CN116143534A - Preparation method of mixed polycarbosilane reinforced silicon carbide ceramic matrix composite - Google Patents
Preparation method of mixed polycarbosilane reinforced silicon carbide ceramic matrix composite Download PDFInfo
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- CN116143534A CN116143534A CN202310111949.8A CN202310111949A CN116143534A CN 116143534 A CN116143534 A CN 116143534A CN 202310111949 A CN202310111949 A CN 202310111949A CN 116143534 A CN116143534 A CN 116143534A
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- 229920003257 polycarbosilane Polymers 0.000 title claims abstract description 72
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000011153 ceramic matrix composite Substances 0.000 title claims abstract description 25
- 239000000835 fiber Substances 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 25
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 238000010894 electron beam technology Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005336 cracking Methods 0.000 claims description 9
- 238000001723 curing Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000009954 braiding Methods 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 230000004584 weight gain Effects 0.000 abstract 1
- 235000019786 weight gain Nutrition 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000005191 phase separation Methods 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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Abstract
The invention relates to a preparation method of a mixed polycarbosilane reinforced silicon carbide ceramic matrix composite, which comprises a preparation procedure of a precursor, a preparation procedure of a fiber preform and a PIP method preparation procedure of the ceramic matrix composite, wherein the preparation procedure of the precursor is to polish solid polycarbosilane until the particle size is smaller than 75um, dissolve the solid polycarbosilane in liquid polycarbosilane to form precursor liquid, the PIP method preparation procedure of the ceramic matrix composite is to impregnate the fiber preform prepared in the preparation procedure of the fiber preform into the precursor liquid in a vacuum impregnation furnace, the impregnated fiber preform is subjected to electron beam irradiation in an inert gas atmosphere, the irradiated fiber preform is subjected to pretreatment in the inert gas atmosphere, and then the fiber preform is put into a high-temperature furnace to be heated to 1240 ℃ for curing pyrolysis, and is subjected to cyclic impregnation and curing pyrolysis until the weight gain of the fiber preform is smaller than 1%. The invention can improve the product performance and the process is more environment-friendly.
Description
Technical Field
The invention relates to a preparation method of a mixed polycarbosilane reinforced silicon carbide ceramic matrix composite.
Background
The silicon carbide ceramic matrix composite has excellent performance and can be applied to the fields of military and aerospace aircrafts. The precursor dipping cracking method is a common method for preparing the silicon carbide ceramic matrix composite material, and the main advantages of the precursor dipping cracking method can be prepared at a lower temperature, and the precursor can be converted into a ceramic material at 800-1000 ℃. The precursor soaking cracking process mainly comprises the steps of precursor synthesis, non-melting treatment (crosslinking) and high-temperature pyrolysis. The common method for synthesizing the precursor is to dissolve solid polycarbosilane in organic solvents such as xylene divinylbenzene and the like, a large amount of harmful solvents such as xylene or divinylbenzene and the like are used for dissolving the solid polycarbosilane, the human body is injured, the organic solvents volatilize in the pyrolysis process, the reduction of porosity is not facilitated, and the ceramic yield is low. In addition, in the existing preparation process of the silicon carbide ceramic matrix composite, the preparation period is relatively long, the cost is relatively high, the porosity of the product is relatively high, and the yield is relatively low.
In view of this, the present inventors have conducted intensive studies on the above problems, and have produced the present invention.
Disclosure of Invention
The invention aims to provide a preparation method of a mixed polycarbosilane reinforced silicon carbide ceramic matrix composite material, which can improve the product performance and is more environment-friendly.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing a mixed polycarbosilane reinforced silicon carbide ceramic matrix composite comprises a precursor preparation process, a fiber preform preparation process and a PIP method preparation process for preparing the ceramic matrix composite,
the preparation process of the precursor comprises the steps of polishing solid polycarbosilane to a particle size smaller than 75 mu m, dissolving the solid polycarbosilane in liquid polycarbosilane to form precursor liquid, wherein the mass ratio of the solid polycarbosilane to the liquid polycarbosilane is 1:2-1:1;
the PIP method is used for preparing the ceramic matrix composite material, the fiber preform manufactured in the fiber preform preparation process is immersed in precursor liquid in a vacuum immersing furnace, the immersed fiber preform is subjected to electron beam irradiation in an inert gas atmosphere, the irradiated fiber preform is subjected to pretreatment in the inert gas atmosphere, the pretreatment temperature is 405-415 ℃, the heat is preserved for 6-8 hours, and then the fiber preform is placed in a high-temperature furnace, heated to 1240-1260 ℃ and subjected to curing pyrolysis, and the cyclic immersing and curing pyrolysis are carried out until the weight of the fiber preform is increased by less than 1%.
