon alloy powder or zirconium silicon alloy powder are used for reactive melting and infiltration, reacting with carbon to generate an ultra-high temperature ceramic matrix. The ceramic matrix composite material components prepared by this invention have the same composition at both ends, and will not generate large stress due to abrupt changes in composition during high-temperature applications, thus avoiding potential hazards.
[0029] According to some preferred embodiments, the density of the carbon fiber preform is preferably 0.45-0.65 g / cm³. 3 Before carbon deposition, a high-temperature preheating treatment of 1800-2000℃ for 2-3 hours is performed. In the chemical vapor deposition process, propylene is used as the carbon source, nitrogen as the carrier gas, and the preferred deposition temperature is 800-1100℃. The deposition time depends on the density of the carbon fiber preform after pyrolytic carbon deposition. The preferred density of the preform after pyrolytic carbon deposition is 0.9-1.1 g / cm³. 3 .
[0030] According to some preferred embodiments, the curing temperature of the hafnium (or zirconium) silicon integrated ceramic precursor solution is 200-300℃, and the time is 1-10h; and / or the high-temperature pyrolysis temperature is 1200-1800℃, and the time is 1-5h.
[0031] According to some preferred embodiments, the phenolic resin is vacuum impregnated for 1-3 hours under a vacuum of 5-100 kPa; the curing temperature is 100-350℃, the curing pressure is 3-10 MPa, and the curing time is 0.5-2 hours; the high-temperature pyrolysis temperature is 700-1000℃, and the pyrolysis time is 2-4 hours; the porous low-density C / C substrate obtained after the pyrolysis of the phenolic resin has a density of 1.2-1.4 g / cm³. 3 .
[0032] According to some preferred embodiments, the atomic weight ratio of hafnium or zirconium in the hafnium-silicon alloy powder or zirconium-silicon alloy powder is 10-39%; the reaction melting temperature is preferably 1600-1800℃, and the holding time is preferably 1-2h.
[0033] To more clearly illustrate the technical solution and advantages of the present invention, the present invention will be further described below in conjunction with embodiments.
[0034] Example 1
[0035] A low-cost method for preparing large-size components from ultra-high temperature ceramic matrix composites, the specific steps of which are as follows:
[0036] (1) For a density of 0.6 g / cm³ 3 Large-size needle-punched carbon fiber preforms were preheated at 1800℃ for 2 hours, and then a pyrolytic carbon interface layer was deposited on the fiber surface of the preforms using chemical vapor deposition. The carbon source was propylene, the carrier gas was nitrogen, and the preferred deposition temperature was 900℃. The density of the preform after pyrolytic carbon deposition was 1.02 g / cm³. 3 .
[0037] (2) One end of a large-sized component was impregnated, cured, and subjected to high-temperature pyrolysis using a hafnium-silicon integrated ceramic precursor (the molar ratio of polyhafnium carbide, polycarbosilane, and phenolic resin was 1:0.5:3). The curing temperature was 200℃ and the time was 1h; the high-temperature pyrolysis temperature was 1200℃ and the time was 1h.
[0038] (3) The other end of a large-size carbon fiber preform with a pyrolytic carbon interface layer deposited on it was impregnated with phenolic resin, and then cured and subjected to high-temperature pyrolysis. The impregnation temperature was room temperature, the vacuum impregnation pressure was 50 kPa, and the impregnation time was 1.5 h; the curing temperature was 220 ℃, the curing pressure was 4 MPa, and the curing time was 1.5 h; the high-temperature pyrolysis temperature was 800 ℃, and the pyrolysis time was 3 h.
[0039] (4) HfSi2 powder was used to react and infiltrate one end of a large component after phenolic resin impregnation, curing and high-temperature pyrolysis. The infiltration process parameters were 1800℃ / 1h.
[0040] Example 2
[0041] A low-cost method for preparing large-size components from ultra-high temperature ceramic matrix composites, the specific steps of which are as follows:
[0042] (1) For a density of 0.6 g / cm³ 3Large-size needle-punched carbon fiber preforms were preheated at 1800℃ for 2 hours, and then a pyrolytic carbon interface layer was deposited on the fiber surface of the preforms using chemical vapor deposition. The carbon source was propylene, the carrier gas was nitrogen, and the preferred deposition temperature was 900℃. The density of the preform after pyrolytic carbon deposition was 1.05 g / cm³. 3 .
[0043] (2) One end of a large-sized component was impregnated, cured, and subjected to high-temperature pyrolysis using a zirconium-silicon integrated ceramic precursor (a molar ratio of polyzirconium carbide, polycarbosilane, and phenolic resin of 1:0.5:3). The curing temperature was 200℃ and the time was 1 hour; the high-temperature pyrolysis temperature was 1200℃ and the time was 1 hour.
