CN115991608B - Preparation method of endogenous fiber reinforced carbon/Tao Hou lining material - Google Patents
Preparation method of endogenous fiber reinforced carbon/Tao Hou lining material Download PDFInfo
- Publication number
- CN115991608B CN115991608B CN202211672571.0A CN202211672571A CN115991608B CN 115991608 B CN115991608 B CN 115991608B CN 202211672571 A CN202211672571 A CN 202211672571A CN 115991608 B CN115991608 B CN 115991608B
- Authority
- CN
- China
- Prior art keywords
- carbon
- tao
- hou
- lining material
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 140
- 239000000463 material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 34
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 29
- 238000005087 graphitization Methods 0.000 claims abstract description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 22
- 238000005470 impregnation Methods 0.000 claims abstract description 21
- 238000011049 filling Methods 0.000 claims abstract description 10
- 229920002050 silicone resin Polymers 0.000 claims abstract description 8
- 239000007849 furan resin Substances 0.000 claims abstract description 6
- 238000003754 machining Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000002296 pyrolytic carbon Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 238000009954 braiding Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 238000004513 sizing Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001351 cycling effect Effects 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 49
- 239000000919 ceramic Substances 0.000 abstract description 24
- 238000002679 ablation Methods 0.000 abstract description 8
- 230000008595 infiltration Effects 0.000 abstract description 5
- 238000001764 infiltration Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 238000010000 carbonizing Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- 229910052710 silicon Inorganic materials 0.000 description 15
- 239000010703 silicon Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 210000001170 unmyelinated nerve fiber Anatomy 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- -1 carbon hydrocarbon Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
The invention relates to a preparation method of an endogenous fiber reinforced carbon/Tao Hou lining material, which comprises the following steps: s1, preparing a carbon fiber preform, S2, high-temperature pretreatment of the preform, S3, preparing a low-density carbon/ceramic composite material blank by adopting a CVI (chemical vapor infiltration) process, S4, graphitizing, S5, adding mullite and silicone resin into furan resin to prepare mullite and silicone resin impregnant, S6, filling the blank prepared by S4 and the impregnant prepared by S5 into a vacuum-pressure impregnation tank, pressurizing, impregnating, curing and carbonizing, and performing process circulation for 4-6 times until a high-density carbon/Tao Hou lining material is obtained; s7, carrying out high-temperature graphitization treatment on the blank prepared in the S6 to obtain a ceramic carbon/carbon throat lining material product; s8, machining to obtain the carbon/carbon throat insert blank product. The invention has higher mechanical property and oxidation and ablation resistance, thereby improving the comprehensive performance of the throat liner and further improving the efficiency of the solid rocket engine nozzle.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of an endogenous fiber reinforced carbon/Tao Hou lining material.
Background
When the solid rocket engine is ignited, the solid fuel is combusted in the combustion chamber to generate a large amount of gas, and the engine spray pipe is positioned at the rear end of the combustion chamber, so that the internal energy of the solid fuel is converted into kinetic energy by controlling the expansion of the gas, thereby providing power for the rocket. The throat lining is positioned at the throat of the jet pipe, and can bear high temperature of about 3000 ℃ at the moment of rocket ignition and emission, the temperature of the throat lining material can rise at the speed of about 2000 ℃/s, and in the high-temperature environment, if the throat lining material is severely ablated or deformed and cracked, the working efficiency of the engine can be greatly influenced.
Carbon/carbon (C/C) composites, also known as carbon fiber reinforced carbon matrix composites, combine the inherent high temperature resistance of carbon matrices with the excellent mechanical properties of carbon fiber reinforcements. The material has the advantages of low density, small thermal expansion coefficient, long service life, strong designability, excellent friction and wear performance and higher specific strength and specific modulus. In addition, the mechanical strength does not decrease and rise with the increase of temperature (up to 2200 ℃) in an inert environment. The excellent characteristics and performances enable the carbon/carbon composite material to be widely applied to the throat lining of the rocket engine, however, the throat lining can bear the airflow scouring of carrying solid particles or liquid drops at high flow speed in a high-temperature and high-pressure environment, so that the throat lining material is oxidized, deformed and cracked, and the mechanical property and the high-temperature oxidation resistance of the carbon/carbon composite material in the high-temperature environment are required to be improved.
At present, the technology for developing the carbon/carbon throat lining has the lowest cost and the easiest preparation is a CVI+PIC composite technology, namely, firstly, when a carbon/carbon throat lining blank is deposited to a certain density (1.0-1.5 g/cm < 3 >) by adopting the CVI technology, the PIC is adopted to continue densification until the density of the material reaches more than 1.86g/cm < 3 >. However, the carbon/carbon throat lining is easy to oxidize at high temperature, so that the density of the carbon/carbon throat lining is reduced, the mechanical strength is reduced, and the mechanical property and the ablation resistance of the carbon/carbon throat lining material are seriously affected.
Disclosure of Invention
Technical problem to be solved by the invention
The invention provides a preparation method of an endogenous fiber reinforced carbon/Tao Hou lining material, which aims to solve the problems that the existing carbon/carbon throat lining material adopts CVI (isothermal chemical vapor infiltration) +PIC (resin impregnation curing carbonization) compounding, has high ablation rate, serious oxidation and the like.
In order to solve the technical problems, the invention adopts the technical proposal
The preparation method of the endogenous fiber reinforced carbon/Tao Hou lining material comprises the following preparation processes:
s1: preparing a carbon fiber preform, and preparing the carbon fiber into a quasi-three-dimensional or three-dimensional preform by a needling technology, a puncturing technology or a braiding technology;
S2: pretreating the preform at high temperature, namely placing the preform prepared in the step S1 into a graphitization furnace for high-temperature pretreatment, wherein the temperature is 1800-2200 ℃, the time is 1-3 h, and sizing agent and impurities on the surface of the carbon fiber are removed;
S3: preparing a low-density carbon/Tao Hou lining material blank by adopting a CVI process, loading the prefabricated body prepared in the step S2 into a chemical vapor deposition furnace, vacuumizing, heating to a set temperature, introducing a gaseous precursor and carrier gas, and maintaining the pressure balance in the furnace by adjusting the gas flow and the pumping force of a vacuum pump until the low-density carbon/Tao Hou lining material blank with the density of about 1.3g/cm < 3 > is obtained;
s4: graphitizing, namely filling the low-density carbon/Tao Hou lining material prepared in the step S3 into a temperature equalizing area of a graphitizing hearth, vacuumizing and heating according to a preset heating system, if equipment is needed, introducing argon at a high temperature, preserving heat at the highest temperature until the carbon structure is fully converted into graphite, then cooling to gradually cool a blank, discharging from the furnace and cleaning until the graphitizing is completed, wherein the graphitizing heating rate is 100-300 ℃/h, and the graphitizing temperature is 2200-2400 ℃ and the heat preservation time is 1-3 h;
S5: preparing mullite and a silicone impregnant, adding 0-10wt% of mullite and 0-15wt% of silicone into furan resin, and fully and uniformly mixing to prepare the mullite and the silicone impregnant;
s6: filling the low-density carbon/Tao Hou lining material blank prepared in the step S4 into a vacuum-pressure impregnation tank, adding the mullite prepared in the step S5 and a silicone resin impregnant into the impregnation tank, carrying out pressurized impregnation under a certain pressure, and carrying out curing and carbonization treatment, wherein the process is repeatedly circulated for 4-6 times until the density of the carbon/carbon material reaches more than 1.87g/cm < 3 >, so as to obtain the high-density carbon/Tao Hou lining material;
S7: finally graphitizing the carbon/Tao Hou lining material prepared in the step S6 at a high temperature of 2000-2500 ℃ to obtain a carbon/Tao Hou lining material product;
S8: the carbon/Tao Hou liner blank article was obtained by machining.
Further, the carbon fiber in the S1 is one or more of T300, T700, T800 and HTA.
Further, the carbon hydrocarbon precursor gas of the S3 CVI process is hydrocarbon gas.
Further, the hydrocarbon precursor gas of the S3 CVI process is any one of propylene, methane, ethylene or natural gas.
Further, the carrier gas of the S3 CVI process is any one of nitrogen, hydrogen or argon.
Further, the furnace pressure of the S3 is 2 kPa-10 kPa, pyrolytic carbon is generated under the condition of 900-1200 ℃, and the pyrolytic carbon is deposited for 300-500 hours until a low-density carbon/Tao Hou lining material blank with the density of about 1.3g/cm3 is obtained.
Further, the impregnation pressure of the S6 is 2.2-2.6 MPa, the curing temperature is 190 ℃, and the carbonization temperature is 900 ℃.
The invention has the technical effects that
Compared with the carbon/carbon composite material prepared by adopting isothermal CVI+PIC, the throat liner prepared by the method has higher mechanical property and oxidation ablation resistance, thereby improving the comprehensive performance of the throat liner and further improving the efficiency of the solid rocket engine nozzle. The preparation method does not need to change the existing molding process, equipment and tools, has the production cycle, cost and processability equivalent to those of the existing carbon/carbon composite material, and has wide engineering application prospect.
