CN110407598A - One kind having ZrB2The preparation method of the Cf/SiC composite material at interface - Google Patents

One kind having ZrB2The preparation method of the Cf/SiC composite material at interface Download PDF

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CN110407598A
CN110407598A CN201910737155.6A CN201910737155A CN110407598A CN 110407598 A CN110407598 A CN 110407598A CN 201910737155 A CN201910737155 A CN 201910737155A CN 110407598 A CN110407598 A CN 110407598A
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zrb
carbon fiber
interface
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temperature
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王钺
陈燕云
杨建铃
周俊霖
何海静
陆薪宇
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Southwest Petroleum University
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/628—Coating the powders or the macroscopic reinforcing agents
    • C04B35/62844—Coating fibres
    • C04B35/62857—Coating fibres with non-oxide ceramics
    • C04B35/806—
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3804—Borides
    • C04B2235/3813—Refractory metal borides
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    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract

The invention discloses one kind to have ZrB2The preparation method of the Cf/SiC composite material at interface, comprising: carbon fiber surface is activated, the preparation of interface phase, the preparation of porous fibre precast body, the preparation of silicon carbide substrate；It is characterized in that, silicon carbide substrate is filled in fiber preform, Ceramic Matrix Composites Reinforced by Carbon Fibers is formed, and boundary layer wraps up the surface of carbon fiber in the composite.Fire-resistant oxidation resistant ZrB is made in carbon fiber surface in the present invention2Interface phase remains the original mechanical property of carbon fiber, improves carbon-fiber high-temperature inoxidizability.The technical issues of present invention solves Conventional silicon carbide ceramic matric composite preparation method long preparation period, and toughening phase carbon fiber and silicon carbide substrate interface compatibility and carbon fiber are easy to happen oxidation reaction under the use environment of high temperature oxidation stability in Cf/SiC composite material.

Description

One kind having ZrB2The preparation method of the Cf/SiC composite material at interface
Technical field
The present invention relates to Ceramic Matrix Composites Reinforced by Carbon Fibers technical fields, and in particular to one kind has ZrB2 The preparation method of the Cf/SiC composite material at interface.
Background technique
Ceramic Matrix Composites Reinforced by Carbon Fibers (Cf/SiC) has lightweight, high temperature resistant, high specific strength, Gao Bimo Amount, low thermal coefficient of expansion, base densities degree height, resistance to thermal shock, anti-ablation, the good and resistance to harsh environment of thermo-chemical stability are adaptable Etc. characteristics, be it is a kind of integrate structural bearing and resistance to oxidation/ablation novel light composite material, be widely applied to The fields such as aerospace, satellite, military project and nuclear industry.Carbon fiber has high-modulus, high intensity, low-density, low thermal expansion, resistance to height It is warm, anti-oxidant, without creep, the excellent performance such as high thermal conductivity, corrosion-resistant can be used as the reinforcement of composite material, these characteristics So that carbon fiber is used widely in the composite material that the materials such as ceramics, resin, metal, carbon are matrix.But carbon fiber It has just been aoxidized in 400 DEG C or more of air, antioxygenic property is poor, causes the performance of material to decline, and without table The carbon fiber surface activity of surface treatment is lower, and bad with the wellability of certain matrixes, binding ability is poor, also results in carbon fiber Enhance the reduced performance of carbon/silicon carbide ceramic matrix composite.Moreover, in the case where preparing composite temperature, carbon fiber is easy to It reacts with matrix, to damage fiber, seriously reduces the performance of Ceramic Matrix Composites Reinforced by Carbon Fibers.It is existing Technology is common by the antioxygenic property for coating antioxidant coating on the surface of basis material to enhance basis material and has The means of effect, but be difficult to play the work of effective high-temperature oxidation resistant protection in Cf/SiC composite material surface coating single coating, lead to The antioxidant coating system of normal Cf/SiC approach by thermal expansion coefficient and matrix and had the adhesive layer of good bonding effect, can be to painting Layer crackle carries out the active function layer of self-healing and can resist the Anti-erosion layer composition of air-flow erosion.
Carrying out surface covering to carbon fiber can be with the effective solution above problem.Coating can not only improve the antioxygen of carbon fiber Change performance, and it can prevent carbon fiber and matrix from interfacial reaction occurs as the barrier layer between carbon fiber and matrix, and Improve the interface compatibility problem of Fiber In Composite Material and matrix.In addition, a small amount of high-temperature oxidation resistant pottery is added in matrix On the one hand porcelain particle can play the role of particulate reinforcement, composite material high-temperature oxidation resistance on the other hand also can be improved.Zirconium boride (ZrB2) with high-melting-point, high rigidity, high-temperature stability, inoxidizability and with carbon fiber have good chemical compatibility, energy Preferably meet the requirement under hyperthermal environments, these advantages become a kind of high temperature resistant antioxygen with development potential Change coating.SiBNC with good high-temperature stability, inoxidizability and has good chemical compatibility with carbon fiber, lazy Property gas shield under when being lower than 1700 DEG C without thermal weight loss and split-phase, 2000 DEG C of Shi Caiyou crystalline transitions are SiC and Si3N4And it is a small amount of Amorphous BN, and the antioxygenic property at 1700 DEG C in air is much better than SiC and Si3N4, these advantages also become one The fire-resistant oxidation resistant material of kind with development potential, and suitable SiBNC particle is added in the base, increasing can also be played Tough effect improves the mechanical property of Ceramic Matrix Composites Reinforced by Carbon Fibers.
ZrB2Main preparation methods have metal and boron in inert gas or vacuum flux synthesis procedure, carbon reduction method, from Spread high-temperature synthesis, chemical vapor infiltration.The route of previous zirconium boride synthesis is mainly: will synthesize ZrB2Required powder Raw material are mixed in a certain ratio, and reaction generates ZrB at high temperature2, this method, which is not suitable for preparing in carbon fiber surface, to be applied Layer, and synthesis reaction temperature is high, impurity is high；CVD technique prepares ZrB2, find suitable ZrB2Precursor and presoma toxicity compared with Greatly, synthesis reaction temperature is high, and complex process needs special equipment, and is unsuitable for the uniform coating of multidimensional fiber surface；Using having Machine polymer cracking method, needs first to prepare precursor polymer, then Pintsch process goes out ZrB2, this method is complicated for operation, and It is unsuitable for preparing fine and close interface phase coating in fiber surface.2015,105331921 A of Chinese invention patent CN was disclosed A kind of spraying powder, thermal spraying in-situ synthesis of boride zirconium-zirconium carbide base ceramic coating and preparation method thereof, it be with include aluminium powder, Zirconium powder and boron carbide powder are raw material according to certain proportion, using in the compound painting of thermal spraying in-situ reactive synthesis zirconium boride Layer, the preparation method of zirconium boride composite coating relate generally to boride to the plating of the base materials such as metal, ceramics, are unsuitable for In the interface phase coating that fiber surface preparation is fine and close.And the present invention is used using polyvinyl alcohol, boric acid, inorganic zirconium salts as raw material Low temperature precursor solution infiltration pyrolysis method be suitable for variform carbon fiber surface coating, the preparation method is not only in carbon fiber The ZrB of uniformly continuous densification is prepared in dimension table face2Coating, and entire coating liquid preparation process, simple process, without special Equipment, energy saving, the prices of raw materials are cheap, and are easily obtained, easy to accomplish, formed after lower heat treatment temperature Coating not only improves the antioxygenic property of fiber and the interface problem of fiber and matrix, also overcomes drawbacks described above.Together When, the present invention uses high concentration ZrB2- SiBNC precursor solution impregnates fiber preform, obtains ZrB after Pintsch process2-SiBNC Blapharoplast can be evenly distributed on inside precast body, formed ZrB2The Quito-SiBNC hole fiber preform, prevents due to adopting It is easy to reunite in fiber preform powder inside with the sintering of direct powder synthetic reaction, it is unevenly distributed, impurity is more, and sintering temperature mistake Height causes a series of problems of damage, and the fiber preform of even porous to carbon fiber, is subsequent filling in situ silicon carbide Matrix, and the Ceramic Matrix Composites Reinforced by Carbon Fibers for obtaining fine and close high-temperature oxidation resistant creates condition.
The present invention provides a kind of with ZrB2The preparation method of the Cf/SiC composite material at interface, it is therefore an objective to solve Cf/SiC It is anti-to be easy to happen oxidation under the use environment of high temperature oxidation stability for reinforced phase carbon fiber and its composite material in composite material The technical issues of answering.
Summary of the invention
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, provide a kind of with ZrB2The Cf/SiC at interface The preparation method of composite material, it is therefore an objective to reinforced phase carbon fiber and its composite material in Cf/SiC composite material are solved, in height Under the use environment of warm oxidisability, the technical issues of being easy to happen oxidation reaction, to improve Cf/SiC composite material in high temperature Service performance under environment.
The present invention is achieved by the following technical solutions: one kind having high-temperature oxidation resistant ZrB2The Cf/SiC at interface is compound The preparation method of material, its technology path are that silicon carbide substrate is filled in fiber preform, form fibre reinforced carbonization Silicon ceramic matric composite, and high-temperature oxidation resistant ZrB2Boundary layer is wrapped in Ceramic Matrix Composites Reinforced by Carbon Fibers The surface of carbon fiber specifically specifically includes that carbon fiber surface is activated, carbon fiber surface high-temperature oxidation resistant ZrB2Interface phase Preparation, ZrB2The preparation of the Quito-SiBNC hole fiber preform, the preparation of fine and close silicon carbide substrate finally obtain fine and close tool There is the ZrB of high-temperature oxidation resistant2The Cf/SiC ceramic matric composite at interface.
The present invention the following steps are included:
(1) carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 30~40 minutes progress degumming process, it will be except the carbon after glue Fiber, which is placed in concentrated nitric acid, to be impregnated etching 60~100 minutes, carbon fiber surface Liquid Residue is then washed with deionized water, through drying Carbon fiber after obtaining surface activation process afterwards.
(2) precursor infiltration and pyrolysis method is used, by the carbon fiber ultrasonic immersing in above-mentioned (1) after drying in ZrB2Low concentration In precursor solution, ZrB is prepared in carbon fiber surface2Interface phase coating is obtained through precursor Pintsch process technique with ZrB2Boundary The carbon fiber precast body of face phase coating.
(3) SiBNC nano ceramic powder is dispersed in high concentration ZrB2In precursor solution, ZrB is prepared2-SiBNC Matrix precursor solution, the carbon fiber precast body ultrasonic immersing that above-mentioned (2) are obtained is in ZrB2- SiBNC matrix precursor solution In, ZrB of filling in situ2- SiBNC matrix obtains ZrB through precursor Pintsch process technique2The Quito-SiBNC hole fibre preforms Body.
(4) ZrB for obtaining above-mentioned (3)2The Quito-SiBNC hole fiber preform is impregnated in the divinyl of Polycarbosilane In benzene precursor solution, in the ZrB prepared2Filling in situ silicon carbide substrate in the fiber preform of the Quito-SiBNC hole, through more Secondary precursor infiltration and pyrolysis technique obtains fine and close having ZrB2The Cf/SiC composite material at interface.
In the present invention, carbon fiber surface ZrB described in above-mentioned steps (2)2Interface phase low concentration precursor solution Preparation step is as follows:
A) using polyvinyl alcohol, boric acid as solute, deionized water is solvent, prepares boric acid solution respectively and polyvinyl alcohol is molten Liquid.
B) inorganic zirconium salts are dissolved in deionized water and uniformly mixed, addition ammonium hydroxide adjusting pH value to 9.5, generation is stirred at room temperature White precipitate will be dissolved in nitric acid with the white precipitate after deionized water eccentric cleaning, is controlled solution ph less than 2, is obtained Zirconia sol.
C) ethyl alcohol is added in boric acid solution and is stirred at room temperature to it and is uniformly mixed, obtain boric acid alcohol solution.
D) by poly-vinyl alcohol solution be quickly poured into it is above-mentioned c) in and be stirred at room temperature to its be uniformly mixed.
E) it b) is added to above-mentioned in above-mentioned solution d), obtains the ZrB after being stirred at room temperature 2~3 hours2Interface phase Low concentration precursor solution.
Due to ZrB2Contain various ingredients in the preparation system of interface phase precursor solution, the hydrolysising condition of every kind of component is all Respectively different, so that the stability of solution is difficult to control, for example boric acid solution and poly-vinyl alcohol solution are in room temperature, low temperature and high temperature Under the conditions of mix immediately occur viscous flocculent deposit and with the evolution of a large amount of bubbles (boric anhydride of boric acid and generation in solution have compared with Big volatility), and the colloidal sol being added in coating solution how to be enable to be stabilized, how to prepare and is clarified uniformly in room temperature Stable ZrB2Precursor solution, so that it is not had flocculate, be a difficult thing.In the method for the invention, it changes Previous preparation ZrB2Main method: ZrB will be synthesized2Required powder raw material is mixed in a certain ratio, at high temperature reaction life At ZrB2, this method is not suitable in carbon fiber surface prepares coating, and synthesis reaction temperature is high, and impurity is high；CVD technique system Standby ZrB2, find suitable ZrB2Precursor and presoma is more toxic, synthesis reaction temperature is high, and complex process needs specially to set It is standby, and it is unsuitable for the uniform coating of multidimensional fiber surface；Using organic polymer cracking process, need first to prepare presoma polymerization Object, then Pintsch process go out ZrB2, this method is complicated for operation, and is unsuitable for preparing fine and close interface phase coating in fiber surface. Entire ZrB in the present invention2Appropriate modifier second is added in interface phase precursor solution preparation process at room temperature in boric acid group water solution Alcohol, cooperate various reagents addition sequence and content control, overcome boric acid solution mixed with poly-vinyl alcohol solution i.e. precipitate Problem can make at room temperature and clarify uniform and stable ZrB2Precursor solution, and in process for preparation ethyl alcohol be added boric acid It is required to directly be quickly poured into solution, when polyvinyl alcohol is added in boric acid alcohol solution, and in the past when preparing solution, it is added Mode is often slowly dropped in other solution, this process of the invention has not only been saved the time, also easy to operate, is not necessarily to Special equipment, whole preparation process simple process is energy saving, and pollution-free, the prices of raw materials are cheap, and are easily obtained, and is easy It realizes, and the present invention can prepare the coating of uniformly continuous densification in fiber surface.
Preferably, ZrB described in above-mentioned steps (2)2Interface phase low concentration precursor solution refers to poly- second Enol, boric acid, the ethyl alcohol group water solution that inorganic zirconium salts are raw material.
Preferably, ZrB described in above-mentioned steps (2)2Boric acid is molten in the phase low concentration precursor solution of interface Liquid concentration is 0.4~0.8mol/L.
Preferably, ZrB described in above-mentioned steps (2)2Polyvinyl alcohol in the phase low concentration precursor solution of interface Solution concentration is 0.8~1.2mol/L.
Preferably, ZrB described in above-mentioned steps (2)2Inorganic zirconium salts in the phase low concentration precursor solution of interface For ZrOCl2·8H2O、Zr(NO3)4·xH2O、ZrO(NO3)2·xH2O、ZrCl4、Zr(SO4)2One of aqueous inorganic salt, institute Zirconium ion concentration can be adjusted between 0.3~0.6mol/L by the way that the amount of deionized water is added in the zirconia sol stated.
Preferably, ZrB described in above-mentioned steps (2)2Ethyl alcohol and boron in the phase low concentration precursor solution of interface The volume ratio of acid solution is (1.2~2.8): 1.
Preferably, ZrB described in above-mentioned steps (2)2Polyvinyl alcohol in the phase low concentration precursor solution of interface, Boric acid, zirconium ion molar ratio be (3.5~3.7): (0.9~1.1): (0.20~0.43).
Preferably, carbon fiber surface ZrB described in above-mentioned steps (2)2Interface phase coating layer thickness be 120~ 1100nm。
Preferably, interface phase coating described in above-mentioned steps (2) refers to ZrB2Coating.
Preferably, carbon fiber described in above-mentioned steps (1) is that carbon fiber bundle, carbon cloth and three-dimensional carbon fiber are pre- One of body processed is a variety of.
Preferably, the particle size of SiBNC nano ceramic powder described in above-mentioned steps (3) be 40~ 80nm, the HfB2The volume content of SiBNC ceramic powders is 25~35% in-SiBNC matrix precursor solution, described High concentration refers to preparation ZrB2Boric acid solution concentration in precursor solution is 0.8~1.2mol/L, poly-vinyl alcohol solution concentration For 1.5~2.2mol/L, zirconium ion concentration is 0.6~1.2mol/L.
Preferably, above-mentioned steps (2) and carbon fiber surface ZrB described in (3)2Interface phase coating and ZrB2- The precursor Pintsch process technique of the Quito SiBNC hole fiber preform refer in tube furnace under nitrogen protection, with 2~3 DEG C/ The heating rate of min is heated to 300 DEG C and keeps the temperature 10~15 minutes, then is heated to 500 DEG C with the heating rate of 5 DEG C/min, heat preservation 30~60 minutes, then 800 DEG C are heated to the heating rate of 8~10 DEG C/min, 30~60 minutes are kept the temperature, then with 6~8 DEG C/min Heating rate be heated to 1200~1350 DEG C of Pintsch process temperature, keep the temperature 2~3 hours.
Preferably, in precursor solution described in above-mentioned steps (4) Polycarbosilane and divinylbenzene matter Amount is than being (0.6~0.65): 1.
Preferably, the dipping of silicon carbide precursor described in above-mentioned steps (4) refers to ultrasonic immersing or Vaccum Permeating One of stain dip time 2~3 hours, stands 18~24 hours in air later.
Preferably, silicon carbide substrate precursor synthesis method technique described in above-mentioned steps (4) refers in tube furnace Under interior nitrogen protection, 400 DEG C are heated to the heating rate of 9~11 DEG C/min, then heat with the heating rate of 4~5 DEG C/min 1200~1480 DEG C are heated to 800 DEG C, then with the heating rate of 9~10 DEG C/min, keeps the temperature 30~40 minutes.
Preferably, densification described in above-mentioned steps (4) refers to repeat the above steps (4), through multiple precursor Dipping-cracking technology, until Cf/SiC composite material rate of body weight gain less than 1%, Cf/SiC composite material density be 1.86~ 2.15g/cm3, open porosity is 6~13%.
The present invention is the low temperature precursor solution infiltration pyrolysis method of use using polyvinyl alcohol, boric acid, inorganic zirconium salts as raw material Suitable for the carbon fiber surface coating of variform, which has not only prepared uniformly continuous densification in carbon fiber surface ZrB2Coating, and entire coating liquid preparation process, simple process are not necessarily to special equipment, and energy saving, the prices of raw materials are just Preferably, it and is easily obtained, easy to accomplish, the coating formed after lower heat treatment temperature improves the inoxidizability of fiber The interface compatibility of energy and fiber and matrix.Meanwhile the present invention uses high concentration ZrB2- SiBCN precursor solution dipping is fine Precast body is tieed up, obtains ZrB after Pintsch process2The blapharoplast of-SiBCN can be evenly distributed on inside precast body, form ZrB2- The Quito SiBCN hole fiber preform is prevented easy in fiber preform powder inside due to being sintered using direct powder synthetic reaction Reunite, be unevenly distributed, impurity is more, and sintering temperature excessively high a series of problems, such as causing damage to carbon fiber, and even porous Fiber preform, not only effectively shorten the manufacturing cycle of ceramic porous precast body, it is also silicon carbide-based for subsequent filling in situ Body, and obtain the fine and close ZrB with high-temperature oxidation resistant2The Ceramic Matrix Composites Reinforced by Carbon Fibers of interface phase is created Condition.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention prepares ZrB using polyvinyl alcohol, boric acid, inorganic zirconium salts as raw material2Interface phase low concentration precursor is molten Liquid, the prices of raw materials are cheap, are easily obtained, easy to accomplish, and preparation process is simple, saving power and preventing pollution dye, no especial equipment requirements, Strong operability is suitble to industrialized production.
(2) in the present invention, carbon fiber surface ZrB2Interface phase coating uniform is completely fine and close, non-microcracked, obtained boundary Face phase coating can improve the interface compatibility between fiber and Cf/SiC matrices of composite material, and carbon fiber carries out silicon carbide ceramics It is toughened and reinforced, effectively increase the intensity and structural stability of Cf/SiC composite material.
(3) in the present invention, carbon fiber surface ZrB2Mutually the coating is uniform and compact at interface, and high-temperature oxidation resistance is excellent, to carbon Fibre damage is small, interface phase ZrB2Reinforced phase carbon fiber is tightly wrapped up, carbon fiber is effectively prevented from and occurs under high temperature environment Oxidation reaction, to improve the high-temperature oxidation resistance of Cf/SiC composite material.
(4) in the present invention, ZrB2The fiber preform internal particle of-SiBNC base even porous is evenly distributed, impurity is few, The manufacturing cycle for not only effectively shortening ceramic porous precast body has played the effect of particulate reinforcement, is also subsequent filling in situ Silicon carbide substrate, and obtain fine and close Ceramic Matrix Composites Reinforced by Carbon Fibers and create condition.
(5) in the present invention, preparation has ZrB2The Cf/SiC composite material at interface, stretch modulus be 77~ 91GPa, tensile strength are 163~185MPa, bending modulus is 81~96GPa, bending strength is 292~307MPa；With comparison It is the stretch modulus 63GPa of the Cf/SiC composite material without interface, tensile strength 136MPa, bending modulus 57GPa in example, curved Qu Qiangdu 205MPa is compared, and achieves the technical effect for significantly improving the mechanical property of Cf/SiC composite material.
Detailed description of the invention
Fig. 1 is the carbon fiber scanning electron microscope (SEM) photograph of non-coating.
Fig. 2 is carbon fiber surface high-temperature oxidation resistant ZrB2The scanning electron microscope (SEM) photograph of interface phase coating.
The Fracture scan electron microscope of Cf/SiC composite material prepared by Fig. 3 embodiment 1.
Specific embodiment
To be more clear the objectives, technical solutions, and advantages of the present invention, the present invention is made below by specific embodiment It further illustrates.
Embodiment 1
One kind having ZrB2The preparation method of the Cf/SiC composite material at interface, it the following steps are included:
Carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 30 minutes progress degumming process, will be set except the carbon fiber after glue It is impregnated in concentrated nitric acid etching 60 minutes, is then washed with deionized water carbon fiber surface Liquid Residue, obtains surface after drying Carbon fiber after activation processing；By the carbon fiber precast body ultrasonic immersing of above-mentioned drying in ZrB2Interface phase low concentration precursor is molten 28 minutes in liquid, it is put into baking oven after the carbon fiber after coating is stood 12 hours at room temperature and keeps the temperature 60 minutes in 60 DEG C, so It is placed in tube furnace again afterwards, is heated to 300 DEG C under nitrogen protection with the heating rate of 3 DEG C/min and keeps the temperature 10 minutes, then with 5 DEG C/heating rate of min is heated to 500 DEG C, 40 minutes are kept the temperature, then be heated to 800 DEG C with the heating rate of 8 DEG C/min, heat preservation 30 minutes, then 1200 DEG C of Pintsch process temperature are heated to the heating rate of 6 DEG C/min, 3 hours are kept the temperature, is coated with ZrB2The thickness of the carbon fiber precast body of interface phase, interface phase coating is about 320nm；The SiBNC that volume content is 30% is received Rice ceramic powders are uniformly dispersed in high concentration ZrB by magnetic agitation2In precursor solution, then above-mentioned precast body is impregnated 2 hours in precursor solution, takes out after standing 20 hours, be placed in tube furnace, under nitrogen protection with the liter of 3 DEG C/min Warm speed is heated to 300 DEG C and keeps the temperature 12 minutes, then is heated to 500 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 40 minutes, then with The heating rate of 10 DEG C/min is heated to 800 DEG C, keeps the temperature 60 minutes, then be heated to high anneal crack with the heating rate of 8 DEG C/min 1300 DEG C of temperature of solution keeps the temperature 3 hours, obtains ZrB2The Quito-SiBNC hole fiber preform；Polycarbosilane is dissolved in divinyl In base benzole soln, the mass ratio of Polycarbosilane and divinylbenzene is 0.65:1, by ZrB2- SiBNC base porous preform ultrasound Be impregnated in precursor solution 3 hours, take out stand 20 hours after, be placed in tube furnace, under nitrogen protection with 11 DEG C/ The heating rate of min is heated to 400 DEG C, then is heated to 800 DEG C with the heating rate of 5 DEG C/min, then with the heating speed of 9 DEG C/min Degree is heated to 1250 DEG C, keeps the temperature 40 minutes, after the above-mentioned polycarbosilane precusor solution of repetition impregnates-cracks 8 times, composite material Rate of body weight gain less than 1%, obtain with high-temperature oxidation resistant ZrB2The Cf/SiC composite material at interface, density 2.01g/cm3, Open porosity is 9%, and stretch modulus 87GPa, tensile strength 181MPa, bending modulus 90GPa, bending strength are 305MPa.Fig. 3 is the Fracture scan electron microscope of Cf/SiC composite material.
Comparative example 1
A kind of preparation method of Cf/SiC composite material, it the following steps are included:
Carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 30 minutes progress degumming process, will be set except the carbon fiber after glue It is impregnated in concentrated nitric acid etching 60 minutes, is then washed with deionized water carbon fiber surface Liquid Residue, obtains surface after drying Carbon fiber after activation processing；Polycarbosilane is dissolved in divinyl benzole soln, the matter of Polycarbosilane and divinylbenzene Amount is than being 0.65:1；By carbon fiber precast body ultrasonic immersing 3 hours in precursor solution, takes out after standing 20 hours, set In in tube furnace, 400 DEG C are heated to the heating rate of 11 DEG C/min under nitrogen protection, then with the heating rate of 5 DEG C/min 800 DEG C are heated to, then is heated to 1250 DEG C with the heating rate of 9 DEG C/min, keeps the temperature 40 minutes；Repeat above-mentioned dipping-cracking 11 After secondary, the rate of body weight gain of composite material obtains Cf/SiC composite material, density 1.75g/cm less than 1%3, open pores Rate is 17%.Its stretch modulus is 63GPa, tensile strength 136MPa, bending modulus 57GPa, bending strength 205MPa.
Embodiment 2
One kind having ZrB2The preparation method of the Cf/SiC composite material at interface, it the following steps are included:
Carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 40 minutes progress degumming process, will be set except the carbon fiber after glue It is impregnated in concentrated nitric acid etching 60 minutes, is then washed with deionized water carbon fiber surface Liquid Residue, obtains surface after drying Carbon fiber after activation processing；By the carbon fiber precast body ultrasonic immersing of above-mentioned drying in ZrB2Interface phase low concentration precursor is molten 40 minutes in liquid, it is put into baking oven after the carbon fiber after coating is stood 15 hours at room temperature and keeps the temperature 60 minutes in 60 DEG C, so It is placed in tube furnace again afterwards, is heated to 300 DEG C under nitrogen protection with the heating rate of 3 DEG C/min and keeps the temperature 15 minutes, then with 5 DEG C/heating rate of min is heated to 500 DEG C, 40 minutes are kept the temperature, then be heated to 800 DEG C with the heating rate of 9 DEG C/min, heat preservation 40 minutes, then 1350 DEG C of Pintsch process temperature are heated to the heating rate of 7 DEG C/min, 2 hours are kept the temperature, is coated with ZrB2The thickness of the carbon fiber precast body of interface phase, interface phase coating is about 470nm；The SiBNC that volume content is 35% is received Rice ceramic powders are uniformly dispersed in high concentration ZrB by magnetic agitation2In precursor solution, then above-mentioned precast body is impregnated 2 hours in precursor solution, takes out after standing 20 hours, be placed in tube furnace, under nitrogen protection with the liter of 3 DEG C/min Warm speed is heated to 300 DEG C and keeps the temperature 12 minutes, then is heated to 500 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 40 minutes, then with The heating rate of 10 DEG C/min is heated to 800 DEG C, keeps the temperature 60 minutes, then be heated to high anneal crack with the heating rate of 8 DEG C/min 1300 DEG C of temperature of solution keeps the temperature 3 hours, obtains ZrB2The Quito-SiBNC hole fiber preform；Polycarbosilane is dissolved in divinyl In base benzole soln, the mass ratio of Polycarbosilane and divinylbenzene is 0.63:1, by ZrB2- SiBNC base porous preform ultrasound Be impregnated in precursor solution 3 hours, take out stand 20 hours after, be placed in tube furnace, under nitrogen protection with 10 DEG C/ The heating rate of min is heated to 400 DEG C, then is heated to 800 DEG C with the heating rate of 4 DEG C/min, then with the heating speed of 9 DEG C/min Degree is heated to 1200 DEG C, keeps the temperature 40 minutes, after the above-mentioned polycarbosilane precusor solution of repetition impregnates-cracks 7 times, composite material Rate of body weight gain less than 1%, obtain with high-temperature oxidation resistant ZrB2The Cf/SiC composite material at interface, density 2.15g/cm3, Open porosity is 6%, and stretch modulus 91GPa, tensile strength 185MPa, bending modulus 96GPa, bending strength are 307MPa。
Embodiment 3
One kind having ZrB2The preparation method of the Cf/SiC composite material at interface, it the following steps are included:
Carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 30 minutes progress degumming process, will be set except the carbon fiber after glue It is impregnated in concentrated nitric acid etching 100 minutes, is then washed with deionized water carbon fiber surface Liquid Residue, obtains surface after drying Carbon fiber after activation processing；By the carbon fiber precast body ultrasonic immersing of above-mentioned drying in ZrB2Interface phase low concentration precursor is molten 10 minutes in liquid, it is put into baking oven after the carbon fiber after coating is stood 13 hours at room temperature and keeps the temperature 60 minutes in 60 DEG C, so It is placed in tube furnace again afterwards, is heated to 300 DEG C under nitrogen protection with the heating rate of 3 DEG C/min and keeps the temperature 15 minutes, then with 5 DEG C/heating rate of min is heated to 500 DEG C, 40 minutes are kept the temperature, then be heated to 800 DEG C with the heating rate of 10 DEG C/min, heat preservation 30 minutes, then 1300 DEG C of Pintsch process temperature are heated to the heating rate of 8 DEG C/min, 2 hours are kept the temperature, is coated with ZrB2The thickness of the carbon fiber precast body of interface phase, interface phase coating is about 120nm；The SiBNC that volume content is 25% is received Rice ceramic powders are uniformly dispersed in high concentration ZrB by magnetic agitation2In precursor solution, then above-mentioned precast body is impregnated 2 hours in precursor solution, takes out after standing 20 hours, be placed in tube furnace, under nitrogen protection with the liter of 3 DEG C/min Warm speed is heated to 300 DEG C and keeps the temperature 12 minutes, then is heated to 500 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 40 minutes, then with The heating rate of 10 DEG C/min is heated to 800 DEG C, keeps the temperature 60 minutes, then be heated to high anneal crack with the heating rate of 8 DEG C/min 1300 DEG C of temperature of solution keeps the temperature 3 hours, obtains ZrB2The Quito-SiBNC hole fiber preform；Polycarbosilane is dissolved in divinyl In base benzole soln, the mass ratio of Polycarbosilane and divinylbenzene is 0.60:1, by ZrB2- SiBNC base porous preform ultrasound Be impregnated in precursor solution 3 hours, take out stand 20 hours after, be placed in tube furnace, under nitrogen protection with 10 DEG C/ The heating rate of min is heated to 400 DEG C, then is heated to 800 DEG C with the heating rate of 5 DEG C/min, then with the heating speed of 9 DEG C/min Degree is heated to 1250 DEG C, keeps the temperature 35 minutes, after the above-mentioned polycarbosilane precusor solution of repetition impregnates-cracks 9 times, composite material Rate of body weight gain less than 1%, obtain with high-temperature oxidation resistant ZrB2The Cf/SiC composite material at interface, density 1.96g/cm3, Open porosity is 11%, and stretch modulus 79GPa, tensile strength 167MPa, bending modulus 83GPa, bending strength are 294MPa。
Embodiment 4
One kind having ZrB2The preparation method of the Cf/SiC composite material at interface, it the following steps are included:
Carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 40 minutes progress degumming process, will be set except the carbon fiber after glue It is impregnated in concentrated nitric acid etching 80 minutes, is then washed with deionized water carbon fiber surface Liquid Residue, obtains surface after drying Carbon fiber after activation processing；By the carbon fiber precast body ultrasonic immersing of above-mentioned drying in ZrB2Interface phase low concentration precursor is molten 100 minutes in liquid, it is put into baking oven after the carbon fiber after coating is stood 15 hours at room temperature and keeps the temperature 60 minutes in 60 DEG C, so It is placed in tube furnace again afterwards, is heated to 300 DEG C under nitrogen protection with the heating rate of 2 DEG C/min and keeps the temperature 15 minutes, then with 5 DEG C/heating rate of min is heated to 500 DEG C, 40 minutes are kept the temperature, then be heated to 800 DEG C with the heating rate of 8 DEG C/min, heat preservation 30 minutes, then 1350 DEG C of Pintsch process temperature are heated to the heating rate of 6 DEG C/min, 3 hours are kept the temperature, is coated with ZrB2The thickness of the carbon fiber precast body of interface phase, interface phase coating is about 1200nm；The SiBNC that volume content is 28% is received Rice ceramic powders are uniformly dispersed in high concentration ZrB by magnetic agitation2In precursor solution, then above-mentioned precast body is impregnated 2 hours in precursor solution, takes out after standing 20 hours, be placed in tube furnace, under nitrogen protection with the liter of 3 DEG C/min Warm speed is heated to 300 DEG C and keeps the temperature 12 minutes, then is heated to 500 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 40 minutes, then with The heating rate of 10 DEG C/min is heated to 800 DEG C, keeps the temperature 60 minutes, then be heated to high anneal crack with the heating rate of 8 DEG C/min 1350 DEG C of temperature of solution keeps the temperature 3 hours, obtains ZrB2The porous fibre precast body of-SiBNC base；Polycarbosilane is dissolved in diethyl In alkenyl benzole soln, the mass ratio of Polycarbosilane and divinylbenzene is 0.62:1, by ZrB2- SiBNC base porous preform is super Sound is impregnated in precursor solution 3 hours, take out stand 20 hours after, be placed in tube furnace, under nitrogen protection with 11 DEG C/ The heating rate of min is heated to 400 DEG C, then is heated to 800 DEG C with the heating rate of 5 DEG C/min, then with the heating speed of 9 DEG C/min Degree is heated to 1250 DEG C, keeps the temperature 40 minutes, after the above-mentioned polycarbosilane precusor solution of repetition impregnates-cracks 8 times, composite material Rate of body weight gain less than 1%, obtain high-temperature oxidation resistant ZrB2Boundary layer Cf/SiC composite material, density 2.07g/cm3, opening Porosity is 8%, and stretch modulus 79GPa, tensile strength 168MPa, bending modulus 84GPa, bending strength are 297MPa。

Claims (5)

1. one kind has ZrB2The preparation method of the Cf/SiC composite material at interface, the method are precursor solution infiltration pyrolysis Method, comprising: carbon fiber surface is activated, the preparation of interface phase, the preparation of porous fibre precast body, the system of silicon carbide substrate It is standby；It is characterized in that, silicon carbide substrate is filled in ZrB2In the fiber preform of the Quito-SiBNC hole, fibre reinforced carbonization is formed Silicon ceramic matric composite, and boundary layer is wrapped in the surface of carbon fiber in Ceramic Matrix Composites Reinforced by Carbon Fibers, Include the following steps:
(1) carbon fiber is placed in tube furnace at 450 DEG C and keeps the temperature 30~40 minutes progress degumming process, it will be except the carbon fiber after glue It is placed in concentrated nitric acid and impregnates etching 60~100 minutes, be then washed with deionized water carbon fiber surface Liquid Residue, after drying Carbon fiber after to surface activation process；
(2) precursor infiltration and pyrolysis method is used, by the carbon fiber ultrasonic immersing in above-mentioned (1) after drying in ZrB2Interface is mutually low dense It spends in precursor solution, prepares ZrB in carbon fiber surface2Interface phase coating is obtained through precursor Pintsch process technique with ZrB2 The carbon fiber precast body of interface phase coating；
(3) SiBNC nano ceramic powder is dispersed in high concentration ZrB2In precursor solution, ZrB is prepared2- SiBNC matrix Precursor solution, the carbon fiber precast body ultrasonic immersing that above-mentioned (2) are obtained is in ZrB2It is former in-SiBNC matrix precursor solution ZrB of position filling2- SiBNC matrix obtains ZrB through precursor Pintsch process technique2The Quito-SiBNC hole fiber preform；
(4) ZrB for obtaining above-mentioned (3)2The Quito-SiBNC hole fiber preform is impregnated in the divinylbenzene pioneer of Polycarbosilane In liquid solution, in the ZrB prepared2Filling in situ silicon carbide substrate in the fiber preform of the Quito-SiBNC hole, through multiple pioneer Body dipping-cracking technology obtains fine and close having ZrB2The Cf/SiC composite material at interface.
2. as described in claim 1 a kind of with ZrB2The preparation method of the Cf/SiC composite material at interface, which is characterized in that ZrB described in above-mentioned steps (2)2Interface phase low concentration precursor solution refers to that polyvinyl alcohol, boric acid, inorganic zirconium salts are raw material Ethyl alcohol group water solution；The low concentration refers to ZrB2Boric acid solution concentration in the phase precursor solution of interface is 0.4~ 0.8mol/L, poly-vinyl alcohol solution concentration are 0.8~1.2mol/L, and zirconium ion concentration is 0.3~0.6mol/L；The carbon fiber Dimension table face ZrB2Interface phase coating layer thickness is 120~1100nm.
3. as described in claim 1 a kind of with ZrB2The preparation method of the Cf/SiC composite material at interface, which is characterized in that The particle size of SiBNC nano ceramic powder described in above-mentioned steps (3) is 40~80nm；The ZrB2- SiBNC matrix The volume content of SiBNC nano ceramic powder is 25~35% in precursor solution；The high concentration refers to ZrB2Precursor Boric acid solution concentration in solution is 0.8~1.2mol/L, and poly-vinyl alcohol solution concentration is 1.5~2.2mol/L, and zirconium ion is dense Degree is 0.6~1.2mol/L.
4. as described in claim 1 a kind of with ZrB2The preparation method of the Cf/SiC composite material at interface, which is characterized in that Precursor Pintsch process technique described in above-mentioned steps (2) and (3) refers in tube furnace under nitrogen protection, with 2~3 DEG C/ The heating rate of min is heated to 300 DEG C and keeps the temperature 10~15 minutes, then is heated to 500 DEG C with the heating rate of 5 DEG C/min, heat preservation 30~60 minutes, then 800 DEG C are heated to the heating rate of 8~10 DEG C/min, 30~60 minutes are kept the temperature, then with 6~8 DEG C/min Heating rate be heated to 1200~1350 DEG C of Pintsch process temperature, keep the temperature 2~3 hours.
5. as described in claim 1 a kind of with ZrB2The preparation method of the Cf/SiC composite material at interface, which is characterized in that The mass ratio of Polycarbosilane and divinylbenzene is (0.6~0.65) in precursor solution described in above-mentioned steps (4): 1；Institute The dipping stated refers to one of ultrasonic immersing or vacuum impregnation, dip time 2~3 hours, stand 18 in air later~ 24 hours；The precursor synthesis method technique is referred to and is added in tube furnace under nitrogen protection with the heating rate of 9~11 DEG C/min Heat is heated to 800 DEG C to 400 DEG C, then with the heating rate of 4~5 DEG C/min, then is heated to the heating rate of 9~10 DEG C/min 1200~1480 DEG C, keep the temperature 30~40 minutes；The densification refers to repeat the above steps (4), impregnates-splits through multiple precursor Solution technique, until the rate of body weight gain of Cf/SiC composite material is 1.86~2.15g/ less than the density of 1%, Cf/SiC composite material cm3, open porosity is 6~13%.
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CN114478041A (en) * 2022-03-24 2022-05-13 湖南一众电子陶瓷科技有限公司 Preparation method of high-toughness alumina ceramic
CN115611649A (en) * 2022-08-11 2023-01-17 北京航空航天大学 Silicon carbide ceramic matrix composite material and preparation method and application thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478041A (en) * 2022-03-24 2022-05-13 湖南一众电子陶瓷科技有限公司 Preparation method of high-toughness alumina ceramic
CN115611649A (en) * 2022-08-11 2023-01-17 北京航空航天大学 Silicon carbide ceramic matrix composite material and preparation method and application thereof
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