CN117682861A - Graphene-toughened ceramic-based composite material and preparation method thereof - Google Patents
Graphene-toughened ceramic-based composite material and preparation method thereof Download PDFInfo
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a graphene-toughened ceramic matrix composite material and a preparation method thereof. The method comprises the following steps: alternately laminating carbon cloth and foam nickel sheets, and manufacturing a preform by adopting a puncture process after alternately laminating; depositing pyrolytic carbon and graphene in the preform by a chemical vapor deposition method, and then soaking in an acid solution to obtain a porous carbon/carbon composite material from which foam nickel is removed; depositing a hafnium carbide interface layer in the porous carbon/carbon composite material from which the foam nickel is removed by using an oxygen-free hafnium carbide ceramic precursor as a reactant through a chemical vapor deposition method to obtain a carbon/carbon composite material with the hafnium carbide interface layer; and reacting the oxygen-free hafnium carbide ceramic precursor with the carbon/carbon composite material with the hafnium carbide interface layer by an immersion cracking method to prepare the graphene-toughened ceramic-based composite material. The ceramic matrix composite material prepared by the invention has the advantages of high toughness and strong oxidation resistance, and the mechanical property of the ceramic matrix composite material is obviously improved in a high-temperature aerobic environment.
Description
Technical Field
The invention belongs to the technical field of preparation of ceramic matrix composite materials, and particularly relates to a graphene-toughened ceramic matrix composite material and a preparation method thereof.
Background
Compared with the traditional metal and carbon/carbon composite materials, the carbon fiber toughened ceramic-based composite material has the excellent characteristics of light weight, high strength, high temperature resistance and the like, and is a main candidate material for various thermal structural component materials. The composite material mainly comprises four parts of carbon fiber, an interface layer, a ceramic matrix and a coating. The carbon fiber mainly plays a role in improving toughness of the composite material, the interface layer is a connecting tie of the carbon fiber and the ceramic matrix, moderate acting force is formed between the carbon fiber and the interface layer, toughness of the composite material is facilitated, and brittle fracture is avoided. Due to the characteristics of carbon fiber tows and easiness in braiding, carbon fibers in the composite material are unevenly distributed, and the ceramic matrix in the area is brittle and is easy to form penetrating cracks. In addition, the conventional interface layer is mainly composed of pyrolytic carbon, carbon fibers and pyrolytic carbon are both carbon materials, and the carbon materials have poor oxidation resistance and are extremely easy to cause damage to the structure and performance of the carbon fibers. In order to meet the use requirements of ceramic matrix composites in extreme environments, there is a need to improve the toughness, mechanical properties and/or oxidation resistance of ceramic matrix composites.
Disclosure of Invention
In order to solve one or more technical problems in the prior art, the invention provides a graphene-toughened ceramic matrix composite material and a preparation method thereof. The invention solves the problems of general toughness, poor oxidation resistance and the like of the traditional carbon fiber toughened ceramic matrix composite material, and improves the toughness and the service performance of the ceramic matrix composite material in an extreme heat environment.
The invention provides a preparation method of a graphene-toughened ceramic matrix composite material in a first aspect, which comprises the following steps:
(1) Alternately laminating carbon cloth and foam nickel sheets, and manufacturing a preform by adopting a puncture process after alternately laminating;
(2) Depositing pyrolytic carbon and graphene in the preform by a chemical vapor deposition method to obtain a porous carbon/carbon composite material;
(3) Soaking the porous carbon/carbon composite material in an acid solution to obtain a porous carbon/carbon composite material from which foam nickel is removed;
(4) Depositing a hafnium carbide interface layer in the porous carbon/carbon composite material from which the foam nickel is removed by using an oxygen-free hafnium carbide ceramic precursor as a reactant through a chemical vapor deposition method to obtain a carbon/carbon composite material with the hafnium carbide interface layer;
(5) And reacting the oxygen-free hafnium carbide ceramic precursor with the carbon/carbon composite material with the hafnium carbide interface layer by an immersion cracking method to prepare the graphene-toughened ceramic-based composite material.
Preferably, the thickness of the foam nickel sheet is 0.02-0.08 mm, and/or the areal density of the foam nickel sheet is 150-370 g/m 2 。
Preferably, the density of the preform is 0.8-1.2 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the preform, the volume ratio of the foam nickel sheet is 5-20%; and/or in step (2), the porous carbon/carbon composite has a density of 0.9 to 1.3g/cm 3 。
Preferably, in step (2): the deposition is carried out in an atmosphere comprising nitrogen, hydrogen and methane in a volume flow ratio of 10:3: (2-5); and/or the temperature of the deposition is 800-1000 ℃, and the time of the deposition is 0.5-2 h.
Preferably, in step (3): the acid solution is one or more of hydrochloric acid, nitric acid solution and sulfuric acid solution; the concentration of the acid solution is not more than 1mol/L; and/or the soaking temperature is 25-50 ℃, and the soaking time is 2-5 h.
Preferably, in step (4): heating an anaerobic hafnium carbide ceramic precursor, introducing nitrogen into a chemical vapor deposition furnace through carrier gas, and simultaneously introducing hydrogen and methane into the chemical vapor deposition furnace to deposit a hafnium carbide interface layer; wherein, the volume flow ratio of nitrogen, hydrogen and methane is 10:6: (4-10).
Preferably, the heating temperature of the oxygen-free hafnium carbide ceramic precursor is 80-100 ℃; the temperature of the hafnium carbide interface layer is 1020-1550 ℃, the time is 0.5-2 h, and the pressure in the chemical vapor deposition furnace is 20-200 Pa.
Preferably, the thickness of the hafnium carbide interface layer is 0.5-1.5 mu m; and/or the density of the graphene-toughened ceramic matrix composite is 3.1-3.6 g/cm 3 。
Preferably, in step (4) and step (5), the preparation of the oxygen-free hafnium carbide ceramic precursor is as follows: performing amine exchange reaction on tetra (dimethylamino) hafnium or tetra (diethylamino) hafnium and amine compounds, and performing reduced pressure distillation to obtain an anaerobic hafnium carbide ceramic precursor; the amine compound is one or more of di-n-propylamine, diisopropylamine, diallylamine, di-n-butylamine, diisobutylamine, di-n-pentylamine, tetrahydropyrrole and piperidine.
The present invention provides in a second aspect a graphene toughened ceramic matrix composite material made by the method of the present invention described in the first aspect.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) According to the invention, through the laminated weaving of the ultrathin foam nickel sheet and the carbon cloth, the graphene is uniformly distributed in the ceramic matrix, the problems of difficult dispersion and extremely easy agglomeration in the traditional graphene adding method are avoided, and the toughness of the ceramic matrix composite material can be remarkably improved.
(2) According to the invention, a chemical vapor deposition technology is adopted, the oxygen-free hafnium carbide ceramic precursor is used as a reactant, the HfC interface layer is prepared on the surface of the carbon fiber pyrolytic carbon interface layer and the graphene, and the HfC has excellent oxidation resistance and ablation resistance, and compared with the traditional pyrolytic carbon single interface layer, the oxidation resistance of the composite material can be improved. In addition, in the traditional mode of forming the hafnium carbide interface layer, the adopted hafnium carbide ceramic precursor is of an alkoxy structure and is of an aerobic system, and needs to undergo a high-temperature carbothermal reduction process, wherein the reaction temperature is generally not lower than 1600 ℃, so that carbon fibers can be damaged to a certain extent, and the performance of the ceramic matrix composite material can be adversely affected; the invention adopts the oxygen-free hafnium carbide ceramic precursor as the novel hafnium-based ceramic precursor, can realize the direct molding of hafnium carbide by the chemical vapor deposition technology, and simultaneously can avoid the structural and performance damage caused by the corrosion of byproduct hydrogen chloride gas to carbon fibers in the traditional process by the chemical vapor deposition technology, thereby effectively improving the oxidation resistance, high-temperature mechanical properties and the like of the ceramic-based composite material.
(3) The graphene toughened ceramic matrix composite material prepared by the method has the advantages of high toughness and strong oxidation resistance, and is characterized in that the mechanical property of the ceramic matrix composite material in a high-temperature aerobic environment is remarkably improved, the service performance of the ceramic matrix composite material in an extreme heat environment is improved, and the problems of low toughness and poor oxidation resistance of the ceramic matrix composite material are solved.
Drawings
Fig. 1 is a microstructure view (SEM image) of a graphene-toughened ceramic matrix composite material prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a graphene-toughened ceramic matrix composite material in a first aspect, which comprises the following steps:
(1) Alternately laminating carbon cloth and foam nickel sheets, and manufacturing a preform by adopting a puncture process after alternately laminating; in the invention, laminated arrangement is carried out in the thickness direction, a layer of foam nickel sheets is arranged between every two layers of carbon cloth, and after alternate lamination, a puncture preform is woven through a puncture process; the foam nickel sheet is thin and has higher porosity, and a prefabricated body can be prepared by a puncture process and carbon cloth; in the invention, the foam nickel sheet can be ultrasonically cleaned for 1-3 times by ethanol or acetone before being used, for example, so as to remove impurities on the surface; the condition of the puncture process is not particularly limited, and the conventional puncture process in the field is adopted; in the invention, the carbon cloth is woven by carbon fibers;
(2) Depositing pyrolytic carbon and graphene in (inside) the preform by a chemical vapor deposition method to obtain a porous carbon/carbon composite material;
(3) Soaking the porous carbon/carbon composite material in an acid solution to remove foam nickel and obtain a porous carbon/carbon composite material from which the foam nickel is removed;
(4) Depositing a hafnium carbide interface layer in the porous carbon/carbon composite material from which foam nickel is removed by a chemical vapor deposition method by taking an anaerobic hafnium carbide ceramic precursor (also called a polymer anaerobic hafnium carbide ceramic precursor) as a reactant to obtain a carbon/carbon composite material with the hafnium carbide interface layer; specifically, for example, placing a porous carbon/carbon composite material with foam nickel removed in a chemical vapor deposition furnace, controlling the heating temperature of a polymer oxygen-free hafnium carbide ceramic precursor, introducing nitrogen, hydrogen and methane in a vacuum high-temperature state, and forming a hafnium carbide interface layer on the surface of continuous carbon fiber and graphene after a certain time;
(5) Reacting an oxygen-free hafnium carbide ceramic precursor with the carbon/carbon composite material with the hafnium carbide interface layer by an impregnation cracking method to prepare a graphene-toughened ceramic-based composite material;in the invention, the oxygen-free hafnium carbide ceramic precursor does not contain an oxygen element; in the invention, when an oxygen-free hafnium carbide ceramic precursor reacts with the carbon/carbon composite material with a hafnium carbide interface layer through an immersion cracking method (PIP process of immersion/solidification/cracking), filling the liquid oxygen-free hafnium carbide ceramic precursor into pores of the carbon/carbon composite material, and finally forming the graphene-toughened ceramic-based composite material through the solidification cracking process; in the present invention, it is preferable that the impregnation is first vacuum impregnation at a pressure of, for example, 20 to 200Pa, then pressure impregnation at a pressure of 2 to 3MPa for 1 to 2 hours each time, the curing at a temperature of 250 to 400 ℃ for 2 to 4 hours each time, the curing in an argon atmosphere at a temperature of 1400 to 1600 ℃ for 2 to 4 hours each time, and the decomposition in an argon atmosphere, the number of times of repeating the impregnation curing decomposition is not specifically limited until the density of the material reaches 3.1 to 3.6g/cm 3 The preparation method is finished; in the present invention, the pressures referred to are all absolute pressures.
According to the invention, the foam nickel is used as a substrate, and is woven with the carbon cloth to form the preform, and the graphene is uniformly distributed in the ceramic matrix by a chemical vapor deposition technology, so that the problems of difficult dispersion and extremely easy agglomeration in the traditional graphene adding method are avoided, the toughness of the ceramic matrix composite material can be greatly improved, meanwhile, the oxidation resistance of the ceramic matrix composite material can be remarkably improved by the hafnium carbide interface layer, and the problems of low toughness and poor oxidation resistance commonly faced by the ceramic matrix composite material are solved.
According to the invention, a chemical vapor deposition technology is adopted, the oxygen-free hafnium carbide ceramic precursor is used as a reactant, the HfC interface layer is prepared on the surface of the carbon fiber pyrolytic carbon interface layer and the graphene, and the HfC has excellent oxidation resistance and ablation resistance, and compared with the traditional pyrolytic carbon single interface layer, the oxidation resistance of the composite material can be improved. In addition, in the traditional mode of forming the hafnium carbide interface layer, as the adopted hafnium carbide ceramic precursor is of an alkoxy structure, the reaction temperature is generally not lower than 1600 ℃ in the carbothermic reduction process, and the carbon fiber is damaged to a certain extent, so that the performance of the ceramic matrix composite material is also adversely affected; the invention adopts the oxygen-free hafnium carbide ceramic precursor as the novel hafnium-based ceramic precursor, can realize the direct molding of hafnium carbide, and simultaneously can avoid the structural and performance damage caused by the corrosion of byproduct hydrogen chloride gas to carbon fibers in the traditional process by the chemical vapor deposition technology, thereby effectively improving the oxidation resistance, high-temperature mechanical properties and the like of the ceramic-based composite material.
According to some preferred embodiments, the foamed nickel sheet has a thickness of 0.02 to 0.08mm (e.g., 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, or 0.08 mm), and/or the foamed nickel sheet has an areal density of 150 to 370g/m 2 (e.g., 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, or 370 g/m) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the In the invention, the thickness of the foam nickel sheet is preferably 0.02-0.08 mm, and the invention discovers that the control of the thickness of the foam nickel sheet is very critical, and if the thickness is higher than 0.08mm, the pores are too large after the acid solution is removed, so that the mechanical property of the composite material is affected; if the thickness is lower than 0.02mm, the subsequent graphene content is lower, and the toughened composite material cannot be better; in the invention, the thickness of the foam nickel sheet is 0.02-0.08 mm, and the foam nickel sheet can be also called an ultrathin foam nickel sheet.
According to some preferred embodiments, the density of the preform is 0.8 to 1.2g/cm 3 (e.g., 0.8, 0.9, 1.0, 1.1 or 1.2 g/cm) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the In the preform, the volume ratio of the foamed nickel sheet is 5 to 20% (e.g., 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%), in other words, the volume ratio of the foamed nickel sheet in the preform is 5 to 20%; the number of layers of the carbon cloth and the foam nickel sheet which are alternately laminated is not particularly limited, so that the volume ratio of the foam nickel sheet in the preform is 5-20%; and/or in step (2), the porous carbon/carbon composite has a density of 0.9 to 1.3g/cm 3 (e.g., 0.9, 1.0, 1.1, 1.2, or 1.3 g/cm) 3 ). In the invention, the volume ratio of the foam nickel sheet is preferably 5-20% in the preform, and the invention discovers that the mechanical property of the ceramic matrix composite material can be effectively regulated and controlled by controlling the volume ratio of the foam nickel sheet, when the volume ratio of the foam nickel sheet is higher than 20%, the pores are too large after the acid solution is removed to influence the mechanical property of the composite material, and when the volume ratio of the foam nickel sheet is lower than 5%, the subsequent graphene content is lower, and the composite material cannot be toughened well.
According to some preferred embodiments, in step (2): the deposition is carried out in an atmosphere comprising nitrogen, hydrogen and methane in a volume flow ratio of 10:3: (2-5) (e.g., 10:3:2, 10:3:2.5, 10:3:3, 10:3:3.5, 10:3:4, 10:3:4.5, or 10:3:5); and/or the temperature of the deposition is 800-1000 ℃ (e.g. 800 ℃, 850 ℃, 900 ℃, 950 ℃ or 1000 ℃), the time of the deposition is 0.5-2 h (e.g. 0.5, 1, 1.5 or 2 h).
The invention discovers that when pyrolytic carbon and graphene are deposited in the prefabricated body, the key point is to regulate the flow ratio of nitrogen, hydrogen and methane, namely the deposition is carried out in the step (2), and the volume flow ratio of the nitrogen, the hydrogen and the methane is preferably 10:3: (2-5), the ceramic matrix composite with high toughness and strong oxidation resistance can be prepared, and the mechanical properties of the prepared ceramic matrix composite in a high-temperature aerobic environment can be obviously improved. Although there is a report that pyrolytic carbon interface layers are grown on the surfaces of carbon fibers or graphene is grown on the surfaces of foam nickel, it is difficult to uniformly prepare pyrolytic carbon and graphene in the same sample in the same cavity, and the prior art is not related. This is because methane deposition on the carbon fiber surface is a non-catalytic growth, while on the foam nickel surface is a metal catalytic growth, the two growth mechanisms differ greatly. The flow ratio of nitrogen, hydrogen and methane is creatively controlled at 10:3: (2-5), good pyrolytic carbon and graphene growth effects can be achieved simultaneously; the invention finds that if the flow ratio of the three components is lower than 10:3:2, the graphene on the surface of the foam nickel grows well, and the deposition effect of pyrolytic carbon on the surface of the carbon fiber is poor; if the flow ratio of the three components is higher than 10:3:5, it would result in the formation of amorphous carbon on the nickel foam surface more readily than graphene.
According to some specific embodiments, step (2) is: placing the prefabricated body obtained in the step (1) in a high-temperature furnace chamber (also called as a chemical vapor deposition reaction furnace chamber or a chemical vapor deposition furnace chamber), vacuumizing to 20-200Pa, removing air in the chamber, continuously filling nitrogen and hydrogen into the chamber, and raising the temperature to 800-1000 ℃ at a heating rate of 1-8 ℃/min, wherein the flow ratio of methane, nitrogen and hydrogen is controlled at 10:3:2-5, stopping heating after the reaction is finished for 0.5-2h, continuously introducing nitrogen until the temperature of the cavity is reduced to room temperature, and taking out a sample to obtain the porous carbon/carbon composite material; in the present invention, the room temperature is, for example, 15 to 35 ℃.
According to some preferred embodiments, in step (3): the acid solution is one or more of hydrochloric acid, nitric acid solution and sulfuric acid solution; the concentration of the acid solution is not more than 1mol/L; and/or the soaking temperature is 25-50deg.C (e.g., 25deg.C, 30deg.C, 35deg.C, 40deg.C, 45deg.C or 50deg.C), and the soaking time is 2-5 h (e.g., 2, 3, 4 or 5 h).
According to some specific embodiments, step (3) is: soaking the porous carbon/carbon composite material obtained in the step (2) in any one of hydrochloric acid, dilute nitric acid or dilute sulfuric acid, and then placing the porous carbon/carbon composite material in distilled water for repeated times to ensure that foam nickel is completely removed.
According to some preferred embodiments, in step (4): heating an anaerobic hafnium carbide ceramic precursor, introducing nitrogen into a chemical vapor deposition furnace through carrier gas, and simultaneously introducing hydrogen and methane into the chemical vapor deposition furnace to deposit a hafnium carbide interface layer; wherein, the volume flow ratio of nitrogen, hydrogen and methane is 10:6: (4-10) (e.g., 10:6:4, 10:6:5, 10:6:6, 10:6:7, 10:6:8, 10:6:9, or 10:6:10).
According to some preferred embodiments, the heating temperature of the oxygen-free hafnium carbide ceramic precursor is 80-100 ℃ (e.g., 80 ℃, 90 ℃, or 100 ℃); depositing the hafnium carbide interface layer at a temperature of 1020-1550 ℃ (e.g., 1020 ℃, 1050 ℃, 1080 ℃, 1100 ℃, 1120 ℃, 1150 ℃, 1180 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃, 1500 ℃ or 1550 ℃) for a time of 0.5-2 hours (e.g., 0.5, 1, 1.5 or 2 hours) and a pressure in the chemical vapor deposition furnace of 20-200 Pa (e.g., 20, 50, 80, 100, 120, 150, 180 or 200 Pa); in some preferred embodiments, the temperature at which the hafnium carbide interfacial layer is deposited is 1020 to 1180 ℃.
According to the invention, a great number of creative tests show that when a hafnium carbide interface layer is deposited in the porous carbon/carbon composite material for removing foam nickel by using an oxygen-free hafnium carbide ceramic precursor as a reactant through a chemical vapor deposition method, the chemical vapor deposition temperature in a reaction furnace is preferably controlled to be 1020-1550 ℃ and the flow ratio of nitrogen, hydrogen and methane is preferably controlled to be 10:6: (4-10), so that the ceramic matrix composite with strong oxidation resistance and obviously improved mechanical properties in a high-temperature aerobic environment can be obtained; the invention discovers that if the chemical vapor deposition temperature is too high, the oxygen-free hafnium carbide ceramic precursor can be heated to decompose at too high a rate, substances such as amorphous carbon and the like can be formed, and the oxidation resistance of the ceramic matrix composite material can be reduced; if the chemical vapor deposition temperature is lower than 1020 ℃, the cracking of the oxygen-free hafnium carbide ceramic precursor is insufficient, a stable HfC interface layer is not formed, the oxidation resistance of the ceramic matrix composite is reduced, and if the flow ratio of nitrogen, hydrogen and methane is higher than 10:6:10, excessive methane is easier to form amorphous carbon, so that the oxidation resistance of the material is reduced; and below 10:6:4, insufficient methane supply can easily result in poor HfC crystal form and likewise affect its oxidation resistance.
According to some preferred embodiments, the hafnium carbide interfacial layer has a thickness of 0.5 to 1.5 μm (e.g., 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, or 1.5 μm).
According to some specific embodiments, step (4) is: placing the porous carbon/carbon composite material with foam nickel removed in a chemical vapor deposition furnace, vacuumizing, controlling the pressure in the reaction furnace to be 20-200Pa, controlling the temperature in the reaction furnace to be 1020-1550 ℃ and preserving the heat for 10min to ensure that the interior of the furnace body reaches a uniform temperature state. Then, the heated anaerobic hafnium carbide ceramic precursor is taken into a chemical vapor deposition furnace chamber by taking nitrogen as carrier gas, the heating temperature of the anaerobic hafnium carbide ceramic precursor is controlled to be 80-100 ℃, hydrogen and methane are also introduced into the chemical vapor deposition furnace chamber (furnace chamber) while the carrier gas continuously carries the anaerobic hafnium carbide ceramic precursor into the chamber, and the volume flow ratio of the carrier gas nitrogen to the hydrogen to the methane is controlled to be 10:6: 4-10, wherein the nitrogen flow is controlled to be 1-3L/min. After the reaction furnace is insulated for 0.5-2h, a hafnium carbide interface layer is formed on the surfaces of the carbon fiber (continuous carbon fiber) and the graphene, and the thickness is 0.5-1.5 mu m. And then cooling, stopping heating the anaerobic hafnium carbide ceramic precursor and stopping introducing methane and hydrogen in sequence, introducing nitrogen in the whole process of cooling until the temperature is reduced to room temperature, and taking out the sample.
According to some preferred embodiments, the graphene-toughened ceramic matrix composite has a density of 3.1 to 3.6g/cm 3 . The graphene-toughened ceramic matrix composite material is prepared by taking an anaerobic hafnium carbide ceramic precursor as a reactant in a precursor dipping and cracking mode, and preferably has the density of 3.1-3.6 g/cm 3 Is a graphene toughened ceramic matrix composite. The graphene toughened ceramic matrix composite material prepared by the method has the advantages of high toughness and strong oxidation resistance, and the mechanical properties of the graphene toughened ceramic matrix composite material are obviously improved in a high-temperature aerobic environment.
According to some preferred embodiments, in step (4) and step (5), the preparation of the oxygen-free hafnium carbide ceramic precursor is as follows: performing amine exchange reaction on tetra (dimethylamino) hafnium or tetra (diethylamino) hafnium and amine compounds, and performing reduced pressure distillation to obtain an anaerobic hafnium carbide ceramic precursor; in the invention, amine compounds and tetra (dimethylamino) hafnium or tetra (diethylamino) hafnium undergo an amine exchange reaction, by-products are dimethylamine or diethylamine with low boiling point, and the oxygen-free hafnium carbide ceramic precursor can be obtained after removing the low boiling point by-products by reduced pressure distillation, wherein the amine exchange reaction is carried out in an inert gas atmosphere, for example, in an argon atmosphere; the amine compound is selected from one or more of di-n-propylamine, diisopropylamine, diallylamine (diallylamine), di-n-butylamine, diisobutylamine, di-n-pentylamine, tetrahydropyrrole and piperidine; the molar ratio of the tetra (dimethylamino) hafnium or the tetra (diethylamino) hafnium to the amine compound is 1: (1-4); the temperature of the amine exchange reaction is 20-30 ℃ and the time is 12-18 hours; the amino is used as a ligand for stabilizing a metal center, so that the prepared anaerobic hafnium carbide ceramic precursor does not contain oxygen element, the residual oxygen content of a pyrolysis product is reduced, the performance of the ceramic matrix composite is improved, and the obtained anaerobic hafnium carbide ceramic precursor is in a liquid state.
The present invention provides in a second aspect a graphene toughened ceramic matrix composite material made by the method of the present invention described in the first aspect.
The invention will be further illustrated by way of example, but the scope of the invention is not limited to these examples. The present invention is capable of other and further embodiments and its several details are capable of modification and variation in accordance with the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims. The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents and the like used in the examples described below, unless otherwise specified, were all obtained commercially or prepared by conventional methods.
The preparation of the oxygen-free hafnium carbide ceramic precursor according to the present invention in the following examples and comparative examples is as follows:
vacuumizing a three-port bottle for multiple times, filling argon to replace air, adding tetra (diethylamino) hafnium, adding diallylamine, stirring and reacting for 18 hours at 30 ℃ in an argon atmosphere, and then distilling reactants under reduced pressure to remove low-boiling-point substances to obtain a liquid anaerobic hafnium carbide ceramic precursor; wherein, the molar ratio of the tetra (diethylamino) hafnium to the diallylamine dosage is 1:1.
Example 1
(1) Foam nickel sheet: the thickness of the ultrathin foam nickel sheet is 0.05mm, and the surface density is 350g/m 2 Ultrasonic cleaning with ethanol for 2 times, and removing impurities on the surface.
(2) Weaving a preform: the foam nickel sheets and the carbon cloth are arranged in a laminated mode, and a penetrating process is adopted to weave the foam nickel sheets into a prefabricated body, so that the volume ratio of the foam nickel sheets is 12%; the density of the preform obtained was 1.05g/cm 3 。
(3) Preparing a porous carbon/carbon composite material: placing the preform in a chemical vapor deposition furnace chamber, vacuumizing to 80Pa, removing air in the chamber, continuously filling nitrogen and hydrogen into the chamber, and raising the temperature to 1000 ℃ at a heating rate of 6 ℃/min, wherein the volume flow ratio of the methane to the nitrogen is controlled at 10:3: and 4, stopping heating after the reaction is finished for 1h, continuously introducing nitrogen until the temperature of the cavity is reduced to room temperature, and taking out the sample to obtain the porous carbon/carbon composite material.
(4) Removing foam nickel: soaking the porous carbon/carbon composite material in 0.5mol/L hydrochloric acid solution, soaking for 3 hours at 50 ℃, then placing in distilled water for cleaning, and sequentially repeating the soaking in the hydrochloric acid solution and the cleaning in the distilled water for a plurality of times to ensure that the foam nickel is completely removed, and drying to obtain the porous carbon/carbon composite material with the foam nickel removed.
(5) Preparing an HfC interface layer: placing the porous carbon/carbon composite material with foam nickel removed in a chemical vapor deposition reaction furnace, vacuumizing, controlling the pressure in the reaction furnace to be 150Pa, controlling the temperature in the reaction furnace to be 1075 ℃, and preserving the temperature for 10min to ensure that the interior of the furnace body reaches a uniform temperature state. Then, the heated anaerobic hafnium carbide ceramic precursor is taken into a chemical vapor deposition reaction furnace chamber by taking nitrogen as carrier gas, the heating temperature of the anaerobic hafnium carbide ceramic precursor is controlled at 90 ℃, hydrogen and methane are introduced into the furnace chamber while the carrier gas nitrogen continuously carries the anaerobic hafnium carbide ceramic precursor into the chamber, and the volume flow ratio of the nitrogen to the hydrogen to the methane is 10:6:5, wherein the nitrogen flow is controlled at 2L/min. After the reaction furnace is insulated for 1h at 1075 ℃, a hafnium carbide interface layer (HfC interface layer) with the thickness of 1.0 μm is formed on the surfaces of the carbon fiber and the graphene. And then cooling, stopping heating the anaerobic hafnium carbide ceramic precursor and stopping introducing methane and hydrogen in sequence, introducing nitrogen in the whole process of cooling until the temperature is reduced to room temperature, and taking out the sample to obtain the carbon/carbon composite material with the hafnium carbide interface layer.
(6) Preparing a graphene-toughened ceramic matrix composite: the oxygen-free hafnium carbide ceramic precursor is used as a reactant, and is reacted with the carbon/carbon composite material with the hafnium carbide interface layer by an immersion cracking method (PIP process of immersion/solidification/cracking) to prepare the ceramic material with the density of 3.3g/cm 3 A graphene toughened ceramic matrix composite; in each impregnation/curing/cracking round, the impregnation is performed in vacuum, the pressure of the vacuum impregnation is 200Pa, then the pressure impregnation is performed, the pressure of the pressure impregnation is 2MPa, the time of each vacuum impregnation is 1.5h, the time of each pressure impregnation is 1.5h, the temperature of the curing is 280 ℃, the time of each curing is 3h, the curing is performed in an argon atmosphere, the temperature of the cracking is 1500 ℃, the time of each cracking is 3h, and the cracking is performed in the argon atmosphere.
Mechanical property test under high-temperature aerobic environment: the graphene-toughened ceramic matrix composite material prepared in the embodiment is measured, and the bending strength of the graphene-toughened ceramic matrix composite material is 342MPa in an air environment at 1500 ℃.
Example 2
(1) Foam nickel sheet: the thickness of the ultrathin foam nickel sheet is 0.08mm, and the surface density is 350g/m 2 Ultrasonic cleaning with ethanol for 2 times, and removing impurities on the surface.
(2) Weaving a preform: the foam nickel sheets and the carbon cloth are arranged in a laminated mode, and a penetrating process is adopted to weave the foam nickel sheets into a prefabricated body, so that the volume ratio of the foam nickel sheets is 18%; the density of the preform obtained was 1.15g/cm 3 。
(3) Preparing a porous carbon/carbon composite material: placing the preform in a chemical vapor deposition furnace chamber, vacuumizing to 80Pa, removing air in the chamber, continuously filling nitrogen and hydrogen into the chamber, and raising the temperature to 1000 ℃ at a heating rate of 6 ℃/min, wherein the volume flow ratio of the methane to the nitrogen is controlled at 10:3: and 4, stopping heating after the reaction is finished for 1h, continuously introducing nitrogen until the temperature of the cavity is reduced to room temperature, and taking out the sample to obtain the porous carbon/carbon composite material.
(4) Removing foam nickel: soaking the porous carbon/carbon composite material in 0.5mol/L hydrochloric acid solution, soaking for 3 hours at 50 ℃, then placing in distilled water for cleaning, and sequentially repeating the soaking in the hydrochloric acid solution and the cleaning in the distilled water for a plurality of times to ensure that the foam nickel is completely removed, and drying to obtain the porous carbon/carbon composite material with the foam nickel removed.
(5) Preparing an HfC interface layer: placing the porous carbon/carbon composite material with foam nickel removed in a chemical vapor deposition reaction furnace, vacuumizing, controlling the pressure in the reaction furnace to be 150Pa, controlling the temperature in the reaction furnace to be 1075 ℃, and preserving the temperature for 10min to ensure that the interior of the furnace body reaches a uniform temperature state. Next, the heated anaerobic hafnium carbide ceramic precursor is taken into a chemical vapor deposition reaction furnace chamber by taking nitrogen as carrier gas, the heating temperature of the anaerobic hafnium carbide ceramic precursor is controlled at 90 ℃, hydrogen and methane are introduced into the furnace chamber while the carrier gas continuously carries the anaerobic hafnium carbide ceramic precursor into the chamber, and the volume flow ratio of the nitrogen to the hydrogen to the methane is 10:6:5, wherein the nitrogen flow is controlled at 2L/min. After the reaction furnace is insulated for 1h at 1075 ℃, a hafnium carbide interface layer (HfC interface layer) with the thickness of 1.0 μm is formed on the surfaces of the carbon fiber and the graphene. And then cooling, stopping heating the anaerobic hafnium carbide ceramic precursor and stopping introducing methane and hydrogen in sequence, introducing nitrogen in the whole process of cooling until the temperature is reduced to room temperature, and taking out the sample to obtain the carbon/carbon composite material with the hafnium carbide interface layer.
(6) Preparing a graphene-toughened ceramic matrix composite: the oxygen-free hafnium carbide ceramic precursor is used as a reactant, and is reacted with the carbon/carbon composite material with the hafnium carbide interface layer by an immersion cracking method (PIP process of immersion/solidification/cracking) to prepare the ceramic material with the density of 3.5g/cm 3 A graphene toughened ceramic matrix composite; in each dip +.In the curing/cracking cycle, the impregnation is first vacuum impregnation, the pressure of the vacuum impregnation is 200Pa, then the pressure impregnation is carried out, the pressure of the pressure impregnation is 2MPa, the time of each vacuum impregnation is 1.5h, the time of each pressure impregnation is 1.5h, the curing temperature is 280 ℃, the time of each curing is 3h, the curing is carried out in an argon atmosphere, the cracking temperature is 1500 ℃, the time of each cracking is 3h, and the cracking is carried out in an argon atmosphere.
Mechanical property test under high-temperature aerobic environment: the graphene-toughened ceramic matrix composite material prepared in the embodiment is measured, and the bending strength of the graphene-toughened ceramic matrix composite material is 371MPa in an air environment at 1500 ℃.
Example 3
(1) Foam nickel sheet: the thickness of the ultrathin foam nickel sheet is 0.05mm, and the surface density is 350g/m 2 Ultrasonic cleaning with ethanol for 2 times, and removing impurities on the surface.
(2) Weaving a preform: the foam nickel sheets and the carbon cloth are arranged in a laminated mode, and a penetrating process is adopted to weave the foam nickel sheets into a prefabricated body, so that the volume ratio of the foam nickel sheets is 12%; the density of the preform obtained was 1.05g/cm 3 。
(3) Preparing a porous carbon/carbon composite material: placing the preform in a chemical vapor deposition furnace chamber, vacuumizing to 80Pa, removing air in the chamber, continuously filling nitrogen and hydrogen into the chamber, and raising the temperature to 1000 ℃ at a heating rate of 6 ℃/min, wherein the volume flow ratio of the methane to the nitrogen is controlled at 10:3: and 4, stopping heating after the reaction is finished for 1h, continuously introducing nitrogen until the temperature of the cavity is reduced to room temperature, and taking out the sample to obtain the porous carbon/carbon composite material.
(4) Removing foam nickel: soaking the porous carbon/carbon composite material in 0.5mol/L hydrochloric acid solution, soaking for 3 hours at 50 ℃, then placing in distilled water for cleaning, and sequentially repeating the soaking in the hydrochloric acid solution and the cleaning in the distilled water for a plurality of times to ensure that the foam nickel is completely removed, and drying to obtain the porous carbon/carbon composite material with the foam nickel removed.
(5) Preparing an HfC interface layer: placing the porous carbon/carbon composite material with foam nickel removed in a chemical vapor deposition reaction furnace, vacuumizing, controlling the pressure in the reaction furnace to be 150Pa, controlling the temperature in the reaction furnace to be 1075 ℃, and preserving the temperature for 10min to ensure that the interior of the furnace body reaches a uniform temperature state. Then, the heated anaerobic hafnium carbide ceramic precursor is taken into a chemical vapor deposition reaction furnace chamber by taking nitrogen as carrier gas, the heating temperature of the anaerobic hafnium carbide ceramic precursor is controlled at 90 ℃, hydrogen and methane are introduced into the furnace chamber while the carrier gas nitrogen continuously carries the anaerobic hafnium carbide ceramic precursor into the chamber, and the volume flow ratio of the nitrogen to the hydrogen to the methane is 10:6:5, wherein the nitrogen flow is controlled at 2L/min. After the reaction furnace is insulated for 2 hours at 1075 ℃, a hafnium carbide interface layer (HfC interface layer) with the thickness of 1.5 mu m is formed on the surfaces of the carbon fiber and the graphene. And then cooling, stopping heating the anaerobic hafnium carbide ceramic precursor and stopping introducing methane and hydrogen in sequence, introducing nitrogen in the whole process of cooling until the temperature is reduced to room temperature, and taking out the sample to obtain the carbon/carbon composite material with the hafnium carbide interface layer.
(6) Preparing a graphene-toughened ceramic matrix composite: the oxygen-free hafnium carbide ceramic precursor is used as a reactant, and is reacted with the carbon/carbon composite material with the hafnium carbide interface layer by an immersion cracking method (PIP process of immersion/solidification/cracking) to prepare the ceramic material with the density of 3.4g/cm 3 A graphene toughened ceramic matrix composite; in each impregnation/curing/cracking round, the impregnation is performed in vacuum, the pressure of the vacuum impregnation is 200Pa, then the pressure impregnation is performed, the pressure of the pressure impregnation is 2MPa, the time of each vacuum impregnation is 1.5h, the time of each pressure impregnation is 1.5h, the temperature of the curing is 280 ℃, the time of each curing is 3h, the curing is performed in an argon atmosphere, the temperature of the cracking is 1500 ℃, the time of each cracking is 3h, and the cracking is performed in the argon atmosphere.
Mechanical property test under high-temperature aerobic environment: the graphene-toughened ceramic matrix composite material prepared by the embodiment is measured to have the bending strength of 386MPa in an air environment at 1500 ℃.
As is clear from the above examples 1 to 3, in example 2, when the nickel foam sheet is selected, the thickness of the nickel foam sheet is increased from 0.05mm to 0.08mm, so that the volume ratio of the nickel foam in the preform is increased from 12% to 18%, the volume ratio of the graphene obtained by growth is higher, the mechanical properties of the final ceramic matrix composite are significantly improved, and the bending strength is increased from 342MPa to 371MPa in an air environment at 1500 ℃. Compared with example 1, in example 3, when the HfC interface layer is prepared, the thickness of the HfC interface layer is increased from 1.0 μm to 1.5 μm, the capability of effectively protecting carbon fibers and graphene is improved, the oxidation resistance of the final ceramic matrix composite is obviously improved, and the bending strength of the ceramic matrix composite in an air environment at 1500 ℃ is increased from 342MPa to 386MPa.
Examples 4 to 11
The specific process parameters of examples 4 to 11 and the performance index of the finally produced ceramic matrix composite are shown in Table 1, and the other preparation processes are the same as in example 1.
As can be seen from table 1, when the thickness of the nickel foam sheet is reduced from 0.05mm to 0.01mm in example 4 compared with example 1, the volume ratio of the nickel foam in the preform is reduced from 12% to 2%, resulting in lower volume ratio of graphene that can be grown, lower mechanical properties of the finally obtained ceramic matrix composite, and reduced bending strength from 342MPa to 269MPa in an air environment at 1500 ℃. In example 5, compared with example 1, when the thickness of the foam nickel sheet is increased from 0.05mm to 0.1mm, so that the volume proportion of the foam nickel in the preform is increased from 12% to 24%, the pores are too large after the acid solution is removed, the mechanical properties of the ceramic matrix composite are obviously affected, and the bending strength is reduced from 342MPa to 193MPa in an air environment at 1500 ℃. Compared with example 1, in example 6, when the deposition temperature of the oxygen-free hafnium carbide ceramic precursor is selected, the deposition temperature is reduced from 1075 ℃ to 950 ℃, so that the precursor is insufficiently decomposed, the HfC deposition effect is poor, the oxidation resistance of the final ceramic matrix composite is poor, and the bending strength of the ceramic matrix composite is reduced from 342MPa to 216MPa in an air environment at 1500 ℃. In example 7, when the deposition temperature of the oxygen-free hafnium carbide ceramic precursor is selected, compared with example 1, the deposition temperature is increased from 1075 ℃ to 1700 ℃, and the thermal decomposition rate is too high, so that substances such as amorphous carbon and the like can be formed, and the oxidation resistance of the material is reduced, and the bending strength of the material in an air environment at 1500 ℃ is reduced from 342MPa to 237MPa. In example 8, compared to example 1, the flow ratio of nitrogen, hydrogen and methane was 10:3:4 to 10:3:1, the graphene on the surface of the foam nickel grows well, and the deposition effect of pyrolytic carbon on the surface of the carbon fiber is poor, so that the mechanical property of the composite material is obviously influenced, and the bending strength is reduced from 342MPa to 284MPa in an air environment at 1500 ℃. In example 9, compared to example 1, the flow ratio of nitrogen, hydrogen and methane was 10:3:4 to 10:3:8, the amorphous carbon is easier to form on the surface of the foam nickel than the graphene, and the bending strength is reduced from 342MPa to 220MPa in an air environment at 1500 ℃. In example 10, compared to example 1, the nitrogen, hydrogen and methane flow ratios were set to 10:6:5 to 10:6:2, insufficient methane supply easily causes poor HfC crystal form, influences the oxidation resistance of the ceramic matrix composite, and reduces the bending strength from 342MPa to 231MPa in an air environment at 1500 ℃. In example 11, compared to example 1, the nitrogen, hydrogen and methane flow ratios were set to 10:6:5 to 10:6:12, the excessive methane is easier to form amorphous carbon, and the ceramic matrix composite material is also poor in oxidation resistance, and the bending strength is reduced from 342MPa to 201MPa in an air environment at 1500 ℃.
Comparative example 1
(1) Providing continuous carbon fibers (polyacrylonitrile-based carbon fibers) having an average diameter of 7 μm; preparing single-layer graphene oxide (the average size of the single-layer graphene oxide is 2 mu m) into a graphene oxide solution with the concentration of 0.1mg/mL by using acetone and water in a volume ratio of 1:1; uniformly spraying graphene oxide solution on the surface of continuous carbon fiber, placing the sprayed carbon fiber in a drying oven at 0 ℃ for low-temperature treatment for 600 minutes, slowly volatilizing a mixed solvent of acetone and water, and sequentially repeatingThe steps of spraying and low-temperature treatment are repeated until a graphene oxide interface layer with the thickness of 0.3 mu m is formed on the surface of the continuous carbon fiber; the continuous carbon fiber with the surface formed with the graphene oxide interface layer is adopted to weave the graphene oxide interface layer into the material with the density of 0.4g/cm 3 Is a preform structure of (a); and (3) placing the prefabricated body structure in a high-temperature furnace, heating to 600 ℃ under the protection of argon, introducing hydrogen at a heating rate of 2 ℃/min, keeping the temperature for 240 minutes at a constant temperature, enabling the graphene oxide interface layer to be converted into a graphene interface layer, naturally cooling to room temperature, and taking out the prefabricated body to obtain the carbon fiber prefabricated body.
(2) And (3) depositing a pyrolytic carbon interface layer with the thickness of 5 mu m on the basis of the graphene interface layer of the carbon fiber preform obtained in the step (1) by a chemical vapor deposition method to obtain a porous C/C matrix with the graphene/pyrolytic carbon composite interface layer.
(3) Preparing an HfC interface layer: and placing the porous C/C matrix with the graphene/pyrolytic carbon composite interface layer in a chemical vapor deposition reaction furnace, vacuumizing, wherein the pressure in the reaction furnace is 150Pa, controlling the temperature in the reaction furnace at 1075 ℃ and preserving heat for 10min so as to ensure that the interior of the furnace body reaches a uniform temperature state. Then, the heated anaerobic hafnium carbide ceramic precursor is taken into a chemical vapor deposition reaction furnace chamber by taking nitrogen as carrier gas, the heating temperature of the anaerobic hafnium carbide ceramic precursor is controlled at 90 ℃, hydrogen and methane are introduced into the furnace chamber while the carrier gas nitrogen continuously carries the anaerobic hafnium carbide ceramic precursor into the chamber, and the volume flow ratio of the nitrogen to the hydrogen to the methane is 10:6:5, wherein the nitrogen flow is controlled at 2L/min. After the reaction furnace is insulated for 1h at 1075 ℃, a hafnium carbide interface layer (HfC interface layer) with the thickness of 1.0 μm is formed on the basis of the graphene/pyrolytic carbon composite interface layer. And then cooling, stopping heating the anaerobic hafnium carbide ceramic precursor and stopping introducing methane and hydrogen in sequence, introducing nitrogen in the whole process of cooling until the temperature is reduced to the room temperature, and taking out the sample to obtain the carbon/carbon composite material with the graphene/pyrolytic carbon composite interface layer/hafnium carbide interface layer.
(4) Preparing a ceramic matrix composite: reacting oxygen-free hafnium carbide ceramic precursorReacting oxygen-free hafnium carbide ceramic precursor with carbon/carbon composite material with graphene/pyrolytic carbon composite interface layer/hafnium carbide interface layer by dip cracking (PIP process of dip/solidification/cracking) to obtain a ceramic material with density of 3.3g/cm 3 Is a ceramic matrix composite of (a) a ceramic matrix composite; in each impregnation/curing/cracking round, the impregnation is performed in vacuum, the pressure of the vacuum impregnation is 200Pa, then the pressure impregnation is performed, the pressure of the pressure impregnation is 2MPa, the time of each vacuum impregnation is 1.5h, the time of each pressure impregnation is 1.5h, the temperature of the curing is 280 ℃, the time of each curing is 3h, the curing is performed in an argon atmosphere, the temperature of the cracking is 1500 ℃, the time of each cracking is 3h, and the cracking is performed in the argon atmosphere.
Mechanical property test under high-temperature aerobic environment: the ceramic matrix composite material prepared in the comparative example is measured to have a bending strength of 307MPa in an air environment at 1500 ℃.
Comparative example 2
(1) The procedure is as in step (1) of example 1.
(2) The same as in step (2) of example 1.
(3) The procedure is as in step (3) of example 1.
(4) The procedure is as in step (4) of example 1.
(5) Soaking the porous carbon/carbon composite material from which the foam nickel is removed in a nitric acid solution with the concentration of 6mol/L, preserving the heat at 80 ℃ for 150min, and then drying in an oven at 80 ℃ for 240min to obtain the modified carbon/carbon composite material.
(6) Hf (NO) was formulated at a concentration of 0.1mol/L 3 ) 4 Soaking the modified carbon/carbon composite material obtained in the step (5) in Hf (NO) 3 ) 4 The water solution is soaked under pressure for 240min, the pressure is 0.3MPa, the drying treatment is carried out in an oven at 80 ℃ for 240min, then the water solution is placed in a sintering device, the temperature is raised to 600 ℃ under the protection of inert gas argon, the temperature raising rate is 5 ℃/min, the temperature is kept at 600 ℃ for 120 min, and the temperature is lowered to the room temperature at the rate of 5 ℃/min.
(7) Repeating the step (6) for a plurality of times until a carbon/carbon composite material having a hafnium oxide layer with a thickness of 1 μm is obtained.
(8) And (3) placing the carbon/carbon composite material with the hafnium oxide layer with the thickness of 1 μm in a high-temperature device, heating to 1600 ℃ under the protection of inert gas argon, keeping the temperature at 1600 ℃ for 120 minutes, and performing carbothermic reduction reaction to convert the hafnium oxide layer into a hafnium carbide layer, and cooling to room temperature at the speed of 5 ℃ to obtain the carbon/carbon composite material with the hafnium carbide layer with the thickness of 1 μm.
(9) Preparing a ceramic matrix composite: the oxygen-free hafnium carbide ceramic precursor is used as a reactant, and is reacted with the carbon/carbon composite material with the hafnium carbide layer by an immersion cracking method (PIP process of immersion/solidification/cracking) to prepare the ceramic material with the density of 3.3g/cm 3 Is a ceramic matrix composite of (a) a ceramic matrix composite; in each impregnation/curing/cracking round, the impregnation is performed in vacuum, the pressure of the vacuum impregnation is 200Pa, then the pressure impregnation is performed, the pressure of the pressure impregnation is 2MPa, the time of each vacuum impregnation is 1.5h, the time of each pressure impregnation is 1.5h, the temperature of the curing is 280 ℃, the time of each curing is 3h, the curing is performed in an argon atmosphere, the temperature of the cracking is 1500 ℃, the time of each cracking is 3h, and the cracking is performed in the argon atmosphere.
Mechanical property test under high-temperature aerobic environment: the ceramic matrix composite prepared in the comparative example has a bending strength of 286MPa in an air environment at 1500 ℃.
The invention is not described in detail in a manner known to those skilled in the art.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the graphene-toughened ceramic matrix composite material is characterized by comprising the following steps of:
(1) Alternately laminating carbon cloth and foam nickel sheets, and manufacturing a preform by adopting a puncture process after alternately laminating;
(2) Depositing pyrolytic carbon and graphene in the preform by a chemical vapor deposition method to obtain a porous carbon/carbon composite material;
(3) Soaking the porous carbon/carbon composite material in an acid solution to obtain a porous carbon/carbon composite material from which foam nickel is removed;
(4) Depositing a hafnium carbide interface layer in the porous carbon/carbon composite material from which the foam nickel is removed by using an oxygen-free hafnium carbide ceramic precursor as a reactant through a chemical vapor deposition method to obtain a carbon/carbon composite material with the hafnium carbide interface layer;
(5) And reacting the oxygen-free hafnium carbide ceramic precursor with the carbon/carbon composite material with the hafnium carbide interface layer by an immersion cracking method to prepare the graphene-toughened ceramic-based composite material.
2. The method of manufacturing according to claim 1, characterized in that:
the thickness of the foam nickel sheet is 0.02-0.08 mm, and/or the surface density of the foam nickel sheet is 150-370 g/m 2 。
3. The method of manufacturing according to claim 1, characterized in that:
The density of the preform is 0.8-1.2 g/cm 3 ；
In the preform, the volume ratio of the foam nickel sheet is 5-20%; and/or
In the step (2), the density of the porous carbon/carbon composite material is 0.9-1.3 g/cm 3 。
4. The method of claim 1, wherein in step (2):
the deposition is carried out in an atmosphere comprising nitrogen, hydrogen and methane in a volume flow ratio of 10:3: (2-5); and/or
The deposition temperature is 800-1000 ℃, and the deposition time is 0.5-2 h.
5. The method of claim 1, wherein in step (3):
the acid solution is one or more of hydrochloric acid, nitric acid solution and sulfuric acid solution;
the concentration of the acid solution is not more than 1mol/L; and/or
The soaking temperature is 25-50 ℃, and the soaking time is 2-5 h.
6. The method of claim 1, wherein in step (4):
heating an anaerobic hafnium carbide ceramic precursor, introducing nitrogen into a chemical vapor deposition furnace through carrier gas, and simultaneously introducing hydrogen and methane into the chemical vapor deposition furnace to deposit a hafnium carbide interface layer; wherein, the volume flow ratio of nitrogen, hydrogen and methane is 10:6: (4-10).
7. The method of manufacturing according to claim 6, wherein:
the heating temperature of the oxygen-free hafnium carbide ceramic precursor is 80-100 ℃;
the temperature of the hafnium carbide interface layer is 1020-1550 ℃, the time is 0.5-2 h, and the pressure in the chemical vapor deposition furnace is 20-200 Pa.
8. The method of manufacturing according to claim 1, characterized in that:
the thickness of the hafnium carbide interface layer is 0.5-1.5 mu m; and/or
The density of the graphene-toughened ceramic matrix composite is 3.1-3.6 g/cm 3 。
9. The method of any one of claims 1 to 8, wherein in step (4) and step (5), the preparation of the oxygen-free hafnium carbide ceramic precursor is:
performing amine exchange reaction on tetra (dimethylamino) hafnium or tetra (diethylamino) hafnium and amine compounds, and performing reduced pressure distillation to obtain an anaerobic hafnium carbide ceramic precursor;
the amine compound is one or more of di-n-propylamine, diisopropylamine, diallylamine, di-n-butylamine, diisobutylamine, di-n-pentylamine, tetrahydropyrrole and piperidine.
10. A graphene toughened ceramic matrix composite made by the method of any of claims 1 to 9.
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