[0044] (3) The other end of a large-size carbon fiber preform with a pyrolytic carbon interface layer deposited on it was impregnated with phenolic resin, and then cured and subjected to high-temperature pyrolysis. The impregnation temperature was room temperature, the vacuum impregnation pressure was 50 kPa, and the impregnation time was 1.5 h; the curing temperature was 220 ℃, the curing pressure was 4 MPa, and the curing time was 1.5 h; the high-temperature pyrolysis temperature was 800 ℃, and the pyrolysis time was 3 h.
[0045] (4) ZrSi2 powder was used to react and infiltrate one end of a large component after phenolic resin impregnation, curing and high-temperature pyrolysis. The infiltration process parameters were 1750℃ / 1h.
[0046] The specific embodiments of the present invention disclosed above are intended to help understand the content of the present invention and to implement it accordingly. Those skilled in the art will understand that various substitutions, changes, and modifications are possible without departing from the spirit and scope of the present invention. The present invention should not be limited to the content disclosed in the embodiments of this specification; the scope of protection of the present invention is defined by the claims.
Claims
1. A method for preparing large-size components of ultra-high temperature ceramic matrix composites at low cost, comprising the following steps: A pyrolytic carbon interface layer was deposited on the fiber surface of large-size carbon fiber preforms using chemical vapor deposition; the density of the carbon fiber preforms after pyrolytic carbon deposition was 0.9-1.1 g / cm³. 3 ; The PIP process for large-size components includes: impregnating, curing, and high-temperature pyrolysis one end of the large-size carbon fiber preform after depositing a pyrolytic carbon interface layer with a hafnium silicon integrated ceramic precursor solution or a zirconium silicon integrated ceramic precursor solution; The large-size component RMI process includes: based on the PIP process, impregnating the other end of the large-size carbon fiber preform component with phenolic resin, followed by curing and high-temperature pyrolysis. The porous low-density C / C substrate obtained after impregnation with the phenolic resin has a density of 1.2-1.4 g / cm³. 3 The other end is then embedded with a high-temperature alloy infiltration agent for reactive melting and infiltration to obtain a large-size ceramic matrix composite component. The high-temperature alloy infiltration agent is hafnium silicon alloy powder or zirconium silicon alloy powder. When one end of the large-size carbon fiber preform component uses a hafnium silicon integrated ceramic precursor solution, the other end of the large-size carbon fiber preform component uses hafnium silicon alloy powder as the high-temperature alloy infiltration agent. When one end of the large-size carbon fiber preform component uses a zirconium silicon integrated ceramic precursor solution, the other end of the large-size carbon fiber preform component uses zirconium silicon alloy powder as the high-temperature alloy infiltration agent. This ensures that the two ends of the prepared large-size ceramic matrix composite component have the same composition, and will not generate large stress due to abrupt changes in composition during high-temperature applications.
2. The preparation method according to claim 1, characterized in that, The carbon source used in the chemical vapor deposition method is propylene, the carrier gas is nitrogen, the deposition temperature is 800-1100℃, and the deposition time depends on the density of the carbon fiber preform after pyrolysis carbon deposition.
3. The preparation method according to claim 1, characterized in that, The hafnium-silicon integrated ceramic precursor solution comprises polyhafnium carbide, polycarbosilane, and phenolic resin, with a molar ratio of 1:(0.25-4):(2-6); the zirconium-silicon integrated ceramic precursor solution comprises polyzirconium carbide, polycarbosilane, and phenolic resin, with a molar ratio of 1:(0.25-4):(2-6); the viscosity of the hafnium-silicon integrated ceramic precursor solution or the zirconium-silicon integrated ceramic precursor solution is 50-500 mPa·s.
4. The preparation method according to claim 1, characterized in that, The curing temperature of the hafnium-silicon integrated ceramic precursor solution or the zirconium-silicon integrated ceramic precursor solution is 200-300℃, and the time is 1-10h; the high-temperature pyrolysis temperature in the impregnation, curing, and high-temperature pyrolysis process is 1200-1800℃, and the time is 1-5h.
5. The preparation method according to claim 1, characterized in that, The phenolic resin is vacuum impregnated for 1-3 hours under a vacuum of 5-100 kPa; the curing temperature and high-temperature pyrolysis are 100-350℃, 3-10 MPa, and 0.5-2 hours, respectively; the high-temperature pyrolysis temperature is 700-1000℃ and the pyrolysis time is 2-4 hours.
6. The preparation method according to claim 1, characterized in that, The atomic weight percentage of hafnium or zirconium in the hafnium-silicon alloy powder or zirconium-silicon alloy powder is 10-39%.
7. The preparation method according to claim 1, characterized in that, The reaction melting temperature is 1600-1800℃, and the holding time is 1-2h.
8. The preparation method according to claim 1, characterized in that, The carbon fiber preform is a needle-punched preform with a density of 0.45-0.65 g / cm³. 3 ; and / or preheat the carbon fiber preform at a high temperature of 1800-2000℃ and for 2-3 hours before depositing the pyrolytic carbon interface layer.
9. Large-size components of ultra-high temperature ceramic matrix composites prepared by the method according to any one of claims 1-8.
Citation Information
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