CN115385712A - High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof - Google Patents
High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof Download PDFInfo
- Publication number
- CN115385712A CN115385712A CN202110569439.6A CN202110569439A CN115385712A CN 115385712 A CN115385712 A CN 115385712A CN 202110569439 A CN202110569439 A CN 202110569439A CN 115385712 A CN115385712 A CN 115385712A
- Authority
- CN
- China
- Prior art keywords
- sic
- entropy
- ceramic matrix
- temperature
- ultrahigh
- 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
- 239000011216 ultra-high temperature ceramic matrix composite Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 49
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 41
- 239000004917 carbon fiber Substances 0.000 claims abstract description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000919 ceramic Substances 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 239000011215 ultra-high-temperature ceramic Substances 0.000 claims abstract description 16
- 239000010936 titanium Substances 0.000 claims description 146
- 239000010955 niobium Substances 0.000 claims description 137
- 238000002679 ablation Methods 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 37
- 239000000843 powder Substances 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 31
- 238000005470 impregnation Methods 0.000 claims description 22
- 238000005452 bending Methods 0.000 claims description 18
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 16
- 229920003257 polycarbosilane Polymers 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- UFDVWCFBDLHWGE-UHFFFAOYSA-N [Zr].[Hf].[Nb].[Ta] Chemical compound [Zr].[Hf].[Nb].[Ta] UFDVWCFBDLHWGE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 230000004907 flux Effects 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 241000486661 Ceramica Species 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 19
- 239000012071 phase Substances 0.000 description 18
- 238000001723 curing Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007598 dipping method Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 5
- KXOIKGAHZZAVKH-UHFFFAOYSA-N [Zr].[Hf].[Nb].[Ta].[Ti] Chemical compound [Zr].[Hf].[Nb].[Ta].[Ti] KXOIKGAHZZAVKH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
-
- 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
-
- 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
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3839—Refractory metal carbides
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3839—Refractory metal carbides
- C04B2235/3843—Titanium carbides
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention relates to a high-entropy ultrahigh-temperature ceramic matrix composite and a preparation method thereof, in particular to a C-type ultrahigh-temperature ceramic matrix composite f /(Ti a Zr b Hf c Nb d Ta e ) A C high-entropy ultra-high temperature ceramic matrix composite material and a preparation method thereof. Said C is f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite material comprises: carbon fiber preform, and (Ti) formed in the carbon fiber preform in sequence a Zr b Hf c Nb d Ta e ) C high-entropy ultra-high-temperature ceramicA matrix and a SiC ceramic matrix, wherein a = 18-22%, b = 18-22%, c = 18-22%, d = 18-22%, e = 18-22%, and a + b + c + d + e =1; the (Ti) a Zr b Hf c Nb d Ta e ) The content of the C high-entropy ultrahigh-temperature ceramic matrix is 40-60 wt%.
Description
Technical Field
The invention relates to a high-entropy ultrahigh-temperature ceramic matrix composite and a preparation method thereof, in particular to a C-type ultrahigh-temperature ceramic matrix composite f /(Ti a Zr b Hf c Nb d Ta e ) A C high-entropy ultra-high temperature ceramic matrix composite and an efficient preparation method thereof belong to the technical field of preparation of ultra-high temperature ceramic matrix composites.
Background
The continuous fiber reinforced superhigh temperature ceramic-based composite material has the advantages of light weight, superhigh temperature resistance, high specific strength, good chemical stability, oxidation ablation resistance, strong performance designability and the like, and is considered as a preferred material for extreme service environments such as a thermal structure of a novel high-speed aircraft. With the development of new high-speed flight technologies, more stringent requirements are placed on thermal structural materials.
The carbide ceramic in the ultra-high temperature ceramic is widely applied to the continuous fiber reinforced ultra-high temperature ceramic matrix composite because of the highest melting point, excellent mechanical property and high temperature stability; and the high-entropy carbide ceramic formed by solid solution of various ultra-high-temperature carbides has the performances of higher hardness and modulus, better oxidation resistance, lower thermal conductivity, potential excellent high-temperature oxidation ablation resistance and the like compared with single-component carbides. The high-entropy carbide ceramic is used for carrying out matrix modification on the carbon fiber reinforced ultrahigh-temperature ceramic-based composite material, and the obtained high-entropy ultrahigh-temperature ceramic-based composite material has wide application prospect in a novel high-speed aircraft thermal structure. However, the formation of high entropy carbide solid solutions often requires temperatures above 1900 ℃, making it difficult to efficiently bond high entropy carbides to continuous fibers and avoid fiber damage.
Disclosure of Invention
Therefore, the invention aims to provide C with high compactness, low fiber/interface damage, excellent mechanical property and excellent ablation property f /(Ti a Zr b Hf c Nb d Ta e ) A C high-entropy ultra-high temperature ceramic matrix composite material and a high-efficiency preparation method thereof.
In one aspect, the invention provides a compound C f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultra-high temperature ceramic matrix composite material comprises: carbon fiber preform, and (Ti) formed in the carbon fiber preform in sequence a Zr b Hf c Nb d Ta e ) The SiC high-entropy ultrahigh-temperature ceramic matrix consists of a = 18-22%, b = 18-22%, C = 18-22%, d = 18-22%, e = 18-22%, and a + b + C + d + e =1; the (Ti) is a Zr b Hf c Nb d Ta e ) The content of the C high-entropy ultrahigh-temperature ceramic matrix is 40-60 wt%.
Preferably, the volume fraction of the carbon fiber preform is 20 to 50vol%.
Preferably, the content of the SiC ceramic matrix is 30-50 wt%.
Preferably, the surface of the carbon fiber in the carbon fiber preform further comprises an interface layer; the interface layer is selected from at least one of a PyC layer, a BN layer, a PyC layer/SiC layer and a BN/SiC layer; the thickness of the interface layer is 0.1 to 1 μm.
Preferably, said C f /(Ti a Zr b Hf c Nb d Ta e ) The bending strength of the C-SiC high-entropy ultra-high temperature ceramic matrix composite material is more than or equal to 300MPa, and the fracture toughness is more than or equal to 8 MPa-m 1/2 。
Preferably at 5MW/m 2 Heat flux density under air plasma ablation conditions, C f /(Ti a Zr b Hf c Nb d Ta e ) C-SiC high-entropy ultrahigh-temperature ceramic matrix compositeThe ablation rate of the material line is less than or equal to 1 mu m/s.
In another aspect, the present invention provides C f /(Ti a Zr b Hf c Nb d Ta e ) The preparation method of the C-SiC high-entropy ultra-high temperature ceramic matrix composite adopts a vacuum impregnation method to sequentially introduce (Ti) into a carbon fiber preform a Zr b Hf c Nb d Ta e ) C high-entropy ultra-high-temperature ceramic matrix and SiC ceramic matrix to obtain the C f /(Ti a Zr b Hf c Nb d Ta e ) C-SiC high-entropy ultrahigh-temperature ceramic matrix composite.
Preferably, the (Ti) is introduced into the carbon fiber preform a Zr b Hf c Nb d Ta e ) The method of the C high-entropy ultrahigh-temperature ceramic matrix comprises the following steps:
(1) Introduction of (Ti) into carbon fiber preforms by vacuum impregnation a Zr b Hf c Nb d Ta e ) C precursor is solidified and heat treated to obtain C f /(Ti a Zr b Hf c Nb d Ta e ) A C intermediate;
(2) Repeating the step (1) for 2 to 4 times to obtain the porous C f /(Ti a Zr b Hf c Nb d Ta e ) And C, material. Preferably, the curing temperature is 150-300 ℃ and the curing time is 2-4 hours; the heat treatment temperature is 1500-1800 ℃, the time is 0.5-3 hours, and the atmosphere is vacuum or inert atmosphere.
Further, it is preferable that (Ti) is mentioned a Zr b Hf c Nb d Ta e ) C precursor contains (Ti) a Zr b Hf c Nb d Ta e ) C powder, a polymer with a main chain containing titanium, zirconium, hafnium, niobium and tantalum, acetylacetone and a solvent;
preferably, the atomic ratio of Ti, zr, hf, nb and Ta in the polymer with the titanium-containing zirconium hafnium niobium tantalum main chain is (18-22%): (18-22%): (18-22%): (18-22%): (18-22%);
preferably, the (Ti) is 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The grain diameter of the C powder is submicronMeter-scale, more preferably 100 to 500nm;
preferably, the solvent is at least one of ethanol and butanol; the contents of the polymer, the acetylacetone and the alcohols containing the titanium zirconium hafnium niobium tantalum as the main chain are respectively 25-30 wt%, calculated by taking the mass sum of the polymer, the acetylacetone and the alcohols containing the titanium zirconium hafnium niobium tantalum as the main chain as 100%: 3-5 wt%: 65-70 wt%;
preferably, the (Ti) a Zr b Hf c Nb d Ta e ) C precursor solution (Ti) a Zr b Hf c Nb d Ta e ) The solid content of the C powder is 30-60 wt%, and the solution viscosity is 20-300 mPas. Because in the carbon fiber preform, (Ti) a Zr b Hf c Nb d Ta e ) The C high-entropy powder mainly fills macropores and micropores among fiber bundles, and a small amount of closed pores can be formed after impregnation. Introduction of (Ti) a Zr b Hf c Nb d Ta e ) The content of the C high-entropy ceramic powder is related to the number of pores in the carbon fiber preform, and according to the number of pores, (Ti) is introduced after one-time impregnation a Zr b Hf c Nb d Ta e ) The minimum amount of C high-entropy ceramic powder is indicated to be introduced when the mass is not increased any more after multiple times of dipping (Ti) a Zr b Hf c Nb d Ta e ) C maximum amount of high-entropy ceramic powder. When the amount of the composite material is small, the ablation resistance of the composite material is obviously reduced, the content of SiC is reduced when the composite material is excessive, the content of a liquid phase is reduced during ablation, and the ablation performance is reduced.
Preferably, the method for introducing the SiC ceramic matrix comprises the following steps:
(1) To the porous C by vacuum impregnation f /(Ti a Zr b Hf c Nb d Ta e ) Introducing SiC precursor into the material C, and curing and cracking to obtain the material C f /(Ti a Zr b Hf c Nb d Ta e ) A C-SiC intermediate;
(2) Repeating the step (1) for 2-4 times to obtain the C f /(Ti a Zr b Hf c Nb d Ta e ) C-SiC high-entropy ultra-high-temperature ceramic matrix composite.
Preferably, the SiC precursor is liquid polycarbosilane PCS, and the ceramic yield is more than or equal to 60wt%; the curing temperature is 80-170 ℃, and the curing time is 2-4 hours; the cracking temperature is 1000-1300 ℃, the time is 1-2 hours, and the atmosphere is vacuum or inert atmosphere.
Has the beneficial effects that:
the invention is achieved by f /(Ti a Zr b Hf c Nb d Ta e ) Adding superfine Ti into the precursor solution a Zr b Hf c Nb d Ta e ) C high-entropy ultra-high-temperature ceramic powder and adopts liquid polycarbosilane with high ceramic yield as raw material, thereby realizing C f /(Ti a Zr b Hf c Nb d Ta e ) High efficiency densification of C-SiC composites. Prepared C f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite has uniform composition, low fiber/interface damage and excellent mechanical and ablation resistance.
Drawings
FIG. 1 shows the present invention C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) A route diagram for preparing the C-SiC high-entropy ultra-high-temperature ceramic matrix composite;
FIG. 2 is C prepared in example 1 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The XRD pattern of the C-SiC high-entropy ultra-high temperature ceramic matrix composite material can see that SiC and (Ti) with good crystallization are formed in the composite material 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C phase;
FIG. 3 is C prepared in example 1 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) A microstructure photo of the C-SiC high-entropy ultra-high temperature ceramic matrix composite material is shown in the figure, wherein a black area is carbon fiber, a gray dendritic phase is SiC, and a white part is (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Phase C, it is clear from the figure that the carbon fiber preform has a good crystalline structure(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C and SiC, with SiC being predominantly filled (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, forming a gap by volume shrinkage in the forming process;
FIG. 4 is C prepared in example 1 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The fracture morphology of the C-SiC high-entropy ultra-high temperature ceramic matrix composite material can be known from the figure that due to the existence of an interface, weak bonding is formed between carbon fibers and a matrix, and the fracture process of the composite material is accompanied by the extraction of a large amount of long fibers, so that obvious non-brittle fracture is shown;
FIG. 5 is C prepared in comparative example 1 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The microstructure picture of the C-SiC high-entropy ultra-high temperature ceramic matrix composite material shows that only Ti passes through 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Introducing a precursor solution of C (Ti) into the carbon fiber 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) In the phase C, the macropores in the fiber preform cannot be filled due to low viscosity of the precursor solution and low ceramic yield;
FIG. 6 is C prepared in example 1 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Microstructure photograph of C-SiC high-entropy ultra-high temperature ceramic matrix composite material, from which the direction (Ti) is known 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Adding (Ti) into the precursor solution of C 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Compact (Ti) is introduced into the fiber preform after the C high-entropy ceramic powder 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Phase C, thus C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite material has excellent mechanical property and ablation resistance.
Detailed Description
The present invention is further illustrated by the following examples, which are to be construed as merely illustrative, and not a limitation of the present invention.
In the present invention, C f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultra-high-temperature ceramic matrix composite mainly comprises a carbon fiber preform and (Ti) a Zr b Hf c Nb d Ta e ) A C phase and a SiC phase. Wherein the volume content of the carbon fiber can be 20-50 vol%. (Ti) a Zr b Hf c Nb d Ta e ) The contents of the C phase and the SiC phase may be 40 to 60wt% and 30 to 50wt%, respectively. Obtained C f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite material has high density, low fiber/interface damage and excellent mechanical property and ablation property.
As shown in FIG. 1, the compound of the present invention contains (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Of C powder (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Using C precursor solution and liquid Polycarbosilane (PCS) as initial raw materials, and introducing (Ti) into the fiber preform step by adopting a vacuum impregnation method 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C and SiC ceramic matrix, and C with excellent mechanical property and ablation resistance f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C-SiC high-entropy ultra-high-temperature ceramic matrix composite. The invention is characterized by (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Adding superfine Ti into the precursor solution 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C high-entropy ultrahigh-temperature ceramic powder and adopts liquid polycarbosilane with high ceramic yield as raw material, so that C is greatly improved f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Densification efficiency of the C-SiC composite. The effect of using the high-entropy ceramic powder is to increase (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The ceramic yield of the precursor C, the large pores between the bundles which are difficult to fill by using the high-entropy powder to fill pure precursor solution, and simultaneously, the dipping effect is improved and the dipping period is shortened. The density of the composite material and the content of the matrix ultra-high temperature phase are equivalently improved, so that the mechanical property and the ablation resistance are improved. The following is an exemplary description (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) A preparation method of a C-SiC high-entropy ultrahigh-temperature ceramic matrix composite.
A carbon fiber preform. In the present invention, the fiber surface of the carbon fiber preform (or called carbon fiber woven body) has at least one of PyC, BN, pyC/SiC and BN/SiC composite interface layer. Preferably, the total thickness of the interface may be 0.1 to 1 μm. The carbon fiber preform may have an open porosity of 50vol% to 80vol%.
Introduction of (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) And (5) phase C. The inventor finds that the viscosity of a pure precursor solution is low, the impregnation efficiency is low, and the impregnation period is long; the pure ceramic powder slurry has large powder particle size, is difficult to fill gaps in fiber bundles, and has high impregnation porosity. The inventor specially combines the precursor solution and the ceramic powder, and can improve the dipping effect and shorten the dipping period. The compactness of the composite material and the content of the matrix ultrahigh-temperature phase are equivalently improved, so that the mechanical property and the ablation resistance are improved. The (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C precursor solution (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The solid content of the C powder can be 30-60 wt%. Does not contain (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Of C powder (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The component of the precursor solution C comprises a polymer with a main chain containing titanium zirconium hafnium niobium tantalum, acetylacetone and a solvent ethanol/butanol. The contents of the three components can be respectively 25-30 wt%, 3-5 wt% and 65-70 wt%. The atomic ratio of Ti, zr, hf, nb and Ta in the polymer with the titanium-zirconium-hafnium-niobium-tantalum-containing main chain can be 20%:20%:20％：20％：20％。
Introduction of (Ti) -containing carbon fiber preform by vacuum impregnation 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Of C powder (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) And C precursor solution (the solution viscosity is 20-300 mPas). Wherein, the vacuum degree of vacuum impregnation can be-0.08 to-0.10 MPa, and the impregnation time can be 0.5 to 2 hours. Curing and high-temperature heat treatment, and repeating the above steps for 2-4 times to obtain porous C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) And C, material. Wherein the curing temperature can be 150-300 ℃ and the curing time can be 2-4 hours. The heat treatment temperature can be 1500-1800 ℃, the time can be 0.5-3 hours, and the atmosphere can be vacuum or inert atmosphere. In the process of preparing the ceramic matrix composite containing the high-entropy ceramic powder, the introduction of (Ti) is determined 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The curing temperature system and the heat treatment temperature of the C high-entropy ultrahigh-temperature ceramic matrix are difficult. Determined by thermogravimetric analysis and XRD analysis comparison after heat treatment at different temperatures (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C precursor solution to (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) And C, the phase transition process of the ceramic powder, and finally determining a curing temperature system and a heat treatment temperature.
Introducing SiC ceramic matrix. Liquid Polycarbosilane (PCS) with high ceramic yield is taken as a precursor, and is dipped into the porous C by vacuum under the condition that the vacuum degree is-0.08 to-0.10 MPa f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) SiC is introduced into the material, and the dipping time is 0.5 to 2 hours. The impregnation-solidification-cracking was repeated 2 to 4 times to fill SiC (Ti) as much as possible 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Pores generated by volume shrinkage in the process of C formation are obtained to finally obtain the C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C-SiC high-entropy ultra-high-temperature ceramic matrix composite. Wherein the curing temperature can be 80-170 ℃ and the curing time can be 2-4 hours. The cracking temperature can be 1000-1300 ℃, the time can be 1-2 hours, and the atmosphere can be vacuum or inert atmosphere.
In the present invention, in the composite material, (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C phase and the SiC phase are in a dispersion distribution or continuous distribution form in the carbon fiber, (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The elements in the C phase are uniformly distributed. Prepared C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite has uniform components, low fiber/interface damage, excellent mechanical property and high-temperature ablation resistance. It should be noted that the above examples are given by Ti though 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 As an example, but when a =18 to 22%, b =18 to 22%, c =18 to 22%, d =18 to 22%, e =18 to 22%, and a + b + c + d + e =1, are all applicable to the above-described preparation process.
In the invention, the method for measuring C by adopting Archimedes drainage method f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The open porosity of the C-SiC high-entropy ultra-high temperature ceramic matrix composite material is less than 12vol%.
In the present invention, C is measured by an Instron-5566 model electronic universal tester f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The three-point bending strength of the C-SiC high-entropy ultra-high temperature ceramic matrix composite material is more than or equal to 300MPa, and the fracture toughness is more than or equal to 8 MPa-m 1/2 。
In the present invention, C is prepared f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has the molecular weight of 5MW/m 2 After the heat flow density air plasma ablates for 300s, the line ablation rate is less than or equal to 1 μm/s.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing description are intended to be included within the scope of the invention. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The preparation method of the C-SiC high-entropy ultrahigh-temperature ceramic matrix composite material comprises the following specific steps:
(1) And (4) processing the fiber preform. Depositing a PyC/SiC composite interface on the surface of the carbon fiber woven body by a chemical vapor deposition method, wherein the total thickness of the interface is 1 mu m, and the open porosity of the fiber preform is 70vol%;
(2) Introduction of (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) And C phase. Introduction of (Ti) -containing carbon fiber preform by vacuum impregnation 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) Of C powder (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C precursor solution, wherein (Ti) in the precursor 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C, the solid content of the high-entropy ceramic powder is 50wt% (the mass ratio of the polymer containing titanium, zirconium, hafnium, niobium and tantalum as main chains, acetylacetone and ethanol is 29wt%:3wt%:68wt%. The atomic ratio of Ti, zr, hf, nb and Ta in the polymer containing titanium, zirconium, hafnium, niobium and tantalum in the main chain is 20%:20%:20%:20%: 20%). The vacuum degree of vacuum impregnation is-0.10 MPa, and the impregnation time is 2 hours; curing at 250 deg.C for 2 hr, and heat treating at 1700 deg.C under vacuum for 2 hr; repeating the impregnation curing and the high-temperature heat treatment for 3 times to obtain the porous C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) A material C;
(3) Introducing a SiC phase. Liquid polycarbosilane is used as a precursor, the liquid polycarbosilane is dipped for 1 hour under the condition that the vacuum degree is minus 0.10MPa, the liquid polycarbosilane is solidified for 2 hours at the temperature of 120 ℃, and thenCracking for 2 hours at 1000 ℃ in Ar atmosphere to form porous C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) SiC is introduced into the material. Repeating the impregnation, curing and cracking for 3 times to finally obtain compact C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C-SiC high-entropy ultrahigh-temperature ceramic matrix composite. Wherein the volume fraction of the carbon fiber preform is 30vol%, (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The content of the C high-entropy ultrahigh-temperature ceramic matrix is 42wt%, and the content of the SiC ceramic matrix is 35wt%.
C prepared in example 1 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 8vol%, a bending strength of 385MPa and a fracture toughness of 9.0MPa m 1/2 At 5MW/m 2 Heat flow density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 0.7 μm/s.
Example 2
Similar to the procedure of example 1, except that: the carbon fiber surface of the carbon fiber woven body was deposited with a PyC interface having a thickness of 1 μm.
Example 2 prepared C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 8vol%, a bending strength of 325MPa and a fracture toughness of 8.1MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 0.9 μm/s.
Example 3
Similar to the procedure of example 1, except that: the surface of the carbon fiber woven body was deposited with a PyC/SiC interface of 0.5 μm thickness.
Example 3 prepared C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 10vol%, a bending strength of 370MPa, and a fracture toughness of 8.5MPa m 1/2 At 5MW/m 2 Thermal flux density air plasma ablation conditionsThe lower part is ablated for 300s, and the ablation rate of the material line is 0.85 mu m/s.
Example 4
Similar to the procedure of example 1, except that: the initial open porosity of the fiber preform was 60vol%.
Example 4 prepared C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 7vol%, a bending strength of 398MPa, and a fracture toughness of 9.5MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 1.0. Mu.m/s.
Example 5
Similar to the procedure of example 1, except that: the heat treatment temperature in the step (2) was 1600 ℃.
C prepared in example 5 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 8vol%, a bending strength of 393MPa and a fracture toughness of 8.6MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 1.0. Mu.m/s.
Example 6
Similar to the procedure of example 1, except that: the heat treatment temperature in the step (2) was 1800 ℃.
C prepared in example 6 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 7vol%, a bending strength of 377MPa, and a fracture toughness of 8.5MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 0.7 μm/s.
Example 7
Similar to the procedure of example 1, except that: in the step (2), the processes of dipping, curing and high-temperature treatment are repeated for 4 times.
Example 7 prepared C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C-SiC composite material open porosity E up to C7vol%, flexural strength 372MPa, and fracture toughness 8.8MPa m 1/2 At 5MW/m 2 Heat flow density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 0.6 μm/s.
Example 8
Similar to the procedure of example 1, except that: in the precursor solution (Ti) in the step (2) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The solid content of the C high-entropy ceramic powder is 40wt%.
C prepared in example 8 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 12vol%, a bending strength of 362MPa, and a fracture toughness of 8.2MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 1.0. Mu.m/s.
Example 9
Similar to the procedure of example 1, except that: in the precursor solution in the step (2) (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The solid content of the C high-entropy ceramic powder is 60wt%.
Example 9 prepared C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 7vol%, a bending strength of 392MPa, and a fracture toughness of 9.8MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 0.6 μm/s.
Example 10
Similar to the procedure of example 1, except that: the cracking temperature of the polycarbosilane in the step (3) is 1200 ℃.
C prepared in example 10 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 8vol%, a bending strength of 396MPa, and a fracture toughness of 9.6 MPa.m 1/2 At 5MW/m 2 The material line is ablated for 300s under the condition of heat flow density and air plasma ablation, and the ablation rate of the material line is 0.8 mu m/s.
Example 11
Similar to the procedure of example 1, except that: in the step (3), the impregnation-solidification-cracking process is repeated for 4 times to introduce SiC.
EXAMPLE 11 prepared C f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 7vol%, a bending strength of 391MPa, and a fracture toughness of 9.5MPa m 1/2 At 5MW/m 2 The material line is ablated for 300s under the condition of heat flow density and air plasma ablation, and the ablation rate of the material line is 0.8 mu m/s.
Example 12
Similar to the procedure of example 12, except that: the dipping-curing-high temperature treatment process in the step (2) is repeated for 2 times.
C prepared in example 12 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 10vol%, a bending strength of 355MPa and a fracture toughness of 8.1MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 1.0. Mu.m/s.
Comparative example 1
Similar to the procedure in example 1, except that: pure (Ti) is introduced into the carbon fiber preform in the step (2) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) C precursor solution, free of (Ti) 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) And C, powder.
C prepared in comparative example 1 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 25vol%, a bending strength of 278MPa and a fracture toughness of 6.8MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 5.0. Mu.m/s.
Comparative example 2
Similar to the procedure in example 2, except that: in the step (2), slurry prepared from (TiZrHfNbTa) C high-entropy powder, PVB, resin and an ethanol solvent is introduced into the carbon fiber preform, wherein the mass content of the (TiZrHfNbTa) C high-entropy powder is 60%, and the slurry does not contain a polymer with a main chain containing Ti, zr, hf, nb and Ta.
C prepared in comparative example 2 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 20vol%, a bending strength of 308MPa, and a fracture toughness of 7.0MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 2.2 μm/s.
Comparative example 3
Similar to the procedure in example 1, except that: the dipping-curing-high temperature treatment process in the step (2) is repeated for 1 time.
C prepared in comparative example 2 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 15vol%, a bending strength of 335MPa, and a fracture toughness of 7.3MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 1.5 μm/s.
Comparative example 4
Similar to the procedure in example 1, except that: in the step (2), the processes of dipping, curing and high-temperature treatment are repeated for 5 times.
C prepared in comparative example 2 f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The C-SiC composite material has an open porosity of 8vol%, a bending strength of 368MPa, and a fracture toughness of 8.5MPa m 1/2 At 5MW/m 2 Heat flow Density ablation was carried out for 300s under air plasma ablation conditions, and the ablation rate of the material line was 0.9 μm/s. The fiber interface is damaged due to the high-temperature treatment times, so that the bending strength is reduced, and the ablation resistance is reduced.
Table 1 shows C prepared according to the invention f /(Ti 0.2 Zr 0.2 Hf 0.2 Nb 0.2 Ta 0.2 ) The performance of the C-SiC composite material is as follows:
Claims (10)
1. c f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite material is characterized by comprising: carbon fiber preform, and (Ti) formed in the carbon fiber preform in sequence a Zr b Hf c Nb d Ta e ) The SiC ceramic matrix, wherein a = 18-22%, b = 18-22%, C = 18-22%, d = 18-22%, e = 18-22%, and a + b + C + d + e =1; the (Ti) a Zr b Hf c Nb d Ta e ) The content of the C high-entropy ultrahigh-temperature ceramic matrix is 40-60 wt%.
2. C according to claim 1 f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite is characterized in that the volume fraction of the carbon fiber preform is 20-50 vol%, and the content of the SiC ceramic matrix is 30-50 wt%.
3. C according to claim 1 or 2 f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultrahigh-temperature ceramic matrix composite is characterized in that the surface of carbon fiber in the carbon fiber preform further comprises an interface layer; the interface layer is selected from at least one of a PyC layer, a BN layer, a PyC layer/SiC layer and a BN/SiC layer; the thickness of the interface layer is 0.1 to 1 μm.
4. The C of any one of claims 1-3 f /(Ti a Zr b Hf c Nb d Ta e ) The C-SiC high-entropy ultra-high temperature ceramic matrix composite is characterized in that,said C is f /(Ti a Zr b Hf c Nb d Ta e ) The bending strength of the C-SiC high-entropy ultrahigh-temperature ceramic matrix composite material is more than or equal to 300MPa, and the fracture toughness is more than or equal to 8 MPa-m 1/2 (ii) a At 5MW/m 2 Heat flux density under air plasma ablation conditions, C f /(Ti a Zr b Hf c Nb d Ta e ) The ablation rate of the C-SiC high-entropy ultrahigh-temperature ceramic matrix composite material is less than or equal to 1 mu m/s.
5. C according to any one of claims 1 to 4 f /(Ti a Zr b Hf c Nb d Ta e ) The preparation method of the C-SiC high-entropy ultrahigh-temperature ceramic matrix composite is characterized in that (Ti) is sequentially introduced into the carbon fiber preform by adopting a vacuum impregnation method a Zr b Hf c Nb d Ta e ) C high entropy ultra high temperature ceramic substrate and SiC ceramic substrate to obtain C f /(Ti a Zr b Hf c Nb d Ta e ) C-SiC high-entropy ultra-high-temperature ceramic matrix composite.
6. The method according to claim 5, characterized in that the (Ti) is introduced in a carbon fiber preform a Zr b Hf c Nb d Ta e ) The method for preparing the C high-entropy ultrahigh-temperature ceramic matrix comprises the following steps:
(1) Introduction of (Ti) into carbon fiber preforms by vacuum impregnation a Zr b Hf c Nb d Ta e ) C precursor is solidified and heat treated to obtain C f /(Ti a Zr b Hf c Nb d Ta e ) A C intermediate; preferably, the curing temperature is 150-300 ℃ and the curing time is 2-4 hours; the heat treatment temperature is 1500-1800 ℃, the time is 0.5-3 hours, and the atmosphere is vacuum or inert atmosphere;
(2) Repeating the step (1) for 2 to 4 times to obtain the porous C f /(Ti a Zr b Hf c Nb d Ta e ) And C, material.
7. The method according to claim 6, wherein the (Ti) is a Zr b Hf c Nb d Ta e ) C precursor contains (Ti) a Zr b Hf c Nb d Ta e ) C powder, a polymer with a main chain containing titanium, zirconium, hafnium, niobium and tantalum, acetylacetone and a solvent;
preferably, the atomic ratio of Ti, zr, hf, nb and Ta in the polymer with the titanium-containing zirconium hafnium niobium tantalum main chain is (18-22%): (18-22%): (18-22%): (18-22%): (18-22%);
preferably, the (Ti) a Zr b Hf c Nb d Ta e ) The particle size of the C powder is submicron, and is more preferably 100-500 nm;
preferably, the solvent is an alcoholic solvent, preferably at least one of ethanol and butanol; the contents of the polymer with the titanium-containing zirconium hafnium niobium tantalum main chain, the acetylacetone and the solvent are respectively 25-30 wt% in terms of that the mass sum of the polymer with the titanium-containing zirconium hafnium niobium tantalum main chain, the acetylacetone and the solvent is 100%: 3-5 wt%: 65-70 wt%;
preferably, the (Ti) a Zr b Hf c Nb d Ta e ) C precursor solution (Ti) a Zr b Hf c Nb d Ta e ) The solid content of the C powder is 30-60 wt%, and the solution viscosity is 20-300 mPas.
8. The production method according to claim 6 or 7, wherein the SiC ceramic base is introduced by:
(1) To the porous C by vacuum impregnation f /(Ti a Zr b Hf c Nb d Ta e ) Introducing SiC precursor into the material C, and curing and cracking to obtain the material C f /(Ti a Zr b Hf c Nb d Ta e ) A C-SiC intermediate;
(2) Repeating the step (1) for 2-4 times to obtain the C f /(Ti a Zr b Hf c Nb d Ta e ) C-SiC high-entropy ultrahigh-temperature ceramic matrix composite.
9. The preparation method according to claim 8, wherein the SiC precursor is liquid polycarbosilane PCS, and the ceramic yield is more than or equal to 60wt%; the curing temperature is 80-170 ℃, and the curing time is 2-4 hours; the cracking temperature is 1000-1300 ℃, the time is 1-2 hours, and the atmosphere is vacuum or inert atmosphere.
10. The production method according to any one of claims 5 to 9, wherein the vacuum degree of the vacuum impregnation is from-0.08 to-0.10 MPa, and the impregnation time is from 0.5 to 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110569439.6A CN115385712A (en) | 2021-05-25 | 2021-05-25 | High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110569439.6A CN115385712A (en) | 2021-05-25 | 2021-05-25 | High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115385712A true CN115385712A (en) | 2022-11-25 |
Family
ID=84114466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110569439.6A Pending CN115385712A (en) | 2021-05-25 | 2021-05-25 | High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115385712A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784761A (en) * | 2022-12-02 | 2023-03-14 | 无锡博智复合材料有限公司 | High-entropy ceramic coating and matrix synergistically modified carbon/carbon composite material and preparation method thereof |
| CN115784746A (en) * | 2022-12-08 | 2023-03-14 | 航天特种材料及工艺技术研究所 | High-entropy ceramic matrix composite and preparation method thereof |
| CN116217233A (en) * | 2023-03-27 | 2023-06-06 | 广东工业大学 | Complex-phase ceramic of SiC whisker and high-entropy boride hardened and toughened high-entropy carbide, and preparation method and application thereof |
| CN116715526A (en) * | 2023-06-09 | 2023-09-08 | 中南大学 | C/C- (Ti, zr, hf, nb, ta) C-SiC composite material and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020164432A1 (en) * | 2000-04-20 | 2002-11-07 | William Hofmeister | Method and system for thick-film deposition of ceramic materials |
| US20090074604A1 (en) * | 2007-09-19 | 2009-03-19 | Industrial Technology Research Institute | Ultra-hard composite material and method for manufacturing the same |
| CN109912313A (en) * | 2019-03-06 | 2019-06-21 | 中南大学 | A kind of single-phase superhigh temperature ceramics modifying carbon/carbon composite material of new multicomponent and preparation method thereof |
| CN110002892A (en) * | 2019-05-08 | 2019-07-12 | 航天特种材料及工艺技术研究所 | A kind of hafnium tantalum silicon ternary complex phase ceramic presoma, carbon/hafnium tantalum carbon solid solution-carbon/silicon carbide ceramic matrix composite and preparation method thereof |
| US20200199027A1 (en) * | 2018-12-21 | 2020-06-25 | Rolls-Royce Corporation | Thermal and/or environmental barrier coating system |
| CN112062576A (en) * | 2020-08-19 | 2020-12-11 | 广东工业大学 | Graphene-toughened high-entropy silicide ceramic and preparation method and application thereof |
-
2021
- 2021-05-25 CN CN202110569439.6A patent/CN115385712A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020164432A1 (en) * | 2000-04-20 | 2002-11-07 | William Hofmeister | Method and system for thick-film deposition of ceramic materials |
| US20090074604A1 (en) * | 2007-09-19 | 2009-03-19 | Industrial Technology Research Institute | Ultra-hard composite material and method for manufacturing the same |
| US20200199027A1 (en) * | 2018-12-21 | 2020-06-25 | Rolls-Royce Corporation | Thermal and/or environmental barrier coating system |
| CN109912313A (en) * | 2019-03-06 | 2019-06-21 | 中南大学 | A kind of single-phase superhigh temperature ceramics modifying carbon/carbon composite material of new multicomponent and preparation method thereof |
| CN110002892A (en) * | 2019-05-08 | 2019-07-12 | 航天特种材料及工艺技术研究所 | A kind of hafnium tantalum silicon ternary complex phase ceramic presoma, carbon/hafnium tantalum carbon solid solution-carbon/silicon carbide ceramic matrix composite and preparation method thereof |
| CN112062576A (en) * | 2020-08-19 | 2020-12-11 | 广东工业大学 | Graphene-toughened high-entropy silicide ceramic and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| FEIYAN CAI等: "Fabrication and properties of Cf(Ti0.2Zr0.2Hf0.2Nb0.2Ta0.2)C-SiC high-entropy ceramic matrix composites via precursor infiltration and pyrolysis", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| 李贺军等: "《先进复合材料学》", 31 December 2016, 西北工业大学出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784761A (en) * | 2022-12-02 | 2023-03-14 | 无锡博智复合材料有限公司 | High-entropy ceramic coating and matrix synergistically modified carbon/carbon composite material and preparation method thereof |
| CN115784761B (en) * | 2022-12-02 | 2023-09-19 | 无锡博智复合材料有限公司 | High-entropy ceramic coating and matrix synergistically modified carbon/carbon composite material and preparation method thereof |
| CN115784746A (en) * | 2022-12-08 | 2023-03-14 | 航天特种材料及工艺技术研究所 | High-entropy ceramic matrix composite and preparation method thereof |
| CN115784746B (en) * | 2022-12-08 | 2024-01-16 | 航天特种材料及工艺技术研究所 | High-entropy ceramic matrix composite material and preparation method thereof |
| CN116217233A (en) * | 2023-03-27 | 2023-06-06 | 广东工业大学 | Complex-phase ceramic of SiC whisker and high-entropy boride hardened and toughened high-entropy carbide, and preparation method and application thereof |
| CN116217233B (en) * | 2023-03-27 | 2024-01-09 | 广东工业大学 | Complex-phase ceramic of SiC whisker and high-entropy boride hardened and toughened high-entropy carbide, and preparation method and application thereof |
| CN116715526A (en) * | 2023-06-09 | 2023-09-08 | 中南大学 | C/C- (Ti, zr, hf, nb, ta) C-SiC composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115385712A (en) | High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof | |
| CN110256082B (en) | Method for preparing single crystal silicon carbide nanofiber/silicon carbide ceramic matrix composite material by reaction sintering | |
| CN112341235B (en) | Multiphase coupling rapid densification method for ultrahigh-temperature self-healing ceramic matrix composite | |
| CN105016759A (en) | Rapid preparation method for C/SiC composite material | |
| CN112341229B (en) | Gradient C/ZrC-SiC superhigh temperature ceramic matrix composite and preparation method thereof | |
| CN113321510B (en) | High-entropy ceramic matrix composite and preparation method thereof | |
| CN112341233A (en) | Multi-element single-phase ultra-high temperature ceramic TaxHf1-xPreparation method of C modified carbon/carbon composite material | |
| CN112898023B (en) | Cf/Ta4HfC5-SiC superhigh temperature ceramic matrix composite material and preparation method thereof | |
| CN110627514A (en) | C/SiC-HfB2Composite material and preparation method thereof | |
| CN109251049A (en) | A method of limitation matrices of composite material propagation of internal cracks | |
| CN110642634A (en) | C/SiC-ZrB2Composite material and preparation method thereof | |
| CN114573357A (en) | SiC nanowire reinforced SiC ceramic matrix composite and preparation method thereof | |
| CN108178648B (en) | Three-dimensional carbon fiber reinforced alumina-zirconia composite material and preparation method thereof | |
| US20060269683A1 (en) | Silicon carbide-based, porous, lightweight, heat-resistant structural material and manufacturing method therefor | |
| CN112521156B (en) | Hybrid matrix SiCf/SiC composite material and preparation method thereof | |
| CN114702328A (en) | SiC nanowire network reinforced layered porous SiC ceramic and preparation method thereof | |
| EP1284251A1 (en) | Silicon carbide-based, porous, lightweight, heat-resistant structural material and manufacturing method therefor | |
| CN112374901B (en) | Ablation-resistant modified C/SiC composite material and preparation method thereof | |
| CN108147796B (en) | Three-dimensional silicon carbide fiber reinforced silicon oxide-zirconium oxide composite ceramic composite material and preparation method thereof | |
| Kim et al. | Nicalon-fibre-reinforced silicon-carbide composites via polymer solution infiltration and chemical vapour infiltration | |
| CN109608235A (en) | Gel infiltration ceramic modification method for C/C composite material special-shaped part | |
| JPH08501523A (en) | Method of manufacturing fiber composite material | |
| CN115124360B (en) | Carbon fiber toughened ceramic material and preparation method thereof | |
| CN108033803B (en) | Three-dimensional silicon carbide fiber reinforced alumina-zirconia composite material and preparation method thereof | |
| CN115716760A (en) | C/SiC-HfC ceramic matrix composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20221125 |