Drawings
Fig. 1: a preparation flow chart of the ultra-high temperature ceramic modified carbon/Tao Hou lining blank.
Detailed Description
The invention relates to a preparation method of an internal fiber reinforced carbon/Tao Hou lining material, which is to add mullite and silicone resin into impregnating resin in the traditional CVI+PIC composite technology. The porous carbon/carbon composite material prepared by a Chemical Vapor Infiltration (CVI) method is immersed in a mixed solution of mullite and silicon resin and then subjected to high-temperature heat treatment, so that the porous carbon/carbon composite material containing the silicon resin and the mullite is formed, and then carburization treatment is carried out, so that the superhigh-temperature ceramic modified carbon/Tao Hou lining material is prepared. The method is simple to operate, does not need to change the existing process equipment, has the production cycle, cost and processability equivalent to those of the existing carbon/carbon throat lining material, and has wide engineering application prospect. The carbon ceramic (C/C-3 Al2O 3.2SiO2) composite material prepared by the internal fiber has high melting point, high hardness, corrosion resistance, excellent physical and chemical properties and good ablation resistance, and the series of excellent properties lead the carbon ceramic (C/C-3 Al2O 3.2SiO2) composite material to be an ideal high-temperature structural material and to be widely applied in the fields of aerospace and the like. Because mullite (3 Al2O3 & 2SiO 2) can generate liquid phase filling in a composite material matrix at 1810 ℃ to form a stable crystal structure, a continuous and compact protective layer can be formed inside the composite material, the effect of preventing oxygen infiltration and the gradient and compact distribution of ceramics are realized, and the ceramic has excellent anti-ablation performance. In addition, by adding silicon resin into the preform, cracking the preform under 1400 ℃ and nitrogen atmosphere, and generating organic-inorganic conversion into a three-dimensional network polymer (SiOC ceramic) and C fibers, the C fibers follow a 'gas-liquid-solid' growth mechanism and play a bridging role on C/C-3Al2O3 & 2SiO2 together with the SiOC ceramic, and the interface combination can improve the mechanical property and the ablation resistance of the C/C composite material.
The preparation method of the endogenous fiber reinforced carbon/Tao Hou lining material comprises the following preparation processes:
1) Preparing a carbon fiber preform, and preparing the carbon fiber into a quasi-three-dimensional or three-dimensional preform by a needling technology, a puncturing technology or a braiding technology, wherein the carbon fiber is one or more of carbon fibers such as T300, T700, T800, HTA and the like;
2) Pretreating the preform at high temperature, namely placing the carbon fiber preform into a graphitization furnace for high-temperature pretreatment, wherein the high-temperature pretreatment temperature is 1800-2200 ℃, the time is 1-3 h, and sizing agent, impurities and the like on the surface of the carbon fiber are removed;
3) Preparing a low-density carbon/Tao Hou lining material blank by adopting a CVI process, loading the high-temperature pretreated preform into a chemical vapor deposition furnace, vacuumizing after loading, starting heating, heating to a set temperature, introducing a gaseous precursor and carrier gas, measuring the gas flow by using a rotameter, maintaining the pressure balance of the furnace by regulating the gas flow and the pumping force of a vacuum pump, and pumping the generated waste gas from the furnace top by the vacuum pump, wherein the carbon hydrocarbon precursor gas of the CVI process is any one of propylene, methane, ethylene, natural gas or other hydrocarbon gases, the carrier gas is one of nitrogen, hydrogen, argon and the like, the furnace pressure is 2 kPa-10 kPa, pyrolyzing to generate pyrolytic carbon at 900-1200 ℃, and depositing for 300-500 hours until the low-density carbon/ceramic composite material blank with the density of about 1.3g/cm < 3 > is obtained;
4) And (3) graphitizing, namely filling the low-density carbon/carbon composite material in the step (3) into a uniform temperature region of a graphitizing hearth, vacuumizing and heating according to a preset heating system, if required by equipment, introducing argon at a high temperature, preserving heat at the highest temperature until the carbon structure is fully converted into graphite, and then cooling to gradually cool a blank, discharging and cleaning until graphitizing is completed. The graphitization heating rate is 100-300 ℃/h, the graphitization temperature is 2200-2400 ℃, and the heat preservation time is 1-3 h;
5) Mullite and silicone impregnant are prepared. Adding 0-10wt% of mullite and 0-15wt% of silicon resin into furan resin, and fully and uniformly mixing to prepare mullite and silicon resin impregnant;
6) PIC is used for preparing carbon/ceramic composite material. Filling the low-density carbon/carbon composite material blank prepared in the step 4) into a vacuum-pressure impregnation tank, adopting the mullite and the silicon resin impregnant prepared in the step 5), then carrying out pressurized impregnation under a certain pressure to enable the impregnant to fully permeate pores in the low-density carbon/carbon composite material, and carrying out curing and carbonization treatment, and carrying out high-temperature heat treatment on the impregnated-cured-carbonized blank if necessary. The dipping pressure is 2.2-2.6 MPa, the curing highest temperature is 190 ℃, the carbonization highest temperature is 900 ℃, the process is repeatedly circulated for 4-6 times until the density of the carbon/carbon material reaches more than 1.87g/cm < 3 >, and the high-density carbon/Tao Hou lining material is obtained;
7) And finally graphitizing. Carrying out high-temperature graphitization treatment on the carbon/ceramic composite material obtained in the step 6), wherein the graphitization treatment temperature is 2000-2500 ℃, and obtaining a ceramic carbon/carbon throat lining material product;
8) And (5) machining to obtain the carbon/carbon throat insert blank product.
In order to make the objects, features and advantages of the technical scheme of the present invention more obvious and comprehensible, embodiments of the technical scheme of the present invention will be described clearly and completely with reference to the accompanying drawings. It is obvious that the described embodiments are only some embodiments of the proposed solution, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation process of the embodiment 1 of the invention is as follows:
1) Preparing a tubular carbon fiber preform with a needling structure.
2) And (5) treating the preform at a high temperature. And (3) placing the carbon fiber preform into a graphitization furnace for high-temperature pretreatment, wherein the high-temperature pretreatment temperature is 2200 ℃, the heat preservation time is 1h, and the volume density of the preform after the high-temperature pretreatment is 0.71g/cm < 3 >.
3) And preparing a low-density carbon/carbon composite material blank by adopting a CVI process. Filling the preform into a chemical vapor deposition furnace, heating to 950 ℃, and then introducing mixed gas of propylene and nitrogen, wherein the ratio of the propylene to the nitrogen is 1:3, depositing for 200 hours to obtain a green body with the density of about 1.1g/cm 3; the process was repeated once to obtain a green body having a density of 1.33g/cm 3.
4) Graphitizing the low density carbon/carbon composite material. Loading the carbon/carbon composite material prepared in the step 3) into a uniform temperature region of a graphitization furnace, vacuumizing and heating to 1500 ℃ at 100 ℃/h, stopping a vacuum pump, introducing argon to be close to normal pressure, continuously heating to 2200 ℃ at 100 ℃/h, preserving heat for 2h, powering off the graphitization furnace, cooling along with the furnace, and discharging a blank body. The carbon/carbon material density at this time was 1.30g/cm3.
5) Preparing silicon resin and mullite impregnant. Adding 0-10wt% mullite (100 meshes) +10wt% silicon resin into furan resin according to a proportion, and uniformly dispersing by adopting an ultrasonic oscillation method to prepare the silicon resin and mullite impregnant.
6) PIC is used for preparing carbon/ceramic composite material. Filling the low-density carbon/carbon composite material subjected to the graphitization treatment in a vacuum-pressure impregnation tank, heating the impregnation tank to 62 ℃ and vacuumizing to about 100 Pa; placing the silicon resin prepared in the step 6) and the mullite impregnant into a preheating tank, adding the curing agent industrial phosphoric acid according to the proportion of 7%, and uniformly stirring; and then sucking the resin from the preheating tank into the dipping tank, keeping the temperature at 62 ℃, pressurizing with N2 to 2.4MPa, and keeping the pressure for dipping for 4 hours. And (3) decompressing after the impregnation is finished, discharging excessive resin, continuously pressurizing to 2.4MPa, maintaining the pressure, curing at 190 ℃, decompressing and cooling after the curing is finished, and discharging. And (3) loading the carbon/carbon composite material after being discharged from the furnace into a carbonization furnace for carbonization, wherein the carbonization heating rate is 10 ℃/h, the carbonization temperature is 860 ℃, and then cooling and discharging to obtain the carbon/carbon composite material with the density of 1.58g/cm < 3 >. After 3 times of circulation, the density of the material reaches 1.69g/cm3, graphitization treatment is carried out for 2 hours at 2000 ℃, the silicon resin is completely cracked into (SiOC ceramic) and C fibers exist in the carbon/ceramic composite material in the process, the vacuum-pressure impregnation process is circulated for 5 times, and graphitization treatment is carried out for 2 times in the middle, wherein the density of the material reaches 1.88g/cm3.
7) And finally graphitizing. And (3) carrying out final graphitization treatment on the carbon/ceramic composite material obtained in the step (6), wherein the graphitization heating rate is 10 ℃/h, the treatment temperature is 2200 ℃, and the carbon/Tao Hou lining material product with the density of 1.87g/cm < 3 > is obtained.
The preparation process of the embodiment 2 of the invention is as follows:
1) And preparing a carbon fiber preform with a puncture structure.
2) And (5) treating the preform at a high temperature. And (3) placing the carbon fiber preform into a graphitization furnace for high-temperature pretreatment, wherein the high-temperature pretreatment temperature is 2100 ℃, the treatment time is 1h, and the volume density of the preform after the high-temperature pretreatment is 0.41g/cm < 3 >.
3) The CVI technology is adopted to prepare the low-density carbon/carbon composite material. Loading the high-temperature pretreated preform into a chemical vapor deposition furnace, vacuumizing, heating to 1150 ℃ for 7 hours, preserving heat for 2 hours, introducing precursor methane and carrier gas nitrogen, measuring the gas flow by a rotameter, depositing for 150 hours, and weighing after discharging to obtain a carbon/carbon composite material blank with the density of 1.04g/cm < 3 >. This procedure was repeated three times to obtain a low density carbon/carbon laryngeal mask blank having a density of 1.34g/cm 3.
4) Graphitizing the low density carbon/carbon composite material. Loading the carbon/carbon composite material in the step 3) into a uniform temperature region of a graphitization furnace, vacuumizing, heating to 1600 ℃ at 120 ℃/h, stopping a vacuum pump, introducing argon to be close to normal pressure, heating to 2300 ℃ at 100 ℃/h, preserving heat for 2h, powering off the graphitization furnace, cooling along with the furnace, and discharging a blank body. The carbon/carbon material density at this time was 1.32g/cm3.
5) Preparing silicon resin and mullite impregnant. Adding 0-5wt% mullite (100 meshes) +15wt% silicon resin into furan resin, and uniformly dispersing by adopting an ultrasonic oscillation method to prepare the silicon resin and mullite impregnant.
6) PIC is used for preparing carbon/ceramic composite material. Loading the low-density carbon/carbon composite material subjected to the graphitization treatment in a vacuum-pressure impregnation tank, heating the impregnation tank to 68 ℃ and vacuumizing to about 120 Pa; placing the silicon resin prepared in the step 5) and the mullite impregnant into a preheating tank, adding 7% of curing agent (industrial phosphoric acid), and uniformly stirring; then sucking the impregnant from the preheating tank into the impregnating tank, maintaining the temperature at 68 ℃, pressurizing with N2 to 2.5MPa, and maintaining the pressure for 5 hours. And (3) decompressing after the impregnation is finished, discharging excessive resin, continuously pressurizing to 2.5MPa, maintaining the pressure, curing at 190 ℃, decompressing and cooling after the curing is finished, and discharging. And (3) loading the carbon/carbon composite material after being discharged from the furnace into a carbonization furnace for carbonization, wherein the carbonization heating rate is 12 ℃/h, the carbonization temperature is 880 ℃, and the carbon/carbon composite material with the density of 1.60g/cm < 3 > is obtained after cooling and discharging after carbonization. After 3 times of circulation, the density of the material reaches 1.71g/cm3, and the material is graphitized for 2 hours at 2000 ℃. The silicone resin is totally broken down into (SiOC ceramic) and C fibers are present in the carbon/ceramic composite during this process. The vacuum-pressure impregnation process was cycled 4 times and the intermediate graphitization was performed 2 times, at which time the material density reached 1.87g/cm3.
7) And finally graphitizing. And (3) carrying out final graphitization treatment on the carbon/ceramic composite material obtained in the step (6), wherein the graphitization heating rate is 10 ℃/h, the treatment temperature is 2300 ℃, and the carbon/Tao Maopi finished product with the density of 1.86g/cm < 3 > is obtained.
According to the method for preparing the internal carbon/Tao Hou lining composite material, in the traditional CVI+PIC composite process, mullite and silicone resin are added into impregnating resin, a porous carbon/carbon composite material prepared by a Chemical Vapor Infiltration (CVI) method is placed into a mullite and silicone resin mixed solution for impregnation, and after high-temperature pyrolysis in a nitrogen atmosphere, the porous carbon/ceramic composite material containing mullite and internal carbon fibers is formed, so that the carbon/ceramic composite material with good mechanical properties is prepared, and the application of the composite material in extreme environments is realized.
The invention discloses an internal fiber reinforced carbon/ceramic (C/C-3 Al2O3 & 2SiO 2) throat lining material and a preparation method thereof, which are superior to carbon/carbon throat lining composite materials prepared by similar processes in that the mechanical property of the carbon/Tao Hou lining material prepared by the internal fiber is improved by more than 30%, the ablation resistance is improved by more than 25%, the mechanical property of the carbon/carbon throat lining material can be maintained at normal temperature in high temperature and ultra-high temperature environments, and the comprehensive performance of the carbon/carbon throat lining material is effectively improved.
Claims (6)
1. The preparation method of the endogenous fiber reinforced carbon/Tao Hou lining material is characterized by comprising the following steps of:
s1: preparing a carbon fiber preform, and preparing the carbon fiber into a quasi-three-dimensional or three-dimensional preform by a needling technology, a puncturing technology or a braiding technology;
S2: pretreating the preform at high temperature, namely placing the preform prepared in the step S1 into a graphitization furnace for high-temperature pretreatment, wherein the temperature is 1800-2200 ℃, the time is 1-3 h, and sizing agent and impurities on the surface of the carbon fiber are removed;
s3: preparing a low-density carbon/Tao Hou lining material blank by adopting a CVI process, loading the prefabricated body prepared in the step S2 into a chemical vapor deposition furnace, vacuumizing, heating to a set temperature, introducing a gaseous precursor and carrier gas, maintaining the balance of the pressure in the furnace by adjusting the gas flow and the pumping force of a vacuum pump, and pyrolyzing the furnace at the temperature of 900-1200 ℃ to generate pyrolytic carbon, and depositing for 300-500 h until the low-density carbon/Tao Hou lining material blank with the density of about 1.3g/cm < 3 > is obtained;
s4: graphitizing, namely filling the low-density carbon/Tao Hou lining material prepared in the step S3 into a temperature equalizing area of a graphitizing hearth, vacuumizing and heating according to a preset heating system, if equipment is needed, introducing argon at a high temperature, preserving heat at the highest temperature until the carbon structure is fully converted into graphite, then cooling to gradually cool a blank, discharging from the furnace and cleaning until the graphitizing is completed, wherein the graphitizing heating rate is 100-300 ℃/h, and the graphitizing temperature is 2200-2400 ℃ and the heat preservation time is 1-3 h;
s5: preparing mullite and a silicone impregnant, adding 5-10wt% of mullite and 10-15wt% of silicone into furan resin, and fully and uniformly mixing to prepare the mullite and the silicone impregnant;
S6: filling the low-density carbon/Tao Hou lining material blank prepared in the step S4 into a vacuum-pressure impregnation tank, adding the mullite prepared in the step S5 and a silicone resin impregnant into the impregnation tank, carrying out pressurized impregnation under a certain pressure, carrying out curing and carbonization treatment, and repeatedly cycling the process for 4-6 times until the density of the carbon/Tao Hou lining material reaches more than 1.87g/cm < 3 >, thereby obtaining the high-density carbon/Tao Hou lining material;
S7: finally graphitizing the carbon/Tao Hou lining material prepared in the step S6 at a high temperature of 2000-2500 ℃ to obtain a carbon/Tao Hou lining material product;
S8: the carbon/Tao Hou liner blank article was obtained by machining.
2. The method for preparing the endogenous fiber-reinforced carbon/Tao Hou lining material according to claim 1, wherein: the carbon fiber in the S1 is one or more of T300, T700, T800 and HTA.
3. The method for preparing the endogenous fiber-reinforced carbon/Tao Hou lining material according to claim 1, wherein: the precursor gas of the S3 CVI process is hydrocarbon gas.
4. The method for preparing the endogenous fiber-reinforced carbon/Tao Hou lining material according to claim 3, wherein: the precursor gas of the S3 CVI process is any one of propylene, methane, ethylene or natural gas.
5. The method for preparing the endogenous fiber-reinforced carbon/Tao Hou lining material according to claim 1, wherein: the carrier gas of the S3 CVI process is any one of nitrogen, hydrogen or argon.
6. The method for preparing the endogenous fiber-reinforced carbon/Tao Hou lining material according to claim 1, wherein: the impregnation pressure of the S6 is 2.2-2.6 MPa, the curing temperature is 190 ℃, and the carbonization temperature is 900 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211672571.0A CN115991608B (en) | 2022-12-26 | 2022-12-26 | Preparation method of endogenous fiber reinforced carbon/Tao Hou lining material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211672571.0A CN115991608B (en) | 2022-12-26 | 2022-12-26 | Preparation method of endogenous fiber reinforced carbon/Tao Hou lining material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115991608A CN115991608A (en) | 2023-04-21 |
| CN115991608B true CN115991608B (en) | 2024-05-10 |
Family
ID=85991621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211672571.0A Active CN115991608B (en) | 2022-12-26 | 2022-12-26 | Preparation method of endogenous fiber reinforced carbon/Tao Hou lining material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115991608B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489408A (en) * | 1993-03-08 | 1996-02-06 | Agency Of Industrial Science & Technology | Method for producing ceramics reinforced with three-dimensional fibers |
| JPH09316217A (en) * | 1996-05-28 | 1997-12-09 | Nissan Motor Co Ltd | Ablator material and its production |
| DE19814588A1 (en) * | 1998-04-01 | 1999-10-07 | Deutsch Zentr Luft & Raumfahrt | Thermal protection layer for an oxidic fiber composite material used especially as a gas turbine combustion chamber coating |
| JP2003201191A (en) * | 2001-12-28 | 2003-07-15 | Kyocera Corp | Corrosion resistant ceramic |
| CN105860526A (en) * | 2016-04-08 | 2016-08-17 | 哈尔滨工业大学 | Silicone resin composition for prepregs, carbon fiber prepreg and carbon fiber-silicone resin composite material |
| WO2017107735A1 (en) * | 2015-12-25 | 2017-06-29 | 深圳市勒马制动科技有限公司 | Method for preparing carbon-ceramic brake material and method for preparing carbon-ceramic brake disc |
| CN108947551A (en) * | 2018-06-28 | 2018-12-07 | 航天特种材料及工艺技术研究所 | A kind of outer heat-insulation composite material and preparation method thereof |
| CN109133959A (en) * | 2016-12-02 | 2019-01-04 | 航天特种材料及工艺技术研究所 | A kind of Carbon Fiber Rigid thermal insulation tile and preparation method thereof |
| CN110819228A (en) * | 2019-11-29 | 2020-02-21 | 北京理工大学 | Heat-insulation ablation-resistant maintainable repair agent and coating dual-purpose slurry, preparation method and application |
| CN111747766A (en) * | 2020-07-10 | 2020-10-09 | 中国人民解放军国防科技大学 | Carbon fiber reinforced SiAlOC composite material and preparation method thereof |
| CN112707743A (en) * | 2020-12-31 | 2021-04-27 | 湖北三江航天江北机械工程有限公司 | Preparation method of variable-density C/C composite throat insert |
| CN113024269A (en) * | 2021-03-19 | 2021-06-25 | 中南大学 | Preparation method of high-performance super-large and super-thick carbon/carbon composite material |
| CN115448744A (en) * | 2022-09-14 | 2022-12-09 | 湖南博云新材料股份有限公司 | Preparation method of carbon/carbon throat insert |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6682821B2 (en) * | 2001-12-28 | 2004-01-27 | Kyocera Corporation | Corrosion-resistant ceramics |
| US20060244165A1 (en) * | 2005-04-27 | 2006-11-02 | Dai Huang | Manufacturing carbon fiber reinforced ceramics as brake discs |
| US12024476B2 (en) * | 2020-02-21 | 2024-07-02 | Honeywell International Inc. | Carbon-carbon composite including antioxidant coating |
-
2022
- 2022-12-26 CN CN202211672571.0A patent/CN115991608B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5489408A (en) * | 1993-03-08 | 1996-02-06 | Agency Of Industrial Science & Technology | Method for producing ceramics reinforced with three-dimensional fibers |
| JPH09316217A (en) * | 1996-05-28 | 1997-12-09 | Nissan Motor Co Ltd | Ablator material and its production |
| DE19814588A1 (en) * | 1998-04-01 | 1999-10-07 | Deutsch Zentr Luft & Raumfahrt | Thermal protection layer for an oxidic fiber composite material used especially as a gas turbine combustion chamber coating |
| JP2003201191A (en) * | 2001-12-28 | 2003-07-15 | Kyocera Corp | Corrosion resistant ceramic |
| WO2017107735A1 (en) * | 2015-12-25 | 2017-06-29 | 深圳市勒马制动科技有限公司 | Method for preparing carbon-ceramic brake material and method for preparing carbon-ceramic brake disc |
| CN105860526A (en) * | 2016-04-08 | 2016-08-17 | 哈尔滨工业大学 | Silicone resin composition for prepregs, carbon fiber prepreg and carbon fiber-silicone resin composite material |
| CN109133959A (en) * | 2016-12-02 | 2019-01-04 | 航天特种材料及工艺技术研究所 | A kind of Carbon Fiber Rigid thermal insulation tile and preparation method thereof |
| CN108947551A (en) * | 2018-06-28 | 2018-12-07 | 航天特种材料及工艺技术研究所 | A kind of outer heat-insulation composite material and preparation method thereof |
| CN110819228A (en) * | 2019-11-29 | 2020-02-21 | 北京理工大学 | Heat-insulation ablation-resistant maintainable repair agent and coating dual-purpose slurry, preparation method and application |
| CN111747766A (en) * | 2020-07-10 | 2020-10-09 | 中国人民解放军国防科技大学 | Carbon fiber reinforced SiAlOC composite material and preparation method thereof |
| CN112707743A (en) * | 2020-12-31 | 2021-04-27 | 湖北三江航天江北机械工程有限公司 | Preparation method of variable-density C/C composite throat insert |
| CN113024269A (en) * | 2021-03-19 | 2021-06-25 | 中南大学 | Preparation method of high-performance super-large and super-thick carbon/carbon composite material |
| CN115448744A (en) * | 2022-09-14 | 2022-12-09 | 湖南博云新材料股份有限公司 | Preparation method of carbon/carbon throat insert |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115991608A (en) | 2023-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109053207B (en) | Yttrium silicate modified silicon carbide fiber reinforced silicon carbide composite material and preparation method thereof | |
| CN109265188B (en) | Carbon fiber reinforced hafnium boride-tantalum boride-carbon ceramic matrix composite material and preparation method thereof | |
| CN112341235B (en) | Multiphase coupling rapid densification method for ultrahigh-temperature self-healing ceramic matrix composite | |
| CN111099911A (en) | Carbon fiber reinforced carbon-silicon carbide-zirconium carbide composite material and preparation method thereof | |
| CN103936464A (en) | Preparation method of HfC-SiC modified carbon/carbon composite material | |
| CN110668839A (en) | Low-cost high-strength carbon fiber reinforced silicon carbide composite material and preparation method thereof | |
| CN115557800B (en) | Method for preparing silicon carbide-based composite material by uniformly ceramifying porous carbon | |
| CN103332943A (en) | Microstructure design and performance control method for preparing carbon-ceramic-based composite materials based on liquid silicon melt infiltration method | |
| CN112299865A (en) | Modified C/SiC composite material and preparation method thereof | |
| CN112851387B (en) | Method for preparing silicon carbide coating on surface of carbon-carbon composite material | |
| CN115448744B (en) | Preparation method of carbon/carbon throat liner | |
| CN114573357A (en) | SiC nanowire reinforced SiC ceramic matrix composite and preparation method thereof | |
| CN108129156A (en) | A kind of carbon ceramic composite material and its precursor impregnation preparation method | |
| CN106882976B (en) | Preparation method of C/HfC-ZrC-SiC composite material | |
| CN114645449B (en) | Preparation method of polyimide resin carbon modified C/C-SiC friction material | |
| CN113336564A (en) | Method for efficiently preparing continuous fiber reinforced silicon carbide ceramic matrix composite | |
| CN113121253B (en) | Ultrahigh-temperature C/SiHfBCN ceramic matrix composite material and preparation method thereof | |
| CN112374901B (en) | Ablation-resistant modified C/SiC composite material and preparation method thereof | |
| CN113087540A (en) | Method for preparing silicon nitride coating on surface of carbon fiber preform | |
| CN115991608B (en) | Preparation method of endogenous fiber reinforced carbon/Tao Hou lining material | |
| CN112125689A (en) | Preparation method of high-thermal-conductivity C/C-SiC composite material | |
| CN114853490B (en) | SiC/SiC ceramic composite material with excellent formability and good mechanical properties and preparation method thereof | |
| CN113307646B (en) | High-heat-conductivity and high-purity graphite-based composite material and preparation method thereof | |
| CN115353414A (en) | SiC and carbonitride interpenetrating ablation-resistant coating and preparation method thereof | |
| CN112174685A (en) | Unidirectional fiber bundle reinforced ZrB2Preparation method of-SiC composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |