CN110304932B - Preparation method of Cf/SiC composite material with HfB2 interface - Google Patents
Preparation method of Cf/SiC composite material with HfB2 interface Download PDFInfo
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Abstract
The invention discloses a catalyst with HfB2The preparation method of the interface Cf/SiC composite material comprises the following steps: activating the surface of carbon fiber, preparing an interface phase, preparing a porous fiber preform, and preparing a silicon carbide substrate; the carbon fiber reinforced silicon carbide ceramic matrix composite is characterized in that a silicon carbide matrix is filled in a fiber preform to form a carbon fiber reinforced silicon carbide ceramic matrix composite, and an interface layer wraps the surface of carbon fibers in the composite. The invention prepares the high temperature resistant and oxidation resistant HfB on the surface of the carbon fiber2The interface phase keeps the original mechanical property of the carbon fiber and improves the high-temperature oxidation resistance of the carbon fiber. The invention solves the technical problems that the preparation period of the traditional preparation method of the silicon carbide ceramic matrix composite material is long, the interface compatibility of the toughening phase carbon fiber and the silicon carbide matrix in the Cf/SiC composite material is high, and the carbon fiber is easy to generate oxidation reaction in a high-temperature oxidizing use environment.
Description
Technical Field
The invention relates to the technical field of carbon fiber reinforced silicon carbide ceramic matrix composite materials, in particular to a composite material with HfB2A preparation method of an interface Cf/SiC composite material.
Background
The carbon fiber reinforced silicon carbide ceramic matrix composite (Cf/SiC) has the characteristics of light weight, high temperature resistance, high specific strength, high specific modulus, low thermal expansion coefficient, high substrate density, thermal shock resistance, ablation resistance, good thermochemical stability, strong severe environment resistance adaptability and the like, is a novel light composite integrating structure bearing and oxidation/ablation resistance, and is widely applied to the fields of aerospace, satellites, war industry, nuclear industry and the like. The carbon fiber has excellent performances of high modulus, high strength, low density, low thermal expansion, high temperature resistance, oxidation resistance, no creep deformation, high heat conduction, corrosion resistance and the like, can be used as a reinforcement of a composite material, and the characteristics enable the carbon fiber to be widely applied to the composite material taking materials such as ceramics, resin, metal, carbon and the like as a matrix. However, carbon fibers are oxidized in the air at a temperature of more than 400 ℃, so that the oxidation resistance is poor, the performance of the material is reduced, the surface activity of the carbon fibers which are not subjected to surface treatment is low, the wettability of the carbon fibers with certain matrixes is poor, the binding capacity is poor, and the performance of the carbon fiber reinforced silicon carbide ceramic matrix composite material is also reduced. Moreover, at the temperature of preparing the composite material, the carbon fibers are easy to react with the matrix, so that the fibers are damaged, and the performance of the carbon fiber reinforced silicon carbide ceramic matrix composite material is seriously reduced. In the prior art, an oxidation-resistant coating is coated on the surface of a base material to enhance the oxidation resistance of the base material, but a single coating is coated on the surface of a Cf/SiC composite material to hardly play a role of effective high-temperature oxidation-resistant protection, and generally, the Cf/SiC oxidation-resistant coating system consists of an adhesive layer, an active functional layer and an anti-erosion layer, wherein the thermal expansion coefficient of the adhesive layer is close to that of the base material, the adhesive layer has a good adhesive effect, the active functional layer can self-heal cracks of the coating, and the anti-erosion layer can resist air flow erosion.
The above problems can be effectively solved by surface coating the carbon fiber. The coating can not only improve the oxidation resistance of the carbon fiber, but also improve the oxidation resistance of the carbon fiberAnd the carbon fiber and the matrix are used as a barrier layer between the carbon fibers and the matrix, so that the interface reaction between the carbon fibers and the matrix can be prevented, and the problem of interface compatibility between the fibers and the matrix in the composite material can be solved. In addition, a small amount of high-temperature oxidation resistant ceramic particles are added into the matrix, so that the toughening effect of the particles can be achieved, and the high-temperature oxidation resistance of the composite material can be improved. Hafnium boride (HfB)2) The crystal structure of the crystal belongs to a hexagonal system, the melting point is as high as 3380 ℃, the crystal has good high-temperature stability and oxidation resistance, has good chemical compatibility with carbon fibers, and can better meet the use requirements in an ultrahigh-temperature environment, and the advantages make the crystal become a high-temperature-resistant oxidation-resistant coating material with great development potential. The SiBNC has good high-temperature stability and oxidation resistance and good chemical compatibility with carbon fiber, no thermal weight loss and phase splitting are generated when the temperature is lower than 1700 ℃ under the protection of inert gas, and the crystal is converted into SiC and Si at 2000 DEG C3N4And a small amount of amorphous BN, and the oxidation resistance in the air at 1700 ℃ is far better than that of SiC and Si3N4The advantages also make the composite material become a high-temperature-resistant anti-oxidation material with great development potential, and the addition of a proper amount of SiBNC particles in the matrix can play a toughening role and improve the mechanical property of the carbon fiber reinforced silicon carbide ceramic matrix composite material.
HfB2The main preparation methods of the method include a melting synthesis method of metal and boron in inert gas or vacuum, a carbon reduction method, a self-propagating high-temperature synthesis method and a chemical vapor infiltration method. The former route for synthesizing hafnium boride is mainly as follows: will synthesize HfB2Mixing the required powder raw materials in a certain proportion, and reacting at high temperature to generate HfB2The method is not suitable for preparing the coating on the surface of the carbon fiber, and has high synthesis reaction temperature and high impurity content; CVD process for preparing HfB2Finding a suitable HfB2The precursor has high toxicity, high synthesis reaction temperature, complex process, special equipment and unsuitability for uniform coating on the surface of the multi-dimensional fiber; by adopting an organic polymer cracking method, a precursor polymer is required to be prepared firstly, and then HfB is cracked at high temperature2The method is complicated to operateAnd are not suitable for producing dense interphase coatings on the fiber surface. The Chinese invention patent CN 107523778A discloses a preparation method of a hafnium boride composite coating, which takes hafnium oxide/boron carbide/aluminum composite powder as a raw material according to a certain proportion, adopts thermal spraying in-situ reaction to synthesize the hafnium boride composite coating, mainly relates to the coating of boride on substrate materials such as metal, ceramics and the like, is not suitable for preparing a compact interface phase coating on the surface of fiber, and is also not suitable for filling high-temperature oxidation-resistant substrate materials in a fiber preform. The invention uses polyvinyl alcohol, boric acid and inorganic hafnium salt as raw materials, adopts a low-temperature precursor solution impregnation pyrolysis method suitable for carbon fiber surface coatings with various forms, and the preparation method not only prepares uniform, continuous and compact HfB on the carbon fiber surface2The coating and the whole preparation process of the coating liquid have the advantages of simple process, no need of special equipment, energy conservation, low price of raw materials, easy acquisition and easy realization, and the coating formed by lower heat treatment temperature not only improves the oxidation resistance of the fiber and the interface problem of the fiber and the matrix, but also overcomes the defects. Meanwhile, the invention adopts high-concentration HfB2Impregnating the fiber preform with SiBNC precursor solution, and pyrolyzing at high temperature to obtain HfB2The matrix particles of SiBNC can be uniformly distributed inside the preform, forming HfB2The SiBNC-based porous fiber preform prevents a series of problems that powder is easy to agglomerate, uneven in distribution, more impurities and damage to carbon fibers due to overhigh sintering temperature in the fiber preform by adopting direct powder synthesis reaction sintering, and creates conditions for subsequent in-situ filling of a silicon carbide substrate and obtaining of a compact high-temperature oxidation-resistant carbon fiber reinforced silicon carbide ceramic matrix composite material.
The invention provides a catalyst with HfB2A preparation method of an interfacial Cf/SiC composite material aims to solve the technical problem that a reinforcing phase carbon fiber in the Cf/SiC composite material and the composite material thereof are easy to generate oxidation reaction in a high-temperature oxidizing use environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and providesTo supply a compound having HfB2A preparation method of an interface Cf/SiC composite material aims to solve the technical problem that a reinforcing phase carbon fiber in the Cf/SiC composite material and the composite material thereof are easy to generate oxidation reaction in a high-temperature oxidizing use environment, so that the use performance of the Cf/SiC composite material in the high-temperature environment is improved.
The invention is realized by the following technical scheme: high-temperature oxidation-resistant HfB2The technological route of the preparation method of the interface Cf/SiC composite material is that a silicon carbide matrix is filled in a fiber preform to form the carbon fiber reinforced silicon carbide ceramic matrix composite material, and the high-temperature oxidation resistance HfB2The interfacial layer wraps up the surface of carbon fiber in the carbon fiber reinforced silicon carbide ceramic matrix composite, specifically mainly includes: surface activation treatment of carbon fiber, high-temperature oxidation resistance HfB on surface of carbon fiber2Preparation of the interphase, HfB2Preparation of-SiBNC-based porous fiber preform, preparation of dense silicon carbide matrix, and finally obtaining dense HfB with high-temperature oxidation resistance2The Cf/SiC ceramic matrix composite material of the interface.
The invention comprises the following steps:
(1) and (2) placing the carbon fiber in a tubular furnace, keeping the temperature at 450 ℃ for 30-40 minutes, carrying out degumming treatment, placing the carbon fiber after degumming in concentrated nitric acid, soaking and etching for 60-100 minutes, then washing residual liquid on the surface of the carbon fiber by deionized water, and drying to obtain the carbon fiber after surface activation treatment.
(2) Ultrasonically dipping the dried carbon fiber in the step (1) in HfB by adopting a precursor dipping pyrolysis method2Preparing HfB on the surface of carbon fiber in low-concentration precursor solution2Interface phase coating obtained by precursor pyrolysis process and having HfB2An interphase coated carbon fiber preform.
(3) Uniformly dispersing SiBNC nano ceramic powder in high-concentration HfB2Preparing HfB in precursor solution2-SiBNC matrix precursor solution, ultrasonic dipping the carbon fiber preform obtained in the step (2) in HfB2In-situ filling once HfB in a precursor solution of an SiBNC substrate2-SiBNC matrix, precursorBulk pyrolysis process to obtain HfB2-a SiBNC-based porous fiber preform.
(4) HfB obtained in the above (3)2-SiBNC-based porous fiber preform is immersed in divinylbenzene precursor solution of polycarbosilane in the preparation of HfB2Filling a silicon carbide substrate in situ in a SiBNC-based porous fiber preform, and performing multiple precursor impregnation-cracking processes to obtain a dense HfB2An interfacial Cf/SiC composite.
In the present invention, the carbon fiber surface HfB described in the above step (2)2The preparation method of the interface phase low-concentration precursor solution comprises the following steps:
a) respectively preparing a boric acid solution and a polyvinyl alcohol solution by using polyvinyl alcohol and boric acid as solutes and deionized water as a solvent.
b) Dissolving inorganic hafnium salt in deionized water, stirring and mixing uniformly at room temperature, adding ammonia water to adjust the pH value to 9.5, generating white precipitate, dissolving the white precipitate centrifugally cleaned by the deionized water in nitric acid, and controlling the pH value of the solution to be less than 2 to obtain the hafnium oxide sol.
c) Adding ethanol into the boric acid solution, and stirring at room temperature until the ethanol and the boric acid solution are uniformly mixed to obtain the boric acid alcohol aqueous solution.
d) The polyvinyl alcohol solution was poured quickly into c) above and stirred at room temperature until it was well mixed.
e) Adding the b) into the solution d), and stirring at room temperature for 2-3 hours to obtain the HfB2Interface phase low concentration precursor solution.
Due to HfB2The preparation system of the interface phase precursor solution contains a plurality of components, the hydrolysis conditions of each component are different, so that the stability of the solution is difficult to control, for example, when a boric acid solution and a polyvinyl alcohol solution are mixed under the conditions of normal temperature, low temperature and high temperature, sticky flocculent precipitation is immediately generated and a large amount of bubbles escape (boric acid in the solution and generated boric anhydride have larger volatility), how to enable sol added into a coating solution to stably exist, and how to prepare the HfB with clarification, uniformity and stability at room temperature2The precursor solution of (a) is free of flocculates and is a trapped massIt is difficult. In the method of the invention, the conventional preparation of HfB is changed2The main method comprises the following steps: will synthesize HfB2Mixing the required powder raw materials in a certain proportion, and reacting at high temperature to generate HfB2The method is not suitable for preparing the coating on the surface of the carbon fiber, and has high synthesis reaction temperature and high impurity content; CVD process for preparing HfB2Finding a suitable HfB2The precursor has high toxicity, high synthesis reaction temperature, complex process, special equipment and unsuitability for uniform coating on the surface of the multi-dimensional fiber; by adopting an organic polymer cracking method, a precursor polymer is required to be prepared firstly, and then HfB is cracked at high temperature2This method is complicated to operate and is not suitable for producing dense interphase coatings on the fiber surface. Whole HfB of the present invention2In the preparation process of the interface phase precursor solution, a proper amount of modifier ethanol is added into the boric acid water-based solution at room temperature, and the addition sequence and content control of various reagents are matched, so that the problem that the boric acid solution and the polyvinyl alcohol solution are mixed to precipitate is solved, and the clear, uniform and stable HfB can be prepared at room temperature2The method has the advantages that the time is saved, the operation is simple, special equipment is not needed, the whole preparation process is simple, the energy is saved, the pollution is avoided, the raw materials are cheap and easy to obtain and realize, and the uniform, continuous and compact coating can be prepared on the surface of the fiber.
As a preferable mode, HfB described in the above step (2)2The interface phase low-concentration precursor solution is an ethanol water-based solution taking polyvinyl alcohol, boric acid and inorganic hafnium salt as raw materials.
As a preferable mode, HfB described in the above step (2)2The concentration of the boric acid solution in the interface phase low-concentration precursor solution is 0.4-0.8 mol/L.
As a preferable mode, HfB described in the above step (2)2Polyvinyl alcohol in interfacial phase low-concentration precursor solutionThe concentration of the solution is 0.8-1.2 mol/L.
As a preferable mode, HfB described in the above step (2)2The inorganic hafnium salt in the interface phase low-concentration precursor solution is HfOCl2·8H2O、Hf(NO3)4·xH2O、HfO(NO3)2·xH2O、HfCl4、Hf(SO4)2One of the aqueous inorganic salts, the concentration of hafnium ions in the hafnium oxide sol can be adjusted between 0.3 mol/L and 0.6mol/L by adding deionized water.
As a preferable mode, HfB described in the above step (2)2The volume ratio of ethanol to boric acid solution in the interface phase low-concentration precursor solution is (1.2-2.8): 1.
as a preferable mode, HfB described in the above step (2)2The molar ratio of polyvinyl alcohol, boric acid and hafnium ions in the interface phase low-concentration precursor solution is (3.5-3.7): (0.9-1.1): (0.20-0.43).
Preferably, the carbon fiber surface HfB described in the step (2) above2The thickness of the interface phase coating is 150-1200 nm.
Preferably, the interphase coating described in the above step (2) is HfB2And (4) coating.
Preferably, the carbon fiber in the step (1) is one or more of a carbon fiber bundle, a carbon fiber cloth and a three-dimensional carbon fiber preform.
Preferably, the particle size of the SiBNC nano ceramic powder in the step (3) is 40-80 nm, and the HfB2The volume content of the SiBNC ceramic powder in the SiBNC matrix precursor solution is 25-35%, and the high concentration refers to the preparation of HfB2The concentration of the boric acid solution in the precursor solution is 0.8-1.2 mol/L, the concentration of the polyvinyl alcohol solution is 1.5-2.2 mol/L, and the concentration of the hafnium ions is 0.6-1.2 mol/L.
Preferably, the carbon fiber surface HfB described in the above steps (2) and (3)2Interphase coating and HfB2The precursor pyrolysis process of the-SiBNC-based porous fiber preform refers to the protection of nitrogen in a tube furnaceThen heating to 300 ℃ at the heating rate of 2-3 ℃/min, preserving heat for 10-15 minutes, heating to 550 ℃ at the heating rate of 5 ℃/min, preserving heat for 30-60 minutes, heating to 800 ℃ at the heating rate of 8-10 ℃/min, preserving heat for 30-60 minutes, heating to the pyrolysis temperature of 1450 ℃ at the heating rate of 6-8 ℃/min, and preserving heat for 2-3 hours.
Preferably, the mass ratio of polycarbosilane to divinylbenzene in the precursor solution in the step (4) is (0.6-0.65): 1.
preferably, the silicon carbide precursor impregnation in the step (4) is one of ultrasonic impregnation and vacuum impregnation, and the impregnation time is 2 to 3 hours, and then the silicon carbide precursor is allowed to stand in the air for 18 to 24 hours.
Preferably, the silicon carbide substrate precursor cracking process in the step (4) is to heat the silicon carbide substrate precursor to 400 ℃ at a heating rate of 9-11 ℃/min under the protection of nitrogen in a tube furnace, heat the silicon carbide substrate precursor to 800 ℃ at a heating rate of 4-5 ℃/min, heat the silicon carbide substrate precursor to 1200-1480 ℃ at a heating rate of 9-10 ℃/min, and keep the temperature for 30-40 minutes.
Preferably, the densifying in the step (4) is performed by repeating the step (4) and performing the precursor impregnation-cracking process for a plurality of times until the weight gain of the Cf/SiC composite material is less than 1% and the density of the Cf/SiC composite material is 1.95-2.25 g/cm3The open porosity is 6-12%.
The invention uses polyvinyl alcohol, boric acid and inorganic hafnium salt as raw materials, adopts a low-temperature precursor solution impregnation pyrolysis method suitable for carbon fiber surface coatings with various forms, and the preparation method not only prepares uniform, continuous and compact HfB on the carbon fiber surface2The coating and the whole preparation process of the coating liquid have the advantages of simple process, no need of special equipment, energy conservation, low price of raw materials, easy acquisition and easy realization, and the coating formed by lower heat treatment temperature improves the oxidation resistance of the fiber and the interface compatibility of the fiber and a matrix. Meanwhile, the invention adopts high-concentration HfB2Impregnating the fiber preform with SiBNC precursor solution, and pyrolyzing at high temperature to obtain HfB2Matrix of SiBNCThe particles can be uniformly distributed in the preform to form HfB2The preparation method has the advantages that the SiBNC-based porous fiber preform prevents a series of problems that powder is easy to agglomerate, uneven in distribution, more in impurities and damages to carbon fibers caused by overhigh sintering temperature due to the fact that the powder is sintered in the fiber preform by adopting direct powder synthesis reaction, the preparation period of the ceramic porous preform is effectively shortened, the silicon carbide substrate is filled in situ subsequently, and compact HfB with high-temperature oxidation resistance is obtained2The carbon fiber reinforced silicon carbide ceramic matrix composite material of the interface phase creates conditions.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention takes polyvinyl alcohol, boric acid and inorganic hafnium salt as raw materials to prepare HfB2The interface phase low-concentration precursor solution has the advantages of low price of raw materials, easy acquisition, easy realization, simple preparation process, energy saving, no pollution, no special equipment requirement, strong operability and suitability for industrial production.
(2) In the present invention, the carbon fiber surface HfB2The interface phase coating is uniform, complete and compact, has no microcrack, can improve the interface compatibility between the fiber and the Cf/SiC composite material matrix, and the carbon fiber can toughen and reinforce the silicon carbide ceramic, thereby effectively improving the strength and the structural stability of the Cf/SiC composite material.
(3) In the present invention, the carbon fiber surface HfB2The interface phase coating is uniform and compact, the high-temperature oxidation resistance is excellent, the damage to the carbon fiber is small, and the interface phase HfB2The reinforcing phase carbon fiber is tightly wrapped, so that the carbon fiber is effectively prevented from undergoing an oxidation reaction in a high-temperature environment, and the high-temperature oxidation resistance of the Cf/SiC composite material is improved.
(4) In the present invention, HfB2The SiBNC-based uniform porous fiber preform has uniform internal particle distribution and less impurities, not only effectively shortens the preparation period of the ceramic porous preform and plays a role in toughening particles, but also creates conditions for subsequent in-situ filling of a silicon carbide substrate and obtaining of a compact carbon fiber reinforced silicon carbide ceramic matrix composite material.
(5) In the present invention, prepared with HfB2The Cf/SiC composite material of the interface has the tensile modulus of 79-90 GPa, the tensile strength of 166-183 MPa, the bending modulus of 84-93 GPa and the bending strength of 295-305 MPa; compared with the tensile modulus 63GPa, the tensile strength 136MPa, the bending modulus 57GPa and the bending strength 205MPa of the Cf/SiC composite material without the interface in the comparative example, the technical effect of obviously improving the mechanical property of the Cf/SiC composite material is achieved.
Drawings
FIG. 1 is a scanning electron micrograph of uncoated carbon fibers.
FIG. 2 shows high-temperature oxidation-resistant HfB on the surface of carbon fiber2Scanning electron micrographs of the interphase coating.
FIG. 3 is a graph of flexural strength versus displacement for the Cf/SiC composite material prepared in example 1.
FIG. 4 scanning electron micrograph of fractures of the Cf/SiC composite prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described below by specific embodiments.
Example 1
Has HfB2The preparation method of the interface Cf/SiC composite material comprises the following steps:
placing the carbon fiber in a tubular furnace, keeping the temperature at 450 ℃ for 30 minutes, carrying out degumming treatment, placing the carbon fiber after degumming in concentrated nitric acid, soaking and etching for 60 minutes, then washing residual liquid on the surface of the carbon fiber by deionized water, and drying to obtain the carbon fiber after surface activation treatment; ultrasonically dipping the dried carbon fiber preform in HfB2Standing the coated carbon fiber in a precursor solution with low concentration of an interface phase for 30 minutes at room temperature for 12 hours, putting the carbon fiber into an oven, preserving heat at 60 ℃ for 60 minutes, then putting the carbon fiber into a tube furnace, heating the carbon fiber to 300 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 10 minutes, heating the carbon fiber to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for 40 minutes, heating the carbon fiber to 800 ℃ at a heating rate of 8 ℃/min, preserving heat for 30 minutes, and heating the carbon fiber to high temperature at a heating rate of 6 ℃/minCracking at 1300 deg.C for 3 hr to obtain coated HfB2The thickness of the interface phase coating of the carbon fiber preform is about 300 nm; uniformly dispersing SiBNC nano ceramic powder with the volume content of 30 percent in high-concentration HfB by magnetic stirring2Soaking the prefabricated body in precursor solution for 2 hr, taking out, standing for 20 hr, placing in a tubular furnace, heating to 300 deg.C at a heating rate of 3 deg.C/min under nitrogen protection, maintaining for 12 min, heating to 550 deg.C at a heating rate of 5 deg.C/min, maintaining for 40 min, heating to 800 deg.C at a heating rate of 10 deg.C/min, maintaining for 60 min, heating to 1400 deg.C at a heating rate of 8 deg.C/min, and maintaining for 3 hr to obtain HfB2-a SiBNC-based porous fiber preform; dissolving polycarbosilane in a divinylbenzene solution, wherein the mass ratio of the polycarbosilane to the divinylbenzene is 0.65: 1, mixing HfB2Ultrasonic dipping of the SiBNC-based porous preform in a precursor solution for 3 hours, taking out and standing for 20 hours, placing in a tube furnace, heating to 400 ℃ at a heating rate of 11 ℃/min under the protection of nitrogen, heating to 800 ℃ at a heating rate of 5 ℃/min, heating to 1250 ℃ at a heating rate of 9 ℃/min, keeping the temperature for 40 minutes, repeating dipping-cracking of the polycarbosilane precursor solution for 8 times, wherein the weight gain of the composite material is less than 1%, and obtaining the HfB with high-temperature oxidation resistance2An interfacial Cf/SiC composite having a density of 2.14g/cm3The open porosity was 9%, the tensile modulus was 86GPa, the tensile strength was 179MPa, the flexural modulus was 90GPa, and the flexural strength was 303 MPa. FIG. 3 is a graph of bending strength versus displacement for a Cf/SiC composite. FIG. 4 is a scanning electron microscope image of a fracture of the Cf/SiC composite material.
Comparative example 1
A preparation method of Cf/SiC composite material comprises the following steps:
placing the carbon fiber in a tubular furnace, keeping the temperature at 450 ℃ for 30 minutes, carrying out degumming treatment, placing the carbon fiber after degumming in concentrated nitric acid, soaking and etching for 60 minutes, then washing residual liquid on the surface of the carbon fiber by deionized water, and drying to obtain the carbon fiber after surface activation treatment; dissolving polycarbosilane in diethylIn the alkenyl benzene solution, the mass ratio of polycarbosilane to divinylbenzene is 0.65: 1; ultrasonically dipping the carbon fiber preform into a precursor solution for 3 hours, taking out and standing for 20 hours, then placing the carbon fiber preform into a tubular furnace, heating the carbon fiber preform to 400 ℃ at a heating rate of 11 ℃/min under the protection of nitrogen, heating the carbon fiber preform to 800 ℃ at a heating rate of 5 ℃/min, heating the carbon fiber preform to 1250 ℃ at a heating rate of 9 ℃/min, and preserving the heat for 40 minutes; after the impregnation and cracking are repeated for 11 times, the weight gain of the composite material is less than 1 percent, and the Cf/SiC composite material is obtained, and the density of the composite material is 1.75g/cm3The open porosity was 17%. The tensile modulus was 63GPa, the tensile strength was 136MPa, the flexural modulus was 57GPa, and the flexural strength was 205 MPa.
Example 2
Has HfB2The preparation method of the interface Cf/SiC composite material comprises the following steps:
placing the carbon fiber in a tubular furnace, keeping the temperature at 450 ℃ for 40 minutes, carrying out degumming treatment, placing the carbon fiber after degumming in concentrated nitric acid, soaking and etching for 60 minutes, then washing residual liquid on the surface of the carbon fiber by deionized water, and drying to obtain the carbon fiber after surface activation treatment; ultrasonically dipping the dried carbon fiber preform in HfB2Standing the coated carbon fiber for 15 hours at room temperature, putting the carbon fiber into an oven, keeping the temperature at 60 ℃ for 60 minutes, then putting the carbon fiber into a tube furnace, heating the carbon fiber to 300 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, keeping the temperature for 10 minutes, heating the carbon fiber to 550 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 40 minutes, heating the carbon fiber to 800 ℃ at a heating rate of 9 ℃/min, keeping the temperature for 30 minutes, heating the carbon fiber to 1350 ℃ at a heating rate of 7 ℃/min, keeping the temperature for 2 hours, and obtaining the coated HfB2The thickness of the interface phase coating is about 420 nm; uniformly dispersing SiBNC nano ceramic powder with the volume content of 35 percent in high-concentration HfB by magnetic stirring2Soaking the preform in the precursor solution for 2 hr, taking out, standing for 20 hr, heating to 300 deg.C under nitrogen protection at a temperature rise rate of 3 deg.C/min for 12 min, and maintaining at 5 deg.C/mHeating to 550 deg.C at in heating rate, maintaining for 40 min, heating to 800 deg.C at 10 deg.C/min, maintaining for 60 min, heating to 1400 deg.C at 8 deg.C/min, and maintaining for 3 hr to obtain HfB2-a SiBNC-based porous fiber preform; dissolving polycarbosilane in a divinylbenzene solution, wherein the mass ratio of the polycarbosilane to the divinylbenzene is 0.63: 1, mixing HfB2Ultrasonic dipping of the SiBNC-based porous preform in a precursor solution for 3 hours, taking out and standing for 20 hours, placing in a tube furnace, heating to 400 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, heating to 800 ℃ at a heating rate of 4 ℃/min, heating to 1200 ℃ at a heating rate of 9 ℃/min, keeping the temperature for 40 minutes, repeating dipping-cracking of the polycarbosilane precursor solution for 7 times, wherein the weight gain of the composite material is less than 1%, and obtaining the HfB with high-temperature oxidation resistance2An interfacial Cf/SiC composite having a density of 2.25g/cm3The open porosity was 6%, the tensile modulus was 90GPa, the tensile strength was 183MPa, the flexural modulus was 93GPa, and the flexural strength was 305 MPa.
Example 3
Has HfB2The preparation method of the interface Cf/SiC composite material comprises the following steps:
placing the carbon fiber in a tubular furnace, keeping the temperature at 450 ℃ for 30 minutes, carrying out degumming treatment, placing the carbon fiber after degumming in concentrated nitric acid, soaking and etching for 100 minutes, then washing residual liquid on the surface of the carbon fiber by deionized water, and drying to obtain the carbon fiber after surface activation treatment; ultrasonically dipping the dried carbon fiber preform in HfB2Standing the coated carbon fiber in a precursor solution with low concentration of an interface phase for 10 minutes at room temperature for 12 hours, putting the carbon fiber into an oven, preserving heat for 60 minutes at 60 ℃, then putting the carbon fiber into a tube furnace, heating the carbon fiber to 300 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 15 minutes, heating the carbon fiber to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for 40 minutes, heating the carbon fiber to 800 ℃ at a heating rate of 10 ℃/min, preserving heat for 30 minutes, heating the carbon fiber to a pyrolysis temperature of 1400 ℃ at a heating rate of 8 ℃/min, preserving heat for 2 hours, and obtaining the coated HfB2Interfacial carbon fiber preformsPreparing a body, wherein the thickness of the interface phase coating is about 155 nm; uniformly dispersing SiBNC nano ceramic powder with the volume content of 25 percent in high-concentration HfB by magnetic stirring2Soaking the prefabricated body in precursor solution for 2 hr, taking out, standing for 20 hr, placing in a tubular furnace, heating to 300 deg.C at a heating rate of 3 deg.C/min under nitrogen protection, maintaining for 12 min, heating to 550 deg.C at a heating rate of 5 deg.C/min, maintaining for 40 min, heating to 800 deg.C at a heating rate of 10 deg.C/min, maintaining for 60 min, heating to 1400 deg.C at a heating rate of 8 deg.C/min, and maintaining for 3 hr to obtain HfB2-a SiBNC-based porous fiber preform; dissolving polycarbosilane in a divinylbenzene solution, wherein the mass ratio of the polycarbosilane to the divinylbenzene is 0.60: 1, mixing HfB2Ultrasonic dipping of the SiBNC-based porous preform in a precursor solution for 3 hours, taking out and standing for 20 hours, placing in a tube furnace, heating to 400 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, heating to 800 ℃ at a heating rate of 5 ℃/min, heating to 1250 ℃ at a heating rate of 9 ℃/min, keeping the temperature for 35 minutes, repeating dipping-cracking of the polycarbosilane precursor solution for 9 times, wherein the weight gain of the composite material is less than 1%, and obtaining the HfB with high-temperature oxidation resistance2The Cf/SiC composite material of the interface has the density of 2.06g/cm3The open porosity was 11%, the tensile modulus was 81GPa, the tensile strength was 172MPa, the flexural modulus was 87GPa, and the flexural strength was 298 MPa.
Example 4
Has HfB2The preparation method of the interface Cf/SiC composite material comprises the following steps:
placing the carbon fiber in a tubular furnace, keeping the temperature at 450 ℃ for 40 minutes, carrying out degumming treatment, placing the carbon fiber after degumming in concentrated nitric acid, soaking and etching for 80 minutes, then washing residual liquid on the surface of the carbon fiber by deionized water, and drying to obtain the carbon fiber after surface activation treatment; ultrasonically dipping the dried carbon fiber preform in HfB2The interface phase low-concentration precursor solution is added into the precursor solution for 100 minutes, the coated carbon fiber is placed in an oven for heat preservation for 60 minutes at 60 ℃ after being kept stand for 12 hours at room temperatureThen placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, preserving heat for 10 minutes, heating to 550 ℃ at a heating rate of 5 ℃/min, preserving heat for 40 minutes, heating to 800 ℃ at a heating rate of 8 ℃/min, preserving heat for 30 minutes, heating to 1350 ℃ at a high-temperature cracking temperature at a heating rate of 6 ℃/min, preserving heat for 3 hours, and obtaining the HfB-coated film2The thickness of the interface phase coating of the carbon fiber preform is 1180 nm; the SiBNC nano ceramic powder with the volume content of 28 percent is evenly dispersed in the high-concentration HfB by magnetic stirring2Soaking the prefabricated body in precursor solution for 2 hr, taking out, standing for 20 hr, placing in a tubular furnace, heating to 300 deg.C at a heating rate of 3 deg.C/min under nitrogen protection, maintaining for 12 min, heating to 550 deg.C at a heating rate of 5 deg.C/min, maintaining for 40 min, heating to 800 deg.C at a heating rate of 10 deg.C/min, maintaining for 60 min, heating to 1400 deg.C at a heating rate of 8 deg.C/min, and maintaining for 3 hr to obtain HfB2-a SiBNC-based porous fiber preform; dissolving polycarbosilane in a divinylbenzene solution, wherein the mass ratio of the polycarbosilane to the divinylbenzene is 0.62: 1, mixing HfB2Ultrasonic dipping of the SiBNC-based porous preform in a precursor solution for 3 hours, taking out and standing for 20 hours, placing in a tube furnace, heating to 400 ℃ at a heating rate of 11 ℃/min under the protection of nitrogen, heating to 800 ℃ at a heating rate of 5 ℃/min, heating to 1250 ℃ at a heating rate of 9 ℃/min, keeping the temperature for 40 minutes, repeating dipping-cracking of the polycarbosilane precursor solution for 8 times, wherein the weight gain of the composite material is less than 1%, and obtaining the HfB with high-temperature oxidation resistance2An interfacial Cf/SiC composite having a density of 2.11g/cm3The open porosity was 8%, the tensile modulus was 83GPa, the tensile strength was 173MPa, the flexural modulus was 88GPa, and the flexural strength was 299 MPa.
Claims (4)
1. Has HfB2C of the interfacefThe preparation method of the/SiC composite material is a precursor solution impregnation cracking method, and comprises the following steps: surface activation treatment of carbon fibers, preparation of interface phase, manyPreparing a porous fiber preform and preparing a silicon carbide matrix; characterized in that a silicon carbide matrix is filled in HfB2-forming a carbon fiber reinforced silicon carbide ceramic matrix composite in the SiBNC-based porous fiber preform, and wrapping the interface layer on the surface of the carbon fiber in the carbon fiber reinforced silicon carbide ceramic matrix composite, comprising the steps of:
(1) placing the carbon fiber in a tubular furnace, keeping the temperature at 450 ℃ for 30-40 minutes, carrying out degumming treatment, placing the carbon fiber subjected to degumming in concentrated nitric acid, soaking and etching for 60-100 minutes, then washing residual liquid on the surface of the carbon fiber with deionized water, and drying to obtain the carbon fiber subjected to surface activation treatment;
(2) ultrasonically dipping the dried carbon fiber in the step (1) in HfB by adopting a precursor dipping pyrolysis method2Preparing HfB on the surface of carbon fiber in interface phase low-concentration precursor solution2Interface phase coating obtained by precursor pyrolysis process and having HfB2A carbon fiber preform of the interphase coating; said HfB2The interface phase low-concentration precursor solution is an ethanol water-based solution taking polyvinyl alcohol, boric acid and inorganic hafnium salt as raw materials, and the specific preparation process comprises the following steps: a) respectively preparing a boric acid solution and a polyvinyl alcohol solution by using polyvinyl alcohol and boric acid as solutes and deionized water as a solvent, b) dissolving inorganic hafnium salt in the deionized water, stirring and mixing the materials at room temperature, adding ammonia water to adjust the pH value to 9.5 to generate a white precipitate, dissolving the white precipitate after centrifugal cleaning by using the deionized water in nitric acid, controlling the pH value of the solution to be less than 2 to obtain hafnium oxide sol, c) adding ethanol into the boric acid solution and stirring at room temperature until the ethanol and the boric acid solution are uniformly mixed to obtain a boric acid alcohol aqueous solution, d) quickly pouring the polyvinyl alcohol solution into the boric acid alcohol aqueous solution obtained in the step c), stirring at room temperature until the hafnium oxide sol is uniformly mixed, and e) adding the hafnium oxide sol obtained in the step b) into the solution obtained in the step d), and stirring at room temperature for 2-3 hours to obtain the precursor solution; the low concentration refers to HfB2The concentration of a boric acid solution in the interface phase precursor solution is 0.4-0.8 mol/L, the concentration of a polyvinyl alcohol solution is 0.8-1.2 mol/L, and the concentration of hafnium ions is 0.3-0.6 mol/L; the boric acid alcoholThe volume ratio of the ethanol to the boric acid solution in the water solution is (1.2-2.8): 1; said HfB2The molar ratio of polyvinyl alcohol, boric acid and hafnium ions in the interface phase low-concentration precursor solution is (3.5-3.7): (0.9-1.1): (0.20 to 0.43); the surface HfB of the carbon fiber2The thickness of the interface phase coating is 150-1200 nm;
(3) uniformly dispersing SiBNC nano ceramic powder in high-concentration HfB2Preparing HfB in precursor solution2-SiBNC matrix precursor solution, ultrasonic dipping the carbon fiber preform obtained in the step (2) in HfB2In-situ filling once HfB in a precursor solution of an SiBNC substrate2-SiBNC matrix, obtaining HfB by precursor pyrolysis process2-a SiBNC-based porous fiber preform;
(4) HfB obtained in the above (3)2-SiBNC-based porous fiber preform is immersed in divinylbenzene precursor solution of polycarbosilane in the preparation of HfB2Filling a silicon carbide substrate in situ in a SiBNC-based porous fiber preform, and performing multiple precursor impregnation-cracking processes to obtain a dense HfB2C of the interfacefa/SiC composite material.
2. The method of claim 1, having HfB2C of the interfacefThe preparation method of the/SiC composite material is characterized in that the particle size of the SiBNC nano ceramic powder in the step (3) is 40-80 nm; said HfB2The volume content of the SiBNC nano ceramic powder in the SiBNC matrix precursor solution is 25-35%; the high concentration refers to HfB2The concentration of the boric acid solution in the precursor solution is 0.8-1.2 mol/L, the concentration of the polyvinyl alcohol solution is 1.5-2.2 mol/L, and the concentration of the hafnium ions is 0.6-1.2 mol/L.
3. The method of claim 1, having HfB2C of the interfacefThe preparation method of the/SiC composite material is characterized in that the precursor pyrolysis process in the steps (2) and (3) is to heat the mixture to 300 ℃ at a heating rate of 2-3 ℃/min for 10-15 minutes in a tubular furnace under the protection of nitrogen, and then to preserve the heat at the temperature of 5 ℃/minHeating to 550 ℃ at a heating rate, preserving heat for 30-60 minutes, heating to 800 ℃ at a heating rate of 8-10 ℃/min, preserving heat for 30-60 minutes, heating to 1350-1450 ℃ at a heating rate of 6-8 ℃/min, and preserving heat for 2-3 hours.
4. The method of claim 1, having HfB2C of the interfacefThe preparation method of the/SiC composite material is characterized in that the mass ratio of polycarbosilane to divinylbenzene in the precursor solution in the step (4) is (0.6-0.65): 1; the dipping is one of ultrasonic dipping or vacuum dipping, the dipping time is 2-3 hours, and then the dipping is kept stand in the air for 18-24 hours; the precursor cracking process is that the precursor is heated to 400 ℃ at a heating rate of 9-11 ℃/min under the protection of nitrogen in a tubular furnace, then heated to 800 ℃ at a heating rate of 4-5 ℃/min, then heated to 1200-1480 ℃ at a heating rate of 9-10 ℃/min, and then kept for 30-40 minutes; the densification refers to repeating the step (4) and carrying out a plurality of precursor impregnation-cracking processes until CfThe weight gain of the/SiC composite material is less than 1 percent, CfThe density of the/SiC composite material is 1.95-2.25 g/cm3The open porosity is 6-12%.
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