CN106966744B - Carbon fiber reinforced alumina ceramic composite material and preparation method thereof - Google Patents
Carbon fiber reinforced alumina ceramic composite material and preparation method thereof Download PDFInfo
- Publication number
- CN106966744B CN106966744B CN201610391203.7A CN201610391203A CN106966744B CN 106966744 B CN106966744 B CN 106966744B CN 201610391203 A CN201610391203 A CN 201610391203A CN 106966744 B CN106966744 B CN 106966744B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- fiber reinforced
- sol
- alumina ceramic
- aluminum nitrate
- 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.)
- Expired - Fee Related
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 66
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 25
- 238000005470 impregnation Methods 0.000 claims abstract description 25
- 238000000280 densification Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000003980 solgel method Methods 0.000 claims abstract description 10
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- 230000002787 reinforcement Effects 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 claims description 9
- 102000002322 Egg Proteins Human genes 0.000 claims description 9
- 108010000912 Egg Proteins Proteins 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000014103 egg white Nutrition 0.000 claims description 9
- 210000000969 egg white Anatomy 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- -1 aluminum ions Chemical class 0.000 claims description 7
- 230000003064 anti-oxidating effect Effects 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000009828 non-uniform distribution Methods 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C04B35/803—
-
- 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
- C04B35/624—Sol-gel processing
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- 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
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a carbon fiber reinforced alumina ceramic composite material and a preparation method thereof. Wherein, the preparation method comprises the following steps: s101: taking the alumina sol as a precursor, carrying out vacuum impregnation on the carbon felt, and then carrying out densification treatment on the carbon felt impregnated with the alumina sol to prepare carbon fiber reinforced alumina ceramic; s102: and (3) carrying out vacuum impregnation on the carbon fiber reinforced alumina ceramic by using a sol-gel method, then drying, sintering and cooling to room temperature to prepare the Si-Al-C coating. According to the preparation method of the carbon fiber reinforced alumina ceramic composite material, the preparation period is short, and the cost is low; the carbon fiber reinforced alumina ceramic composite material provided by the invention has excellent mechanical properties and high temperature resistance.
Description
Technical Field
The invention relates to the field of materials, in particular to a carbon fiber reinforced alumina ceramic composite material and a preparation method thereof.
Background
The alumina ceramic has the advantages of high melting point, good high-temperature chemical stability, high modulus and strength and the like, and can be used for a long time in a high-temperature oxidation environment. However, bulk alumina ceramics are generally less ductile and prone to catastrophic failure, limiting their use in engineered structures. In order to improve the mechanical property of the alumina ceramic, various toughening mechanisms are widely applied, mainly comprising particle reinforcement, whisker reinforcement, fiber reinforcement and other modes, wherein the particle and whisker toughening can obviously improve the strength of the alumina ceramic, but the toughness improvement is lower, and the particle and whisker toughened alumina ceramic is difficult to form large-scale complex construction because a hot pressing process is mostly adopted. The use of high modulus, high strength fibers to toughen ceramics is currently considered a promising approach to improve ceramic toughness. According to the theory of composite materials, when cracks extend to fibers, the fibers are separated from the cross section of the matrix to absorb energy and relieve stress concentration, and when part of the fibers are broken under the action of tensile stress and pulled out of the matrix, a large amount of energy is consumed, which is beneficial to enhancing the toughness of the ceramic material.
There are various methods for preparing alumina ceramics, among which the sol-gel method is a common method for preparing alumina ceramics, and is a method for preparing alumina ceramics by hydrolyzing and polycondensing aluminum alkoxide or aluminum salt at a temperature slightly higher than room temperature to obtain sol and gel, and then thermally cracking the sol and gel. The method has the outstanding characteristics in the aspect of material preparation that: (1) in the gelling process, the size of the particles is in a nanometer level, so that the sintering temperature can be greatly reduced; (2) the chemical components of the single-phase matrix can be very uniform; (3) before cracking, the fiber and the braided fabric thereof are easy to be impregnated and shaped through sol and gel states, so that the fiber reinforced composite material is convenient to prepare.
The preparation of alumina sol can be classified into an organic salt raw material method, an inorganic salt raw material method, and a powder method according to the difference of the alumina raw material prepared by the sol-gel method. The organic salt method is characterized in that aluminum isopropoxide is used as a raw material, the organic raw material is dripped into water in a device with stirring, refluxing and feeding functions, the mixture is stirred vigorously at 80 ℃, most of alcohol is evaporated, and then the mixture is refluxed for several hours. The inorganic salt method is to digest a metal salt in hydrochloric acid or aluminum chloride or to dissolve analytically pure aluminum nitrate in water and adjust the PH of the solution with ammonia. The powder method is to obtain sol by dispersing SB powder (boehmite) or alumina powder.
The carbon fiber has high specific strength, specific modulus and fatigue strength, and is a good reinforcement material, but the carbon fiber is very easy to oxidize at the temperature of more than 400 ℃, so that the catastrophic reduction of the material performance is caused. Silicon carbide fiber is also a very good reinforcement material, and has better heat resistance and oxidation resistance than carbon fiber, but the silicon carbide fiber is very expensive, which limits the application range of the silicon carbide fiber. Therefore, the cost is reduced as much as possible on the basis of solving the problem of oxidation resistance of the carbon fiber, and the method has important significance for expanding the application range of the carbon fiber.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
Therefore, the invention aims to provide a preparation method of the carbon fiber reinforced alumina ceramic composite material, which has excellent mechanical property and high temperature resistance, short preparation period and low cost.
The preparation method of the carbon fiber reinforced alumina ceramic composite material comprises the following steps: s101: taking the alumina sol as a precursor, carrying out vacuum impregnation on the carbon felt, and then carrying out densification treatment on the carbon felt impregnated with the alumina sol to prepare carbon fiber reinforced alumina ceramic; s102: and (3) carrying out vacuum impregnation on the carbon fiber reinforced alumina ceramic by using a sol-gel method, then drying, sintering and cooling to room temperature to prepare the Si-Al-C coating.
According to the carbon fiber reinforced alumina ceramic composite material provided by the embodiment of the invention, the carbon fiber is used as a reinforcement of the alumina ceramic, the specific strength and specific modulus are high, the creep is avoided, the fatigue resistance is good, the thermal expansion coefficient is small, the corrosion resistance is high, the cross section wettability of the alumina sol and the carbon fiber is good, and the interface bonding force is moderate. The carbon fiber ensures the uniform distribution of the reinforcing phase in the form of carbon felt, and avoids the problems of particle reinforcement and non-uniform distribution of whisker reinforcement. The carbon fiber reinforced alumina ceramic composite material is densified by a vacuum impregnation method, so that the mechanical strength of the material is greatly increased. Compared with the preparation of the alumina ceramic by a powder sintering method, the preparation of the alumina ceramic by the sol-gel method can reduce the sintering temperature from 1800 ℃ to 1300 ℃, thereby greatly reducing the equipment requirement and the energy consumption. The Si-Al-C oxidation resistant coating adopted by the invention is very compact, is well combined with an alumina matrix, and can effectively enhance the oxidation resistance of the material.
In addition, the method for preparing the carbon fiber reinforced alumina ceramic composite material according to the above embodiment of the present invention may further have the following additional technical features:
further, in step S102, the carbon fiber reinforced alumina ceramic is subjected to a vacuum impregnation process using a mixed solution of an ethyl orthosilicate based silica sol, an aluminum nitrate based alumina sol, and an egg white solution.
Further, in step S102, the preparation of the mixed solution includes the following steps: adding 30-40 mL of ethyl orthosilicate, 15-25 g of aluminum nitrate and a certain amount of hexamethylenetetramine into 55-65 mL of mixed solution of water and ethanol to prepare ethyl orthosilicate-based silica sol and aluminum nitrate-based alumina sol; and adding 100-130 mL of egg white solution into the tetraethoxysilane-based silica sol and the aluminum nitrate-based alumina sol.
Further, in step S101, the densification processing steps are specifically: drying the carbon felt impregnated with the alumina sol, heating to 1200-1400 ℃ according to the heating rate of 4-6 ℃/min, sintering in vacuum for 1-3 h, and cooling to room temperature.
Further, in step S101, the precursor is an aluminum nitrate sol, wherein the concentration of aluminum ions is 3mol/L to 4mol/L, and the viscosity of the aluminum sol is 4mPa · S to 6mPa · S.
Further, in step S102, the sintering temperature is 1200 ℃ to 1400 ℃.
Further, the preparation method of the aluminum nitrate sol comprises the following steps: adding excess aluminum nitrate to water to prepare an aluminum nitrate solution; heating the aluminum nitrate solution to 85-90 ℃, adding 10-15% ammonia water until the pH value of the liquid is 3.5-5.0 after the aluminum nitrate is completely dissolved, evaporating water until the concentration of aluminum ions reaches 5-6 mol/L, filtering, and taking filtrate to obtain the aluminum nitrate sol.
The invention also aims to provide a carbon fiber reinforced alumina ceramic composite material.
The carbon fiber reinforced alumina ceramic composite material comprises the following components in percentage by weight: the reinforcement is a carbon felt; the matrix is soaked in the gaps of the reinforcement body by a vacuum impregnation method and is prepared into a composite material together with the reinforcement body; and the anti-oxidation coating is a Si-Al-C coating, and wraps the composite material.
Further, the density of the carbon fiber reinforced alumina ceramic composite material is more than or equal to 2.5g/cm3。
Further, the carbon felt is a polyacrylonitrile-based carbon felt.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a flow chart of a method for preparing a carbon fiber reinforced alumina ceramic composite material according to an embodiment of the present invention.
Detailed Description
The method for preparing a carbon fiber reinforced alumina ceramic composite material according to the present invention will be described in detail with reference to the accompanying drawings.
As shown in fig. 1, a method for preparing a carbon fiber reinforced alumina ceramic composite material according to an embodiment of the present invention includes the following steps:
s101: and taking the aluminum sol as a precursor, carrying out vacuum impregnation on the carbon felt, and then carrying out densification treatment on the carbon felt impregnated with the aluminum sol to prepare the carbon fiber reinforced alumina ceramic. Specifically, firstly, taking aluminum nitrate sol as a precursor, carrying out vacuum impregnation on the ultrasonically cleaned carbon felt, then drying, placing the carbon felt into a high-temperature furnace for vacuum sintering after drying, keeping vacuum cooling to room temperature, completing a densification process, and then repeating the steps for 10-12 times until the weight of a sample is not increased any more, so as to obtain the carbon fiber reinforced alumina composite ceramic. The carbon fiber is used as a reinforcement of the alumina ceramic, and has the advantages of high specific strength and specific modulus, no creep, good fatigue resistance, small thermal expansion coefficient, corrosion resistance, good cross section wettability of the alumina sol and the carbon fiber, and moderate interface bonding force. The carbon fiber ensures the uniform distribution of the reinforcing phase in the form of carbon felt, and avoids the problems of particle reinforcement and non-uniform distribution of whisker reinforcement.
S102: and (3) carrying out vacuum impregnation on the carbon fiber reinforced alumina ceramic by using a sol-gel method, then drying, sintering and cooling to room temperature to prepare the Si-Al-C coating. Specifically, a certain amount of egg white is dissolved in a small amount of deionized water, and stirred to obtain a clear liquid, namely liquid A; preparing a certain amount of precursor mixed solution B of tetraethoxysilane-based silica sol and aluminum nitrate-based alumina sol, dripping A into B to obtain C, uniformly stirring, putting the carbon fiber reinforced alumina ceramic into the liquid C, carrying out vacuum impregnation, and then drying; and after drying, placing the dried carbon fiber reinforced alumina ceramic in a vacuum sintering furnace for sintering, and after sintering, keeping vacuum and cooling to room temperature along with the furnace to obtain the carbon fiber reinforced alumina ceramic composite material containing the antioxidant coating. Compared with the preparation of the alumina ceramic by a powder sintering method, the preparation of the alumina ceramic by the sol-gel method can reduce the sintering temperature from 1800 ℃ to 1300 ℃, thereby greatly reducing the equipment requirement and the energy consumption. The Si-Al-C oxidation resistant coating adopted by the invention is very compact, is well combined with an alumina matrix, and can effectively enhance the oxidation resistance of the material.
The carbon fiber reinforced alumina ceramic composite material comprises the following components in percentage by weight: reinforcement, matrix and anti-oxidation coating. Wherein the reinforcement is a carbon felt. The carbon fiber is used as a reinforcement of the alumina ceramic, has high specific strength and specific modulus, no creep deformation, good fatigue resistance, small thermal expansion coefficient and corrosion resistance, and has good section wettability of alumina sol and the carbon fiber and moderate interface bonding force; the carbon fiber ensures the uniform distribution of the reinforcing phase in the form of carbon felt, and avoids the problems of particle reinforcement and non-uniform distribution of whisker reinforcement. The matrix is soaked in the gaps of the reinforcement body by a vacuum impregnation method, and the matrix and the reinforcement body are prepared into a composite material. Compared with the preparation of the alumina ceramic by a powder sintering method, the preparation of the alumina ceramic by the sol-gel method can reduce the sintering temperature from 1800 ℃ to 1300 ℃, thereby greatly reducing the equipment requirement and the energy consumption. The anti-oxidation coating is a Si-Al-C coating, and the composite material is wrapped by the anti-oxidation coating. The Si-Al-C oxidation resistant coating is very compact, is well combined with an alumina matrix, and can effectively enhance the oxidation resistance of the material.
The present invention will be described in detail with reference to specific examples.
Example 1
Embodiment 1 is a specific preparation process of a carbon fiber reinforced alumina ceramic composite material, which takes alumina as a matrix, takes polyacrylonitrile-based carbon felt as a reinforcement, and has a Si-Al-C oxidation resistant coating on the surface, comprising the following specific steps:
and adding deionized water into 100g of aluminum nitrate, heating in a water bath and stirring, wherein the temperature of the water bath is set to be 85 ℃, and continuously stirring in the water bath for 30-40 min to hydrolyze the aluminum nitrate as much as possible. And then adding 12.5% of ammonia water in batches until the pH value of the liquid is 3.5-5, further promoting hydrolysis, stabilizing the sol property and adjusting the size of colloidal particles. And evaporating the liquid to ensure that the concentration of aluminum ions is 6mol/L and the viscosity is about 6mPa & S, and the concentration and the viscosity can increase the impregnation efficiency as much as possible under the condition of ensuring the impregnation effect. Then filtered to obtain translucent alumina sol.
And (2) performing primary densification, namely putting the ultrasonically cleaned carbon felt (the carbon felt has the geometric dimension of about 4.5mm x 5.5mm x 82mm) into alumina sol for vacuum impregnation for 2h, drying for 2h at the temperature of 50 ℃ after the impregnation is completed to enable the sol to become gel, then becoming dry gel without surface cracking, putting the dried sol into a high-temperature furnace for vacuum sintering after the drying is completed, wherein the temperature rise rate is 4-6 ℃, the preset temperature is 1300 ℃, the dry gel is ensured to be converted into α alumina, keeping the temperature for 2h after the preset temperature is reached, completely sintering, keeping the vacuum and cooling to the room temperature, and completing the primary densification process.
And (3) repeated densification: repeating the densification step for 12 times by taking the one-time densification step as a period, and completing the densification process of the composite material after 12 densification periods to obtain the composite material with the density of 2.8g/cm3Carbon fiber reinforced alumina ceramic composite material.
Preparing the Si-Al-C oxidation resistant coating: dissolving 100mL of egg white in a little deionized water, and stirring to obtain a clear liquid, namely liquid A; taking 40mL of ethyl orthosilicate, 20g of aluminum nitrate and 4g of hexamethylenetetramine at room temperature, slowly and uniformly mixing and dissolving the ethyl orthosilicate, the aluminum nitrate and the hexamethylenetetramine into a mixed solution of 60mL of deionized water and 10mL of ethanol, and stirring to obtain a precursor mixed solution of ethyl orthosilicate based silica sol and aluminum nitrate based alumina sol, namely a solution B; dropwise adding the liquid A into the liquid B, and uniformly stirring to obtain a liquid C; placing the carbon fiber reinforced alumina ceramic composite material in the liquid C, vacuum-soaking for 1h, and drying at 40 ℃; under the condition of continuous vacuum pumping, the dried carbon fiber reinforced alumina ceramic composite material is sintered for 30min at 1400 ℃, egg white is rich in macromolecular protein and can be carbonized at the temperature of more than 700 ℃, and a large amount of activated carbon sources are provided. The reaction principle of the coating preparation is as follows:
2Si2O(s)+2Al2O3(s)+7C(s)→4SiAlC(s)+2CO(g)+CO2(g)
after sintering, closing the furnace, cooling, and keeping vacuumizing to room temperature to obtain the carbon fiber reinforced alumina composite material containing the antioxidant coating.
Example 2
Embodiment 2 is a specific preparation process of a carbon fiber reinforced alumina ceramic composite material, which takes alumina as a matrix, takes polyacrylonitrile-based carbon felt as a reinforcement, and has a Si-Al-C oxidation resistant coating on the surface, comprising the following specific steps:
and adding deionized water into 100g of aluminum nitrate, heating in a water bath and stirring, wherein the temperature of the water bath is set to be 90 ℃, and continuously stirring in the water bath for 30-40 min to hydrolyze the aluminum nitrate as much as possible. And then adding 15% ammonia water in batches until the pH value of the liquid is 3.5-5, further promoting hydrolysis, stabilizing the sol property and adjusting the size of colloidal particles. And evaporating the liquid to ensure that the concentration of aluminum ions is 5mol/L and the viscosity is about 6mPa & S, and the concentration and the viscosity can increase the impregnation efficiency as much as possible under the condition of ensuring the impregnation effect. Then filtered to obtain translucent alumina sol.
And (2) performing primary densification, namely putting the ultrasonically cleaned carbon felt (the geometric dimension of the carbon felt is about 4.5mm x 5.5mm x 82mm) into alumina sol for vacuum impregnation for 2h, drying for 2h at 50 ℃ after complete impregnation to enable the sol to become gel, then becoming dry gel without surface cracking, putting the dried gel into a high-temperature furnace for vacuum sintering after the drying is completed, raising the temperature at 4-6 ℃ and the preset temperature at 1400 ℃ to ensure that the dry gel is converted into α alumina, preserving the heat for 2h after the preset temperature is reached to enable the sintering to be complete, and then keeping the vacuum cooling to the room temperature to complete the primary densification process.
And (3) repeated densification: repeating the densification step for 12 times by taking the one-time densification step as a period, and completing the densification process of the composite material after 12 densification periods to obtain the composite material with the density of 2.6g/cm3Carbon fiber reinforced alumina ceramic composite material.
Preparing the Si-Al-C oxidation resistant coating: dissolving 100mL of egg white in a little deionized water, and stirring to obtain a clear liquid, namely liquid A; slowly and uniformly mixing and dissolving 30mL of tetraethoxysilane, 18g of aluminum nitrate and 4g of hexamethylenetetramine into a mixed solution of 65mL of deionized water and 15mL of ethanol at room temperature, and stirring to prepare a precursor mixed solution of tetraethoxysilane-based silica sol and aluminum nitrate-based alumina sol, namely a solution B; dropwise adding the liquid A into the liquid B, and uniformly stirring to obtain a liquid C; placing the carbon fiber reinforced alumina ceramic composite material in the liquid C, vacuum-soaking for 1h, and drying at 35 ℃; under the condition of continuous vacuum pumping, the dried carbon fiber reinforced alumina ceramic composite material is sintered for 30min at 1200 ℃, egg white is rich in macromolecular protein and can be carbonized at the temperature of more than 700 ℃, and a large amount of activated carbon sources are provided. The reaction principle of the coating preparation is as follows:
2Si2O(s)+2Al2O3(s)+7C(s)→4SiAlC(s)+2CO(g)+CO2(g)
after sintering, closing the furnace, cooling, and keeping vacuumizing to room temperature to obtain the carbon fiber reinforced alumina composite material containing the antioxidant coating.
According to the carbon fiber reinforced alumina ceramic composite material, the carbon fiber is used as a reinforcement of the alumina ceramic, the specific strength and specific modulus are high, creep deformation is avoided, the fatigue resistance is good, the thermal expansion coefficient is small, the corrosion resistance is high, the cross section wettability of the alumina sol and the carbon fiber is good, and the interface bonding force is moderate. The carbon fiber ensures the uniform distribution of the reinforcing phase in the form of carbon felt, and avoids the problems of particle reinforcement and non-uniform distribution of whisker reinforcement. Controlling the density of the carbon fiber reinforced alumina ceramic composite material to be more than or equal to 2.5g/cm by a vacuum impregnation method3And the mechanical strength of the material is greatly increased. Compared with the preparation of the alumina ceramic by a powder sintering method, the preparation of the alumina ceramic by the sol-gel method can reduce the sintering temperature from 1800 ℃ to 1300 ℃, thereby greatly reducing the equipment requirement and the energy consumption. The Si-Al-C oxidation resistant coating adopted by the invention is very compact, is well combined with an alumina matrix, and can effectively enhance the oxidation resistance of the material.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (4)
1. The preparation method of the carbon fiber reinforced alumina ceramic composite material is characterized by comprising the following steps:
s101: taking the alumina sol as a precursor, carrying out vacuum impregnation on the carbon felt, and then carrying out densification treatment on the carbon felt impregnated with the alumina sol to prepare carbon fiber reinforced alumina ceramic; the densification treatment comprises the following specific steps: drying the carbon felt impregnated with the alumina sol, heating to 1200-1400 ℃ at a heating rate of 4-6 ℃/min, sintering in vacuum for 1-3 h, and cooling to room temperature; the precursor is aluminum nitrate-based alumina sol, wherein the concentration of aluminum ions is 3-4 mol/L, and the viscosity of the alumina sol is 4-6 mPa & S;
s102: carrying out vacuum impregnation on the carbon fiber reinforced alumina ceramic by using a sol-gel method, then drying, sintering and cooling to room temperature to prepare a Si-Al-C coating; wherein, the carbon fiber reinforced alumina ceramic is subjected to vacuum impregnation by using a mixed solution consisting of ethyl orthosilicate based silica sol, aluminum nitrate based alumina sol and egg white solution; the sintering temperature is 1200-1400 ℃;
the preparation of the mixed solution comprises the following steps:
adding 30-40 mL of ethyl orthosilicate, 15-25 g of aluminum nitrate and a certain amount of hexamethylenetetramine into 55-65 mL of mixed solution of water and ethanol to prepare ethyl orthosilicate-based silica sol and aluminum nitrate-based alumina sol;
adding 100 mL-130 mL of egg white solution into the tetraethoxysilane-based silica sol and the aluminum nitrate-based alumina sol;
the preparation method of the aluminum nitrate-based alumina sol comprises the following steps:
adding excess aluminum nitrate to water to prepare an aluminum nitrate solution;
heating the aluminum nitrate solution to 85-90 ℃, adding 10-15% ammonia water until the pH value of the liquid is 3.5-5.0 after the aluminum nitrate is completely dissolved, evaporating water until the concentration of aluminum ions reaches 5-6 mol/L, filtering, and taking filtrate to obtain the aluminum nitrate-based alumina sol.
2. The carbon fiber reinforced alumina ceramic composite prepared according to the method of claim 1, comprising:
the reinforcement is a carbon felt;
a matrix, wherein the matrix is impregnated in the gaps of the reinforcement body by a vacuum impregnation method to prepare a composite material with the reinforcement body;
the anti-oxidation coating is a Si-Al-C coating, and wraps the composite material.
3. The carbon fiber reinforced alumina ceramic composite of claim 2 wherein the carbon fiber reinforced alumina ceramic composite has a density of 2.5g/cm or greater3。
4. The carbon fiber reinforced alumina ceramic composite of claim 2 wherein the carbon felt is a polyacrylonitrile-based carbon felt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610391203.7A CN106966744B (en) | 2016-06-03 | 2016-06-03 | Carbon fiber reinforced alumina ceramic composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610391203.7A CN106966744B (en) | 2016-06-03 | 2016-06-03 | Carbon fiber reinforced alumina ceramic composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106966744A CN106966744A (en) | 2017-07-21 |
| CN106966744B true CN106966744B (en) | 2020-04-07 |
Family
ID=59334737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610391203.7A Expired - Fee Related CN106966744B (en) | 2016-06-03 | 2016-06-03 | Carbon fiber reinforced alumina ceramic composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106966744B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342897A (en) * | 2018-02-12 | 2018-07-31 | 匡邓吉 | A kind of carbon fiber surface aluminium oxide nano film and preparation method thereof |
| CN108865334A (en) * | 2018-06-05 | 2018-11-23 | 上海加美实业有限公司 | A kind of porcelain fluorine lube oil additive and lubricating oil |
| CN113185313B (en) * | 2021-05-14 | 2023-01-03 | 山东工业陶瓷研究设计院有限公司 | Carbon fiber reinforced ceramic matrix composite and preparation method thereof |
| CN113880597B (en) * | 2021-12-07 | 2022-03-04 | 天津爱思达新材料科技有限公司 | Preparation method of modified carbon fiber toughened alumina self-healing ceramic |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206089A (en) * | 2011-04-07 | 2011-10-05 | 中国人民解放军国防科学技术大学 | Preparation method for reinforcing mullite by using three-dimensional carbon fiber fabric |
| CN105367106A (en) * | 2015-12-04 | 2016-03-02 | 中国人民解放军国防科学技术大学 | Carbon-fiber-reinforced zirconium carbide composite material and preparation method therefor |
| CN105421033A (en) * | 2015-11-06 | 2016-03-23 | 湖南博望碳陶有限公司 | Preparation method of fiber, ceramic and metal three-dimensional network composite material |
-
2016
- 2016-06-03 CN CN201610391203.7A patent/CN106966744B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206089A (en) * | 2011-04-07 | 2011-10-05 | 中国人民解放军国防科学技术大学 | Preparation method for reinforcing mullite by using three-dimensional carbon fiber fabric |
| CN105421033A (en) * | 2015-11-06 | 2016-03-23 | 湖南博望碳陶有限公司 | Preparation method of fiber, ceramic and metal three-dimensional network composite material |
| CN105367106A (en) * | 2015-12-04 | 2016-03-02 | 中国人民解放军国防科学技术大学 | Carbon-fiber-reinforced zirconium carbide composite material and preparation method therefor |
Non-Patent Citations (2)
| Title |
|---|
| 用溶胶-凝胶法制备碳纤维三维编织物增强氧化铝基复合材料的研究;谢征芳;《国防科技大学学报》;19981231;第20卷(第5期);全文 * |
| 硅溶胶强化辅助制备C纤维增韧氧化铝结合莫来石陶瓷基复合材料;陈照峰等;《航空材料学报》;20011231;第21卷(第4期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106966744A (en) | 2017-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107032816B (en) | Silicon carbide nanowire reinforced C/C-SiC-ZrB2Preparation method of ceramic matrix composite | |
| CN101792299B (en) | Preparation method of high-temperature-resistant alumina-silica aerogel heat-insulation composite material | |
| CN106966744B (en) | Carbon fiber reinforced alumina ceramic composite material and preparation method thereof | |
| CN103922778B (en) | Three-dimensional alumina fiber fabric reinforced oxide ceramic and preparation method thereof | |
| CN101550030B (en) | Method for preparing Al2O3 ceramic film on surface of 3D-SiC | |
| CN108751969B (en) | High-temperature-resistant, heat-insulating and wave-transmitting ceramic matrix composite and preparation method thereof | |
| CN105503227B (en) | A kind of preparation method of stereo fabric enhancing silicon carbide diamond composite | |
| CN106045550B (en) | The preparation method of SiC-ZrC gradient modifying carbon/carbon composite materials | |
| CN107805064A (en) | Preparation method of fiber-reinforced high-temperature-resistant magnesia-alumina spinel aerogel | |
| CN106966703B (en) | Alumina fiber reinforced alumina ceramic containing interface phase and preparation method thereof | |
| CN106966731A (en) | The preparation method of carbon fiber surface in-situ growing carbon nano tube interface modification carbon silicon carbide double matrix composite | |
| CN109437943A (en) | A kind of Cf/C-SiC-ZrB2Composite material and preparation method | |
| CN105780126B (en) | A kind of preparation method of the porous mullite formed by generated in-situ whisker overlap joint | |
| CN108774072B (en) | Rigid heat insulation tile and preparation method thereof | |
| CN103614808A (en) | Mullite fiber with villous whisker and preparation method thereof | |
| CN103922794B (en) | Three-dimensional aluminum oxide fabric strengthens porous mullite pottery and preparation method thereof | |
| CN102964128B (en) | Sol-gel preparation method of Yb2Si2O7 powder | |
| CN102674819B (en) | High-toughness aluminum oxide ceramic, and preparation method and application thereof | |
| CN115417683A (en) | Preparation method of oxide continuous filament reinforced oxide ceramic matrix composite | |
| CN114685149A (en) | Functionalized alumina ceramic fiber and preparation method thereof | |
| CN103664218B (en) | High-tenacity high-strength far infrared ceramic and preparation method thereof | |
| CN105503229A (en) | Preparation method of Al2O3f/SiOC radar wave-absorbing composite material | |
| CN117534495A (en) | Method for preparing ceramic matrix composite by combining precursor dipping, cracking and reaction infiltration | |
| CN109748595A (en) | A kind of mixing penetration enhancer, purposes and reaction infiltration preparation method | |
| CN111039695A (en) | Preparation method of silicon carbide rubbing skeleton structure reinforced alumina porous ceramic |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200407 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |