CN116903395A - Carbon ceramic composite material and preparation method and application thereof - Google Patents
Carbon ceramic composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116903395A CN116903395A CN202310866881.4A CN202310866881A CN116903395A CN 116903395 A CN116903395 A CN 116903395A CN 202310866881 A CN202310866881 A CN 202310866881A CN 116903395 A CN116903395 A CN 116903395A
- Authority
- CN
- China
- Prior art keywords
- carbon
- composite material
- ceramic
- temperature
- ceramic composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 239000000919 ceramic Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 56
- 238000000151 deposition Methods 0.000 claims abstract description 41
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000000197 pyrolysis Methods 0.000 claims abstract description 32
- 230000008021 deposition Effects 0.000 claims abstract description 26
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 21
- 239000007791 liquid phase Substances 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 24
- 239000004917 carbon fiber Substances 0.000 claims description 24
- 238000005524 ceramic coating Methods 0.000 claims description 15
- 238000005229 chemical vapour deposition Methods 0.000 claims description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 230000000630 rising effect Effects 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000001294 propane Substances 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229920001709 polysilazane Polymers 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- 229920003257 polycarbosilane Polymers 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims 2
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000835 fiber Substances 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005336 cracking Methods 0.000 description 7
- 238000007740 vapor deposition Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000003754 machining Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005498 polishing Methods 0.000 description 4
- 238000005475 siliconizing Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002296 pyrolytic carbon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 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
- 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
- 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
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/5059—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/5066—Silicon nitride
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details specially adapted for crucible or pot furnaces
- F27B14/10—Crucibles
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B14/00—Crucible or pot furnaces
- F27B14/08—Details specially adapted for crucible or pot furnaces
- F27B14/14—Arrangements of heating devices
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Products (AREA)
Abstract
The invention provides a carbon ceramic composite material, and a preparation method and application thereof. The preparation method comprises the following steps: depositing a ceramic precursor on the surface of the carbon-carbon green body, curing and performing high-temperature pyrolysis to obtain the carbon-ceramic composite material; the deposition method comprises liquid phase deposition; the pyrolysis comprises the step of carrying out pyrolysis through gradient heating and heat preservation. According to the preparation method of the carbon-ceramic composite material, the specific process steps are selected, so that the finally obtained carbon-ceramic composite material has excellent mechanical properties and corrosion resistance, the internal fibers are prevented from being corroded, the use effect is good, the service life is long, the preparation process is simple, and the cost is low.
Description
Technical Field
The invention belongs to the technical field of heater preparation, and particularly relates to a carbon-ceramic composite material, and a preparation method and application thereof.
Background
Most of the external crucible and the heater of the existing thermal field are made of carbon-carbon composite materials, and silicon vapor, silicon-containing gas and main components forming the quartz crucible in the high-temperature environment of the thermal field are silicon dioxide, so that the silicon vapor, the silicon-containing gas and the main components react with the carbon-carbon crucible, the interior of the crucible is severely corroded, and the service life is short. Therefore, it is important to improve the corrosion resistance, the service life and the mechanical properties of heating equipment such as a crucible.
At present, the prior art mostly adopts vapor deposition of ceramic materials on the surface of carbon materials, so that the corrosion resistance of the carbon ceramic materials is improved. For example, CN113277867a discloses a method for preparing a carbon/silicon carbide composite crucible, comprising: and carrying out gas phase siliconizing on the surface of the crucible blank body so as to form a compact silicon carbide coating. However, the deposition efficiency of preparing silicon carbide by gas phase siliconizing is low, the process is complex, the cost is high in the actual production process, and silicon vapor also easily permeates into the crucible blank body to corrode carbon fibers, so that the mechanical property of the material is reduced, and the service life of the material is short.
In addition, patent CN111848201a also discloses a carbon/carbon crucible in which a silicon carbide coating/silicon coating is formed on the surface of the carbon/carbon crucible by a plasma spraying method to achieve the improvement of the siliconizing corrosion resistance of the carbon/carbon crucible, thereby achieving the improvement of the service life of the crucible, but the method has limited ability to inhibit the corrosion of silicon vapor to carbon fibers in the carbon/carbon crucible and has high cost.
Therefore, the development of the preparation method of the carbon-ceramic composite material, which can effectively prevent the corrosion of the carbon-carbon material, improve the mechanical property of the carbon-ceramic composite material, prolong the service life of the carbon-ceramic composite material, has simple process and low cost, is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a carbon-ceramic composite material and a preparation method and application thereof. According to the preparation method of the carbon ceramic composite material, the specific process steps are adopted, so that the finally obtained carbon ceramic composite material has excellent mechanical properties and corrosion resistance, the internal fibers are prevented from being corroded, the use effect is good, the service life is long, the preparation process is simple, and the cost is low.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a carbon ceramic composite material, the method comprising the steps of: depositing a ceramic precursor on the surface of the carbon-carbon green body, curing and performing high-temperature pyrolysis to obtain the carbon-ceramic composite material; the deposition method comprises liquid phase deposition; the pyrolysis comprises the step of carrying out pyrolysis through gradient heating and heat preservation.
According to the invention, the ceramic precursor is deposited on the surface of the carbon-carbon blank in a liquid phase manner, and the ceramic coating is formed through solidification and pyrolysis, so that the corrosion of the carbon-carbon blank can be delayed, the service life of the carbon-ceramic composite material is prolonged, and compared with gas phase siliconizing, the silicon vapor is prevented from penetrating into the carbon blank by liquid phase deposition, the corrosion of internal carbon fibers is prevented, and the mechanical property and the service life of the material are improved; meanwhile, the material has less impurity content and better use effect by matching with a specific gradient heating and heat-preserving cracking process.
Preferably, the density of the carbon-carbon blank is 1 to 1.2g/cm -3 For example, it may be 1g/cm -3 、1.02g/cm -3 、1.04g/cm -3 、1.06g/cm -3 、1.08g/cm -3 、1.1g/cm -3 、1.12g/cm -3 、1.14g/cm -3 、1.16g/cm -3 、1.18g/cm -3 、1.2g/cm -3 Etc.
According to the invention, the low-density carbon blank is adopted for liquid phase deposition, namely, the density of the carbon blank is within the above-defined range, so that the ceramic precursor can be more easily permeated into carbon, the performance of the obtained carbon-ceramic composite material is better, and the process is simpler; if the density of the carbon-carbon green body is larger, the content of the ceramic precursor entering the carbon-carbon is smaller, and finally the relative content of the ceramic is lower; in addition, the higher the density of the carbon blank, the higher the cost, and after the density is increased to a certain degree, the surface crust needs to be removed by machining and then deposition is continued, so that the process flow is also more complex; if the density of the carbon-carbon green body is too small, the whole green body may not be fully hardened, and deform in the process of liquid phase deposition of the ceramic precursor, so that the appearance characteristics of the final product are affected.
Preferably, the preparation method of the carbon-carbon blank comprises the following steps: and carrying out chemical vapor deposition treatment on the carbon fiber preform to obtain the carbon-carbon blank.
Preferably, the chemical vapor deposited carbon source comprises natural gas and/or propane.
Preferably, the temperature of the chemical vapor deposition is 900 to 1400 ℃, and may be 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, or the like, for example.
Preferably, the pressure of the chemical vapor deposition is 0.5 to 5KPa, for example, 0.5KPa, 0.8KPa, 1.5KPa, 1.6KPa, 1.8KPa, 2KPa, 2.2KPa, 2.4KPa, 2.6KPa, 2.8KPa, 3KPa, 3.2KPa, 3.4KPa, 3.6KPa, 3.8KPa, 4KPa, 4.2KPa, 4.5KPa, 4.8KPa, 5KPa, etc. can be used.
Preferably, the time of the chemical vapor deposition is 50-400 h, for example, 50h, 80h, 100h, 120h, 150h, 180h, 200h, 220h, 250h, 280h, 300h, 380h, 400h, etc.
In the present invention, the preparation method of the carbon fiber preform is not required, and exemplary steps include:
according to the required structure, carbon fiber non-woven cloth and carbon fiber net tyre are alternately laminated and needled to prepare a carbon fiber preform; wherein the density of the laid fabric layer is 0.55-0.65 g/cm 3 (e.g., may be 0.55 g/cm) 3 、0.58g/cm 3 、0.6g/cm 3 、0.62g/cm 3 、0.64g/cm 3 、0.65g/cm 3 Etc.), the density of the net tire layer is 0.25-0.35 g/cm 3 (e.g., may be 0.25 g/cm) 3 、0.28g/cm 3 、0.3g/cm 3 、0.32g/cm 3 、0.34g/cm 3 、0.35g/cm 3 Etc.), the density of the obtained carbon fiber preform is 0.45-0.65 g/cm 3 (e.g., may be 0.45 g/cm) 3 、0.48g/cm 3 、0.5g/cm 3 、0.52g/cm 3 、0.54g/cm 3 、0.55g/cm 3 、0.58g/cm 3 、0.6g/cm 3 、0.62g/cm 3 、0.64g/cm 3 、0.65g/cm 3 Etc.); when in lamination, the single-layer laid cloth and the single-layer net tyre are sequentially and circularly paved, wherein the layer density is 13-16 layers/(10 mm) (for example, 13 layers, 14 layers, 15 layers, 16 layers and the like can be adopted); during needling, the density of needling holes is 5-10 per cm 2 (e.g., may be 5/cm) 2 6/cm 2 7 pieces/cm 2 8 pieces of/cm 2 9 pieces/cm 2 10 pieces/cm 2 )。
Preferably, before depositing the ceramic precursor on the surface of the carbon-carbon green body, the method further comprises the step of heat-treating the carbon-carbon green body.
The temperature of the heat treatment is preferably 2000 to 2300 ℃, and may be 2000 ℃, 2050 ℃, 2100 ℃, 2150 ℃, 2200 ℃, 2250 ℃, 2300 ℃, or the like.
Preferably, the time of the heat treatment is 0.5 to 4 hours, and may be, for example, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, and the like.
Preferably, the heat treatment is performed under vacuum conditions.
In the invention, the heat treatment further comprises the step of rough machining and polishing the carbon-carbon blank body to enable the rough surface state of the carbon-carbon blank body to be consistent.
Preferably, the method of depositing a ceramic precursor comprises coating a ceramic precursor on the surface of a carbon-carbon green body.
Preferably, the method of coating comprises spraying.
Preferably, the ceramic precursor comprises polysilazane or polycarbosilane.
Preferably, the curing temperature is 250 to 300 ℃, for example, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃ and the like.
Preferably, the curing time is 2 to 4 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, etc.
Preferably, the pyrolysis comprises a first warm keeping stage and a second warm keeping stage.
Preferably, the first temperature-raising and maintaining stage is raised to 400 to 600 ℃, for example, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 600 ℃, and the like.
Preferably, the heat-preserving time of the first temperature raising and preserving stage is 0.5 to 1h, for example, may be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, etc.
Preferably, the temperature rising rate of the first temperature rising and maintaining stage is 3-8 ℃ per minute, for example, 3 ℃/min, 3.2 ℃/min, 3.4 ℃/min, 3.6 ℃/min, 3.8 ℃/min, 4 ℃/min, 4.2 ℃/min, 4.4 ℃/min, 4.6 ℃/min, 4.8 ℃/min, 5 ℃/min, 5.2 ℃/min, 5.4 ℃/min, 5.6 ℃/min, 5.8 ℃/min, 6 ℃/min, 6.2 ℃/min, 6.5 ℃/min, 6.8 ℃/min, 7 ℃/min, 7.2 ℃/min, 7.5 ℃/min, 7.8 ℃/min, 8 ℃/min, etc.
Preferably, the second temperature-raising and maintaining stage is raised to 800 to 1000 ℃, for example, 800 ℃, 810 ℃, 820 ℃, 830 ℃, 840 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃, and the like.
Preferably, the heat-preserving time of the second temperature raising and preserving stage is 1 to 2 hours, for example, 1 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, etc.
Preferably, the temperature rising rate of the second temperature rising and maintaining stage is 0.5-3 ℃ per minute, for example, 0.5 ℃ per minute, 0.6 ℃ per minute, 0.7 ℃ per minute, 0.8 ℃ per minute, 1 ℃ per minute, 1.1 ℃ per minute, 1.2 ℃ per minute, 1.3 ℃ per minute, 1.4 ℃ per minute, 1.5 ℃ per minute, 1.6 ℃ per minute, 1.7 ℃ per minute, 1.8 ℃ per minute, 1.9 ℃ per minute, 2 ℃/minute, 2.1 ℃/minute, 2.2 ℃/minute, 2.3 ℃/minute, 2.4 ℃/minute, 2.5 ℃/minute, 2.6 ℃/minute, 2.7 ℃/minute, 2.8 ℃/minute, 2.9 ℃/minute, 3 ℃/minute, etc.
In the invention, a specific cracking process is adopted, so that the obtained product has better use effect, is not a specific process, is insufficient in cracking, and affects the use effect.
Preferably, the pyrolysis is performed in the presence of a protective atmosphere; the protective atmosphere includes, but is not limited to, nitrogen, argon, and the like.
Preferably, the preparation method further comprises repeating the processes of depositing the ceramic precursor, curing and pyrolysis.
In the invention, the repeated means that the ceramic precursor is deposited, solidified and cracked at high temperature into a process flow, and the process flow is repeated.
Preferably, the number of repetitions is 4 to 8, and may be, for example, 4 times, 5 times, 6 times, 7 times, 8 times, etc.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) Taking natural gas and/or propane as a carbon source, depositing a carbon material on the surface of a carbon fiber preform at a chemical vapor deposition temperature of 900-1400 ℃ and a chemical vapor deposition pressure of 0.5-5 KPa, and performing chemical vapor deposition for 50-400 h to obtain a carbon fiber preform with a density of 1-1.2 g/cm -3 Is a carbon-carbon green body of (2);
(2) Carrying out heat treatment on the carbon blank obtained in the step (1) for 0.5-4 hours under the conditions of vacuum and 2000-2300 ℃ to obtain a heat-treated carbon blank;
(3) Performing liquid phase deposition of a ceramic precursor on the surface of the heat-treated carbon blank obtained in the step (2), curing for 2-4 hours at the temperature of 250-300 ℃, and then performing high-temperature pyrolysis; the pyrolysis process comprises the following steps: heating to 400-600 ℃ at a speed of 3-8 ℃/min in the presence of protective atmosphere, preserving heat for 0.5-1 h, and then heating to 800-1000 ℃ at a speed of 0.5-3 ℃/min, preserving heat for 1-2 h, so as to obtain a carbon-carbon blank with a ceramic coating on the surface;
(4) Repeating the step (3) for 4-8 times to obtain the carbon-ceramic composite material.
Compared with the defects that the process period is long, the cost is too high and the ceramic coating with specific thickness cannot be obtained caused by direct vapor deposition of ceramic, the preparation method provided by the invention is short in period, low in cost and controllable in ceramic coating thickness.
In a second aspect, the present invention provides a carbon-ceramic composite comprising a carbon green body and a ceramic coating on a surface thereof; the carbon ceramic composite material is prepared by adopting the preparation method described in the first aspect.
Preferably, the thickness of the ceramic coating is 60 to 100 μm, for example, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, etc.
Preferably, the material of the ceramic coating comprises silicon carbide or silicon nitride.
Preferably, the density of the carbon ceramic composite material is 1.4-1.6 g/cm 3 For example, it may be 1.4g/cm 3 、1.42g/cm 3 、1.44g/cm 3 、1.46g/cm 3 、1.48g/cm 3 、1.5g/cm 3 、1.52g/cm 3 、1.54g/cm 3 、1.56g/cm 3 、1.58g/cm 3 、1.6g/cm 3 Etc.
In a third aspect, the present invention provides a heating apparatus comprising a carbon ceramic composite material as described in the second aspect.
Preferably, the heating device comprises a carbon ceramic heater or crucible.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the carbon-ceramic composite material, the ceramic precursor is deposited on the surface of the carbon blank in a liquid phase, and the ceramic coating is formed through solidification and pyrolysis, so that the corrosion of the carbon blank can be delayed, the service life of the carbon-ceramic composite material is prolonged, and compared with vapor deposition, the vapor deposition avoids the penetration of silicon vapor into the carbon blank, avoids the corrosion of internal carbon fibers, and improves the mechanical property and the service life of the material; meanwhile, the specific gradient heating and thermal insulation cracking process is matched, so that the impurity content in the material is low, the use effect is better, the process is simple, and the cost is low.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Carbon fiber preform: alternately laminating carbon fiber laid cloth and carbon fiber net tires and needling to prepare a carbon fiber preform; density of weft-free cloth layerAbout 0.6g/cm 3 The density of the net layer is about 0.3g/cm 3 The density of the obtained carbon fiber preform was about 0.55g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the When in lamination, a single-layer non-woven cloth and a single-layer net tyre are sequentially and circularly paved, and the layer density is about 14 layers/(10 mm); during needling, the density of needling holes is about 8 per cm 2 。
Example 1
The embodiment provides a preparation method of a carbon ceramic composite material, which specifically comprises the following steps:
(1) Putting the carbon fiber preform into a vapor deposition furnace to deposit pyrolytic carbon, taking propane as a carbon source, wherein the deposition temperature is 1000 ℃, the deposition pressure is 1KPa, the deposition time is 100h, and the density is 1.1g/cm 3 Is a carbon-carbon green body of (2);
(2) Carrying out rough machining and polishing on the carbon blank obtained in the step (1) under the conditions of vacuum and 2100 ℃ for 2 hours, so that the rough surface state of the carbon blank tends to be consistent, and obtaining the carbon blank after treatment;
(3) Liquid phase deposition of polysilazane (the mass percentage content is 30%) on the surface of the treated carbon blank obtained in the step (2), curing for 3 hours at 280 ℃, and then carrying out high-temperature pyrolysis; the pyrolysis process comprises the following steps: heating to 500 ℃ at a speed of 5 ℃/min in the presence of nitrogen, preserving heat for 1h, and then heating to 900 ℃ at a speed of 2 ℃/min, preserving heat for 1.5h, so as to obtain a carbon-carbon blank with a ceramic coating on the surface;
(4) And (3) repeating the step (3) for 6 times to obtain the carbon-ceramic composite material.
Example 2
The embodiment provides a preparation method of a carbon ceramic composite material, which specifically comprises the following steps:
(1) Placing the carbon fiber preform into a vapor deposition furnace to deposit pyrolytic carbon, taking propane as a carbon source, wherein the deposition temperature is 1300 ℃, the deposition pressure is 3KPa, and the deposition time is 50h, so as to obtain the carbon fiber preform with the density of 1.2g/cm 3 Is a carbon-carbon green body of (2);
(2) Carrying out rough machining and polishing on the carbon blank obtained in the step (1) under the conditions of vacuum and 2000 ℃ for 4 hours, so that the rough surface state of the carbon blank tends to be consistent, and obtaining the carbon blank after treatment;
(3) Liquid phase deposition of polysilazane on the surface of the treated carbon blank obtained in the step (2), curing for 4 hours at the temperature of 250 ℃, and then carrying out high-temperature pyrolysis; the pyrolysis process comprises the following steps: heating to 550 ℃ at a speed of 6 ℃/min for 0.8h in the presence of nitrogen, and then heating to 950 ℃ at a speed of 2.5 ℃/min for 1.8h to obtain a carbon-carbon blank with a ceramic coating on the surface;
(4) And (3) repeating the step (3) for 5 times to obtain the carbon-ceramic composite material.
Example 3
The embodiment provides a preparation method of a carbon ceramic composite material, which specifically comprises the following steps:
(1) Placing the carbon fiber preform into a vapor deposition furnace to deposit pyrolytic carbon, wherein natural gas is used as a carbon source, the deposition temperature is 1300 ℃, the deposition pressure is 2KPa, the deposition time is 100h, and the density is 1.2g/cm -3 Is a carbon-carbon green body of (2);
(2) Carrying out rough machining and polishing on the carbon blank obtained in the step (1) under the conditions of vacuum and 2200 ℃ for 3 hours, so that the rough surface state of the carbon blank tends to be consistent, and obtaining the carbon blank after treatment;
(3) Liquid phase deposition of carbosilane (the mass percentage content is 30%) on the surface of the treated carbon-carbon blank body obtained in the step (2), curing for 2 hours at 300 ℃, and then carrying out high-temperature pyrolysis; the pyrolysis process comprises the following steps: heating to 460 ℃ at a speed of 4 ℃/min in the presence of nitrogen, preserving heat for 1h, and then heating to 850 ℃ at a speed of 1.5 ℃/min, preserving heat for 2h, so as to obtain a carbon-carbon blank with a ceramic coating on the surface;
(4) And (3) repeating the step (3) for 7 times to obtain the carbon-ceramic composite material.
Example 4
The present embodiment provides a method for preparing a carbon-ceramic composite material, which differs from embodiment 1 only in that the pyrolysis process includes: the temperature was raised to 600℃at a rate of 3℃per minute for 0.5h, followed by a temperature rise to 800℃at a rate of 1℃per minute for 2h, and the other steps and parameters were the same as in example 1.
Example 5
The present embodiment provides a method for preparing a carbon-ceramic composite material, which differs from embodiment 1 only in that the pyrolysis process includes: the temperature was raised to 400℃at a rate of 8℃per minute for 1 hour, followed by a temperature rise to 1000℃at a rate of 3℃per minute for 1 hour, and the other steps and parameters were the same as in example 1.
Example 6
The embodiment provides a preparation method of a carbon-ceramic composite material, which is different from embodiment 1 only in that in the high-temperature cracking process, the temperature is raised to 700 ℃ for the first time, and the temperature is kept for 20min; raising the temperature to 750 ℃ for the second time, and preserving heat for 3 hours; other steps and parameters were the same as in example 1.
Example 7
The embodiment provides a preparation method of a carbon-ceramic composite material, which is different from embodiment 1 only in that in the high-temperature cracking process, the temperature is raised to 350 ℃ for the first time, and the temperature is kept for 2 hours; the second temperature was raised to 1100℃and maintained for 0.5h, the other steps and parameters were the same as in example 1.
Example 8
The present embodiment provides a method for preparing a carbon-ceramic composite material, which is different from embodiment 1 only in that in the pyrolysis process, the heating rate of the first heating is 2 ℃/min, the heating rate of the second heating is 5 ℃/min, and other steps and parameters are the same as those of embodiment 1.
Example 9
The present embodiment provides a method for preparing a carbon-ceramic composite material, which is different from embodiment 1 only in that in the pyrolysis process, the heating rate of the first heating is 10 ℃/min, the heating rate of the second heating is 0.2 ℃/min, and other steps and parameters are the same as those of embodiment 1.
Example 10
This example provides a method for preparing a carbon-ceramic composite material, which differs from example 1 only in that the density of the carbon-carbon green body obtained in step (1) is 1.4g/cm -3 The deposition time of the carbon-carbon green body was 300h, and the other steps and parameters were the same as in example 1.
Example 11
This example provides a method for preparing a carbon-ceramic composite material, which differs from example 1 only in that the density of the carbon-carbon green body obtained in step (1) is 0.8g/cm -3 The deposition time of the carbon-carbon green body was 50h, and the other steps and parameters were the same as in example 1.
Comparative example 1
This comparative example provides a method for preparing a carbon ceramic composite material, which differs from example 1 only in that the pyrolysis process includes: the temperature was raised to 1200℃at a rate of 5℃per minute in the presence of nitrogen for 2 hours, and the other steps and parameters were the same as in example 1.
Performance testing
(1) Density: calculating the density of the material by adopting the ratio of the mass to the volume, wherein the mass is measured by a balance with the precision of 0.001g, and the volume is calculated after the size is measured by a vernier caliper;
(2) Mechanical properties: testing the bending strength of the material by using an Instron 3345 electronic universal tester;
(3) The using effect is as follows: the resulting carbon ceramic material was fabricated into a thermal field crucible member and the surface state and silicon vapor erosion thickness were observed after 360 days of use.
The specific test results are shown in table 1:
TABLE 1
As can be seen from the table, the preparation method of the carbon-ceramic composite material provided by the invention can delay the corrosion of the carbon blank by liquid phase deposition of the ceramic precursor on the surface of the carbon blank and adopting a specific cracking process, improves the mechanical property and service life of the material, and has better use effect; and the process is simple and the cost is low.
As is clear from the comparison of examples 1 to 5 with examples 6 to 11 and comparative examples, the carbon ceramic composite material obtained by the method is not specific in process, and has poor performance, low bending strength, poor silicon vapor corrosion resistance, poor use effect and low service life.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the carbon ceramic composite material is characterized by comprising the following steps of:
depositing a ceramic precursor on the surface of the carbon-carbon green body, curing and performing high-temperature pyrolysis to obtain the carbon-ceramic composite material;
the deposition method comprises liquid phase deposition;
the pyrolysis comprises the step of carrying out pyrolysis through gradient heating and heat preservation.
2. The method of claim 1, wherein the carbon-carbon green body has a density of 1 to 1.2g/cm -3 ；
Preferably, the preparation method of the carbon-carbon blank comprises the following steps: and carrying out chemical vapor deposition treatment on the carbon fiber preform to obtain the carbon-carbon blank.
3. The method of claim 2, wherein the chemical vapor deposited carbon source comprises natural gas and/or propane;
preferably, the temperature of the chemical vapor deposition is 900-1400 ℃;
preferably, the pressure of the chemical vapor deposition is 0.5-5 KPa;
preferably, the chemical vapor deposition time is 50-400 hours.
4. A method according to any one of claims 1 to 3, further comprising the step of heat treating the carbon green body before depositing the ceramic precursor on the surface of the carbon green body;
preferably, the temperature of the heat treatment is 2000-2300 ℃;
preferably, the time of the heat treatment is 0.5 to 4 hours;
preferably, the heat treatment is performed under vacuum conditions.
5. The method according to any one of claims 1 to 4, wherein the liquid phase deposition comprises coating a ceramic precursor on the surface of the carbon-carbon green body;
preferably, the method of coating comprises spraying;
preferably, the ceramic precursor comprises polysilazane or polycarbosilane.
6. The method of any one of claims 1 to 5, wherein the temperature of curing is 250 to 300 ℃;
preferably, the curing time is 2 to 4 hours.
7. The method according to any one of claims 1 to 6, wherein the pyrolysis comprises a first warm-up incubation period and a second warm-up incubation period;
preferably, the first temperature rising and maintaining stage rises to 400-600 ℃;
preferably, the heat preservation time of the first temperature rising and heat preservation stage is 0.5-1 h;
preferably, the temperature rising rate of the first temperature rising and preserving stage is 3-8 ℃/min;
preferably, the second temperature rising and maintaining stage rises to 800-1000 ℃;
preferably, the heat preservation time of the second heating and heat preservation stage is 1-2 h;
preferably, the temperature rising rate of the second temperature rising and preserving stage is 0.5-3 ℃/min;
preferably, the pyrolysis is performed in the presence of a protective atmosphere;
preferably, the preparation method further comprises repeatedly performing the processes of depositing the ceramic precursor, curing and pyrolysis;
preferably, the number of repetitions is 4 to 8.
8. The preparation method according to any one of claims 1 to 7, characterized in that the preparation method comprises the steps of:
(1) Taking natural gas and/or propane as a carbon source, depositing a carbon material on the surface of a carbon fiber preform at a chemical vapor deposition temperature of 900-1400 ℃ and a chemical vapor deposition pressure of 0.5-5 KPa, and performing chemical vapor deposition for 50-400 h to obtain a carbon fiber preform with a density of 1-1.2 g/cm -3 Is a carbon-carbon green body of (2);
(2) Carrying out heat treatment on the carbon blank obtained in the step (1) for 0.5-4 hours under the conditions of vacuum and 2000-2300 ℃ to obtain a heat-treated carbon blank;
(3) Depositing a ceramic precursor on the surface of the heat-treated carbon blank obtained in the step (2), wherein the deposition method comprises liquid phase deposition; then, after curing for 2-4 hours at the temperature of 250-300 ℃, carrying out high-temperature pyrolysis; the pyrolysis process comprises the following steps: heating to 400-600 ℃ at a speed of 3-8 ℃/min in the presence of protective atmosphere, preserving heat for 0.5-1 h, and then heating to 800-1000 ℃ at a speed of 0.5-3 ℃/min, preserving heat for 1-2 h, so as to obtain a carbon-carbon blank with a ceramic coating on the surface;
(4) Repeating the step (3) for 4-8 times to obtain the carbon-ceramic composite material.
9. A carbon-ceramic composite material, which is characterized by comprising a carbon-carbon green body and a ceramic coating on the surface of the carbon-carbon green body;
the carbon-ceramic composite material is prepared by the preparation method according to any one of claims 1 to 8;
preferably, the thickness of the ceramic coating is 60-100 μm;
preferably, the material of the ceramic coating comprises silicon carbide or silicon nitride;
preferably, the density of the carbon ceramic composite material is 1.4-1.6 g/cm 3 。
10. A heating apparatus comprising the carbon ceramic composite material of claim 9;
preferably, the heating device comprises a carbon ceramic heater or crucible.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310866881.4A CN116903395A (en) | 2023-07-14 | 2023-07-14 | Carbon ceramic composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310866881.4A CN116903395A (en) | 2023-07-14 | 2023-07-14 | Carbon ceramic composite material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116903395A true CN116903395A (en) | 2023-10-20 |
Family
ID=88354374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310866881.4A Pending CN116903395A (en) | 2023-07-14 | 2023-07-14 | Carbon ceramic composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116903395A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284685A (en) * | 1988-08-31 | 1994-02-08 | Aerospatiale Societe Nationale Industrielle | Composite material with carbon reinforced fibers and its production |
| CN105237039A (en) * | 2015-08-31 | 2016-01-13 | 长安大学 | Anti-oxidizing coating material of carbon/carbon brake material and method of preparing the coating |
| CN111517810A (en) * | 2020-04-23 | 2020-08-11 | 山东工业陶瓷研究设计院有限公司 | High-temperature-resistant ceramic matrix composite interface composite coating and preparation method thereof |
| CN113087540A (en) * | 2019-12-23 | 2021-07-09 | 袁瑶 | Method for preparing silicon nitride coating on surface of carbon fiber preform |
| CN113149686A (en) * | 2021-05-17 | 2021-07-23 | 湖南世鑫新材料有限公司 | Carbon/carbon composite material crucible with composite ceramic layer and preparation method thereof |
| CN115180954A (en) * | 2022-07-08 | 2022-10-14 | 西安航空制动科技有限公司 | Preparation method of carbon-based composite material brake pad |
-
2023
- 2023-07-14 CN CN202310866881.4A patent/CN116903395A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284685A (en) * | 1988-08-31 | 1994-02-08 | Aerospatiale Societe Nationale Industrielle | Composite material with carbon reinforced fibers and its production |
| CN105237039A (en) * | 2015-08-31 | 2016-01-13 | 长安大学 | Anti-oxidizing coating material of carbon/carbon brake material and method of preparing the coating |
| CN113087540A (en) * | 2019-12-23 | 2021-07-09 | 袁瑶 | Method for preparing silicon nitride coating on surface of carbon fiber preform |
| CN111517810A (en) * | 2020-04-23 | 2020-08-11 | 山东工业陶瓷研究设计院有限公司 | High-temperature-resistant ceramic matrix composite interface composite coating and preparation method thereof |
| CN113149686A (en) * | 2021-05-17 | 2021-07-23 | 湖南世鑫新材料有限公司 | Carbon/carbon composite material crucible with composite ceramic layer and preparation method thereof |
| CN115180954A (en) * | 2022-07-08 | 2022-10-14 | 西安航空制动科技有限公司 | Preparation method of carbon-based composite material brake pad |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108117412B (en) | C/C-SiC-ZrB with laminated structure2Composite material and preparation method thereof | |
| CN109053207B (en) | A kind of yttrium silicate modified silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof | |
| CN103553692B (en) | Carbon/silicon carbide composite material crucible preparation method | |
| JP6196246B2 (en) | Silicon carbide-tantalum carbide composite and susceptor | |
| CN102674845B (en) | Preparation method of silicon carbide fibers with silicon nitride surface layer | |
| CN101628822B (en) | Method for producing a friction part from a carbon/carbon composite material | |
| CN105541363B (en) | A kind of high-temperature composite material and preparation method | |
| CN103804006B (en) | A kind of wave transparent type Si 3n 4fiber reinforced Si 3n 4the preparation method of ceramic matric composite | |
| CN108046819A (en) | A kind of structure-function integration C/C-SiC friction materials and preparation method | |
| CN103613400A (en) | A preparation method of carbon fiber reinforced carbon-silicon carbide binary ceramic matrix gradient composite material | |
| CN106966748B (en) | Superhigh temperature resistant and there is ceramic matric composite of self-healing capability and preparation method thereof | |
| CN108947588B (en) | C/SiC composite material, antioxidant coating used for same and preparation method thereof | |
| CN109293367B (en) | A kind of cerium phosphate modified silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof | |
| CN104030715A (en) | A kind of preparation method of Cf/BN-SiC composite material | |
| CN114195537A (en) | Pyrolytic carbon interface phase, preparation method and application thereof, carbon fiber reinforced silicon carbide ceramic matrix composite and preparation method thereof | |
| CN113979752B (en) | Mullite fiber reinforced ceramic matrix composite and preparation method thereof | |
| CN109320253A (en) | A kind of C/C composite material and preparation method thereof | |
| CN105198437A (en) | Method for preparing porous silicon carbide ceramics | |
| CN102167609A (en) | Quartz/quartz-boron nitride high-temperature wave-permeable material and preparation method thereof | |
| CN117024164B (en) | Ceramic modified carbon-carbon composite nose cone and preparation method thereof | |
| CN116003146B (en) | SiC (silicon carbide) f SiC composite material and preparation method and application thereof | |
| CN109053195A (en) | A kind of composite material and preparation method of the method preparing anti-oxidant compound interface layer on fiber preform and excellent combination property | |
| CN116903395A (en) | Carbon ceramic composite material and preparation method and application thereof | |
| CN113121253B (en) | Ultrahigh-temperature C/SiHfBCN ceramic matrix composite material and preparation method thereof | |
| CN113800934A (en) | Mullite fiber reinforced ceramic matrix composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |