CN113929481A - Nitride fiber reinforced composite material and preparation method and application thereof - Google Patents
Nitride fiber reinforced composite material and preparation method and application thereof Download PDFInfo
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 50
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 87
- 238000007598 dipping method Methods 0.000 claims abstract description 77
- 238000011282 treatment Methods 0.000 claims abstract description 69
- 238000001035 drying Methods 0.000 claims abstract description 47
- 229910052582 BN Inorganic materials 0.000 claims abstract description 44
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005121 nitriding Methods 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 31
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004202 carbamide Substances 0.000 claims abstract description 27
- 238000005336 cracking Methods 0.000 claims abstract description 27
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004327 boric acid Substances 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 13
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009941 weaving Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000005470 impregnation Methods 0.000 claims description 26
- 239000012298 atmosphere Substances 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- VGRSPALDTNRXMC-UHFFFAOYSA-N [B].[N].[Si] Chemical group [B].[N].[Si] VGRSPALDTNRXMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000012700 ceramic precursor Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 32
- 229910000831 Steel Inorganic materials 0.000 abstract 1
- 239000010959 steel Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 27
- 238000001723 curing Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 11
- 238000000280 densification Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000001321 HNCO Methods 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64C—AEROPLANES; HELICOPTERS
- B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
- B64C1/36—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like adapted to receive antennas or radomes
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- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62857—Coating fibres with non-oxide ceramics
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- C04B35/62868—Boron nitride
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62886—Coating the powders or the macroscopic reinforcing agents by wet chemical techniques
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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Abstract
The invention relates to the technical field of fiber composite materials, and provides a nitride fiber reinforced composite material and a preparation method and application thereof, wherein the preparation method of the nitride fiber reinforced composite material comprises the following steps: (1) weaving silicon nitride fibers to obtain a prefabricated body; (2) carrying out dipping and drying treatment on the preform by using dipping liquid containing boric acid and urea to obtain a dipped preform; then sequentially carrying out nitriding treatment and heat treatment on the impregnated preform to obtainA fiber preform having a boron nitride interface layer on a surface thereof; (3) dipping the fiber preform with the boron nitride interface layer by a nitride precursor, and then sequentially carrying out crosslinking curing and cracking; (4) and (4) repeating the step (3) at least once to obtain the nitride fiber reinforced composite material. The density of the composite material prepared by the invention at room temperature is 1.74-1.76 g/cm3The tensile strength is 46-60 MPa, and the high-strength high-toughness steel has high strength and toughness.
Description
Technical Field
The invention relates to the technical field of fiber composite materials, in particular to a nitride fiber reinforced composite material and a preparation method and application thereof.
Background
The development of high-speed aircrafts puts higher demands on high-performance wave-transmitting materials resistant to higher temperature. In the fiber-reinforced silicon-boron-nitrogen wave-transmitting composite material, the temperature resistance of the matrix is improved due to the addition of the boron element in the matrix, and the obtained composite material has good high-temperature mechanical property, stable dielectric property and better ablation resistance, and is an ideal material for a new-generation aircraft radome. At present, the main process method for preparing the composite material taking silicon, boron and nitrogen as the matrix is the PIP process.
In fiber-reinforced composites, fibers are a major source of strength and toughness in the composite. Because the matrix in the composite material is formed by the organic-inorganic conversion of the precursor, the composite material has higher activity and corrosivity, the interface reaction is easy to occur at the interface to cause over-strong combination, the fiber can not be pulled out to play the role of strengthening and toughening, the phenomenon similar to brittle fracture is generated, and the mechanical property of the composite material is lower; therefore, the interface bonding strength is weakened in a certain mode, the mechanical property of the composite material is further improved, and the method plays an important role in improving the interface bonding state of the composite material.
The reinforcing and toughening effects of the fibers can be better realized by introducing a gap interface phase between the fibers and the matrix. The currently commonly used interface phase is a carbon coating and a boron nitride coating, and the boron nitride coating is generally selected as the interface phase because the carbon can influence the dielectric property and is not suitable for being used in the wave-transparent ceramic matrix composite. Compared with a chemical vapor deposition method, the solution dipping method is a common method for preparing the uniform and smooth boron nitride coating, avoids the defects of high equipment requirement, high energy consumption, low raw material utilization rate and larger pollution, has the characteristics of simple process and strong designability, is easy to realize the enlarged production of products, and is more suitable for preparing the coating of large-size components. The layered structure of the boron nitride coating can promote the deflection of cracks in the coating, weaken the interface bonding strength, further improve the mechanical property of the composite material, and play an important role in improving the interface bonding state of the composite material.
Therefore, the interface bonding state between the silicon nitride fiber and the matrix is improved, the reinforcing and toughening effects of the fiber can be better exerted, the mechanical property of the composite material is further improved, the expansion of the application range of the composite material is facilitated, and the method has important significance for the development of the fiber reinforced nitride composite material.
Disclosure of Invention
The invention aims to solve the technical problems that the fiber toughening effect is not obvious due to too strong interface bonding between a nitride precursor and fibers, and the mechanical property of a composite material is low, and provides a nitride fiber reinforced composite material and a preparation method and application thereof aiming at the defects in the prior art.
In order to solve the above technical problems, in a first aspect, the present invention provides a method for preparing a nitride fiber reinforced composite material, the method comprising the steps of:
(1) weaving silicon nitride fibers to obtain a prefabricated body;
(2) carrying out dipping and drying treatment on the preform by using dipping liquid containing boric acid and urea to obtain a dipped preform; then sequentially carrying out nitriding treatment and heat treatment on the impregnated preform to obtain a fiber preform with a boron nitride interface layer on the surface;
(3) dipping the fiber preform with the boron nitride interface layer by a nitride precursor, and then sequentially carrying out crosslinking curing and cracking;
(4) and (4) repeating the step (3) at least once to obtain the nitride fiber reinforced composite material.
The nitride fiber reinforced composite material prepared by the preparation method provided by the invention not only has a better interface combination state, but also has sufficient cross-linking between the precursor and the fiber preform, and the composite material has good comprehensive performance. The method solves the problem of over-strong interface bonding by particularly utilizing the solution dipping method treatment and precursor dipping, curing and cracking mode in the step (2), so that the interface bonding of the matrix and the fiber is more suitable, the fiber reinforcement effect is more obvious, and the strength of the composite material is higher.
In the application, compared with a chemical vapor deposition method for preparing the boron nitride interface layer, the boric acid and the urea are common chemical raw materials, are non-toxic and low in cost, and have the advantages of strong designability, simple process and good repeatability. Meanwhile, the preparation method not only improves the efficiency of preparing the boron nitride coating, but also can realize the preparation of the boron nitride coating on a large-size fiber preform and is applied to industrial production.
Preferably, in step (1), the preform has a fiber volume content of 30% to 50% (e.g., may be 30%, 35%, 40%, 45%, 50%, etc.);
the weave is a three-dimensional weave.
In the invention, the preform with the fiber volume content of 30-50% is preferably adopted in the step (1), which has better performance and operability. For the preform, generally, the higher the fiber content, the higher the strength of the final material after densification, but the greater the difficulty of weaving, and the greater the difficulty of impregnation due to the small pores. Meanwhile, the length and width of the preform according to the present invention may be determined according to actual needs, and the length is generally controlled within a range of not more than 1000mm, and the thickness is generally controlled within a range of not more than 50 mm.
Preferably, in the step (2), the molar mass ratio of the boric acid to the urea in the impregnation liquid is (0.2 to 2: 1) (for example, may be 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, or the like);
the impregnation liquid also comprises a solvent; wherein the solvent is an aqueous solution containing 0 wt% -30 wt% of methanol or an aqueous solution containing 0 wt% -30 wt% of ethanol.
The range of 0 wt% to 30 wt% means any value of 0 wt% to 30 wt%, and for example, may be 0 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%.
In the invention, a solution dipping-nitriding method is adopted in the step (2), specifically, the boric acid and the urea are weighed according to the molar mass ratio, then the weighed boric acid and urea are put into a solvent, and the solution is stirred for 1 to 2 hours to obtain a dipping solution; the impregnation liquid is prepared by stirring for 1 to 2 hours while controlling the concentration of boric acid in the impregnation liquid to be 0.1 to 1mol/L (for example, 0.1 to 0.2 to 0.3 to 0.5 to 0.7 to 0.8 to 1mol/L) and the concentration of urea to be 0.1 to 2mol/L (for example, 0.1 to 0.2 to 0.3 to 0.5 to 0.7 to 0.8 to 1mol/L), 1 to 1.1 to 1.2 to 1.5 to 1.7 to 1.8 to 2 mol/L).
In the present invention, boric acid and urea are completely reacted according to the reaction formula (I) in a molar mass ratio of 2:1, but the molar mass ratio of boric acid and urea is usually selected to be (0.2-2: 1) so that urea is in excess, thereby contributing to an increase in the yield of boron nitride.
2H3BO3+CO(NH2)2→2BN+CO2↑+5H2O↑ (Ⅰ)
Preferably, in the step (2), the number of the dipping and drying treatments is 3 to 9 (for example, 3, 4, 5, 6, 7, 8 or 9 times); the drying temperature of the impregnation drying is 40 ℃ to 100 ℃ (for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃ and the like can be adopted), and the drying time is 2h to 4h (for example, 2h, 2.5h, 3h, 3.5h or 4h and the like can be adopted).
In the invention, in the process of dipping and drying, the preform is firstly put into a vacuum dipping device, the vacuum degree is vacuumized to be less than or equal to minus 0.08MPa, then the dipping liquid is sucked into the vacuum dipping device, the vacuum degree is continuously vacuumized for not less than 10min, and finally the preform is taken out and put into a drying oven to be dried for 2 to 4 hours at the temperature of between 40 and 100 ℃, thus finishing the primary dipping and drying treatment. The dipping and drying treatment is repeated for 3-9 times.
Preferably, in the step (2), the atmosphere used in the nitriding treatment is ammonia gas;
the temperature of the nitriding treatment is 800 to 1200 ℃ (for example, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, etc.);
the heat-retaining time of the nitriding treatment is 3 to 9 hours (for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, or 9 hours).
In the present invention, the nitriding treatment specifically comprises: and (3) putting the impregnated preform subjected to 3-9 times of impregnation drying into an isothermal zone of an atmosphere furnace, and performing nitridation treatment on the impregnated preform by using ammonia gas as a reaction gas, so that boric acid which does not participate in the reaction formula (I) can be further subjected to full reaction to obtain boron nitride, and the yield of the boron nitride is further improved. Wherein the nitriding treatment process results in an interfacial boron nitride layer by reaction as shown in equations (I), (II) and (III):
2H3BO3→B2O3↑+3H2O↑ (Ⅱ)
B2O3+2NH3→2BN+3H2O↑ (Ⅲ)
wherein the unreacted excess urea is removed during the nitriding treatment by a reaction according to equation (iv):
CO(NH2)2→NH3↑+HNCO↑ (Ⅳ)。
in the invention, the crystallinity of the boron nitride interface layer tends to increase along with the increase of the temperature, the interface bonding state of the finally prepared composite material is obviously improved, but when the temperature exceeds 1000 ℃, the damage to the fiber is gradually increased. Therefore, in view of this, the temperature of the nitriding treatment is preferably 800 to 1200 ℃.
The holding time for the nitriding treatment is mainly selected depending on the required interface thickness, and generally, the longer the holding time, the larger the interface layer thickness. The thickness of the coating may change the fracture mode of the fiber-matrix interface, which is expected to have a large impact on the mechanical properties of the composite: the precursor in the composite material is formed by organic-inorganic conversion, so that the composite material has high activity and corrosivity, and is easy to generate interface reaction with fibers at an interface to cause over-strong bonding, and the fibers cannot be pulled out to play a role in enhancing and toughening, so that the mechanical property of the composite material is low; fibers may not effectively reduce interfacial bonding if the coating is too thin, while coating too thick may result in interfacial bonding that is too weak to allow the interface to effectively transfer loads. Therefore, the holding time selected herein is 3h to 9 h.
Preferably, in the step (2), the atmosphere used for the heat treatment is nitrogen;
the temperature of the heat treatment is 1200 to 1800 ℃ (for example, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1600 ℃, 1650 ℃, 1700 ℃, 1750 ℃ or 1800 ℃ and the like);
the heat treatment is carried out for a holding time of 0.5 to 3 hours (for example, 0.5 hour, 0.8 hour, 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours, 3 hours, etc.).
In the present invention, the heat treatment is a high temperature treatment process, specifically: and (3) putting the impregnated preform subjected to the nitriding treatment in the step (2) into a heat treatment furnace, adding nitrogen, keeping the temperature for 0.5-6 h at 1200-1800 ℃, cooling the impregnated preform subjected to the heat treatment to room temperature in the nitrogen atmosphere, and taking out the impregnated preform to obtain the fiber preform with the boron nitride interface layer. Wherein the reaction involved in the heat treatment is represented by the reaction formula (V); it should be noted that the surface of any fiber in the fiber preform has a hexagonal boron nitride coating;
B2O3+2N2→2BN+O2↑ (Ⅴ)
in the heat treatment process, along with the increase of the treatment temperature or the extension of the heat preservation time, the crystallinity of the boron nitride interface layer shows an increasing trend, the interface bonding state of the composite material is improved more obviously, but the damage to the fiber is increased gradually. By combining the factors, the yield of boron nitride is improved, and meanwhile, in order to reduce the damage to the fibers as much as possible, the selected heat treatment temperature is 1200-1800 ℃, and the heat preservation time is 0.5-3 h, which is lower than that of nitriding treatment.
Preferably, in the step (3), the nitride precursor is a silicon-boron-nitrogen precursor;
preferably, the silicon-boron-nitrogen precursor is a polysilaboron-nitrogen-based polymer ceramic precursor.
The silicon-boron-nitrogen precursor is a polysilaboron-nitrogen-alkane polymer ceramic precursor, and is prepared by using silazane, silane and boron trichloride as raw materials and mainly by a coemmonolysis mode.
Preferably, in step (3), the impregnation is vacuum suction-injection method impregnation.
In the present invention, the densification of the nitride fiber reinforced composite material can be achieved by impregnating in step (3) by using a vacuum suction-injection method.
Preferably, in the step (3), the temperature of the crosslinking curing is 100 ℃ to 300 ℃ (for example, may be 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 240 ℃, 260 ℃, 300 ℃, etc.); the time for the crosslinking curing is 5h to 20h (for example, 5h, 7h, 9h, 13h, 15h, 18h or 20h and the like can be used).
In the invention, the crosslinking curing reaction can be initiated by regulating and controlling the temperature, and the pressurizing operation needs to be carried out in the curing device by nitrogen in the curing process, and meanwhile, an inert atmosphere is provided.
Preferably, in step (3), the temperature of the cleavage is 400 to 1000 ℃ (for example, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or the like can be possible); the time for the cleavage is 3 to 9 hours (for example, 3, 4, 5, 6, 7, 8, or 9 hours).
In the invention, for the fiber preform which is dipped in the nitride precursor and provided with the boron nitride interface layer, ammonia gas is introduced into the cracking device in the cracking process, so that the good ventilation of the cracking device is ensured, the residue of the precursor reaction product in the blank is reduced, the residual carbon content is reduced, and the wave-transmitting performance of the composite material is optimized.
Preferably, in step (4), the number of times of repeating step (3) is 3 to 6 times (for example, it may be 3 times, 4 times, 5 times, or 6 times).
In a second aspect, the present invention provides a nitride fiber reinforced composite material prepared by the preparation method according to the first aspect.
Preferably, the density of the nitride fiber reinforced composite material is 1.74g/cm3～1.76g/cm3；
Preferably, the tensile strength of the nitride fiber reinforced composite material is 46 to 60 MPa.
The tensile strength of the present invention generally refers to the tensile strength at room temperature (25 ℃).
The nitride fiber reinforced composite material provided by the invention has good strength and toughness.
In a third aspect, the present invention provides a use of a nitride fiber reinforced composite material according to the second aspect in a wave-transparent system of an aircraft.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the nitride fiber reinforced composite material prepared by the preparation method provided by the invention not only has a better interface combination state, but also has sufficient cross-linking between the precursor and the fiber preform, and the composite material has good comprehensive performance. The invention solves the problem of interface combination by using a solution impregnation method for treatment and precursor impregnation, curing and cracking, so that the interface combination of the matrix and the fiber is more suitable, the fiber reinforcement effect is more obvious, and the strength of the composite material is higher.
(2) The density of the prepared nano-particles at room temperature is 1.74g/cm3～1.76g/cm3And the nitride fiber reinforced composite material with the tensile strength of 46 MPa-60 MPa has good strength and toughness.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer and more complete, the technical solutions in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
The silicon nitride fibers used in the following examples 1-14 of the present invention had a density of about 2.3g/cm3The nitride precursor used is polysilaborazine.
Example 1
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) dipping the preform in the step (1) by adopting a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(3) repeating the step (2)4 times to complete the densification process to obtain the product with the density of 1.71g/cm at room temperature3And a tensile strength of 30 MPa.
Example 2
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) the fiber preform is treated by a solution impregnation method: carrying out 3 times of dipping and drying treatment on the preform in the step (1) by using dipping liquid containing boric acid and urea to obtain a dipped preform; wherein, the molar mass ratio of the boric acid to the urea is 0.5:1, and the solvent in the dipping solution is an aqueous solution containing 30 wt% of methanol; during each dipping and drying treatment, firstly dipping the prefabricated body in dipping liquid, and then placing the prefabricated body at the drying temperature of 60 ℃ for 3 hours;
and then sequentially carrying out nitriding treatment (placing in an ammonia atmosphere and preserving heat at 1000 ℃ for 6 hours) and heat treatment (placing in a nitrogen atmosphere and preserving heat at 1400 ℃ for 1 hour) on the impregnated preform to obtain the fiber preform with the boron nitride interface layer on the surface.
(3) Dipping the fiber preform with the boron nitride interface layer by using a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(4) repeating the step (3)4 times to complete the densification process to obtain the product with the density of 1.74g/cm at room temperature3And a nitride fiber-reinforced composite material having a tensile strength of 48 MPa.
Example 3
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) the fiber preform is treated by a solution impregnation method: carrying out 6 times of dipping and drying treatment on the preform in the step (1) by using dipping liquid containing boric acid and urea to obtain a dipped preform; wherein, the molar mass ratio of the boric acid to the urea is 0.5:1, and the solvent in the dipping solution is an aqueous solution containing 30 wt% of methanol; at each impregnation drying treatment: firstly, soaking a prefabricated body in a soaking solution, and then, placing the prefabricated body at a drying temperature of 60 ℃ for 3 hours;
and then sequentially carrying out nitriding treatment (placing in an ammonia atmosphere and preserving heat at 1000 ℃ for 6 hours) and heat treatment (placing in a nitrogen atmosphere and preserving heat at 1400 ℃ for 1 hour) on the impregnated preform to obtain the fiber preform with the boron nitride interface layer on the surface.
(3) Dipping the fiber preform with the boron nitride interface layer by using a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(4) repeating the step (3)4 times to complete the densification process to obtain the product with the density of 1.75g/cm at room temperature3And a nitride fiber-reinforced composite material having a tensile strength of 60 MPa.
Example 4
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) the fiber preform is treated by a solution impregnation method: carrying out 9 times of dipping and drying treatment on the preform in the step (1) by using dipping liquid containing boric acid and urea to obtain a dipped preform; wherein, the molar mass ratio of the boric acid to the urea is 0.5:1, and the solvent in the dipping solution is an aqueous solution containing 30 wt% of methanol; during each dipping and drying treatment, firstly dipping the prefabricated body in dipping liquid, and then placing the prefabricated body at the drying temperature of 60 ℃ for 3 hours;
and then sequentially carrying out nitriding treatment (placing in an ammonia atmosphere and preserving heat at 1000 ℃ for 6 hours) and heat treatment (placing in a nitrogen atmosphere and preserving heat at 1400 ℃ for 1 hour) on the impregnated preform to obtain the fiber preform with the boron nitride interface layer on the surface.
(3) Dipping the fiber preform with the boron nitride interface layer by using a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(4) repeating the step (3)4 times to complete the densification process to obtain the product with the density of 1.76g/cm at room temperature3And a nitride fiber-reinforced composite material having a tensile strength of 52 MPa.
Example 5
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) the fiber preform is treated by a solution impregnation method: carrying out 6 times of dipping and drying treatment on the preform in the step (1) by using dipping liquid containing boric acid and urea to obtain a dipped preform; wherein, the molar mass ratio of the boric acid to the urea is 0.5:1, and the solvent in the dipping solution is an aqueous solution containing 30 wt% of methanol; during each dipping and drying treatment, firstly dipping the prefabricated body in dipping liquid, and then placing the prefabricated body at the drying temperature of 60 ℃ for 3 hours;
and then sequentially carrying out nitriding treatment (placing in an ammonia atmosphere and keeping the temperature at 800 ℃ for 6 hours) and heat treatment (placing in a nitrogen atmosphere and keeping the temperature at 1400 ℃ for 1 hour) on the impregnated preform to obtain the fiber preform with the boron nitride interface layer on the surface.
(3) Dipping the fiber preform with the boron nitride interface layer by using a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(4) repeating the step (3)4 times to complete the densification process to obtain the product with the density of 1.75g/cm at room temperature3And a tensile strength of 66 MPa.
Example 6
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) the fiber preform is treated by a solution impregnation method: carrying out 6 times of dipping and drying treatment on the preform in the step (1) by using dipping liquid containing boric acid and urea to obtain a dipped preform; wherein, the molar mass ratio of the boric acid to the urea is 0.5:1, and the solvent in the dipping solution is an aqueous solution containing 30 wt% of methanol; during each dipping and drying treatment, firstly dipping the prefabricated body in dipping liquid, and then placing the prefabricated body at the drying temperature of 60 ℃ for 3 hours;
and then sequentially carrying out nitriding treatment (placing in an ammonia atmosphere and keeping the temperature at 1200 ℃ for 6 hours) and heat treatment (placing in a nitrogen atmosphere and keeping the temperature at 1400 ℃ for 1 hour) on the impregnated preform to obtain the fiber preform with the boron nitride interface layer on the surface.
(3) Dipping the fiber preform with the boron nitride interface layer by using a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(4) repeating the step (3)4 times to complete the densification process to obtain the product with the density of 1.75g/cm at room temperature3And a nitride fiber-reinforced composite material having a tensile strength of 54 MPa.
Example 7
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) the fiber preform is treated by a solution impregnation method: carrying out 6 times of dipping and drying treatment on the preform in the step (1) by using dipping liquid containing boric acid and urea to obtain a dipped preform; wherein, the molar mass ratio of the boric acid to the urea is 0.5:1, and the solvent in the dipping solution is an aqueous solution containing 30 wt% of methanol; during each dipping and drying treatment, firstly dipping the prefabricated body in dipping liquid, and then placing the prefabricated body at the drying temperature of 60 ℃ for 3 hours;
and then sequentially carrying out nitriding treatment (placing in an ammonia atmosphere and keeping the temperature at 1000 ℃ for 6 hours) and heat treatment (placing in a nitrogen atmosphere and keeping the temperature at 1200 ℃ for 1 hour) on the impregnated preform to obtain the fiber preform with the boron nitride interface layer on the surface.
(3) Dipping the fiber preform with the boron nitride interface layer by using a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(4) repeating the step (3)4 times to complete the densification process to obtain the product with the density of 1.75g/cm at room temperature3And a nitride fiber-reinforced composite material having a tensile strength of 55 MPa.
Example 8
(1) Processing the silicon nitride fiber into a prefabricated body with the fiber volume content of 40% by adopting a three-dimensional weaving mode;
(2) the fiber preform is treated by a solution impregnation method: carrying out 6 times of dipping and drying treatment on the preform in the step (1) by using dipping liquid containing boric acid and urea to obtain a dipped preform; wherein, the molar mass ratio of the boric acid to the urea is 0.5:1, and the solvent in the dipping solution is an aqueous solution containing 30 wt% of methanol; during each dipping and drying treatment, firstly dipping the prefabricated body in dipping liquid, and then placing the prefabricated body at the drying temperature of 60 ℃ for 3 hours;
and then sequentially carrying out nitriding treatment (placing in an ammonia atmosphere and preserving heat at 1000 ℃ for 6 hours) and heat treatment (placing in a nitrogen atmosphere and preserving heat at 1800 ℃ for 1 hour) on the impregnated preform to obtain the fiber preform with the boron nitride interface layer on the surface.
(3) Dipping the fiber preform with the boron nitride interface layer by using a silicon boron nitrogen precursor through a vacuum suction injection method, then crosslinking and curing in a nitrogen atmosphere (the temperature of crosslinking and curing is 220 ℃ for 10 hours), and then carrying out a cracking reaction in an ammonia atmosphere (the temperature of cracking is 900 ℃ for 3 hours);
(4) repeating the step (3)4 times to complete the densification process to obtain the product with the density of 1.75g/cm at room temperature3And a nitride fiber-reinforced composite material having a tensile strength of 46 MPa.
Example 9
Example 9 is essentially the same as example 3, except that: the number of dipping and drying in the step (2) is 1.
Example 10
Example 10 is essentially the same as example 3, except that: the number of dipping and drying in the step (2) was 12.
Example 11
Example 11 is essentially the same as example 3, except that: the temperature of the nitriding treatment in the step (2) was 600 ℃.
Example 12
Example 12 is essentially the same as example 3, except that: the temperature of the nitriding treatment in the step (2) was 1400 ℃.
Example 13
Example 13 is essentially the same as example 3, except that: the temperature of the heat treatment in the step (2) was 1000 ℃.
Example 14
Example 14 is essentially the same as example 3, except that: the temperature of the heat treatment in the step (2) was 2000 ℃.
The nitride fiber reinforced composites prepared in examples 1 to 14 were tested for their density and tensile strength at room temperature (25 c), respectively, and the measured density and tensile strength data are shown in table 1.
TABLE 1
As can be seen from table 1, the raw materials and molding processes for preparing the nitride fiber-reinforced composite materials used in examples 1 to 8 were completely the same, and the fiber volume content of the preform, the nitride precursor impregnation, curing and cracking processes were the same, except that the fiber preform having a boron nitride interface layer on the surface thereof was treated differently from the preform. While the preform was directly subjected to the nitride precursor impregnation without treatment in example 1, examples 2 to 8 all added the treatment steps (i.e., dip drying treatment-nitriding treatment-heat treatment) for the preform before the nitride precursor impregnation. Specifically, the numbers of dip drying treatments were gradually increased in examples 2 to 4, the nitriding treatment temperatures were gradually increased in examples 5 and 6, and the heat-temperature treatment temperatures were gradually increased in examples 7 and 8, and it can be seen from table 1 that the nitride fiber reinforced composite materials obtained in the above respective examples each had a lower density and a higher tensile strength.
As can be seen from table 1, in examples 9 to 14, the number of immersion drying treatments, the nitriding treatment temperature, and the heat treatment temperature did not significantly affect the density of the nitride fiber reinforced composite material. However, when the dipping and drying times are too small, the prepared boron nitride interface layer is too thin to completely coat the fiber to form an effective interface, so that the tensile strength of the prepared nitride fiber reinforced composite material is low; when the dipping and drying times are too many, the fiber is damaged to a certain extent in the treatment process, so that the tensile strength of the prepared nitride fiber reinforced composite material is also reduced. Meanwhile, when the temperature of the nitriding treatment or the heat treatment is too low, the reaction is insufficient at low temperature, and a sufficient boron nitride interface layer is difficult to form, so that crack deflection cannot be realized at the interface layer, and the tensile strength of the prepared nitride fiber reinforced composite material is lower; when the temperature of the nitriding treatment or the heat treatment is too high, the fiber is more damaged due to high temperature, or the formed boron nitride interface layer is thick, so that the toughening mechanism of crack deflection is difficult to realize, and further the tensile strength of the compound fiber reinforced composite material is low. As described above, the number of dipping and drying treatments, the temperature of the nitriding treatment, and the temperature of the heat treatment greatly affect the tensile strength of the density of the nitride fiber reinforced composite material.
Therefore, in summary, in combination with table 1, it can be seen that, when the boron nitride coating layer prepared by the solution dipping method treatment (i.e. dipping drying treatment-nitriding treatment-heat treatment) is used as the interface between the fiber and the matrix of the composite material, not only the tensile strength of the prepared composite material is improved, but also the interface bonding state between the fiber and the matrix is improved. The density of the composite material is slightly influenced by different times of dipping and drying treatment, the nitriding treatment temperature and the heat treatment temperature, but the tensile strength is greatly influenced: the formed boron nitride interface layer has poor structural order degree by adopting lower nitriding treatment temperature or heat treatment temperature, which can cause limited effect; by adopting higher nitriding treatment temperature or heat treatment temperature, three-dimensional order in the formed boron nitride interface structure is gradually increased, but the high temperature aggravates the damage of the fiber and also causes the effect to be reduced; therefore, the temperature of the nitriding treatment is selected to be 800-1200 ℃, and the temperature of the heat treatment is selected to be 1200-1800 ℃.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention. The invention has not been described in detail and is in part known to those of skill in the art.
Claims (10)
1. A preparation method of a nitride fiber reinforced composite material is characterized by comprising the following steps:
(1) weaving silicon nitride fibers to obtain a prefabricated body;
(2) carrying out dipping and drying treatment on the preform by using dipping liquid containing boric acid and urea to obtain a dipped preform; then sequentially carrying out nitriding treatment and heat treatment on the impregnated preform to obtain a fiber preform with a boron nitride interface layer on the surface;
(3) dipping the fiber preform with the boron nitride interface layer by a nitride precursor, and then sequentially carrying out crosslinking curing and cracking;
(4) and (4) repeating the step (3) at least once to obtain the nitride fiber reinforced composite material.
2. The production method according to claim 1, wherein in step (1):
the fiber volume content of the preform is 30-50%;
the weave is a three-dimensional weave.
3. The production method according to claim 1, wherein in step (2):
the molar mass ratio of the boric acid to the urea in the impregnation liquid is (0.2-2) to 1;
the impregnation liquid also comprises a solvent; wherein the solvent is an aqueous solution containing 0 wt% -30 wt% of methanol or an aqueous solution containing 0 wt% -30 wt% of ethanol; and/or
The dipping and drying treatment is carried out for 3-9 times; the drying temperature of the dipping and drying is 40-100 ℃, and the drying time is 2-4 h.
4. The production method according to claim 1, wherein in step (2):
the atmosphere adopted by the nitriding treatment is ammonia;
the temperature of the nitriding treatment is 800-1200 ℃;
the heat preservation time of the nitriding treatment is 3-9 h.
5. The production method according to claim 1, wherein in the step (2):
the atmosphere adopted by the heat treatment is nitrogen;
the temperature of the heat treatment is 1200-1800 ℃;
the heat preservation time of the heat treatment is 0.5 h-3 h.
6. The production method according to claim 1, wherein in step (3):
the nitride precursor is a silicon-boron-nitrogen precursor;
preferably, the silicon-boron-nitrogen precursor is a polysilaboron-nitrogen-alkane polymer ceramic precursor;
preferably, the impregnation is vacuum suction and injection method impregnation.
7. The production method according to claim 1, wherein in step (3):
the temperature of the crosslinking curing is 100-300 ℃; the time for crosslinking and curing is 5-20 h; and/or
The cracking temperature is 400-1000 ℃; the cracking time is 3-9 h.
8. The method of claim 1, wherein:
in the step (4), the number of times of repeating the step (3) is 3-6.
9. The nitride fiber-reinforced composite material produced by the production method according to any one of claims 1 to 8, characterized in that:
preferably, the density of the nitride fiber reinforced composite material is 1.74g/cm3～1.76g/cm3；
Preferably, the tensile strength of the nitride fiber reinforced composite material is 46 to 60 MPa.
10. Use of the nitride fiber reinforced composite according to claim 9 in a wave-transparent system of an aircraft.
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