CN117945764A - SiBCN interface layer, siBCN interface layer protection SiCfSiC ceramic matrix composite and preparation method thereof - Google Patents
SiBCN interface layer, siBCN interface layer protection SiCfSiC ceramic matrix composite and preparation method thereof Download PDFInfo
- Publication number
- CN117945764A CN117945764A CN202410035940.8A CN202410035940A CN117945764A CN 117945764 A CN117945764 A CN 117945764A CN 202410035940 A CN202410035940 A CN 202410035940A CN 117945764 A CN117945764 A CN 117945764A
- Authority
- CN
- China
- Prior art keywords
- sic
- sibcn
- interface layer
- temperature
- fiber preform
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011153 ceramic matrix composite Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 claims abstract description 133
- 239000000463 material Substances 0.000 claims abstract description 84
- 238000000151 deposition Methods 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 33
- 230000006641 stabilisation Effects 0.000 claims abstract description 30
- 238000011105 stabilization Methods 0.000 claims abstract description 30
- 230000008021 deposition Effects 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003085 diluting agent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000012159 carrier gas Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 222
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 221
- 238000000034 method Methods 0.000 claims description 61
- 230000008595 infiltration Effects 0.000 claims description 50
- 238000001764 infiltration Methods 0.000 claims description 50
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 42
- 238000005336 cracking Methods 0.000 claims description 37
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 31
- 238000000280 densification Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000001723 curing Methods 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 11
- 239000012895 dilution Substances 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 9
- 238000005475 siliconizing Methods 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000005720 sucrose Substances 0.000 claims description 7
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003502 gasoline Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000009941 weaving Methods 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 49
- 238000005452 bending Methods 0.000 description 27
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 238000007598 dipping method Methods 0.000 description 21
- 239000002131 composite material Substances 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 15
- 238000005229 chemical vapour deposition Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 5
- 229910015844 BCl3 Inorganic materials 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000011226 reinforced ceramic Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 4
- 230000004584 weight gain Effects 0.000 description 4
- 235000019786 weight gain Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 229920003257 polycarbosilane Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 239000011184 SiC–SiC matrix composite Substances 0.000 description 1
- ZQOBAJVOKBJPEE-UHFFFAOYSA-N [B].[C].[N].[Si] Chemical compound [B].[C].[N].[Si] ZQOBAJVOKBJPEE-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
The invention relates to a SiBCN interface layer, siBCN interface layer protection SiCf/SiC ceramic matrix composite material and a preparation method thereof. The preparation method of the SiBCN interface layer comprises the following steps: (1) Fixing the fiber preform by using a clamp, placing the fiber preform in a reaction chamber in a furnace, heating the fiber preform to a deposition temperature of 600-850 ο ℃ in a vacuum state, and preserving the temperature for 0.5-2 h; (2) The preparation method comprises the steps of taking CH 3Cl3 Si as a silicon source and a carbon source, taking BCl 3 as a boron source, taking NH 3 as a nitrogen source, taking H 2 as diluent gas and carrier gas, taking Ar as diluent gas, controlling NH 3 and BCl 3 to be respectively conveyed into a reaction chamber through different conveying pipelines, depositing for 2-20H at the temperature of 0.01-3 KPa and the temperature of 600-850 ℃, and preparing SiBCN interface layers on the surfaces of fibers in a fiber preform; (3) And carrying out stabilization treatment on the fiber preform deposited with the SiBCN interface layer to obtain the high-performance SiBCN interface layer.
Description
Technical Field
The invention relates to a high-performance SiBCN interface layer, a SiBCN interface layer-protected SiC fiber reinforced SiC ceramic matrix composite and a preparation method thereof, and belongs to the technical field of fiber reinforced ceramic matrix composite preparation.
Background
The SiC f/SiC ceramic matrix composite is a novel high-temperature heat structural material, has high specific strength and modulus, low density, excellent thermochemical stability performance, oxidation resistance and other performances, and is successfully applied to high-temperature structural members such as a turbine outer ring, a combustion chamber lining, turbine blades, a tail nozzle regulating sheet, a sealing sheet and the like of an aeroengine. The structural members need to withstand complex environments such as repeated flushing of high-temperature fuel gas for a long time in the use process, and the stability of the materials in the high-temperature oxidation environment plays a decisive influence factor on the successful use of the materials. The interfacial phase is taken as an important component in the whole SiC f/SiC ceramic matrix composite material, plays a key role in effectively playing the mechanical property of the material, and is particularly important in developing the interfacial phase.
Silicon boron carbon nitrogen (SiBCN) ceramic is a high-temperature structural ceramic material, and has excellent high-temperature resistance, thermal shock resistance, creep resistance, oxidation resistance and ablation resistance, and the oxidation resistance is superior to that of the traditional SiC and Si 3N4 ceramic. In recent years, the use of interfacial layers and matrix phases as ceramic matrix composites has received attention and intense research from many practitioners. Currently, methods for preparing SiBCN ceramics mainly comprise a chemical vapor deposition method, a polymer cracking method, a mechanical alloy method and the like. In the polymer cracking method, small molecules overflow in the high-temperature cracking process of the precursor, so that the generated SiBCN interface layer is easily undensified and porous on the surface, and cracks are easily formed on the surface, so that the fiber cannot be completely and effectively protected; the mechanical alloy method is easy to damage SiC fibers because of the need of high-temperature hot-pressing sintering in the preparation process, is only suitable for preparing samples with simple shapes, and is not suitable for complex special-shaped structural members; the chemical vapor deposition method is the preparation method with the most prospect of SiBCN interface coating deposition in the fiber preform due to the remarkable advantages of controllable precursor components and product components, high product purity, low deposition temperature, low damage to the fiber and the like.
There are few reports of the use of a Chemical Vapor Deposition (CVD) process to prepare SiBCN interface coatings and to apply them to ceramic matrix composites. Chinese patent 1 (application number 201310178800.8) discloses a chemical vapor deposition method of Si-B-C-N amorphous ceramic, which uses SiCH 3Cl3 or SiCl 4、BCl3、NH3 as a precursor, uses hydrogen and argon as carrier gas and diluent gas, and successfully prepares a SiBCN interface on the surface of a carbon fiber, but it does not give specific numerical values of material properties when SiBCN is used as an interface coating, and according to the technological parameters and conditions mentioned in the patent, a SiC fiber reinforced ceramic matrix composite with high mechanical properties (three-point bending strength) cannot be obtained on the basis of depositing only the SiBCN interface phase, because the properties of the material are not only determined by the interface phase, the matrix density also determines the requirements of the mechanical properties of the material on the interface phase to a great extent, and the SiC fiber is completely different from the carbon fiber, and the two are not comparable. Chinese patent 2 (application number 202110323658.6) discloses that a chemical vapor deposition method is adopted to prepare a SiBCN interfacial layer, where N 2/Ar is a diluent gas, the white byproducts on the surface of the fiber bundle are obviously reduced, the deposition effect of the interfacial coating is obviously improved, and when H 2/Ar is a diluent gas, the surface of the fiber bundle is wrapped by the white byproducts, and the interface cannot uniformly and effectively wrap the fibers, which can adversely affect the densification of the matrix and the material performance in the later period of the material. Sun Xun in journal Ceramics International, "Effects of CVD SiBCN interphases on mechanical and dielectric properties ofSiCf/SiC composites fabricated via a PIP process",, which adopts borazine and liquid polycarbosilane as precursors to prepare SiBCN interfaces on the surfaces of KD-II SiC fibers and adopts a precursor impregnation cracking method (PIP) to densify the materials, and Polycarbosilane (PCS) is an organic precursor, wherein the prepared SiBCN-containing interface phase SiC/SiC materials have remarkable oxidation resistance, but the three-point bending strength of the materials is remarkably low (only 69.2 MPa), meanwhile, the breaking displacement of the materials is remarkably low, and the mechanical properties of the materials are far from the engineering application use requirements.
Disclosure of Invention
Aiming at the current situation that the mechanical property of the material is low when SiBCN is adopted as an interface phase for the SiC f/SiC ceramic matrix composite material, the invention provides a high-performance SiBCN interface layer and a preparation method thereof, and the SiBCN interface layer protects the SiC f/SiC ceramic matrix composite material. Specifically, the SiBCN interface coating prepared by the method provided by the invention has excellent interface debonding and mechanical transmission effects, the prepared material can meet the application requirements of practical engineering to a certain extent, and the method provided by the invention has strong repeatability, can be effectively regulated and controlled, has simple interface deposition operation, and provides a new research thought and method for further developing an interface phase for SiC f/SiC composite materials.
In a first aspect, the present invention provides a method for preparing a high performance SiBCN interfacial layer, which is characterized by comprising: (1) Fixing the fiber preform by using a clamp, placing the fiber preform in a reaction chamber in a furnace, heating the fiber preform to a deposition temperature of 600-850 ℃ in a vacuum state, and preserving the temperature for 0.5-2 h; (2) The preparation method comprises the steps of taking CH 3Cl3 Si as a silicon source and a carbon source, taking BCl 3 as a boron source, taking NH 3 as a nitrogen source, taking H 2 as diluent gas and carrier gas, taking Ar as diluent gas, controlling NH 3 and BCl 3 to be respectively conveyed into a reaction chamber through different conveying pipelines, depositing for 2-20H at the temperature of 0.01-3 KPa and the temperature of 600-850 ℃, and preparing SiBCN interface layers on the surfaces of fibers in a fiber preform; (3) Stabilizing the fiber preform deposited with the SiBCN interface layer to obtain the high-performance SiBCN interface layer
Preferably, in step (1), the SiC fiber preform includes: at least one of SiC fiber bundles, siC fiber cloth, siC fiber two-dimensional lamination, siC fiber two-dimensional stitching, siC fiber 3D weaving and SiC fiber 2.5D weaving preform.
Preferably, in step (1), the mold comprises one of a graphite mold, an alumina ceramic mold, a silicon carbide ceramic mold, and a silicon nitride ceramic mold; the vacuum degree in the vacuum state is 5Pa or less, preferably 3Pa or less.
Preferably, in step (1), the temperature increasing system of the deposition temperature includes: the temperature rising rate is 6-10 ℃/min below 500 ℃, and the temperature rising rate is 1-5 ℃/min above 500 ℃.
Preferably, in the step (2), the molar ratio of the NH 3 to the BCl 3 is 0.5-20; the molar ratio of BCl 3 to MTS is 0.1-5; the molar ratio of the diluent gas Ar to the BCl 3 is 5-30; the molar ratio of H 2 to BCl 3 is 0.5-30.
Preferably, in the step (3), the temperature of the stabilizing treatment is 1100-1500 ℃ and the time is 0.5-3 h.
In a second aspect, the present invention provides a SiC fiber preform protected by a SiBCN interface layer prepared according to the preparation method described above, where the thickness of the SiBCN interface layer in the SiC fiber preform protected by the SiBCN interface layer is not more than 2 μm.
In a third aspect, the invention provides a preparation method of a SiBCN interface layer-protected SiC f/SiC ceramic matrix composite, comprising the following steps: (1) Performing preliminary SiC densification on the SiBCN interface layer-protected SiC fiber preform in claim 7 by adopting a chemical vapor infiltration process to obtain a preliminary densified SiBCN interface layer-protected SiC f/SiC ceramic matrix composite; impregnating the obtained primarily densified SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material with a liquid resin solution, taking out, and then solidifying and cracking; (2) Repeating the soaking, curing and cracking in the step (1) for at least 2 times to obtain a carbon-containing porous preform; (3) And carrying out siliconizing treatment on the carbon-containing porous preform by adopting a reaction fusion deposition method to obtain the SiBCN interface layer protection SiC f/SiC ceramic matrix composite.
Preferably, the parameters for preliminary SiC densification using a chemical vapor infiltration process include: adopting trichloromethylsilane as a SiC precursor; the dilution gas is hydrogen and argon, the molar ratio is 1-5, and the total flow of the dilution gas is 1000-4000 ml/min; the carrier gas is hydrogen, and the flow is 100-200 ml/min; the infiltration temperature is 850-1050 ℃, the infiltration pressure is 3-20 KPa, and the infiltration time is 20-100 hours.
Preferably, the liquid resin in the liquid resin solution includes: at least one of phenolic resin, furfural resin and asphalt resin; the organic solvent in the liquid resin solution is at least one of polyethylene glycol solution, ethanol, glycol, glycerol, furfuryl alcohol, gasoline, alcohol, formaldehyde, glucose solution and sucrose solution; preferably, the concentration of the polyethylene glycol solution is 5-20wt%, and the solvent is at least one selected from alcohol, gasoline, glycerol, polyethylene glycol and formaldehyde; preferably, the concentration of the glucose solution is 30-60 wt%, and the solvent is at least one selected from ethylene glycol, glycerol, glucose, furfuryl alcohol and formaldehyde; preferably, the concentration of the sucrose solution is 30-60 wt%, and the solvent is at least one selected from ethanol, glycol, glycerol and sucrose.
Preferably, the vacuum degree of the impregnation is 1-10 KPa, and the impregnation time is 10-120 minutes; the curing temperature is 100-200 ℃, and the curing time is 1-12 hours, preferably 5-12 hours; the cracking temperature is 700-1000 ℃, and the cracking time is 0.5-3 hours, preferably 2-3 hours.
Preferably, the parameters of the siliconizing treatment by adopting the reaction fusion deposition method comprise: the infiltration temperature is 1420-1600 ℃ and the infiltration time is 0.5-2 h.
In a second aspect, the invention provides a SiBCN interface layer protection SiC f/SiC ceramic matrix composite material obtained according to the preparation method.
The invention has the beneficial effects that:
(1) The SiBCN interface phase is prepared in the SiC fiber preform by adopting a low-pressure chemical vapor deposition method, and the effective deflection of the interface relative to the internal cracks of the material can be realized by effectively regulating and controlling the components, thickness, structure and uniformity of the interface phase, so that the interface phase can be effectively debonded, and a good reinforcing and toughening effect is achieved;
(2) According to the invention, the chemical vapor infiltration method is adopted to carry out preliminary SiC densification on the SiBCN interface fiber preform, the effective protection of single-bundle fibers in the fiber preform is realized by regulating and controlling the content of SiC matrix, the erosion to fibers in the siliconizing process by the reactive infiltration method is slowed down by regulating and controlling the porous carbon pore distribution and content in the carbon-containing porous preform, the porosity of the prepared material is obviously reduced by combining the two methods, the mechanical property of the material is improved, the bending strength of the material is not lower than 350MPa, and the mechanical property is far higher than that of the conventional SiBCN interface phase-containing SiC/SiC composite material prepared by adopting the same type of method.
Drawings
FIG. 1 is a cross-sectional low-power scanning electron microscope image of an SiC fiber preform in example 1 of the present invention after SiBCN interfacial phase deposition;
FIG. 2 is an analysis of interfacial energy spectrum (EDS) of the SiC fiber surface SIBCN of example 1 of the present invention;
FIG. 3 is a three-point bend-strain plot of SiBCN interfacial layer protected SiC f/SiC ceramic matrix composites prepared in examples 1,2, and 3 of the present invention;
FIG. 4 is a diagram of a polishing-like scanning electron microscope of SiBCN interfacial layer protected SiC f/SiC ceramic matrix composite prepared in example 3 of the present invention.
Detailed Description
The invention is further illustrated by the following embodiments, it being understood that the following embodiments are merely illustrative of the invention and not limiting thereof.
Aiming at the defect that the performance of the SiC fiber reinforced SiC ceramic matrix composite exists when the existing SiBCN is used as an interface layer, the SiBCN interface coating is prepared on the surface of the SiC fiber by adopting a chemical vapor infiltration method, and the SiBCN interface layer is used for protecting the SiC fiber reinforced SiC ceramic matrix composite by adopting the combination of the chemical vapor infiltration method and the reaction infiltration method.
The preparation method of the SiBCN interface layer protection SiC f/SiC ceramic matrix composite material provided by the invention is exemplified below, and comprises the following steps.
And (3) preparing the SiBCN interface protection SiC fiber preform. And depositing SiBCN on the surface of the SiC fiber preform by using a chemical vapor deposition method to obtain a preliminary SiBCN-containing interface protection SiC fiber preform, and obtaining the SiBCN interface protection SiC fiber preform after stabilizing treatment.
In some embodiments, the SiC fiber preform may be selected from at least one of SiC fiber bundles, siC fiber cloth, siC fiber two-dimensional laminate, siC fiber two-dimensional stitch, siC fiber 3D weave, siC fiber 2.5D weave preform.
In some embodiments, the fiber preform is placed into a vertical chemical vapor deposition furnace, and the precursor is correspondingly introduced into the furnace to obtain the SiBCN coating-protected fiber preform. The chemical vapor deposition method comprises the following steps: fixing the fiber preform by using a graphite clamp, placing the fiber preform in a furnace, vacuumizing and flushing the fiber preform for multiple times, heating the fiber preform to 600-850 ℃ under a vacuum state, and preserving heat for 0.5-2 h (preferably, the heating rate below 500 ℃ is 6-10 ℃/min, and the heating rate above 500 ℃ is 1-5 ℃/min); then, introducing chemical vapor deposition precursor gas, and depositing for 2-20 h at the temperature of between 600 and 850 ℃ and 0.01 and 3 KPa.
Wherein, in the chemical vapor deposition precursor gas: CH 3Cl3 Si (trichloromethylsilane, MTS) is a silicon source and a carbon source, and the flow is 100-300ml/min; BCl 3 is a boron source, and the flow is 10-1500ml/min; NH 3 is a nitrogen source, and the flow is 50-6000ml/min; h 2 is dilution gas and carrier gas, the flow is 5-45000ml/min; ar is diluent gas, and the flow is 500-9000ml/min. In some embodiments, the molar ratio of NH 3 to BCl 3 may be controlled to be 0.5-20, the molar ratio of BCl 3 to MTS may be controlled to be 0.1-5, the molar ratio of diluent gas Ar to BCl 3 may be 5-30, and the molar ratio of h 2 to BCl 3 may be 0.5-30.
Preferably, the MTS purity is more than 97%, the BCl 3 purity is 99.9%, and the purity of the rest gases is 99.999%; NH 3 and BCl 3 are respectively conveyed into the chemical vapor deposition reaction chamber through different conveying pipelines.
Preferably, the fiber preform is fixed in the chemical vapor deposition furnace by using a porous graphite jig (with a pore diameter of 50 mm), the shape of the porous graphite jig can be rectangle, square or the like, the shape of the open pore can be diamond, polygon, circle, square, rectangle or the like, and the number of the pores can be 2 or more.
In some embodiments, the temperature of the stabilization treatment is 1100 to 1500 ℃ and the stabilization treatment time is 0.5 to 3 hours. The stabilization treatment can promote the migration of the inter-grain atoms in the interface phase, promote the structural rearrangement and the interface structural transformation between the atoms, and enable the interface structure to be more stable, and in the invention, the stabilization temperature is set in the range because the too high stabilization temperature causes the damage of the fiber strength, is not beneficial to the mechanical performance of the subsequent materials, and the too low stabilization temperature cannot effectively lead the interface phase to have sufficient structural rearrangement.
In some embodiments, the SiBCN interface protected SiC fiber preform may be controlled to a final fiber volume fraction of 18vol% and above, preferably 22vol% or above; the content of the SiBCN interface coating can be 3-30wt%, the maximized exertion of fiber performance is facilitated by regulating the volume fraction of the fiber to be more than 18%, the reinforcing effect of the fiber is fully utilized, and the thickness of the interface phase is indirectly controlled by controlling the content of the interface coating to be 3-30wt%, so that the thermal stress generated in the preparation process of the material is effectively relieved, and the interface phase has good reinforcing and toughening effects.
In some embodiments, the SiBCN interface protective layer may have a thickness of 50nm to 2 μm.
The SiBCN interface protects the preliminary densification of the SiC fiber preform. And performing preliminary SiC densification on the SiBCN interface protection SiC fiber preform by adopting a Chemical Vapor Infiltration (CVI) process to obtain a preliminary densified SiBCN interface protection SiC f/SiC ceramic matrix composite.
In some embodiments, a chemical vapor infiltration process is used to perform a preliminary SiC densification process using trichloromethylsilane (MTS) as the SiC precursor; the dilution gas is hydrogen and argon, the molar ratio is 1-5, and the total flow of the dilution gas is 1000-4000 ml/min; the carrier gas is hydrogen, the flow is 100-200 ml/min, the flow of the diluent gas is controlled to be higher than the flow of the carrier gas, the MTS concentration in the densification process of the SiC is effectively diluted, and the phenomenon that pores are sealed too early due to the too high concentration on the surface of the material is prevented, so that the subsequent densification of the matrix is influenced.
In some embodiments, in the preliminary SiC densification process by the chemical vapor infiltration process, the infiltration temperature can be 850-1050 ℃, the infiltration pressure can be 3-20 KPa, the infiltration time can be 20-100 hours, and the maximized uniform deposition of the SiC matrix in the material can be effectively realized by controlling the process parameters within the above range, so that the effective infiltration of the SiC matrix in the material is realized.
In some embodiments, the ratio of weight gain of the SiC matrix can be controlled to be 20-300% in the primary densification SiBCN interface layer protection SiC f/SiC ceramic matrix composite material, and effective filling of pores inside fiber bundles inside the material can be realized by pre-depositing a CVI SiC matrix with a certain content inside the matrix, so that the material density is improved, and the matrix strength is improved.
The SiBCN interface layer protects the SiC f/SiC ceramic matrix composite. Polishing the surface of the primary densified SiBCN interface layer protection SiC f/SiC ceramic matrix composite, cleaning and drying, then adopting liquid resin and organic solvent to impregnate, taking out, solidifying, drying and cracking, repeating the operations of impregnating, solidifying and cracking for 2-6 times to obtain a carbon-containing porous preform, removing impurities on the surface of the cracked carbon-containing porous preform, and then placing the carbon-containing porous preform into a furnace to carry out siliconizing treatment by adopting a reaction melting deposition (RMI) method to further densify, thus obtaining the SiBCN interface layer protection SiC f/SiC ceramic matrix composite.
In some embodiments, the liquid resin may be at least one of a phenolic resin, a furfural resin, a pitch resin; the organic solvent can be at least one of polyethylene glycol, ethanol, glycerol, furfuryl alcohol, gasoline, alcohol, formaldehyde, glucose and sucrose solution.
In some embodiments, the vacuum of the impregnation is 1 to 10KPa, and the impregnation time may be 10 to 120 minutes; the curing temperature is 100-200 ℃, and the curing time is 1-12 hours, preferably 5-12 hours; the cracking temperature is 700-1000 ℃, the cracking time is 0.5-3 h, preferably 2-3 h, the material impregnation efficiency is effectively improved by controlling the material impregnation under a low-pressure environment, the curing time can be effectively shortened by controlling the curing temperature between 100 and 200 ℃, and the cracking temperature between 700 and 1000 ℃ can be controlled to the maximum to ensure the completion of the cracking without affecting the material performance.
In some embodiments, in the reaction fusion deposition, the infiltration temperature can be 1420-1600 ℃, the infiltration time can be 0.5-2 h, and the infiltration process can be effectively ensured to be carried out and the damage to the fiber strength caused by the overhigh infiltration temperature can be avoided by regulating the infiltration temperature and the infiltration time within the range.
The SiBCN interface coating prepared by the invention realizes good combination with SiC fibers, has good physical and chemical compatibility and thermal stability, and realizes good mechanical reinforcing and toughening effects on the SiC fibers. Compared with the existing CVI and precursor impregnation cracking method (PIP), the method provided by the invention has the advantages that the void defects caused by precursor volume shrinkage and micromolecule overflow in the impregnation cracking process are avoided, the material preparation period is saved, the material preparation efficiency is improved, meanwhile, the CVI and RMI method processes are adopted, the internal porosity of the material is reduced, the mechanical properties of the material are improved, and finally the high-performance SiBCN interface layer protection SiC fiber reinforced ceramic matrix composite material with good energy consumption mechanisms such as interface debonding, fiber pulling, crack deflection and the like is obtained.
The SiBCN interface coating prepared by the invention has good bonding strength with SiC fibers, and has good mechanical reinforcing and toughening effects and high-temperature oxidation resistance. Compared with the prior art, the SiBCN interface layer-protected SiC fiber reinforced ceramic matrix composite material prepared by the method has excellent mechanical properties and high-temperature oxidation resistance, and energy consumption mechanisms such as interface debonding, fiber pulling-out, crack deflection and the like can be fully and effectively exerted in the material fracture failure process, and the mechanical properties of the material are good in repeatability.
The porosity of the finally obtained SiC fiber reinforced composite material is less than or equal to 6% by adopting an Archimedes drainage method; the bending strength of the SiC fiber reinforced composite material is more than or equal to 300MPa, preferably more than or equal to 350MPa, and the bending strain is more than or equal to 0.4%, preferably more than or equal to 0.6% by adopting a three-point bending strength test method of the composite material.
The present invention will be described in more detail by way of examples. It should also be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, since various insubstantial modifications and adaptations of the invention to those skilled in the art based on the foregoing disclosure are intended to be within the scope of the invention and the specific process parameters and the like set forth below are merely one example of a suitable range within which one skilled in the art would choose from the description herein without being limited to the specific values set forth below.
Example 1
The preparation method of the SiBCN interface layer protection SiC f/SiC ceramic matrix composite material comprises the following steps:
(1) And (3) preparing the SiBCN interface protection SiC fiber preform. Fixing SiC fiber cloth with the size of 100X 180mm by using graphite fixtures with square holes with the side length of 30X 30mm, placing a sample in a reaction chamber in a furnace, vacuumizing and inflating for 2 times, heating to 500 ℃ at the rate of 10 ℃ per minute in a vacuum state, preserving heat for half an hour, heating to 850 ℃ at the rate of 5 ℃ per minute, and preserving heat for 1 hour; then, introducing precursor such as trichloromethylsilane (MTS), NH 3、BCl3、H2 and Ar and diluent gas into the furnace, controlling the mole ratio of NH 3 to BCl 3 to be 2, the mole ratio of BCl 3 to MTS to be 1.5, the mole ratio of diluent gas Ar to BCl 3 to be 10, the mole ratio of H 2 to BCl 3 to be 10, and depositing for 15 hours at 3KPa and 820 ℃; and then taking out the SiBCN interface coating SiC fiber after deposition, and putting the SiBCN interface coating SiC fiber into a furnace for stabilization treatment, wherein the stabilization treatment temperature is 1100 ℃, and the stabilization treatment time is 3 hours, so as to obtain the SiBCN interface protection SiC fiber preform.
(2) The SiBCN interface protects the preliminary densification of the SiC fiber preform. Placing the SiBCN interface protection SiC fiber preform into a chemical vapor infiltration furnace for preliminary CVI SiC densification treatment, wherein the carrier gas hydrogen flow is 150ml/min, the dilution gas hydrogen flow is 1500ml/min, the argon flow is 300ml/min, the infiltration temperature is 990 ℃, the furnace pressure is 5KPa, and the infiltration time is 50 hours, so as to obtain the preliminary densification SiBCN interface protection SiC f/SiC ceramic matrix composite; wherein the weight gain proportion of CVI SiC is 30%.
(3) The SiBCN interface layer protects the SiC f/SiC ceramic matrix composite. Polishing the surface of the SiC f/SiC ceramic matrix composite material protected by the interface layer of the preliminary densification SiBCN, cleaning and drying, and then carrying out 3 times of dipping and cracking treatment on a sample by adopting 100g of phenolic resin, 30g of furfuryl alcohol, 30g of polyethylene glycol and 300g of glycerol, wherein the dipping vacuum degree is 5KPa, the dipping time is 120 minutes, the curing temperature is 150 ℃, the curing time is 8 hours, the cracking temperature is 950 ℃, and the time is 2.5 hours; and then cleaning and drying the surface of the sample after soaking and cracking, and then placing the sample into an infiltration furnace for final siliconizing treatment, wherein the infiltration temperature is 1450 ℃, and the infiltration time is 1.5 hours, so as to obtain the SiBCN interface layer protection SiC f/SiC ceramic matrix composite.
FIG. 1 is a cross-sectional low-power scanning electron microscope image of an SiC fiber preform of example 1 of the present invention after SiBCN interfacial phase deposition. As can be seen from the figure, the SiBCN interface coating uniformly penetrated into the fiber preform.
FIG. 2 is an analysis of interfacial energy spectrum (EDS) of the SiC fiber surface SIBCN in example 1 of the present invention. As can be seen from the figure, the prepared SiBCN interface is mainly composed of Si, B, C, N, O elements.
As shown by tests, the porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in the embodiment 1 is 4.80%, the bending strength of the material is 358.43MPa, and the bending strain is 0.6%.
Example 2
The preparation method of the SiBCN interface layer protection SiC f/SiC ceramic matrix composite material comprises the following steps:
(1) And (3) preparing the SiBCN interface protection SiC fiber preform. Fixing 300X 200mm SiC fiber cloth with graphite fixtures with rectangular holes with side length of 20X 25mm on two sides, placing a sample in a reaction chamber in a furnace, vacuumizing and inflating for 2 times, heating to 500 ℃ at a rate of 10 ℃ per minute in a vacuum state, preserving heat for half an hour, heating to 800 ℃ per minute at 5 ℃ per minute, and preserving heat for 1 hour; then, introducing precursor such as trichloromethylsilane (MTS), NH 3、BCl3、H2 and Ar and diluent gas into the furnace, controlling the mole ratio of NH 3 to BCl 3 to be 10, the mole ratio of BCl 3 to MTS to be 2.5, the mole ratio of diluent gas Ar to BCl 3 to be 10, the mole ratio of H 2 to BCl 3 to be 10, and depositing for 13h at 3KPa and 840 ℃; and then taking out the SiBCN interface coating SiC fiber after deposition, and putting the SiBCN interface coating SiC fiber into a furnace for stabilization treatment, wherein the stabilization treatment temperature is 1130 ℃, and the stabilization treatment time is 3 hours, so as to obtain the SiBCN interface protection SiC fiber preform.
(2) The SiBCN interface protects the preliminary densification of the SiC fiber preform. Placing the SiBCN interface protection SiC fiber preform into a chemical vapor infiltration furnace for preliminary CVI SiC densification treatment, wherein the carrier gas hydrogen flow is 150ml/min, the dilution gas hydrogen flow is 1500ml/min, the argon flow is 300ml/min, the infiltration temperature is 990 ℃, the furnace pressure is 5KPa, and the infiltration time is 65 hours, so as to obtain the preliminary densification SiBCN interface protection SiC f/SiC ceramic matrix composite; wherein the weight gain proportion of CVI SiC is 40%.
(3) The SiBCN interface layer protects the SiC f/SiC ceramic matrix composite. Polishing the surface of the SiC f/SiC ceramic matrix composite material protected by the interface layer of the preliminary densification SiBCN, cleaning and drying, and then carrying out 3 times of dipping and cracking treatment on a sample by adopting 80g of phenolic resin, 40g of furfuryl alcohol, 30g of polyethylene glycol and 300g of glycerol, wherein the dipping vacuum degree is 5KPa, the dipping time is 120 minutes, the curing temperature is 150 ℃, the curing time is 8 hours, the cracking temperature is 950 ℃, and the time is 2.5 hours; and then cleaning and drying the surface of the sample after soaking and cracking, and then placing the sample into an infiltration furnace for final siliconizing treatment, wherein the infiltration temperature is 1450 ℃, and the infiltration time is 1.5 hours, so as to obtain the SiBCN interface layer protection SiC f/SiC ceramic matrix composite.
As shown by tests, the porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in the embodiment 2 is 4.50%, the bending strength of the material is 373.54MPa, and the bending strain is 0.66%.
Example 3
The preparation method of the SiBCN interface layer protection SiC f/SiC ceramic matrix composite material comprises the following steps:
(1) And (3) preparing the SiBCN interface protection SiC fiber preform. Fixing SiC fiber cloth with the size of 100 multiplied by 100mm by using porous graphite clamps with the aperture of phi 25mm on two sides, placing a sample in a reaction chamber in a furnace, vacuumizing and inflating for 2 times, heating to 500 ℃ at the rate of 10 ℃ per minute in a vacuum state, preserving heat for half an hour, heating to 780 ℃ per minute at the temperature of 5 ℃ and preserving heat for 1 hour; then, a precursor such as trichlorosilane (MTS), NH 3、BCl3、H2, and Ar, and a dilution gas are introduced into the furnace. The molar ratio of NH 3 to BCl 3 is 15, the molar ratio of BCl 3 to MTS is 4, the molar ratio of diluent gas Ar to BCl 3 is 10, the molar ratio of H 2 to BCl 3 is 10, and the deposition is carried out for 14h at the temperature of 2.5KPa and 830 ℃; and then taking out the SiBCN interface coating SiC fiber after deposition, and putting the SiBCN interface coating SiC fiber into a furnace for stabilization treatment, wherein the stabilization treatment temperature is 1150 ℃, and the stabilization treatment time is 3 hours, so as to obtain the SiBCN interface protection SiC fiber preform.
(2) The SiBCN interface protects the preliminary densification of the SiC fiber preform. Placing the SiBCN interface protection SiC fiber preform into a chemical vapor infiltration furnace for preliminary CVI SiC densification treatment, wherein the carrier gas hydrogen flow is 150ml/min, the dilution gas hydrogen flow is 1500ml/min, the argon flow is 300ml/min, the infiltration temperature is 990 ℃, the furnace pressure is 5KPa, and the infiltration time is 100 hours, so as to obtain the preliminary densification SiBCN interface protection SiC f/SiC ceramic matrix composite; wherein the weight gain proportion of CVI SiC is 60%.
(3) The SiBCN interface layer protects the SiC f/SiC ceramic matrix composite. Polishing the surface of the SiC f/SiC ceramic matrix composite material protected by the interface layer of the preliminary densification SiBCN, cleaning and drying, and then carrying out 3 times of dipping and cracking treatment on a sample by adopting 90g of phenolic resin, 50g of furfuryl alcohol, 30g of polyethylene glycol and 300g of glycerol, wherein the dipping vacuum degree is 5KPa, the dipping time is 120 minutes, the curing temperature is 150 ℃, the curing time is 8 hours, the cracking temperature is 950 ℃, and the time is 2.5 hours; and then cleaning and drying the surface of the sample after soaking and cracking, and then placing the sample into an infiltration furnace for final siliconizing treatment, wherein the infiltration temperature is 1450 ℃, and the infiltration time is 1.5 hours, so as to obtain the SiBCN interface layer protection SiC f/SiC ceramic matrix composite.
As shown by tests, the porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in example 3 is 4.28%, the bending strength of the material is 407.90MPa, and the bending strain is 0.85%.
FIG. 3 is a three-point bend-strain plot of SiBCN interfacial layer protected SiC f/SiC ceramic matrix composites prepared in examples 1,2, and 3 of the present invention. As can be seen from the figures, the composite material prepared by the invention shows remarkable ductile fracture characteristics.
FIG. 4 is a diagram of a polishing-like scanning electron microscope of SiBCN interfacial layer protected SiC f/SiC ceramic matrix composite prepared in example 3 of the present invention. As can be seen from the figure, the material prepared by the method of the invention is very compact in the interior and almost no macropores are seen.
Example 4
The composite material of this example 4 was prepared as described in example 1, except that: and (2) in the step (1), taking out the SiBCN interface coating SiC fibers after deposition, putting the SiBCN interface coating SiC fibers into a furnace for stabilization treatment, wherein the stabilization treatment temperature is 1450 ℃, and the stabilization treatment time is 3 hours, so as to obtain the SiBCN interface protection SiC fiber preform. The porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in the embodiment is 4.38%, the bending strength of the material is 310.1MPa, and the bending strain is 0.61%.
Example 5
The composite material of this example 5 was prepared as described in example 1, except that: and (2) in the step (1), taking out the SiBCN interface coating SiC fibers after deposition, putting the SiBCN interface coating SiC fibers into a furnace for stabilization treatment, wherein the stabilization treatment temperature is 1500 ℃, and the stabilization treatment time is 3 hours, so as to obtain the SiBCN interface protection SiC fiber preform. The SiBCN interface layer prepared in the embodiment protects the porosity of the SiC f/SiC ceramic matrix composite material to be 3.88%, the bending strength of the material to be 319.8MPa, and the bending strain to be 0.61%.
Example 6
The composite material of this example 6 was prepared as described in example 1, except that: and (2) in the step (1), taking out the SiBCN interface coating SiC fibers after deposition, putting the SiBCN interface coating SiC fibers into a furnace for stabilization treatment, wherein the stabilization treatment temperature is 1000 ℃, and the stabilization treatment time is 3 hours, so as to obtain the SiBCN interface protection SiC fiber preform. The SiBCN interface layer prepared in the embodiment protects the porosity of the SiC f/SiC ceramic matrix composite material to be 3.56%, the bending strength of the material to be 351.8MPa, and the bending strain to be 0.48%.
Example 7
The composite material of this example 7 was prepared as described in example 1, except that: and (2) in the step (1), taking out the SiBCN interface coating SiC fibers after deposition, putting the SiBCN interface coating SiC fibers into a furnace for stabilization treatment, wherein the stabilization treatment temperature is 1600 ℃, and the stabilization treatment time is 3 hours, so as to obtain the SiBCN interface protection SiC fiber preform. The porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in the embodiment is 3.78%, the bending strength of the material is 328.1MPa, and the bending strain is 0.41%.
Example 8
The composite material of this example 8 was prepared as described in example 1, except that: in the step (3), the surface of the SiC f/SiC ceramic matrix composite material protected by the interface layer of the preliminary densification SiBCN is polished, and after cleaning and drying, the sample is subjected to 3 times of dipping and cracking treatment by adopting 50g of phenolic resin, 50g of furfuryl alcohol resin/30 g of polyethylene glycol and 300g of glycerol, wherein the dipping vacuum degree is 5KPa, the dipping time is 120 minutes, the curing temperature is 150 ℃, the curing time is 8 hours, the cracking temperature is 950 ℃, and the time is 2.5 hours. The porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in the embodiment is 4.12%, the bending strength of the material is 345.8MPa, and the bending strain is 0.73%.
Example 9
The composite material of this example 9 was prepared as described in example 1, except that: in the step (3), the surface of the SiC f/SiC ceramic matrix composite material protected by the interface layer of the preliminary densification SiBCN is polished, and after cleaning and drying, the sample is subjected to 3 times of dipping and cracking treatment by adopting 50g of phenolic resin, 30g of polyethylene glycol, 50g of furfuryl alcohol and 300g of ethanol, wherein the dipping vacuum degree is 5KPa, the dipping time is 120 minutes, the curing temperature is 150 ℃, the curing time is 8 hours, the cracking temperature is 950 ℃ and the time is 2.5 hours. The SiBCN interface layer prepared in the embodiment protects the porosity of the SiC f/SiC ceramic matrix composite material to be 3.56%, the bending strength of the material to be 340.8MPa, and the bending strain to be 0.75%.
Example 10
The composite material of this example 10 was prepared as described in example 9, except that: in the step (3), the surface of the SiC f/SiC ceramic matrix composite material protected by the interface layer of the preliminary densification SiBCN is polished, and after cleaning and drying, the sample is subjected to 3 times of dipping and cracking treatment by adopting 50g of phenolic resin, 50g of furfuryl alcohol and 300g of glycerol, wherein the dipping vacuum degree is 5KPa, the dipping time is 120 minutes, the curing temperature is 150 ℃, the curing time is 8 hours, the cracking temperature is 950 ℃, and the time is 2.5 hours. The porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in the embodiment is 3.45%, the bending strength of the material is 325.7MPa, and the bending strain is 0.57%.
Example 11
The composite material of this example 11 was prepared as described in example 9, except that: in the step (3), the surface of the SiC f/SiC ceramic matrix composite material protected by the interface layer of the preliminary densification SiBCN is polished, and after cleaning and drying, the sample is subjected to 3 times of dipping and cracking treatment by adopting 50g of phenolic resin, 30g of polyethylene glycol and 300g of ethanol, wherein the dipping vacuum degree is 5KPa, the dipping time is 120 minutes, the curing temperature is 150 ℃, the curing time is 8 hours, the cracking temperature is 950 ℃, and the time is 2.5 hours. The SiBCN interface layer prepared in the embodiment protects the porosity of the SiC f/SiC ceramic matrix composite material to be 5.02%, the bending strength of the material to be 308.0MPa, and the bending strain to be 0.45%.
Comparative example 1
The composite material of this comparative example 1 was prepared as described in example 1, except that: in the step (1), taking out the SiBCN interface coating SiC fiber after deposition without stabilizing treatment, and obtaining the SiBCN interface protection SiC fiber preform. The porosity of the SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material prepared in the comparative example 1 is 4.75%, the bending strength of the material is 246.3MPa, and the bending strain is 0.26%.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (13)
1. The preparation method of the high-performance SiBCN interface layer is characterized by comprising the following steps:
(1) Fixing the fiber preform by using a clamp, placing the fiber preform in a reaction chamber in a furnace, heating the fiber preform to a deposition temperature of 600-850 ο ℃ in a vacuum state, and preserving the temperature for 0.5-2 h;
(2) The preparation method comprises the steps of taking CH 3Cl3 Si as a silicon source and a carbon source, taking BCl 3 as a boron source, taking NH 3 as a nitrogen source, taking H 2 as diluent gas and carrier gas, taking Ar as diluent gas, controlling NH 3 and BCl 3 to be respectively conveyed into a reaction chamber through different conveying pipelines, depositing for 2-20H at the temperature of 0.01-3 KPa and the temperature of 600-850 ℃, and preparing SiBCN interface layers on the surfaces of fibers in a fiber preform;
(3) And carrying out stabilization treatment on the fiber preform deposited with the SiBCN interface layer to obtain the high-performance SiBCN interface layer.
2. The method of producing according to claim 1, wherein in step (1), the SiC fiber preform includes: at least one of SiC fiber bundles, siC fiber cloth, siC fiber two-dimensional lamination, siC fiber two-dimensional stitching, siC fiber 3D weaving and SiC fiber 2.5D weaving preform.
3. The production method according to claim 1 or 2, wherein in the step (1), the mold comprises one of a graphite mold, an alumina ceramic mold, a silicon carbide ceramic mold, and a silicon nitride ceramic mold; the vacuum degree in the vacuum state is 5Pa or less, preferably 3Pa or less.
4. A method according to any one of claims 1 to 3, wherein in step (1), the temperature increase regime of the deposition temperature comprises: the temperature rising rate is 6-10 ℃/min below 500 ℃, and the temperature rising rate is 1-5 ℃/min above 500 ℃.
5. The method according to any one of claims 1 to 4, wherein in the step (2), the molar ratio of NH 3 to BCl 3 is 0.5 to 20; the molar ratio of BCl 3 to MTS is 0.1-5; the molar ratio of the diluent gas Ar to the BCl 3 is 5-30; the molar ratio of H 2 to BCl 3 is 0.5-30.
6. The method according to any one of claims 1 to 5, wherein in the step (3), the temperature of the stabilization treatment is 1100 to 1500 ℃ for 0.5 to 3 hours.
7. A SiBCN interface layer protected SiC fiber preform prepared according to the preparation method of any one of claims 1 to 6, wherein the thickness of the SiBCN interface layer in the SiBCN interface layer protected SiC fiber preform is not more than 2 μm.
8. The preparation method of the SiBCN interface layer protection SiC f/SiC ceramic matrix composite is characterized by comprising the following steps:
(1) Performing preliminary SiC densification on the SiBCN interface layer-protected SiC fiber preform in claim 7 by adopting a chemical vapor infiltration process to obtain a preliminary densified SiBCN interface layer-protected SiC f/SiC ceramic matrix composite;
Impregnating the obtained primarily densified SiBCN interface layer-protected SiC f/SiC ceramic matrix composite material with a liquid resin solution, taking out, and then solidifying and cracking;
(2) Repeating the soaking, curing and cracking in the step (1) for at least 2 times to obtain a carbon-containing porous preform;
(3) And carrying out siliconizing treatment on the carbon-containing porous preform by adopting a reaction fusion deposition method to obtain the SiBCN interface layer protection SiC f/SiC ceramic matrix composite.
9. The method of claim 8, wherein the parameters for preliminary SiC densification using a chemical vapor infiltration process include: adopting trichloromethylsilane as a SiC precursor; the dilution gas is hydrogen and argon, the molar ratio is 1-5, and the total flow of the dilution gas is 1000-4000 ml/min; the carrier gas is hydrogen, and the flow is 100-200 ml/min;
The infiltration temperature is 850-1050 ℃, the infiltration pressure is 3-20 KPa, and the infiltration time is 20-100 hours.
10. The method of preparing according to claim 8, wherein the liquid resin in the liquid resin solution comprises: at least one of phenolic resin, furfural resin and asphalt resin;
The organic solvent in the liquid resin solution is at least one of polyethylene glycol solution, ethanol, glycol, glycerol, furfuryl alcohol, gasoline, alcohol, formaldehyde, glucose solution and sucrose solution;
Preferably, the concentration of the polyethylene glycol solution is 5-20wt%, and the solvent is at least one selected from alcohol, gasoline, glycerol, polyethylene glycol and formaldehyde;
preferably, the concentration of the glucose solution is 30-60 wt%, and the solvent is at least one selected from ethylene glycol, glycerol, glucose, furfuryl alcohol and formaldehyde;
Preferably, the concentration of the sucrose solution is 30-60 wt%, and the solvent is at least one selected from ethanol, glycol, glycerol and sucrose.
11. The method according to claim 8, wherein the vacuum degree of the impregnation is 1 to 10KPa, and the time of the impregnation is 10 to 120 minutes;
The curing temperature is 100-200 ℃, and the curing time is 1-12 hours, preferably 5-12 hours;
The cracking temperature is 700-1000 ℃, and the cracking time is 0.5-3 hours, preferably 2-3 hours.
12. The method according to any one of claims 8 to 11, wherein the parameters of the siliconizing treatment by the reactive melt deposition method include: the infiltration temperature is 1420-1600 ℃ and the infiltration time is 0.5-2 h.
13. A SiBCN interfacial layer protected SiC f/SiC ceramic matrix composite obtained according to the method of preparation of any one of claims 8-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410035940.8A CN117945764A (en) | 2024-01-10 | 2024-01-10 | SiBCN interface layer, siBCN interface layer protection SiCfSiC ceramic matrix composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410035940.8A CN117945764A (en) | 2024-01-10 | 2024-01-10 | SiBCN interface layer, siBCN interface layer protection SiCfSiC ceramic matrix composite and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117945764A true CN117945764A (en) | 2024-04-30 |
Family
ID=90801188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410035940.8A Pending CN117945764A (en) | 2024-01-10 | 2024-01-10 | SiBCN interface layer, siBCN interface layer protection SiCfSiC ceramic matrix composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117945764A (en) |
-
2024
- 2024-01-10 CN CN202410035940.8A patent/CN117945764A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109721377B (en) | Carbon fiber reinforced silicon carbide ceramic matrix composite and preparation method thereof | |
| CN109293383B (en) | Fiber-reinforced carbon-silicon carbide ceramic matrix composite and preparation method thereof | |
| CN101863665B (en) | Method for preparing self-healing anti-oxidation functional fiber reinforced ceramic matrix composite material | |
| CN112341235B (en) | Multiphase coupling rapid densification method for ultrahigh-temperature self-healing ceramic matrix composite | |
| CN110105075B (en) | High-purity carbon fiber reinforced silicon carbide composite material and preparation method thereof | |
| CN102276279B (en) | Preparation method of silicon carbide fiber reinforced silicon carbide composite material | |
| US6291058B1 (en) | Composite material with ceramic matrix and SiC fiber reinforcement, method for making same | |
| EP2089338B1 (en) | Process for manufacturing a thermostructural composite part | |
| CN110423119B (en) | Preparation method of ablation-resistant C/SiC ceramic matrix composite | |
| CN111996473B (en) | Variable-structure ultrahigh-temperature ceramic matrix composite and preparation method thereof | |
| NO342062B1 (en) | Process for manufacturing a part made of impervious thermostructural composite material. | |
| CN113979752B (en) | Mullite fiber reinforced ceramic matrix composite and preparation method thereof | |
| CN109265189B (en) | Method for rapidly preparing wave-absorbing ceramic matrix composite with electromagnetic impedance gradual change matrix | |
| CN114315394B (en) | By using Ti 3 SiC 2 Preparation method of three-dimensional network porous prefabricated body reinforced SiC ceramic matrix composite material | |
| CN109721376A (en) | A kind of SiCw orients the preparation method of high Strengthening and Toughening thicker-walled ceramic based composites | |
| CN112299865A (en) | Modified C/SiC composite material and preparation method thereof | |
| CN114105662B (en) | Multilayer interface coating, preparation method and ceramic matrix composite preparation method | |
| CN113173791B (en) | SiBCN interface coating for SiC fiber reinforced composite material, and preparation method and application thereof | |
| CN112521156B (en) | Hybrid matrix SiCf/SiC composite material and preparation method thereof | |
| CN112374901B (en) | Ablation-resistant modified C/SiC composite material and preparation method thereof | |
| CN113121253B (en) | Ultrahigh-temperature C/SiHfBCN ceramic matrix composite material and preparation method thereof | |
| CN113896557A (en) | C/ZrC-SiC composite material and preparation method and application thereof | |
| CN110407597B (en) | Rare earth oxide modified silicon carbide ceramic matrix composite material and preparation method thereof | |
| CN117945764A (en) | SiBCN interface layer, siBCN interface layer protection SiCfSiC ceramic matrix composite and preparation method thereof | |
| CN113800934B (en) | Mullite fiber reinforced ceramic matrix composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |