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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- zrb
- carbon fiber
- interface
- preparation
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/62802—Powder coating materials
- C04B35/62828—Non-oxide ceramics
- C04B35/62839—Carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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—
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- 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
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- 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
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
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
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%.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910737155.6A CN110407598A (en) | 2019-08-11 | 2019-08-11 | One kind having ZrB2The preparation method of the Cf/SiC composite material at interface |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910737155.6A CN110407598A (en) | 2019-08-11 | 2019-08-11 | One kind having ZrB2The preparation method of the Cf/SiC composite material at interface |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110407598A true CN110407598A (en) | 2019-11-05 |
Family
ID=68366934
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910737155.6A Withdrawn CN110407598A (en) | 2019-08-11 | 2019-08-11 | One kind having ZrB2The preparation method of the Cf/SiC composite material at interface |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110407598A (en) |
Cited By (4)
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 |
CN116178007A (en) * | 2022-12-21 | 2023-05-30 | 中国建筑材料科学研究总院有限公司 | High-temperature-resistant composite material heat accumulating ring and preparation method and application thereof |
CN116639980A (en) * | 2023-05-22 | 2023-08-25 | 中南大学 | Preparation method of multi-carbide ceramic coating |
-
2019
- 2019-08-11 CN CN201910737155.6A patent/CN110407598A/en not_active Withdrawn
Cited By (6)
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 |
CN116178007A (en) * | 2022-12-21 | 2023-05-30 | 中国建筑材料科学研究总院有限公司 | High-temperature-resistant composite material heat accumulating ring and preparation method and application thereof |
CN116178007B (en) * | 2022-12-21 | 2024-02-02 | 中国建筑材料科学研究总院有限公司 | High-temperature-resistant composite material heat accumulating ring and preparation method and application thereof |
CN116639980A (en) * | 2023-05-22 | 2023-08-25 | 中南大学 | Preparation method of multi-carbide ceramic coating |
CN116639980B (en) * | 2023-05-22 | 2024-02-02 | 中南大学 | Preparation method of multi-carbide ceramic coating |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110407598A (en) | One kind having ZrB2The preparation method of the Cf/SiC composite material at interface | |
CN107353025B (en) | Preparation method of 1200-DEG C-resistant and oxidation-resistant ceramic matrix composite | |
CN110304932A (en) | One kind having HfB2The preparation method of the Cf/SiC composite material at interface | |
CN107540400A (en) | A kind of SiC with compound interfacef/ SiC ceramic based composites | |
CN109553430A (en) | A kind of SiC with compound interfacef/ SiC ceramic based composites and preparation method thereof | |
CN110256082B (en) | Method for preparing single crystal silicon carbide nanofiber/silicon carbide ceramic matrix composite material by reaction sintering | |
CN111996473B (en) | Variable-structure ultrahigh-temperature ceramic matrix composite and preparation method thereof | |
CN106045550B (en) | The preparation method of SiC-ZrC gradient modifying carbon/carbon composite materials | |
CN110357632B (en) | ZrC/SiC complex phase ceramic precursor and preparation method thereof | |
CN107326330B (en) | A kind of internal heat type integration evaporation boat with aluminum oxide porous textured buffer layers | |
CN112374917B (en) | High-temperature ceramic coating and preparation method thereof | |
CN110002890A (en) | A kind of Cf/ HfC-SiC ultra-temperature ceramic-based composite material and preparation method thereof | |
CN108484173B (en) | SiCf/SiC composite material and preparation method thereof | |
CN113880597B (en) | Preparation method of modified carbon fiber toughened alumina self-healing ceramic | |
CN114656275B (en) | SiC preparation by vacuum impregnation combined with reaction melt infiltration f Method for preparing/Si-Y-B-C composite material | |
CN109608217B (en) | SiC containing MAX phase interface layerfPreparation method of/SiC composite material | |
CN108774072B (en) | Rigid heat insulation tile and preparation method thereof | |
CN110318253A (en) | A kind of preparation method of carbon fiber surface modification anti-oxidation composite coating | |
CN104926343B (en) | Aluminum silicate fiber reinforced oxide ceramic containing interface phase and preparation method thereof | |
CN102924108B (en) | Method for preparing Y2Si2O7 whisker-toughened mullite composite coating | |
CN110330354A (en) | One kind containing HfZrB2The preparation method of the Cf/SiC composite material at interface | |
CN110451969A (en) | Carbon fiber-zirconium carbide composite material and preparation method | |
CN106083209B (en) | A kind of preparation method of micro-structured configuration interlayer interface Mullite/ yttrium silicate composite coatings | |
CN115894085B (en) | Composite ceramic coating material and preparation method and application thereof | |
CN113135740B (en) | Ceramic matrix composite material and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20191105 |