As a preferred mode of the present invention, the mass ratio of the solid polycarbosilane to the liquid polycarbosilane is 1:1.
As a preferable mode of the invention, the preparation process of the fiber preform is to take third-generation continuous silicon carbide fibers as raw materials, prepare the silicon carbide fiber preform by adopting a 3D braiding process, put the silicon carbide fiber preform into a muffle furnace, heat up to 600-700 ℃ at a speed of 5 ℃/min, keep the temperature for 2 hours, deposit a boron nitride coating on the surface of the carbon fiber preform by adopting a chemical vapor deposition method, and obtain the silicon carbide fiber preform containing BN coating, wherein the thickness of the coating is 200-300nm.
As a preferred mode of the invention, the PIP method is used for preparing the ceramic matrix composite material, the process comprises the steps of putting a silicon carbide fiber preform containing a BN coating into a vacuum dipping furnace, immersing precursor liquid for 8 hours under the vacuum degree of-95 kPa, then putting the immersed silicon carbide fiber preform into a glass tube, vacuumizing, changing into inert gas, repeating for three times, and irradiating gamma rays generated by a Co irradiation source to 3mGy dose; placing the irradiated silicon carbide fiber preform in an atmosphere furnace, vacuumizing, changing inert gas, repeating for three times, heating to 200 ℃ under flowing inert atmosphere, maintaining for 2 hours, heating to 410 ℃ and preserving heat for 4 hours; and then, putting the obtained silicon carbide fiber preform into a high-temperature furnace, heating to 1250 ℃, curing and cracking, and carrying out dipping, curing and cracking for a plurality of cycles until the weight increase is less than 1%.
After the technical scheme of the invention is adopted, the precursor liquid adopts solid polycarbosilane and liquid polycarbosilane, harmful solvents such as dimethylbenzene or divinylbenzene and the like are not used, the harm to human bodies is reduced, volatilization is reduced in the pyrolysis process, the ceramic yield is improved, and the reduction of porosity is facilitated. The bending strength of the ceramic matrix composite material prepared by the invention is more than 460MPa, and the density is more than or equal to 2.45g/cm 3 The flexural modulus is 100GPa, the open porosity is less than 6.2%, and the performance is excellent.
Drawings
Fig. 1 is an SEM scan of the present invention.
FIG. 2 is a SEM image (5 um) of the fracture surface of the present invention.
FIG. 3 is a SEM image (20 um) of a fracture surface according to the present invention.
FIG. 4 is a SEM image (50 um) of a fracture surface of the present invention.
FIG. 5 is a SEM image (100 um) of a fracture surface according to the present invention.
FIG. 6 is a SEM image of a fracture surface (200 um) of the present invention.
Detailed Description
In order to further explain the technical scheme of the present invention, the following is described in detail with reference to examples.
Referring to fig. 1 to 6, a method for manufacturing a hybrid polycarbosilane reinforced silicon carbide ceramic matrix composite includes the steps of:
step one: preparing a precursor:
(1) The solid polycarbosilane (manufactured by Fujian chemical Co., ltd.) was ground to less than 20mm using a grinding bowl, then the polycarbosilane particles were ground to less than 75um in diameter using a ball mill (anhydrous ethanol was used as a solvent), and the powder polycarbosilane was obtained after drying.
(2) Placing liquid polycarbosilane into a reaction bottle, slowly adding solid polycarbosilane which is ground into powder to form precursor liquid, wherein the mass ratio of solid to liquid is 1:1 (when the solid-to-liquid ratio of the mixed polycarbosilane is below 1:1, the content of the solid polycarbosilane is improved to help improve the stability of the crosslinking reaction, when the solid-to-liquid ratio of the mixed polycarbosilane is above 1:1, the content of the solid polycarbosilane is improved to cause the fluidity of the precursor solution to be poor, the occurrence of the crosslinking reaction and the discharge of small molecular gas are not facilitated), and completely dissolving the solid polycarbosilane by using ultrasonic stirring.
The properties of the crosslinked cured product at different solid-to-liquid mass ratios are shown in the following table:
advantages of adding polycarbosilane:
1. the liquid polycarbosilane has a molecular structure similar to that of solid polycarbosilane, and a solid-liquid mixed polycarbosilane precursor which is uniformly mixed can be obtained through a simple physical blending method. In the mixing process, no obvious phase separation phenomenon occurs, and the precursor composition is basically physical superposition of solid polycarbosilane and liquid polycarbosilane.
2. The addition of the liquid polycarbosilane obviously improves the Si-H group content of the precursor, and is beneficial to the subsequent circulation of the dipping-curing-pyrolysis process.
3. The addition of liquid polycarbosilane may reduce the crosslinking temperature or shorten the crosslinking time. The liquid polycarbosilane reduces concentrated heating during oxidative crosslinking and reduces the probability of larger pores on the surface of the product.
4. The liquid polycarbosilane can exist in the precursor relatively stably in the high-temperature melt spinning process, only a small part of the liquid polycarbosilane and the solid polycarbosilane undergo a crosslinking reaction, and the main part of Si-H groups are reserved.
5. The addition of the liquid polycarbosilane can improve the ceramic yield of the product, and under the same conditions, more than 10 percent of the liquid polycarbosilane is added, and the ceramic yield of the product is more than 80 percent only through oxidative crosslinking at 150 ℃.
Step two: preparing a fiber preform:
(1) The third generation continuous silicon carbide fiber (such as Fu established sub-chemical Co., ltd.) is used as raw material, and 3D braiding technology is used to prepare the silicon carbide fiber preform.
(2) And (3) placing the silicon carbide fiber preform into a muffle furnace, heating to 600-700 ℃ at a speed of 5 ℃/min, and preserving heat for 2 hours to remove the sizing agent.
(3) And (3) depositing a boron nitride coating on the surface of the silicon carbide fiber preform by adopting a chemical vapor deposition method to obtain the silicon carbide fiber preform containing the BN coating, wherein the thickness of the coating is 200-300nm (the thickness of the coating is lower than 200nm, the reinforcing effect on a product is smaller, and the coating higher than 300nm is very easy to peel).
Step three: PIP method preparation ceramic matrix composite process:
(1) Slowly placing the BN-coated silicon carbide preform into a vacuum impregnation furnace, slowly filling the precursor liquid, immersing the silicon carbide fiber preform, and impregnating the silicon carbide fiber preform under the vacuum of-95 kPa for 8 hours (fully filling pores under the vacuum to improve the density).
(2) Placing the impregnated silicon carbide fiber preform in a glass tube, vacuumizing, and exchanging inert gases (nitrogen, helium and the like are used for preventing oxygen from entering the mixed polycarbosilane in the pretreatment process), repeating the steps for three times, and irradiating gamma rays generated by a Co irradiation source to 3mGy dose; and (3) immediately placing the irradiated prefabricated product in an atmosphere furnace, vacuumizing, and replacing inert gases (nitrogen, helium and the like are used for preventing oxygen from entering the mixed polycarbosilane in the pretreatment process), repeating the steps for three times, and carrying out defoaming and heating pretreatment. And (3) in flowing inert atmosphere, heating to 200 ℃ according to a certain heating program, keeping for 2 hours, heating to 410 ℃ (the polycarbosilane is subjected to self-crosslinking at more than 400 ℃), and preserving the temperature for 4 hours to obtain the preform. Both electron beam irradiation and pretreatment are beneficial to improving the thermal stability of the polycarbosilane, and the pretreatment process can expand the beneficial effects caused by the electron beam irradiation on the polycarbosilane structure and the pyrolysis performance.
(3) And (3) putting the obtained silicon carbide fiber preform into a high-temperature furnace, heating to 1250 ℃ (along with the increase of sintering temperature, increasing the strength of ceramic fibers converted from the polycarbosilane precursor and the liquid polycarbosilane precursor, when the temperature reaches 1250 ℃, the strength of the fibers reaches the maximum, and then the strength begins to decrease), and carrying out dip-curing and cracking for a plurality of cycles until the weight of the material increases by less than 1%, thereby obtaining the reinforced silicon carbide ceramic matrix composite.
(4) The ceramic matrix composite prepared in the embodiment has the bending strength of 460MPa and the density of 2.45g/cm 3 The flexural modulus is 100GPa, the open porosity is 6.2%, the fracture surface shows more obvious fiber pulling out after the flexural strength test, which indicates that the continuous silicon carbide fiber exerts the reinforcing effect, shows more obvious toughness fracture characteristic and has less pores.
The invention has the following effects:
(1) The increase of the solid polycarbosilane content in the precursor is beneficial to crosslinking, the liquid polycarbosilane is used as an active solvent to dissolve the solid polycarbosilane, the fluidity of the system is ensured, the increase of the porosity caused by the volatilization of the solvent is avoided, the yield of the matrix ceramic is improved, and the performance of the composite material is improved.
(2) The liquid polycarbosilane is a byproduct of spinning-grade solid polycarbosilane production, so that the byproduct treatment cost is reduced, the production economy is improved, and the comprehensive utilization of the liquid polycarbosilane is beneficial to the reduction of the cost of companies.
(3) The liquid polycarbosilane is added, so that the boiling point of the whole reaction raw material is improved, the evaporation capacity is reduced in the reaction process, the ring opening efficiency of a cracking column is facilitated, meanwhile, the introduction of the liquid polycarbosilane is beneficial to the condensation reaction, the reaction time is shortened, the yield is improved, and the molecular weight distribution of the product is improved.
(4) The preparation process of the composite material is greatly shortened, and the preparation time, manpower and material resources are saved.
(5) Harmful solvents such as dimethylbenzene or divinylbenzene are not used, the harm to human bodies is reduced, volatilization is reduced in the pyrolysis process, particularly the later impregnation period is reduced, and the higher the ceramic yield is, the more favorable the reduction of porosity is.
(6) The pretreatment is beneficial to improving the thermal stability of the polycarbosilane, and the ceramic yield after the pretreatment is about 10 percent higher than that of the raw materials.
The product form of the present invention is not limited to the embodiments described herein, and any suitable variations or modifications of the similar concept should be regarded as not departing from the scope of the invention.
Claims (4)
1. The preparation method of the mixed polycarbosilane reinforced silicon carbide ceramic matrix composite comprises the steps of preparing a precursor, preparing a fiber preform and preparing the ceramic matrix composite by a PIP method, and is characterized in that:
the preparation process of the precursor comprises the steps of polishing solid polycarbosilane to a particle size smaller than 75 mu m, dissolving the solid polycarbosilane in liquid polycarbosilane to form precursor liquid, wherein the mass ratio of the solid polycarbosilane to the liquid polycarbosilane is 1:2-1:1;
the PIP method is used for preparing the ceramic matrix composite material, the fiber preform manufactured in the fiber preform preparation process is immersed in precursor liquid in a vacuum immersing furnace, the immersed fiber preform is subjected to electron beam irradiation in an inert gas atmosphere, the irradiated fiber preform is subjected to pretreatment in the inert gas atmosphere, the pretreatment temperature is 405-415 ℃, the heat is preserved for 6-8 hours, and then the fiber preform is placed in a high-temperature furnace, heated to 1240-1260 ℃ and subjected to curing pyrolysis, and the cyclic immersing and curing pyrolysis are carried out until the weight of the fiber preform is increased by less than 1%.
2. The method for preparing the mixed polycarbosilane reinforced silicon carbide ceramic matrix composite according to claim 1, which is characterized by comprising the following steps: the mass ratio of the solid polycarbosilane to the liquid polycarbosilane is 1:1.
3. The method for preparing the mixed polycarbosilane reinforced silicon carbide ceramic matrix composite according to claim 2, which is characterized by comprising the following steps: the preparation process of the fiber preform is to prepare the silicon carbide fiber preform by taking third-generation continuous silicon carbide fibers as raw materials and adopting a 3D braiding process, placing the silicon carbide fiber preform into a muffle furnace, heating to 600-700 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, depositing a boron nitride coating on the surface of the carbon fiber preform by adopting a chemical vapor deposition method, and obtaining the silicon carbide fiber preform containing the BN coating, wherein the thickness of the coating is 200-300nm.
4. A method for preparing a mixed polycarbosilane reinforced silicon carbide ceramic matrix composite according to claim 3, wherein: the PIP method is characterized in that a silicon carbide fiber preform containing a BN coating is placed into a vacuum impregnation furnace, precursor liquid is immersed, the impregnation is carried out for 8 hours under the vacuum degree of-95 kPa, then the impregnated silicon carbide fiber preform is placed into a glass tube, the vacuum pumping is carried out, inert gas is replaced, the process is repeated for three times, and gamma rays generated by a Co irradiation source are utilized to irradiate to 3mGy dose; placing the irradiated silicon carbide fiber preform in an atmosphere furnace, vacuumizing, changing inert gas, repeating for three times, heating to 200 ℃ under flowing inert atmosphere, maintaining for 2 hours, heating to 410 ℃ and preserving heat for 4 hours; and then, putting the obtained silicon carbide fiber preform into a high-temperature furnace, heating to 1250 ℃, curing and cracking, and carrying out dipping, curing and cracking for a plurality of cycles until the weight increase is less than 1%.
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