CN115557791B - Method for preparing variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite - Google Patents
Method for preparing variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite Download PDFInfo
- Publication number
- CN115557791B CN115557791B CN202211178004.XA CN202211178004A CN115557791B CN 115557791 B CN115557791 B CN 115557791B CN 202211178004 A CN202211178004 A CN 202211178004A CN 115557791 B CN115557791 B CN 115557791B
- Authority
- CN
- China
- Prior art keywords
- carbon
- carbon fiber
- sides
- porous carbon
- fiber reinforced
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 39
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 39
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000011216 ultra-high temperature ceramic matrix composite Substances 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 238000002468 ceramisation Methods 0.000 claims abstract description 6
- 239000000155 melt Substances 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 23
- 238000003763 carbonization Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- 238000001764 infiltration Methods 0.000 claims description 14
- 230000008595 infiltration Effects 0.000 claims description 14
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 229920001568 phenolic resin Polymers 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 239000002296 pyrolytic carbon Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910008341 Si-Zr Inorganic materials 0.000 description 5
- 229910006682 Si—Zr Inorganic materials 0.000 description 5
- 238000002679 ablation Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011153 ceramic matrix composite Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005475 siliconizing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910006249 ZrSi Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- -1 hexamethylene tetram Chemical compound 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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
- 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
- C04B35/573—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 obtained by reaction sintering or recrystallisation
-
- 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
- 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/404—Refractory metals
-
- 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
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B2235/5248—Carbon, e.g. graphite
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/614—Gas infiltration of green bodies or pre-forms
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/75—Products with a concentration gradient
-
- 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
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9684—Oxidation resistance
Abstract
The invention discloses a method for preparing a variable-component carbon fiber reinforced ultra-high temperature ceramic matrix composite material, and belongs to the technical field of thermal protection materials for aircrafts. The nano porous carbon with different pore structures is respectively introduced into two sides of a carbon fiber preform, different reaction melts are selected to respectively infiltrate into the two sides, and the variable-composition carbon fiber reinforced ultra-high temperature ceramic matrix composite material is prepared through a uniform ceramization process of the nano porous carbon, wherein the matrixes at the two sides are submicron-level uniformly distributed complex phase ceramics with different components. The composite material obtained by the invention has high density and no residual alloy, the preparation period is only 300-500 h, and meanwhile, the structure and the composition of the material have extremely strong designability, and the use requirements under different service conditions can be met.
Description
Technical Field
The invention relates to the technical field of thermal protection materials for aircrafts, in particular to a method for preparing a variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite.
Background
The development of the high and new technology is very rapid in the world, the requirements of various industries on materials are increasingly improved, and the aerospace field provides severe requirements on high temperature resistance, ablation resistance, high specific strength, high specific stiffness, high toughness and the like for heat protection materials. Meanwhile, as the two sides of the ceramic matrix composite component have the difference of service environments, the components of the ceramic matrix composite component can be designed differently so as to realize the requirements of light weight reduction, cost reduction and the like of the component on the premise of near-zero ablation. Report "NASA/TM-2004-213085" proposes a composition with a variable HfB 2 Composite material of SiC matrix, hfB 2 The concentrated region serves as an outside ablative material and the SiC enriched region serves as a backside antioxidant material, and the structural design greatly reduces the quality and the preparation cost of the material. Patent CN108117412B' describes a C/C, gradient C/C-SiC, C/SiC-ZrB, which are symmetrically distributed from the center to the two sides 2 Composite material and SiC coated composite material. The material improves mechanical property and reduces density by the distribution of carbon and SiC matrix in the center of the material, and passes ZrB 2 Enrichment in the outer layer to achieve ultra-high temperature ablation resistance. It can be seen that the design and preparation of the variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite material combined with the service environment has great significance for improving the comprehensive performance of the thermal protection material. The article "Ceramics International, 2017, 43:16114-16120" indicates that: compared with a ceramic matrix with large-size (several micrometers to tens of micrometers) blocky distribution, a small-size (nano-scale) uniformly distributed complex-phase HfC-SiC matrix has obvious ablation resistance performance advantages. Aiming at the problems, the invention provides a method for preparing the variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite material, and provides a solution for the design and application of the composite material.
Disclosure of Invention
The invention aims to provide a method for preparing a variable-composition carbon fiber reinforced ultra-high temperature ceramic matrix composite material, which is characterized in that nano porous carbon with different pore structures is respectively introduced into two sides of a carbon fiber preform, reaction melts corresponding to the matrix structures are respectively permeated into the two sides, and the variable-composition carbon fiber reinforced ultra-high temperature ceramic matrix composite material is prepared by a nano porous carbon uniform ceramization method, wherein the matrixes on the two sides are nano-scale distributed complex-phase ceramics with different components.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the method is to introduce nano porous carbon with different pore structures at two sides of a carbon fiber preform, then to select different reaction melts to permeate into the two sides respectively, and to prepare the variable component carbon fiber reinforced ultra-high temperature ceramic matrix composite by a nano porous carbon uniform ceramization method.
The method specifically comprises the following steps:
(1) The nano porous carbon with different pore structures is introduced at two sides of the preform, and the process is as follows: sequentially carrying out impregnation, high-pressure curing and carbonization treatment on each side of the carbon fiber preform, and repeating the impregnation-curing-carbonization process for 3-8 times until the carbon matrix completely fills the fiber preform; after the one-side filling is finished, the other side is refilled; the precursor solution comprises phenolic resin, a pore-forming agent and a curing agent;
(2) And selecting proper alloy melt for infiltration reaction of porous carbon matrixes with different pore structures, and uniformly ceramifying nano porous carbon at two sides of a preform after the reaction to prepare the variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite material.
In the step (1), before the precursor solution is immersed, pyrolytic carbon or silicon carbide is deposited on the surface of the carbon fiber by adopting a chemical vapor infiltration process to prepare an interface layer, wherein the total thickness of the interface layer is 0.6-5 mu m.
In the step (1), the impregnation process is as follows: immersing one side of the fiber preform into the precursor solution for 1-4 hours until no obvious bubbles exist; immersing the other side of the fiber preform into the precursor solution for 1-4 hours until no obvious bubbles exist; in the precursor solution, the phenolic resin is common commercial grade resin or modified boron phenolic or barium phenolic and the like; the pore-forming agent is at least one of ethylene glycol, diethylene glycol, polyethylene glycol and polyethylene glycol; the curing agent is at least one of sodium carbonate, propylene carbonate, p-toluenesulfonic acid, phosphoric acid, benzenesulfonic acid, benzenesulfonyl chloride, hexamethylenetetramine and methylol urea; the proportion of phenolic resin, pore-forming agent and curing agent in the precursor solution is 1: (1-6): (0.02-0.20), and controlling the proportion of pore-forming agents in the precursor solution to obtain the nano porous carbon matrix with different pore structures at two sides of the preform.
In the step (1), the precursor solution is immersed and cured under high pressure, and the high pressure curing process is as follows: heating to the curing temperature of 120-250 ℃ at a heating rate of more than 10 ℃/min under the condition of pressurization, and preserving heat for 10-40 h under the pressure range of 1-10 MPa; the phase separation is assisted by high pressure, and the external pressure can inhibit the boiling of pore-forming agents (glycol and the like) and the volatilization of free phenol and other substances, thereby being beneficial to uniform gel formation of porous organic matrixes with uniform pore structures; meanwhile, the high curing temperature can enable more active sites in the phenolic resin molecular system to participate in polymerization reaction so as to form a small-aperture framework structure.
In the step (1), the carbonization treatment process is as follows: and placing the carbon fiber reinforced porous resin matrix composite material obtained after the curing treatment in a vacuum carbonization furnace, and heating the vacuum carbonization furnace to 900-1800 ℃ at a heating rate of 5-10 ℃/min to obtain the nano porous carbon/carbon infiltration preform. The carbonization treatment temperature range is 900-1800 ℃, and the regulation and control of the pore structure of the carbon matrix are further realized by combining micropores and promoting the ordered arrangement of carbon atoms under the high-temperature condition.
In the step (1), the porous carbon substrates at both sides of the carbon fiber preform are distributed with nano-scale holes with uniform structures, but the porosity and the pore size of the porous carbon substrates are obviously different.
In the step (2), the reaction alloy component is selected from two or more of Si, transition metal element (Zr, hf, ti, ta, nb, Y, sc) and lanthanide metal element (La-Lu), and the component selection should correspond to the structure of the porous carbon matrix, i.e. the volume expansion rate of the carbon skeleton converted into the complex phase ceramic in the reaction process should be equal to or slightly lower than the reciprocal of the volume proportion of the carbon skeleton in the porous carbon matrix. Wherein P is the porosity of the porous carbon matrix, and the volume ratio of the carbon skeleton in the porous carbon matrix is 1-P.
In the step (2), the temperature is kept for 0.5 to 3 hours at the temperature 50 to 250 ℃ higher than the melting point of the selected powder in each infiltration reaction process, and the pressure in the infiltration process is less than 20Pa; after the reaction, no residual carbon matrix and excessive reaction melt are generated, and the fiber is not etched, so that the prepared ceramic matrix is compact and different ceramic phases are uniformly distributed in submicron level.
The beneficial effects of the invention are as follows:
(1) The invention takes resin, pore-forming agent and curing agent as raw materials, the prepared precursor solution is immersed into the carbon fiber preform, and a high-pressure condition auxiliary phase separation method is adopted in the subsequent curing process, and the boiling of the pore-forming agent (glycol and the like) and the volatilization of free phenol and other substances are inhibited by external pressure, so that the resin is uniformly gelled to form a porous organic matrix with uniform pore structure; meanwhile, the high curing temperature is adopted, so that more active sites in the phenolic resin molecular system participate in the polymerization reaction, and then a small-aperture framework structure is formed. Finally, the porous carbon matrix with the nanometer pore diameter can be obtained in the carbon fiber preform through carbonization.
(2) According to the invention, nano porous carbon with different pore structures is respectively introduced into two sides of a carbon fiber preform, reaction melts corresponding to the matrix structures are respectively selected to permeate into two sides, and the variable-composition carbon fiber reinforced ultra-high temperature ceramic matrix composite material is prepared by a nano porous carbon uniform ceramic method, wherein the matrixes at two sides are sub-micron-level graded complex phase ceramics with different compositions. The composite material obtained by the invention has high density, no residual alloy, no fiber etching and excellent mechanical and oxidation ablation resistance. The cost of the selected raw materials is low, and the preparation period of the process is only 300-500 hours, so that the process has remarkable process advantages.
(3) Compared with the traditional preparation process, the prepared ultrahigh-temperature ceramic matrix composite material has the characteristics of variable components, adjustable components and strong designability, and can be designed according to the structure and the components of the composite material with different service requirements.
Drawings
FIG. 1 shows porous carbon morphology infiltration with two sides filled respectively in example 1; wherein: (a) 25wt.% side porous carbon matrix morphology for infiltrated Si-Zr, (b) 60wt.% side porous carbon matrix morphology for infiltrated Si-Zr; the two matrices were measured to have average pore diameters of 40.3 nm and 98.7 nm, respectively, differing by more than one time in size, and porosities of 0.52 and 0.68, respectively, differing by more than 30%.
FIG. 2 is a microstructure of the composite material C/SiC-ZrC prepared in example 1; wherein: the a region is a Si-Zr25wt.% infiltration region, the b region is a Si-Zr60wt.% infiltration region, wherein the submicron white phase is ZrC, the gray phase is SiC, and the ZrC contents on both sides can be seen to show obvious difference.
FIG. 3 shows the composition of the composite C/SiC-ZrC prepared in example 1, mainly comprising C, siC and ZrC phases.
FIG. 4 shows the microscopic morphology of the C/SiC-HfC side of the composite material prepared in example 2, wherein the submicron white phase is HfC and the gray phase is SiC.
Detailed Description
The invention will be further illustrated with reference to specific examples.
For a further understanding of the present invention, the present invention is described below with reference to the following examples, which are merely illustrative of the features and advantages of the present invention, and are not intended to limit the claims of the present invention. According to the invention, nano porous carbon with different pore structures is sequentially introduced at two sides of a carbon fiber preform, reaction melts corresponding to the matrix structures are respectively permeated at two sides, and the variable-composition carbon fiber reinforced ultra-high temperature ceramic matrix composite material is prepared by a nano porous carbon uniform ceramization method, wherein the matrixes at two sides are sub-micron-level fraction composite ceramics with different components.
Example 1:
the embodiment uses PAN-based T700 carbon felt prepared by a needling process technology as a fiber preform, and the specific process steps are as follows:
1) PAN-based T700 carbon felt with size of 400 multiplied by 100 multiplied by 10mm and density of 0.52 g/cm is prepared 3 。
2) Adopts chemical vapor infiltration process to prepare pyrolytic carbon interface layer with the temperature of 900 ℃ and argon flow of 0.2 m 3 /h, propane 0.15. 0.15 m 3 And/h, deposition time 100 h.
3) Preparing a precursor solution from phenolic resin, ethylene glycol and benzenesulfonyl chloride according to a mass ratio of 11:10:2, and impregnating one side of the felt body and keeping 2 h.
4) And (3) placing the felt body in a curing furnace for curing, and preserving heat at the temperature of 120-250 ℃ under the pressure of 4 MPa for 40-h.
5) Placing the felt body in a vacuum carbonization furnace for carbonization, and heating up the curve: 20 ℃ to 220 ℃ for 0.5 h,220 ℃ to 550 ℃ for 3 h,550 ℃ to 750 ℃ for 4 h,750 ℃ to 1000 ℃ for 2 h,1000 ℃ to 1200 ℃ for 2 h, and 1200 ℃ for 1 h.
6) Repeating the steps (4), 5 and 6) for 5 times, preparing a precursor solution from phenolic resin, ethylene glycol and benzenesulfonyl chloride according to the mass ratio of 11:15:2, and repeating the infiltration-curing-carbonization process on the other side of the fiber preform.
7) And respectively coating 25wt.% of Si-Zr and 60wt.% of Si-Zr on two sides of the prepared C/C preform, placing the C/C preform in a siliconizing furnace, heating to 1800 ℃ under the pressure environment of less than 20Pa, and preserving heat for 1h to obtain the variable component C/SiC-ZrC composite material with different ZrC contents on two sides.
The morphology of porous carbon filled at 25wt.% and 60wt.% sides of infiltrated Si-Zr is shown in fig. 1 (a) and 1 (b), the microstructure of the matrix of the C/SiC-ZrC composite material and the microstructure of the boundary between the two sides are shown in fig. 2, and the composition of the prepared C/SiC-ZrC composite material is shown in fig. 3. It can be seen that the pore size of the porous carbon can be increased from 40.3 to nm to 98.7 to nm by adjusting the precursor ratio, the size difference is more than one time, and the porosities are respectively 0.52 and 0.68, and the values are different by more than 30%. Meanwhile, the two sides after the reaction form a complex phase ceramic matrix with submicron ZrC uniformly distributed in the SiC matrix, and the ZrC contents at the two sides are greatly different. Therefore, the variable component C/SiC-ZrC composite material can be prepared by adopting the method.
Example 2:
the embodiment uses PAN-based T700 carbon felt prepared by a needling process technology as a fiber preform, and the specific process steps are as follows:
1) PAN-based T700 carbon felt with the size of 400 multiplied by 100 multiplied by 10mm and the density of 0.52 g/cm is prepared 3 。
2) The ICVI process is adopted to prepare a pyrolytic carbon interface layer: argon flow rate is selected to be 0.2 m 3 /h, propane 0.15. 0.15 m 3 And/h, depositing 100 h at 900 ℃ to obtain a pyrolytic carbon interface.
3) Preparing a precursor solution from phenolic resin, polyethylene glycol and hexamethylenetetramine according to a mass ratio of 11:15:2, and soaking one side of the felt body and keeping 2 h.
4) And (3) placing the felt body in a curing furnace for curing, and preserving heat at the temperature of 120-250 ℃ under the pressure of 4 MPa for 40-h.
5) Placing the felt body in a vacuum carbonization furnace for carbonization, and heating up the curve: 20 ℃ to 220 ℃ for 0.5 h,220 ℃ to 550 ℃ for 3 h,550 ℃ to 750 ℃ for 4 h,750 ℃ to 1000 ℃ for 2 h,1000 ℃ to 1200 ℃ for 2 h, and 1200 ℃ for 1 h.
6) Repeating the steps (4), 5 and 6) for 5 times, preparing a precursor solution from phenolic resin, polyethylene glycol and hexamethylene tetram according to the mass ratio of 11:18:2, and repeating the infiltration-curing-carbonization process on the other side of the fiber preform.
7) Coating HfSi on two sides of the prepared C/C preform 2 With ZrSi 2 And (3) placing the slurry in a siliconizing furnace, heating to 1800 ℃ under the pressure environment of less than 20Pa, and preserving heat for 1h to obtain the gradient material with one side being C/SiC-HfC and the other side being C/SiC-ZrC.
The C/SiC-ZrC-HfC prepared in this example has a C/SiC-HfC side morphology as shown in FIG. 4. It can be seen that the resultant HfC-SiC matrix has a submicron size of HfC phase and is uniformly distributed in the SiC phase, similar to the morphology of the ZrC-SiC matrix in example 1, so that the variable component C/SiC-ZrC-HfC composite material can be prepared by the method.
Claims (4)
1. A method for preparing a variable-component carbon fiber reinforced ultra-high temperature ceramic matrix composite material is characterized by comprising the following steps: respectively introducing nano porous carbon with different pore structures to two sides of a carbon fiber preform, then respectively soaking two sides of the carbon fiber preform with reaction melts with different components, and preparing the variable-composition carbon fiber reinforced ultrahigh-temperature ceramic matrix composite material through a uniform ceramization process of the nano porous carbon; the method comprises the following steps:
(1) The nano porous carbon with different pore structures is introduced at two sides of the carbon fiber preform, and the process is as follows: sequentially carrying out precursor solution impregnation, high-pressure curing and carbonization treatment on each side of the carbon fiber preform, and repeating the impregnation-curing-carbonization process for 3-8 times until the carbon matrix is completely filled with the carbon fiber preform; after the one-side filling is finished, the other side is refilled; the precursor solution comprises phenolic resin, a pore-forming agent and a curing agent; the dipping process comprises the following steps: immersing one side of the carbon fiber preform into the precursor solution for 1-4 hours until no obvious bubbles exist; immersing the other side of the fiber preform into the precursor solution for 1-4 hours until no obvious bubbles exist; in the precursor solution, the phenolic resin is common commercial grade resin or modified boron phenolic or barium phenolic; the pore-forming agent is at least one of ethylene glycol, diethylene glycol and polyethylene glycol; the curing agent is at least one of sodium carbonate, propylene carbonate, p-toluenesulfonic acid, phosphoric acid, benzenesulfonic acid, benzenesulfonyl chloride, hexamethylenetetramine and methylol urea; the proportion of phenolic resin, pore-forming agent and curing agent in the precursor solution is 1: (1-6): (0.02-0.20), and controlling the proportion of pore-forming agents in the precursor solution to obtain nano porous carbon matrixes with different pore structures at two sides of the preform;
(2) For porous carbon matrixes with different pore structures, selecting proper alloy melt to infiltrate into two sides through infiltration reaction, and after the reaction, realizing uniform ceramization of porous carbon on two sides of a preform to prepare the variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite material; wherein: preserving heat for 0.5-3 h at the temperature 50-250 ℃ higher than the melting point of the selected alloy in each infiltration reaction process, wherein the pressure in the infiltration process is less than 20Pa; after the reaction, no residual carbon matrix and excessive reaction melt are generated, the fiber is not etched, and the prepared ceramic matrix is compact and different ceramic phases are uniformly distributed in submicron level;
in the step (1), the precursor solution is immersed and then subjected to high-pressure curing, and the high-pressure curing process is as follows: heating to the curing temperature of 120-250 ℃ at a heating rate of more than 10 ℃/min under the condition of pressurization, and preserving heat for 10-40 h under the pressure range of 1-10 MPa;
in the step (2), the reaction alloy component is selected as two or more of Si, transition metal element and lanthanide series metal element, and the component selection is corresponding to the structure of the porous carbon matrix, namely the volume expansion rate of the carbon skeleton converted into the complex phase ceramic in the reaction process is equal to or slightly lower than the reciprocal of the volume proportion of the carbon skeleton in the porous carbon matrix; wherein P is the porosity of the porous carbon matrix, and the volume ratio of the carbon skeleton in the porous carbon matrix is 1-P.
2. The method for preparing the variable component carbon fiber reinforced ultra-high temperature ceramic matrix composite according to claim 1, wherein the method comprises the following steps: in the step (1), before precursor solution impregnation, pyrolytic carbon or silicon carbide is deposited on the surface of the carbon fiber by adopting a chemical vapor infiltration process to prepare an interface layer, wherein the total thickness of the interface layer is 0.6-5 mu m.
3. The method for preparing the variable component carbon fiber reinforced ultra-high temperature ceramic matrix composite according to claim 1, wherein the method comprises the following steps: in the step (1), the carbonization treatment process is as follows: and (3) placing the carbon fiber reinforced porous resin matrix composite material obtained after the curing treatment in a vacuum carbonization furnace, and heating the vacuum carbonization furnace to 900-1800 ℃ from room temperature at a heating rate of 5-10 ℃/min to obtain a carbon/carbon infiltration preform with a matrix of nano porous carbon.
4. The method for preparing the variable component carbon fiber reinforced ultra-high temperature ceramic matrix composite according to claim 1, wherein the method comprises the following steps: in the step (1), the porous carbon matrixes at two sides of the carbon fiber preform are distributed with nanoscale holes with uniform structures, but the porosity and the pore size of the porous carbon matrixes are different by more than 20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211178004.XA CN115557791B (en) | 2022-09-27 | 2022-09-27 | Method for preparing variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211178004.XA CN115557791B (en) | 2022-09-27 | 2022-09-27 | Method for preparing variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115557791A CN115557791A (en) | 2023-01-03 |
| CN115557791B true CN115557791B (en) | 2024-02-09 |
Family
ID=84743386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211178004.XA Active CN115557791B (en) | 2022-09-27 | 2022-09-27 | Method for preparing variable-component carbon fiber reinforced ultrahigh-temperature ceramic matrix composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115557791B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5840221A (en) * | 1996-12-02 | 1998-11-24 | Saint-Gobain/Norton Industrial Ceramics Corporation | Process for making silicon carbide reinforced silicon carbide composite |
| US5916633A (en) * | 1995-05-19 | 1999-06-29 | Georgia Tech Research Corporation | Fabrication of carbon/carbon composites by forced flow-thermal gradient chemical vapor infiltration |
| EP2543650A1 (en) * | 2011-07-07 | 2013-01-09 | Korea Institute of Energy Research | Method for manufacturing high-density fiber reinforced ceramic composite materials |
| CN103722825A (en) * | 2013-09-11 | 2014-04-16 | 太仓派欧技术咨询服务有限公司 | Preparation method of ceramic matrix composite with Sic on surface layer and ZrC on inner layer |
| CA2960342A1 (en) * | 2016-03-23 | 2017-09-23 | General Electric Company | Ceramic matrix composites having monomodal pore size distribution and low fiber volume fraction |
| CN107879758A (en) * | 2016-09-30 | 2018-04-06 | 中国科学院金属研究所 | A kind of sandwich structure C/C SiC ceramic matrix composite materials and preparation method thereof |
| CN108117412A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院金属研究所 | A kind of stepped construction C/C-SiC-ZrB2Composite material and preparation method thereof |
| KR20200068121A (en) * | 2018-12-04 | 2020-06-15 | 현대자동차주식회사 | Brake disk of composite material and manufacturing method thereof |
| CN114380613A (en) * | 2022-03-23 | 2022-04-22 | 中南大学 | Preparation method of ultrahigh-temperature ceramic matrix composite material with axial gradient and planar homogeneity |
| CN114835510A (en) * | 2022-06-02 | 2022-08-02 | 中国航发北京航空材料研究院 | Method for preparing gradient variable modulus silicon carbide fiber reinforced silicon carbide-based composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10227264B2 (en) * | 2015-07-13 | 2019-03-12 | Rolls-Royce High Temperature Composites, Inc. | Method for making ceramic matrix composite articles |
-
2022
- 2022-09-27 CN CN202211178004.XA patent/CN115557791B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5916633A (en) * | 1995-05-19 | 1999-06-29 | Georgia Tech Research Corporation | Fabrication of carbon/carbon composites by forced flow-thermal gradient chemical vapor infiltration |
| US5840221A (en) * | 1996-12-02 | 1998-11-24 | Saint-Gobain/Norton Industrial Ceramics Corporation | Process for making silicon carbide reinforced silicon carbide composite |
| EP2543650A1 (en) * | 2011-07-07 | 2013-01-09 | Korea Institute of Energy Research | Method for manufacturing high-density fiber reinforced ceramic composite materials |
| CN103722825A (en) * | 2013-09-11 | 2014-04-16 | 太仓派欧技术咨询服务有限公司 | Preparation method of ceramic matrix composite with Sic on surface layer and ZrC on inner layer |
| CA2960342A1 (en) * | 2016-03-23 | 2017-09-23 | General Electric Company | Ceramic matrix composites having monomodal pore size distribution and low fiber volume fraction |
| CN107879758A (en) * | 2016-09-30 | 2018-04-06 | 中国科学院金属研究所 | A kind of sandwich structure C/C SiC ceramic matrix composite materials and preparation method thereof |
| CN108117412A (en) * | 2016-11-29 | 2018-06-05 | 中国科学院金属研究所 | A kind of stepped construction C/C-SiC-ZrB2Composite material and preparation method thereof |
| KR20200068121A (en) * | 2018-12-04 | 2020-06-15 | 현대자동차주식회사 | Brake disk of composite material and manufacturing method thereof |
| CN114380613A (en) * | 2022-03-23 | 2022-04-22 | 中南大学 | Preparation method of ultrahigh-temperature ceramic matrix composite material with axial gradient and planar homogeneity |
| CN114835510A (en) * | 2022-06-02 | 2022-08-02 | 中国航发北京航空材料研究院 | Method for preparing gradient variable modulus silicon carbide fiber reinforced silicon carbide-based composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115557791A (en) | 2023-01-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018188436A1 (en) | Method for preparing c/c-sic composite material part and product thereof | |
| RU2176628C2 (en) | Composite material (variants) and method or preparing thereof, method of treating fibrous semi-finished product (variants) | |
| KR100624094B1 (en) | The method of producing carbon fiber reinforced ceramic matrix composites | |
| US6706401B1 (en) | Carbon matrix composites fabricated by a rapid and low-cost process incorporating in-situ polymerization of wetting monomers | |
| CN105152671B (en) | SiCfThe interface modification method of/SiC ceramic matrix composite material | |
| CN109053207B (en) | Yttrium silicate modified silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof | |
| CN112341235B (en) | Multiphase coupling rapid densification method for ultrahigh-temperature self-healing ceramic matrix composite | |
| CN103332943B (en) | Microstructure design and the Properties Control method of carbon pottery based composites is prepared based on liquid silicon infiltration method | |
| RU2668431C2 (en) | Method of fabricating composite parts by low melting point impregnation | |
| CN111454073A (en) | High-heat-conductivity, strong-bonding and ablation-resistant ultrahigh-temperature ceramic matrix composite and preparation method thereof | |
| CN110776321B (en) | Preparation method of large-gradient transition layer of ultrahigh-temperature light thermal protection material | |
| CN108585906A (en) | A kind of Cf/ ZrC-SiC ultra-temperature ceramic-based composite materials and preparation method thereof | |
| CN108484173B (en) | SiCf/SiC composite material and preparation method thereof | |
| CN112409003B (en) | Hybrid matrix silicon carbide-based composite material and preparation method thereof | |
| CN112142486A (en) | Preparation method of ablation-resistant silicon carbide fiber reinforced ceramic matrix composite | |
| CN108892524B (en) | Preparation method of C/SiC composite material | |
| EP2578556B1 (en) | Method and ceramic component | |
| CN113045326A (en) | Preparation method of modified carbon/carbon composite material | |
| CN115385712A (en) | High-entropy ultra-high temperature ceramic matrix composite and preparation method thereof | |
| CN106507783B (en) | The manufacture method of carbon/carbon/silicon carbide ceramic matrix composite brake disc | |
| CN110963799A (en) | Preparation method of liquid-phase silicon-assisted forming thermal protection Z-pins silicide ceramic rod structure | |
| CN112299865A (en) | Modified C/SiC composite material and preparation method thereof | |
| CN113121253B (en) | Ultrahigh-temperature C/SiHfBCN ceramic matrix composite material and preparation method thereof | |
| CN106882976A (en) | A kind of preparation method of C/HfC-ZrC-SiC composites | |
| CN115557800B (en) | Method for preparing silicon carbide-based composite material by uniformly ceramifying porous carbon |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |