CN117602957A - Preparation method of C/SiC composite material - Google Patents
Preparation method of C/SiC composite material Download PDFInfo
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- CN117602957A CN117602957A CN202311811290.3A CN202311811290A CN117602957A CN 117602957 A CN117602957 A CN 117602957A CN 202311811290 A CN202311811290 A CN 202311811290A CN 117602957 A CN117602957 A CN 117602957A
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- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 210000001170 unmyelinated nerve fiber Anatomy 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 39
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 238000000280 densification Methods 0.000 claims abstract description 25
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 5
- 229920003257 polycarbosilane Polymers 0.000 claims description 70
- 239000007787 solid Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002296 pyrolytic carbon Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011858 nanopowder Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 11
- 239000008096 xylene Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 229910052582 BN Inorganic materials 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000005501 phase interface Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 2
- 238000005336 cracking Methods 0.000 description 37
- 238000000151 deposition Methods 0.000 description 15
- 239000012298 atmosphere Substances 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical group ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000009958 sewing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
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- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the technical field of preparation of aerospace thermostructural materials, and particularly discloses a preparation method of a C/SiC composite material. The preparation method of the invention uses the C fiber preform as a reinforcing phase, uses PCS/VHPCS complex phase precursor slurry as a first impregnant, and carries out a first round of PIP cyclic densification treatment to prepare an intermediate; and performing a second round of PIP cyclic densification treatment on the prepared intermediate by taking the polymer silicon carbide precursor without powder as a second impregnant to prepare the C/SiC composite material. The preparation method effectively shortens the preparation period of the PIP process of the C/SiC composite material on the basis of ensuring the mechanical property of the composite material.
Description
Technical Field
The invention belongs to the technical field of preparation of aerospace thermostructural materials, and particularly relates to a preparation method of a C/SiC composite material.
Background
The continuous fiber toughened C/SiC ceramic matrix composite material has the characteristics of high temperature resistance, low density, high strength and the like, and is an important candidate material for aerospace hot end components and hypersonic aircraft heat protection systems. The theoretical long-term use temperature of the carbon fiber can reach 2600 ℃, and the domestic carbon fiber industry is well developed, the technical monopoly is broken gradually, the cost is reduced rapidly, and the method has important significance for the development and application of the C/SiC composite material in the field of aerospace thermal structural materials.
Currently, the preparation of C/SiC ceramic matrix composites is mainly performed by a precursor impregnation cracking process (PIP). The PIP technology has the problems of high porosity and the like due to limited impregnation efficiency of the precursor and escape of cracking products, so that repeated impregnation and cracking are needed to realize densification of the C/SiC composite material matrix. The above characteristics of the PIP process result in longer cycle times required in the preparation of C/SiC composites, which is detrimental to their engineering application in the preparation of advanced hot side components.
Aiming at the defect of long period of the current preparation of the C/SiC composite material by adopting the PIP process, the invention aims to provide a method for preparing the C/SiC composite material so as to effectively shorten the preparation period of the PIP process.
Disclosure of Invention
The invention aims to provide a preparation method of a C/SiC composite material, and the prepared C/SiC composite material and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
In a first aspect, the present invention provides a method for preparing a C/SiC composite material, the method comprising the steps of:
taking a C fiber preform as a reinforcing phase, and taking PCS/VHPCS complex-phase precursor slurry as a first impregnant to perform a first round of PIP cyclic densification treatment to prepare a composite material intermediate;
then, taking a polymer silicon carbide precursor as a second impregnant, and carrying out second round PIP cyclic densification treatment on the prepared composite material intermediate to prepare a C/SiC composite material;
the PCS/VHPCS complex-phase precursor slurry is slurry containing solid Polycarbosilane (PCS), liquid vinyl perhydro polycarbosilane (VHPCS) and SiC nano powder; and/or the number of the groups of groups,
the polymer silicon carbide precursor is solid polycarbosilane solution or liquid vinyl perhydro polycarbosilane or mixed liquid of liquid vinyl perhydro polycarbosilane and solid polycarbosilane. The second impregnant does not contain SiC nano powder.
As one embodiment of the invention, the first round of PIP cycle densification comprises 3 PIP cycles; and/or, the second round of PIP cycle densification comprises 3-5 PIP cycles.
Wherein, a PIP cycle refers to a PIP treatment operation, namely, a vacuum impregnation treatment and a pyrolysis treatment are performed, specifically: vacuum impregnation is carried out in an impregnant, then the impregnant is placed into a cracking furnace, and high-temperature cracking is carried out in an inert atmosphere.
As a specific embodiment of the invention, the preparation method of the C/SiC composite material provided by the invention comprises the following steps:
firstly, vacuum dipping a C fiber preform with an interface layer structure deposited on the surface in a first impregnant, then placing the C fiber preform into a cracking furnace, and performing high-temperature cracking in an inert atmosphere to finish PIP circulation; vacuum impregnating the C fiber preform subjected to the primary PIP circulation treatment in a first impregnant, then placing the C fiber preform into a cracking furnace, and performing high-temperature cracking in an inert atmosphere to complete secondary PIP circulation; and then, performing PIP circulation for 3 times to prepare a composite material intermediate;
then, vacuum impregnating the composite material intermediate in a second impregnant, then placing the composite material intermediate into a cracking furnace, and performing high-temperature cracking under inert atmosphere to complete PIP circulation; vacuum impregnating the intermediate subjected to the primary PIP circulation treatment in a second impregnant, then placing the intermediate into a cracking furnace, and performing high-temperature cracking in an inert atmosphere to complete the secondary PIP circulation; and by analogy, PIP circulation is carried out for 3-5 times, and the C/SiC composite material is prepared.
As one embodiment of the invention, in the first round of PIP cyclic densification treatment, the time of vacuum impregnation is 15-30 hours, and the treatment temperature of pyrolysis is 800-1500 ℃; preferably, in the first round of PIP cyclic densification treatment, the treatment temperature of pyrolysis is 1100-1300 ℃.
As one embodiment of the invention, in the second round of PIP cyclic densification treatment, the time of vacuum impregnation is 15-30 hours, and the treatment temperature of pyrolysis is 800-1500 ℃; preferably, in the second round of PIP cyclic densification treatment, the treatment temperature of pyrolysis is 1100-1300 ℃.
As one embodiment of the invention, in the PCS/VHPCS complex phase precursor slurry, the mass ratio of the solid polycarbosilane to the liquid vinyl perhydro polycarbosilane is 1 (0.5-10), preferably 1 (1-5), more preferably 1 (3-5), and even more preferably 1:4.
As one embodiment of the invention, in the PCS/VHPCS complex phase precursor slurry, the mass of the SiC nano powder is 1-15%, preferably 5-12%, more preferably 9-11%, and even more preferably 10% of the total mass of the solid polycarbosilane and the liquid vinyl perhydro polycarbosilane.
As one embodiment of the invention, the PCS/VHPCS complex-phase precursor slurry is further added with a solvent, wherein the solvent is selected from any one or more of dimethylbenzene, normal hexane, tetrahydrofuran and butyl ether, and preferably the solvent is dimethylbenzene.
As one embodiment of the invention, the amount of the solvent in the PCS/VHPCS complex phase precursor slurry is as follows: the mass ratio of the solvent to the solid polycarbosilane is (0.1 to 10): 1, preferably (0.25 to 9): 1, more preferably (0.8 to 2): 1, still more preferably (0.8 to 1.3): 1, and still more preferably 1:1.
As one embodiment of the invention, when the second impregnant is a solid polycarbosilane solution, the solid polycarbosilane solution is a xylene solution of the solid polycarbosilane, and the mass percentage concentration is 45-55%.
In one embodiment of the present invention, the second impregnating agent is a mixture of liquid vinylperhydro polycarbosilane and solid polycarbosilane, wherein the liquid vinylperhydro polycarbosilane and solid polycarbosilane are mixed in a mass ratio of (2 to 5): 1, preferably in a mass ratio of (3 to 5): 1.
As an embodiment of the present invention, the C-fiber preform is selected from the group consisting of 2D, 2.5D, 3D, C-fiber preforms of needled knit construction.
As one embodiment of the invention, the surface of the C fiber preform is used as a reinforcing phase after being deposited with an interface layer structure; the interface layer is selected from any one of pyrolytic carbon (PyC) interface layer, boron Nitride (BN) interface layer, pyrolytic carbon/SiC (PyC/SiC) complex phase interface layer and boron nitride/SiC complex phase interface layer (BN/SiC).
As a preferred embodiment of the invention, when preparing pyrolytic carbon (PyC) interface layer, a chemical vapor deposition process is adopted, and the gas source is C 3 H 6 Depositing at 800-1000 deg.c and 0.5-4 kPa for 2-60 hr, and depositing C 3 H 6 The flow is 200-800L/h, and the argon flow is 200-800L/h.
As a preferred embodiment of the invention, when preparing the Boron Nitride (BN) interface layer, a chemical vapor deposition process is adopted, the gas source is boron trichloride and ammonia gas, hydrogen gas is adopted as diluent gas, the deposition temperature is 600-1100 ℃, the deposition pressure is 500-2000 Pa, the deposition time is 1-4 h, the flow of boron trichloride is 0.4-1L/h, the flow of ammonia gas is 1.2-3L/h, and the flow of hydrogen gas is 4-8L/h.
As a preferred embodiment of the invention, when preparing the SiC interface layer, a chemical vapor deposition process is adopted, methyl trichlorosilane is adopted as a gas source, hydrogen is adopted as a carrier gas, the deposition temperature is 900-1200 ℃, the pressure is 4-12 kPa, the deposition time is 1-20 hours, and the flow mole ratio of the methyl trichlorosilane to the hydrogen is 1 (4-12).
In a second aspect, the invention provides a C/SiC composite material obtained by the preparation method.
In a third aspect, the invention provides the use of a C/SiC composite material obtainable by the method of the invention, wherein the use comprises the use as an aerospace thermostructural material.
Aiming at the defect of long PIP process route period of the current C/SiC composite material, the preparation method provided by the invention uses solid Polycarbosilane (PCS) and liquid vinyl perhydro polycarbosilane (VHPCS) to prepare a complex phase silicon carbide precursor, and disperses a proper amount of SiC nano powder therein to prepare PCS/VHPCS complex phase precursor slurry which is used as a first matrix impregnant, carries out the first 3 PIP cycles of a carbon fiber preform (namely the C fiber preform), then uses a polymer silicon carbide precursor without powder as a second matrix impregnant, and carries out the subsequent PIP cycles.
In addition, the method can fully utilize the productivity advantages of PCS and SiC nano powder, fully exert the advantages of VHPCS, such as easy crosslinking and solidification, high ceramic yield and the like, and is beneficial to engineering application of the method.
The beneficial effects of the invention are as follows:
(1) The C/SiC composite material prepared by the invention has excellent basic mechanical property which is not lower than 80% of the performance of the C/SiC composite material prepared by the conventional PIP process.
(2) The preparation of the C/SiC composite material only needs 6-8 PIP cycles, and compared with the conventional 12-15 PIP cycles using PCS organic solution as impregnant, the preparation method has the advantage that the period is obviously shortened.
(3) The invention can shorten the cost for preparing the C/SiC composite material, and the cost of the SiC nano powder is lower than that of the precursor derived SiC, so that the preparation cost of the composite material can be further reduced by introducing part of SiC nano powder.
(4) The method can fully utilize the productivity advantages of PCS and SiC nano powder, fully exert the advantages of VHPCS, such as easy crosslinking and solidification, high ceramic yield and the like, and is beneficial to engineering application of the method.
Drawings
FIG. 1 is a SEM topography of a fracture of a C/SiC composite material prepared in example 2 of the present invention;
FIG. 2 is a graph showing comparison of matrix weight gain curves of the C/SiC composite material prepared in example 1 of the present invention obtained in experimental example 1 of the present invention and the C/SiC composite material prepared by a conventional process;
FIG. 3 is a graph showing the comparison of the normal temperature mechanical properties of the C/SiC composites prepared in example 1 and example 2 according to the present invention obtained in Experimental example 2 of the effect of the present invention and the C/SiC composites prepared by the conventional process.
Detailed Description
The technical scheme of the invention is described in further detail below. It should be apparent to those skilled in the art that the detailed description is merely provided to aid in understanding the invention and should not be taken as limiting the invention in any way.
Unless otherwise indicated, the technical means used in the following examples are conventional means well known to those skilled in the art, and all the raw materials used are commercially available conventional products.
Example 1
The embodiment provides a C/SiC composite material, and the preparation method comprises the following steps:
(1) Cutting out C fiber cloth 14 blocks with the size of 100mm multiplied by 100mm, and sewing to prepare a C fiber preform with a two-dimensional structure (2D).
(2) Preparing a Boron Nitride (BN) interface layer on the surface of the C fiber preform by deposition, and adopting a chemical vapor deposition process, wherein the gas source is boron trichloride (BCl) 3 ) And ammonia gas, wherein hydrogen gas is used as diluent gas, the deposition temperature is 900 ℃, the deposition pressure is 800Pa, the deposition time is 4h, the flow of boron trichloride is 0.8L/h, the flow of ammonia gas is 1.2L/h, and the flow of hydrogen gas is 6L/h.
(3) Performing a first round of PIP cyclic densification treatment on the C fiber preform with the surface deposited with a Boron Nitride (BN) interface layer, and adopting PCS/VHPCS complex-phase precursor slurry as a first impregnant;
the preparation method of the first impregnant comprises the following steps: firstly, preparing 400g of solid Polycarbosilane (PCS) xylene solution with the concentration of 50wt%, mixing the solution with 800g of liquid vinyl perhydro polycarbosilane (VHPCS) and 100g of SiC nano powder, and mechanically stirring uniformly to obtain a first impregnant;
vacuum dipping (the relative vacuum degree is less than or equal to minus 0.8 bar) the C fiber preform with the Boron Nitride (BN) interface layer deposited on the surface in a first dipping agent for 20h, placing the dipped C fiber preform in a cracking furnace, and carrying out high-temperature cracking for 1h at 1250 ℃ in nitrogen inert atmosphere to complete one PIP cycle; vacuum impregnating the C fiber preform subjected to primary PIP circulation treatment in a first impregnant for 20h, then placing the C fiber preform into a cracking furnace, and carrying out high-temperature cracking for 1h at 1250 ℃ in a nitrogen atmosphere to complete secondary PIP circulation; and by analogy, carrying out PIP circulation for 3 times to obtain the intermediate of the composite material.
(4) Performing a second round of PIP cyclic densification treatment on the composite material intermediate prepared in the step (3), adopting liquid vinyl perhydro polycarbosilane (VHPCS) as a second impregnant, performing PIP cyclic treatment for 3 times, namely performing vacuum impregnation (the relative vacuum degree is less than or equal to-0.8 bar) on the intermediate in the second impregnant for 20h, placing the impregnated intermediate in a cracking furnace, and performing high-temperature cracking for 2h at 1250 ℃ under nitrogen inert atmosphere to complete one PIP cyclic treatment; vacuum impregnating the intermediate subjected to primary PIP circulation treatment in a second impregnant for 20h, then placing the intermediate into a cracking furnace, and carrying out high-temperature cracking for 2h at 1250 ℃ in a nitrogen atmosphere to complete secondary PIP circulation; and by analogy, PIP circulation is carried out for 3 times, and the C/SiC composite material is prepared.
Example 2
The embodiment provides a C/SiC composite material, and the preparation method comprises the following steps:
(1) Cutting out C fiber cloth 14 blocks with the size of 100mm multiplied by 100mm, and sewing to prepare a C fiber preform with a two-dimensional structure (2D).
(2) Preparing pyrolytic carbon (PyC) interface layer by depositing on the surface of the C fiber preform, adopting a chemical vapor deposition process, wherein the air source is C 3 H 6 Depositing for 20h at 980 ℃ under 800Pa, C 3 H 6 The flow is 8L/min, and the argon flow is 8L/min.
(3) Performing a first round of PIP cyclic densification treatment on a C fiber preform with a surface deposited with a pyrolytic carbon (PyC) interface layer, and adopting PCS/VHPCS complex phase precursor slurry as a first impregnant;
the preparation method of the first impregnant comprises the following steps: firstly, preparing 400g of solid Polycarbosilane (PCS) xylene solution with the concentration of 50wt%, mixing the solution with 800g of liquid vinyl perhydro polycarbosilane (VHPCS) and 100g of SiC nano powder, and mechanically stirring uniformly to obtain a first impregnant;
vacuum impregnating a C fiber preform with a pyrolytic carbon (PyC) interface layer deposited on the surface in a first impregnant (the relative vacuum degree is less than or equal to-0.8 bar) for 25h, placing the impregnated C fiber preform in a cracking furnace, and carrying out high-temperature cracking for 0.5h at 1250 ℃ in an inert nitrogen atmosphere to complete PIP circulation; vacuum impregnating the C fiber preform subjected to primary PIP circulation treatment in a first impregnant for 25h, then placing the C fiber preform into a cracking furnace, and carrying out high-temperature cracking at 1250 ℃ for 0.5h in a nitrogen atmosphere to complete secondary PIP circulation; and by analogy, carrying out PIP circulation for 3 times to obtain the intermediate of the composite material.
(4) Carrying out a second round of PIP cyclic densification treatment on the intermediate prepared in the step (3), adopting a solid polycarbosilane xylene solution with the concentration of 50wt% as a second impregnant, carrying out PIP cyclic treatment for 4 times, namely carrying out vacuum impregnation (the relative vacuum degree is less than or equal to-0.8 bar) on the intermediate in the second impregnant for 20h, placing the impregnated intermediate in a cracking furnace, and carrying out high-temperature cracking for 0.5h at 1250 ℃ under nitrogen inert atmosphere to complete one PIP cyclic treatment; vacuum impregnating the intermediate subjected to primary PIP circulation treatment in a second impregnant for 20h, then placing the intermediate into a cracking furnace, and carrying out high-temperature cracking for 0.5h at 1250 ℃ in a nitrogen atmosphere to complete secondary PIP circulation; and by analogy, carrying out PIP circulation for 4 times, and preparing the C/SiC composite material.
Example 3
The embodiment provides a C/SiC composite material, and the preparation method comprises the following steps:
(1) Cutting out C fiber cloth 14 blocks with the size of 100mm multiplied by 100mm, and sewing to prepare a C fiber preform with a two-dimensional structure (2D).
(2) Preparing pyrolytic carbon (PyC) interface layer by depositing on the surface of the C fiber preform, adopting a chemical vapor deposition process, wherein the air source is C 3 H 6 Depositing at 980 deg.C and 800Pa for 40h, C 3 H 6 The flow is 8L/min, and the argon flow is 8L/min.
(3) Performing a first round of PIP cyclic densification treatment on a C fiber preform with a surface deposited with a pyrolytic carbon (PyC) interface layer, and adopting PCS/VHPCS complex phase precursor slurry as a first impregnant;
the preparation method of the first impregnant comprises the following steps: firstly, preparing 400g of solid Polycarbosilane (PCS) xylene solution with the concentration of 50wt%, mixing the solution with 800g of liquid vinyl perhydro polycarbosilane (VHPCS) and 100g of SiC nano powder, and mechanically stirring uniformly to obtain a first impregnant;
vacuum impregnating a C fiber preform with a pyrolytic carbon (PyC) interface layer deposited on the surface in a first impregnant (the relative vacuum degree is less than or equal to-0.8 bar) for 30h, placing the impregnated C fiber preform in a cracking furnace, and carrying out high-temperature cracking for 1h at 1250 ℃ in an inert nitrogen atmosphere to complete PIP circulation; vacuum impregnating the C fiber preform subjected to primary PIP circulation treatment in a first impregnant for 20h, then placing the C fiber preform into a cracking furnace, and carrying out high-temperature cracking for 1h at 1250 ℃ in a nitrogen atmosphere to complete secondary PIP circulation; and by analogy, carrying out PIP circulation for 3 times to obtain the intermediate.
(4) Performing a second round of PIP cyclic densification treatment on the intermediate prepared in the step (3), and performing 3 times of PIP cyclic treatment by using a liquid vinyl perhydro polycarbosilane and solid polycarbosilane mixed solution (the liquid vinyl perhydro polycarbosilane and the solid polycarbosilane are mixed according to the mass ratio of 4:1) as a second impregnant, namely performing vacuum impregnation (the vacuum degree is less than or equal to-0.8 bar) on the intermediate in the second impregnant for 20 hours, and then placing the impregnated intermediate in a cracking furnace, and performing high-temperature cracking for 1 hour at 1250 ℃ under nitrogen inert atmosphere to complete one PIP cycle; vacuum impregnating the intermediate subjected to primary PIP circulation treatment in a second impregnant for 20h, then placing the intermediate into a cracking furnace, and carrying out high-temperature cracking for 1h at 1250 ℃ in a nitrogen atmosphere to complete secondary PIP circulation; and by analogy, PIP circulation is carried out for 3 times, and the C/SiC composite material is prepared.
The SEM morphology of the fracture of the C/SiC composite material prepared in the embodiment 2 is shown in the figure 1, and obvious phenomena of fiber pulling, debonding, gradient peeling of interfaces and the like can be observed, so that the C/SiC composite material prepared by the process has better toughening performance.
Experimental example 1 of Effect
The C/SiC composite material prepared in the embodiment 1 of the invention is compared with the C/SiC composite material prepared by the conventional PIP process in a matrix weight gain curve, and the comparison chart is shown in figure 2.
As can be seen from fig. 2, the weight gain effect of example 1 after 6 PIP cycles can reach the weight gain effect of the matrix after 11 PIP cycles using the conventional process of PCS xylene solution.
The preparation method of the C/SiC composite material prepared by using the conventional PIP process is different from the preparation method of the embodiment 1 of the invention in that: when the C fiber preform with the Boron Nitride (BN) interface layer deposited on the surface is subjected to PIP cyclic densification treatment, a solid polycarbosilane xylene solution with the concentration of 50wt% is adopted as an impregnant, and PIP is carried out for 11 times to prepare the C/SiC composite material.
Experimental example 2 of Effect
The C/SiC composite materials prepared in the embodiment 1 and the embodiment 2 of the invention are subjected to normal-temperature mechanical property comparison with the C/SiC composite material prepared by using a conventional PIP process, wherein the mechanical property test is carried out according to GBT 6569-2006 related standards.
The comparison of the normal temperature mechanical properties of the C/SiC composite materials prepared in the example 1 and the example 2 and the C/SiC composite materials prepared by the conventional process is shown in FIG. 3. It can be seen from FIG. 3 that the C/SiC composites prepared by the conventional process had flexural strength of 358.2MPa, whereas the C/SiC composites prepared in examples 1 and 2 had flexural strength at room temperature of 322.8MPa and 337.2MPa, respectively, which reached 90% and 94% of the former.
The preparation method of the C/SiC composite material prepared by using the conventional PIP process is different from the preparation method of the embodiment 1 of the invention in that: when the C fiber preform with the Boron Nitride (BN) interface layer deposited on the surface is subjected to PIP cyclic densification treatment, a solid polycarbosilane xylene solution with the concentration of 50wt% is adopted as an impregnant, and PIP is carried out for 11 times to prepare the C/SiC composite material.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the invention. The embodiments of the present application and features in the embodiments may be combined with each other arbitrarily without conflict.
Claims (10)
1. A method for preparing a C/SiC composite material, the method comprising the steps of:
taking a C fiber preform as a reinforcing phase, and adopting PCS/VHPCS complex-phase precursor slurry as a first impregnant to perform a first round of PIP cyclic densification treatment to prepare an intermediate;
then, taking a polymer silicon carbide precursor as a second impregnant, and carrying out PIP cyclic densification treatment on the intermediate in a second round to prepare a C/SiC composite material;
the PCS/VHPCS complex-phase precursor slurry is slurry containing solid polycarbosilane, liquid vinyl perhydro polycarbosilane and SiC nano powder; and/or the number of the groups of groups,
the polymer silicon carbide precursor is solid polycarbosilane solution or liquid vinyl perhydro polycarbosilane and solid polycarbosilane mixed solution.
2. The method of manufacturing according to claim 1, wherein the first round of PIP cycle densification comprises 3 PIP cycles; and/or, the second round of PIP cycle densification comprises 3-5 PIP cycles.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of solid polycarbosilane to liquid vinyl perhydro polycarbosilane in the PCS/VHPCS multiphase precursor slurry is 1 (0.5-10), preferably 1 (1-5), more preferably 1 (3-5); and/or the number of the groups of groups,
in the PCS/VHPCS multiphase precursor slurry, the mass of the SiC nano powder is 1-15% of the total mass of the solid polycarbosilane and the liquid vinyl perhydro polycarbosilane, preferably 5-12%, and more preferably 9-11%.
4. The preparation method according to claim 3, wherein a solvent is further added to the PCS/VHPCS complex phase precursor slurry, the solvent is selected from any one or more of xylene, n-hexane, tetrahydrofuran, and butyl ether, and preferably the solvent is xylene; and/or the number of the groups of groups,
the dosage of the solvent is as follows: the mass ratio of the solvent to the solid polycarbosilane is (0.1 to 10): 1, preferably (0.25 to 9): 1, more preferably (0.8 to 2): 1, and even more preferably (0.8 to 1.3): 1.
5. The method according to any one of claims 1 to 4, wherein when the second impregnating agent is a solid polycarbosilane solution, the solid polycarbosilane solution is a xylene solution of solid polycarbosilane, and the mass percentage concentration is 45 to 55%; and/or the number of the groups of groups,
when the second impregnant is a mixed liquid of liquid vinyl perhydro polycarbosilane and solid polycarbosilane, the liquid vinyl perhydro polycarbosilane and the solid polycarbosilane are mixed according to the mass ratio of (2-5): 1.
6. The method of any one of claims 1-5, wherein the C-fiber preform is selected from the group consisting of 2D, 2.5D, 3D, C-fiber preforms of needled knit construction.
7. The method of claim 6, wherein the surface of the C-fiber preform is deposited with an interfacial layer structure and then used as a reinforcing phase; the interface layer is selected from any one of pyrolytic carbon interface layer, boron nitride interface layer, pyrolytic carbon/SiC complex phase interface layer and boron nitride/SiC complex phase interface layer.
8. The method according to claim 1 or 2, wherein in the first round of PIP cyclic densification, the time of vacuum impregnation is 15 to 30 hours, and the treatment temperature of pyrolysis is 800 to 1500 ℃; and/or, in the second round of PIP circulating densification treatment, the time of vacuum impregnation is 15-30 hours, and the treatment temperature of pyrolysis is 800-1500 ℃.
9. A C/SiC composite material obtainable by the method of any one of claims 1 to 8.
10. Use of the C/SiC composite of claim 9 as an aerospace thermostructural material.
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