CN117623793A - Ceramic matrix composite material capable of controlling deformation and preparation method thereof - Google Patents
Ceramic matrix composite material capable of controlling deformation and preparation method thereof Download PDFInfo
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- 239000011153 ceramic matrix composite Substances 0.000 title claims abstract description 48
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 62
- 238000005336 cracking Methods 0.000 claims abstract description 42
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000004744 fabric Substances 0.000 claims abstract description 27
- 239000000945 filler Substances 0.000 claims abstract description 27
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 19
- 239000004917 carbon fiber Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 150000002978 peroxides Chemical class 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 7
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 239000005011 phenolic resin Substances 0.000 claims abstract description 5
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 35
- 238000010025 steaming Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 10
- 238000001723 curing Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 238000010008 shearing Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- FSGAMPVWQZPGJF-UHFFFAOYSA-N 2-methylbutan-2-yl ethaneperoxoate Chemical compound CCC(C)(C)OOC(C)=O FSGAMPVWQZPGJF-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- -1 polysiloxane Polymers 0.000 claims description 2
- 239000003870 refractory metal Substances 0.000 claims description 2
- 229910021332 silicide Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- 238000013007 heat curing Methods 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 16
- 239000002313 adhesive film Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000280 densification Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 229920001709 polysilazane Polymers 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 239000012700 ceramic precursor Substances 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 6
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- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
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- 239000002245 particle Substances 0.000 description 3
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 238000005475 siliconizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/40—Weight reduction
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Abstract
The invention discloses a ceramic matrix composite material for controlling deformation and a preparation method thereof, comprising the following steps: vacuum heat treatment of silicon-based ceramic precursor and preparation of adhesive film; respectively loading active conformal filler by using polysilazane and polycarbosilane adhesive film added with peroxide crosslinking agent; depositing a 2D carbon fiber cloth on a PyC (pyrolytic carbon) interface; heating and pressing the adhesive film containing the active conformal filler and the carbon fiber cloth with the interface to prepare prepreg; layering the prepreg and performing active conformal filler controlled cracking in nitrogen or ammonia atmosphere; the composite is PIP (precursor dip cracking) densified and repeated multiple times using a low viscosity phenolic resin or a silicone precursor. The prepared ceramic matrix composite has the characteristics of high ceramic yield, high densification efficiency and excellent mechanical property, and realizes the low-deformation first-round cracking of the ceramic matrix composite through the mechanism of in-situ reaction of the active conformal filler and gas-phase carbon micromolecules, strengthening the bonding strength between 2D fabric layers and the like.
Description
Technical Field
The invention relates to the technical field of ceramic matrix composite materials, in particular to a deformation-controlled ceramic matrix composite material and a preparation method thereof.
Background
SiBCN and SiC are used as thermostructural ceramics which are developed for years, and have the characteristics of low density, oxidation resistance, creep resistance, high strength and high reliability. Meanwhile, the SiBCN ceramic matrix is modified by adopting the multi-element ceramic component, so that the oxidation resistance and the normal-high-temperature mechanical property of the SiBCN ceramic matrix can be further improved. The C/SiBCN and C/SiC thermostructural composite material is also gradually widely applied in the aerospace field.
Due to the increasing flying speed and bearing requirements of aircrafts, the design of the ceramic matrix composite bearing structure tends to be shaped and integrated with large size. However, since the ceramic matrix composite preparation process involves high temperature heat treatment, the heat treatment process is difficult to avoid the problems of gas discharge, ceramic crystallization shrinkage, complex thermal stress among multiple phases and the like, and finally most of the ceramic matrix composite preparation processes are difficult to solve the problems of large deformation and high cost of large-size parts and special-shaped parts.
The preparation process of the silicon-based thermal structure composite material mainly comprises precursor impregnation cracking (PIP), slurry Impregnation (SI), chemical vapor deposition/infiltration (CVD/CVI), liquid phase melting siliconizing (LSI) and the like. Chinese patent CN108658614a discloses a method for near net-size forming of SiC ceramic matrix composite shaped pieces, using an organic carbon source to prepare carbon foam and impregnating SiC nanowires therein, and finally removing the carbon foam by oxidation and depositing the SiC matrix using CVI. The technology realizes low deformation of the ceramic matrix composite, but the CVI process is high in cost, and particularly, a plurality of SiC gas sources are easy to generate HCl gas in the cracking process, so that the cost of tail gas treatment is further improved. In the conventional SI process, a complicated pressure die and a high-temperature high-pressure sintering environment are often required for forming the ceramic matrix composite special-shaped piece. The limitation of the large-scale part, the forming die of the special-shaped part and the pressurizing equipment greatly improves the preparation cost of the large-scale complex thermal structure. Moreover, fiber reinforcement is often subject to significant thermal damage due to the high temperature and high pressure sintering environment, resulting in poor mechanical properties of the ceramic matrix composites. Compared with other processes, the PIP process is used for forming large ceramic matrix composite parts, and the special-shaped parts are low in cost and higher in shape freedom, however, in the cracking process, the cracking deformation rate is higher than 30% due to the first-round cracking.
Therefore, it is necessary to provide a technology for preparing a thermostructural ceramic matrix composite material that is simple and inexpensive, has little deformation during molding, and has great flexibility in shape design.
Disclosure of Invention
The invention aims to provide a ceramic matrix composite for controlling deformation and a preparation method thereof, and the ceramic matrix composite is characterized by low cost, good process stability, low deformation and high ceramization yield, wherein an organosilicon precursor which is free of solvent, high in molecular weight and high in viscosity and is added with a medium-temperature peroxide initiator is used for preparing a precursor adhesive film, so that the precursor adhesive film is loaded with an in-situ ceramization active conformal filler, the prepreg is prepared by a compression roller method, and finally the prepreg is subjected to controlled cracking in nitrogen or ammonia atmosphere after layering.
In order to achieve the above object, the present invention provides a ceramic matrix composite for controlling deformation and a method for preparing the same, comprising the steps of:
s1, performing pyrolytic carbon interface deposition on 2D carbon fiber cloth by adopting chemical vapor deposition to form carbon fiber cloth with an interface;
s2, synchronously dissolving a peroxide initiator, a solid organosilicon precursor and a liquid organosilicon precursor by adopting an organic solvent, and dispersing the active conformal filler in the precursor solution by adopting a high-speed shearing disperser after the peroxide initiator, the solid organosilicon precursor and the liquid organosilicon precursor are completely dissolved to obtain a precursor solution loaded with the active conformal filler;
s3, carrying out two-step vacuum spin-steaming treatment on the precursor solution loaded with the active conformal filler, thereby finally obtaining an active conformal filler modified precursor;
the first step of vacuum spin-steaming treatment is to remove the organic solvent in the step S2 by low-temperature low-vacuum spin-steaming, and the second step of vacuum spin-steaming treatment is to remove the low molecules in the precursor solution in the step S2 by high-temperature high-vacuum spin-steaming, so that the average molecular weight of the precursor solution is improved;
s4, preparing a glue film from the active conformal filler modified precursor prepared in the step S3 by adopting a film coating method, and bonding the precursor glue film with the carbon fiber cloth with the interface in the step S1 by adopting a heating and pressing roller method to prepare a prepreg;
s5, layering the prepreg and performing cross-linking curing to obtain a cured composite material;
s6, fixing the cured composite material by adopting a shape-preserving tool, and cracking the cured composite material in a nitrogen or ammonia atmosphere to obtain a porous ceramic matrix composite material;
and S7, heating and pressurizing to impregnate the porous ceramic matrix composite by using a low-viscosity liquid organosilicon precursor or phenolic resin, and repeating cracking for 3-9 times.
Preferably, in step S1, the 2D carbon fiber cloth is UD cloth, plain cloth, twill cloth, satin cloth of commercial T or M series carbon fibers;
and the pyrolytic carbon interface deposition is to use propylene as an air source to carry out interface deposition on the 2D carbon fiber cloth for 1-5 hours at the temperature of 950 ℃, and the interface thickness of the carbon fiber cloth with the interface is 100-600 nm.
Preferably, in the step S2, the peroxide initiator is one of tert-amyl peroxyacetate, di-tert-butyl peroxide, dicumyl peroxide and tert-butyl peroxybenzoate;
the active conformal filler is one or more of boron-containing substances, si simple substances and refractory metal silicides, and the doping amount of the active conformal filler is 4-10 vol% of the total amount of the two precursors;
the solid organosilicon precursor is one of polycarbosilane, polysilabozane and polysiloxane, and the liquid organosilicon precursor is one of liquid polycarbosilane, vinyl polysilabozane and liquid polysilabozane;
the organic solvent is one of alkanes and toluene.
Preferably, in the step S2, the rotation speed of the high-speed shearing disperser is 10000-20000 r/min, and the dispersing time is 10min.
Preferably, in the step S3, the vacuum degree of the first-step vacuum rotary evaporation treatment is 50-100 Pa, and the rotary evaporation temperature is 5-10 ℃ lower than the boiling point of the organic solvent; the second step of vacuum rotary steaming treatment has vacuum degree of 10-50 Pa and rotary steaming temperature of 70-90 deg.c.
Preferably, in the step S4, the heating temperature of the compression roller method is 80-100 ℃, and the linear speed of the compression roller is 4-5 m/min.
Preferably, in step S5, a press vulcanizer or vacuum bagging method is used to mold and cure the mold by heating, and the curing temperature is 180-300 ℃.
Preferably, in step S6, the cleavage temperature is 900 to 1500 ℃.
In step S6, B is adopted 4 When C is used as the conformal active filler, the cracking temperature is 900-1000 ℃, and the cracking atmosphere is ammonia gas; because of the aerobic environment of the organosilicon prepreg during the molding by the atmospheric pressure roller, the precursor has about 15 weight percent of oxygen content, and B4C is oxidized into B 2 O 3 The glass phase, thus the volume expansion resists cracking shrinkage and firmly adheres each layer of fiber, and finally realizes the low shrinkage of first-round cracking; above 800 ℃, part B 2 O 3 Can be reduced to BN by ammonia gas;
in step S6, tiSi is used 2 When the powder is used as an active conformal filler, the cracking temperature is 1300-1500 ℃, and the cracking atmosphere is nitrogen; in the cracking process, tiOC and SiO can first appear 2 An equal phase; with the cracking temperature exceeding 1200 ℃, the oxide phase in the system is reduced to TiC, tiCN, tiN, siC, si successively 3 N 4 And the like, nitrogen fixation and carbon fixation in the cracking process lead the ceramic yield of the system to be improved;
preferably, in step S7, the pressure of the heating and pressurizing impregnation is 0.3-0.5 Mpa, the impregnation temperature is 80-100 ℃, and the viscosity of the low-viscosity impregnation precursor and the viscosity of the phenolic resin are 50-600 mPa.S.
The invention also provides a ceramic matrix composite for controlling deformation.
Therefore, the ceramic matrix composite material for controlling deformation and the preparation method thereof have the following technical effects:
(1) Firstly, the precursor is treated by vacuum spin-steaming to increase the average molecular weight and remove the solvent, and secondly, the initiator is added, and finally, the cracking process is controlled by the active conformal filler to realize high ceramic yield. Compared with the ceramization yield of 50-60 wt% of the conventional precursor, the ceramization yield of the prepared ceramic matrix composite material can reach 80-90 wt%. Compared with the prior art for preparing the PIP, the preparation method has the advantages of shorter preparation time, lower cost and higher densification efficiency due to higher ceramic yield.
(2) The prepreg is prepared by using the organosilicon precursor adhesive film to heat the pressing roller 2D carbon fiber cloth, and the prepared prepreg can be suitable for forming a plurality of types of ceramic matrix composite special-shaped pieces such as a spreading integrated piece, a plate variant piece and the like, and is also suitable for forming a ceramic matrix composite large-sized plate.
(3) The ceramic matrix composite prepared by the method has low deformation rate and excellent process stability compared with other PIP method composite preparation technologies.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
FIG. 1 is a flow chart of the preparation of a ceramic matrix composite for controlling deformation.
Detailed Description
The technical scheme of the invention is further described below through the attached drawings and the embodiments.
Unless defined otherwise, technical or scientific terms used herein should be given the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
As shown in fig. 1, a method for preparing a deformation-controlling ceramic matrix composite material comprises the following specific steps:
(1) T300-1k scrim was used as reinforcement with an areal density of 150g/m 2 . Propylene is adopted as an air source pairCarrying out PyC interface deposition treatment on the carbon fiber plain cloth, wherein the deposition temperature is 950 ℃, the pressure is 1kPa, and the retention time is 3s. The interface thickness of the fiber cloth after deposition is about 150nm on average, and the density after deposition is about 200g/m 2 。
(2) The liquid vinyl polysilazane with low viscosity (300 mPa.S-600 mPa.S) and the solid polysilazane are used for being co-dissolved in normal hexane, and the mass ratio of the two precursors is 1:1, simultaneously dissolving dicumyl peroxide with the mass of 1wt% of the precursor into the system as a medium-temperature initiator. 5vol% of B of precursor volume 4 C ceramic powder (the average grain diameter is 500 nm) is blended with the precursor, and dispersed for 10min by using a high-speed shearing disperser, and the rotating speed is 10000 r/min-20000 r/min. The organic solvent and the oligomer are removed respectively by a two-step vacuum rotary steaming method at different temperatures (50 ℃/75 ℃) and vacuum degrees (100 Pa/50 Pa), the first rotary steaming time is 1h, and the second rotary steaming time is 6h.
(3) And processing the precursor modified by the active conformal filler into a film with the thickness of about 0.3mm by adopting a coating method, and carrying out dipping adhesion on the two precursor films and one layer of 2D carbon fiber fabric by adopting a heating and pressing roller method, wherein the heating temperature is 80 ℃, and the winding speed is 4m/min. And sticking release paper on two sides of the prepared prepreg, carrying out forced air cooling, and refrigerating and light-shielding the prepared prepreg for later use.
(5) And (3) layering the prepreg, and placing the prepared composite material on a flat vulcanizing machine for pressurizing, heating and curing. The curing system is as follows: heating to 150 ℃ within 90min, preserving heat for 1h, and pressurizing to 2MPa during the heat preservation period; heating to 170 ℃ within 10min and preserving heat for 1h; heating to 180 ℃ within 10min and preserving heat for 1h; heating to 200 ℃ within 20min, and preserving heat for 2h, wherein the constant pressurizing value is 4MPa during the heat preservation at 200 ℃; and heating to 280 ℃ within 1h, solidifying and preserving heat for 1h, and finally slowly cooling to room temperature.
(6) And (3) mounting the cured composite material on a graphite-preserving tool, and placing the tool in an atmosphere furnace for cracking, wherein the cracking atmosphere is ammonia gas. The cracking system is as follows: heating to 300 ℃ within 1h, and preserving heat for 15min; heating to 350 ℃ within 15min, and preserving heat for 15min; heating to 400 ℃ within 15min, and preserving heat for 15min; heating to 500 ℃ within 1h, and preserving heat for 1h; heating to 600 ℃ within 1h, and preserving heat for 1h; heating to 700 ℃ within 1h, and preserving heat for 1h; heating to 900 ℃ within 3h and preserving heat for 1h; cooling to 600 ℃ within 3h, and preserving heat for 1h; cooling to 400 ℃ within 1h, and preserving heat for 1h; and then cooling to room temperature within 10 hours.
(7) The cracked porous ceramic matrix composite is placed in an immersion tank to be immersed with low-viscosity polyborosilazane (300 mPa.S-600 mPa.S) precursor, and the porous ceramic matrix composite is heated (100 ℃) and pressurized (0.3 MPa-0.5 MPa) for 10min. And (5) taking out the sample piece after the impregnation is finished, coating the sample piece with aluminum foil paper, and curing the sample piece in an oven, wherein the curing temperature system is the same as that of the step (5). And (3) after curing, carrying out high-temperature pyrolysis on the composite material by adopting an atmosphere furnace, wherein the pyrolysis temperature system is the same as that of the step (6).
(8) Repeating the step (7) for 3 times
The density of the low-deformation rapid densification ceramic matrix composite prepared in the embodiment is 1.86/cm 3 The ceramic yield of first-round cracking can reach 82%, and the thickness deformation rate of first-round cracking is-4.6%;
example two
The second embodiment is substantially the same as the first embodiment except that:
in the step (2), liquid vinyl polycarbosilane with low viscosity (300 mPa.S-600 mPa.S) and solid polycarbosilane are used for being co-dissolved in n-hexane, and the mass ratio of the two precursors is 1:1, simultaneously dissolving dicumyl peroxide with the mass of 1wt% of the precursor into the system as a medium-temperature initiator. TiSi was added in an amount of 5vol% based on the precursor volume 2 The powder (average particle size 3000 nm) was blended with the precursor.
And (6) installing the cured composite material in a shape-preserving graphite tool, and placing the tool in an atmosphere furnace for cracking, wherein the cracking atmosphere is nitrogen. The cracking system is as follows: heating to 1000 ℃ within 6 hours and preserving heat for 1 hour; heating to 1100 ℃ within 1h, and preserving heat for 1h; heating to 1200 ℃ within 1h, and preserving heat for 1h; heating to 1300 ℃ within 1h, and preserving heat for 1h; heating to 1400 ℃ within 1h, and preserving heat for 1h; and then cooling to room temperature within 10 hours.
The density of the low-deformation rapid densification ceramic matrix composite prepared in this example was 2.12g/cm 3 The ceramic yield of the first-round cracking can reach 89%, and the thickness deformation rate of the first-round cracking is +6.6%.
Comparative example one
Comparative example one is substantially the same as example one except that:
in the step (2), high-viscosity (900 mPa.S-1200 mPa.S) liquid vinyl polyborosilazane and solid borosilicate silazane are used for being dissolved in normal hexane, the dissolution process is heated to 50 ℃, and the mass ratio of the two precursors is 7:3, simultaneously dissolving dicumyl peroxide with the mass of 1wt% of the precursor into the system as a medium-temperature initiator. Inert ZrB with 5vol% of precursor volume 2 Powder (average particle size 2000 nm).
The density of the conventional inert filler modified ceramic matrix composite prepared in comparative example one was 1.89g/cm 3 The ceramic yield of the first-round cracking is 67%, and the thickness deformation rate of the first-round cracking is +11.4%.
Comparative example two
The second comparative example is substantially the same as the second example except that:
in the step (2), zrB accounting for 5vol% of the precursor volume 2 The powder (average particle size 2000 nm) was blended as an inert filler with the precursor.
In the step (6), the system is loosened and cracked due to no cracking at 1400 ℃ in the first round, so that the same cracking temperature procedure as in the embodiment is carried out by applying 5Mpa pressure by adopting a hot-pressing sintering furnace.
The density of the conventional inert filler modified ceramic matrix composite prepared in comparative example II is 1.94g/cm 3 The ceramic yield of the first-round cracking is 52%, and the thickness deformation rate of the first-round cracking is-17.6%.
Table 1 Performance indices of examples one to two and comparative examples one to two
| Group of | Density (g/cm) 3 ) | Cracking temperature (. Degree. C.) | First wheel thickness rate of change | First round ceramization yield |
| Example 1 | 1.86 | 900 | -4.6％ | 82％ |
| Example two | 2.12 | 1400 | +6.6％ | 89％ |
| Comparative example one | 1.89 | 900 | +11.4％ | 67％ |
| Comparative example two | 1.94 | 1400 | -17.6％ | 52％ |
Therefore, the ceramic matrix composite material for controlling deformation and the preparation method thereof are adopted, the organic silicon precursor which is solvent-free, high in molecular weight and high in viscosity and is added with the medium-temperature peroxide initiator is adopted to prepare the precursor adhesive film, so that the precursor adhesive film is loaded with the in-situ ceramic active conformal filler, the prepreg is prepared by a compression roller method, and finally the prepreg is subjected to controlled cracking in nitrogen or ammonia atmosphere after layering, so that the prepared ceramic matrix composite material has the characteristics of low cost, good process stability, low deformation and high ceramic yield.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (10)
1. A method for preparing a ceramic matrix composite for controlling deformation, comprising the steps of:
s1, performing pyrolytic carbon interface deposition on 2D carbon fiber cloth by adopting chemical vapor deposition to form carbon fiber cloth with an interface;
s2, synchronously dissolving a peroxide initiator, a solid organosilicon precursor and a liquid organosilicon precursor by adopting an organic solvent, and dispersing the active conformal filler in the precursor solution by adopting a high-speed shearing disperser after the peroxide initiator, the solid organosilicon precursor and the liquid organosilicon precursor are completely dissolved to obtain a precursor solution loaded with the active conformal filler;
s3, carrying out two-step vacuum spin-steaming treatment on the precursor solution loaded with the active conformal filler, thereby finally obtaining an active conformal filler modified precursor;
the first step of vacuum spin-steaming treatment is to remove the organic solvent in the step S2 by low-temperature low-vacuum spin-steaming, and the second step of vacuum spin-steaming treatment is to remove the low molecules in the precursor solution in the step S2 by high-temperature high-vacuum spin-steaming, so that the average molecular weight of the precursor solution is improved;
s4, preparing a glue film from the active conformal filler modified precursor prepared in the step S3 by adopting a film coating method, and bonding the precursor glue film with the carbon fiber cloth with the interface in the step S1 by adopting a heating and pressing roller method to prepare a prepreg;
s5, layering the prepreg and performing cross-linking curing to obtain a cured composite material;
s6, fixing the cured composite material by adopting a shape-preserving tool, and cracking the cured composite material in a nitrogen or ammonia atmosphere to obtain a porous ceramic matrix composite material;
and S7, heating and pressurizing to impregnate the porous ceramic matrix composite by using a low-viscosity liquid organosilicon precursor or phenolic resin, and repeating cracking for 3-9 times.
2. The method for producing a ceramic matrix composite for controlling deformation according to claim 1, wherein in step S1, the 2D carbon fiber cloth is UD cloth, plain cloth, twill cloth, satin cloth of commercial T or M series carbon fibers;
and the pyrolytic carbon interface deposition is to use propylene as an air source to carry out interface deposition on the 2D carbon fiber cloth for 1-5 hours at the temperature of 950 ℃, and the interface thickness of the carbon fiber cloth with the interface is 100-600 nm.
3. The method for producing a ceramic matrix composite for controlling deformation according to claim 1, wherein in step S2, the peroxide initiator is one of t-amyl peroxyacetate, di-t-butyl peroxide, dicumyl peroxide, and t-butyl peroxybenzoate;
the active conformal filler is one or more of boron-containing substances, si simple substances and refractory metal silicides, and the doping amount of the active conformal filler is 4-10 vol% of the total amount of the two precursors;
the solid organosilicon precursor is one of polycarbosilane, polysilabozane and polysiloxane, and the liquid organosilicon precursor is one of liquid polycarbosilane, vinyl polysilabozane and liquid polysilabozane;
the organic solvent is one of alkanes and toluene.
4. The method for producing a ceramic matrix composite according to claim 1, wherein in step S2, the speed of the high-speed shearing disperser is 10000-20000 r/min, and the dispersing time is 10min.
5. The method for preparing a ceramic matrix composite material according to claim 1, wherein in step S3, the degree of vacuum of the first vacuum spin-steaming treatment is 50 to 100Pa, and the spin-steaming temperature is 5 to 10 ℃ lower than the boiling point of the organic solvent; the second step of vacuum rotary steaming treatment has vacuum degree of 10-50 Pa and rotary steaming temperature of 70-90 deg.c.
6. The method for producing a ceramic matrix composite according to claim 1, wherein in step S4, the heating temperature by the press roll method is 80 to 100 ℃, and the linear speed of the press roll machine is 4 to 5m/min.
7. The method for producing a ceramic matrix composite according to claim 1, wherein in step S5, a press vulcanizer or vacuum bagging method is used for molding and heat curing, and the curing temperature is 180 to 300 ℃.
8. The method for producing a ceramic matrix composite according to claim 1, wherein in step S6, the cracking temperature is 900 to 1500 ℃.
9. The method according to claim 1, wherein in the step S7, the impregnation pressure is 0.3 to 0.5Mpa, the impregnation temperature is 80 to 100 ℃, and the viscosity of the low-viscosity impregnation precursor and the viscosity of the phenolic resin are 50 to 600mpa·s.
10. A deformation-controlling ceramic matrix composite prepared according to the method of any one of claims 1-9.
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