CN110423119A - A kind of preparation method of resistance to ablation C/SiC ceramic matric composite - Google Patents
A kind of preparation method of resistance to ablation C/SiC ceramic matric composite Download PDFInfo
- Publication number
- CN110423119A CN110423119A CN201910725957.5A CN201910725957A CN110423119A CN 110423119 A CN110423119 A CN 110423119A CN 201910725957 A CN201910725957 A CN 201910725957A CN 110423119 A CN110423119 A CN 110423119A
- Authority
- CN
- China
- Prior art keywords
- preparation
- composite
- sic
- dipping
- precast body
- 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.)
- Granted
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
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
-
- 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
-
- C04B35/806—
-
- 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
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/421—Boron
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B2235/5248—Carbon, e.g. graphite
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5252—Fibers having a specific pre-form
- C04B2235/5256—Two-dimensional, e.g. woven structures
-
- 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
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
-
- 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
-
- 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
- C04B2235/658—Atmosphere during thermal treatment
-
- 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
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9684—Oxidation resistance
Abstract
The present invention relates to a kind of preparation methods of the C/SiC of resistance to ablation ceramic matric composite.This method comprises the following steps: (1) providing porous C/C composite precast body；(2) precast body is prepared into C/SiC composite material；(3) polysilazane, boron powder and solvent are mixed, the mass percentage of polysilazane in the mixture is 30-40%, and the mass percentage of boron powder in the mixture is 10-30%, and mixture is stirred uniformly, SiBCN precursor solution is obtained；(4) dipping solidification cracking is carried out to the composite material using SiBCN precursor solution, obtains the C/SiC of resistance to ablation ceramic matric composite.It can obtain that consistency is high, ablating rate is low, the composite material of excellent combination property using this method.
Description
Technical field
The present invention relates to ceramic composite technical field more particularly to a kind of C/SiC of resistance to ablation ceramic matric composites
Preparation method.
Background technique
In recent years, high temperature resistant structure ceramics are increasingly subject to the attention of people due to excellent performance.Silicon carbide ceramics tool
There are high temperature resistant, anti-thermal shock, corrosion-resistant, antiscour, wear-resisting and good heat-conductive characteristic, is always high-temperature structural ceramics
Important candidate material.But SiC belongs to covalent bonded material, sintering temperature is high, is difficult to be sintered cause using conventional sintering method
It is close, it usually needs 2100 DEG C or more to be heated to, simultaneously because they when being sintered need that Al is added2O3、Y2O3Or the sintering such as MgO help
Agent leads to mechanical property and antioxygenic property decline under material at high temperature, and these materials can react in water vapor atmosphere,
So that its application is restricted.
There are Si-C in SiBCN structure, the covalent bonds such as Si-N, C-N, its high-temperature behavior ratio SiC is more preferable.Amorphous ceramic is
The preparation of high-compactness composite material may be implemented in a kind of special construction material of shortrange order longrange disorder, reduces the porosity,
The channel that oxygen enters under high temperature is greatly limited, the superhigh temperature performance of material is improved；And it can be under long-time high-temperature condition
Crystallization occurs, generates the SiC phase and BN phase with excellent high temperature resistance performance, then improves its superhigh temperature antioxygenic property and mechanics
Performance.Compared with SiC ceramic, amorphous Si BCN ceramics have the high rigidity of ceramic material, low-density, inoxidizability and resist compacted
The excellent structural behaviour such as become, it is more likely that be applied to the extreme conditions such as high temperature, high pressure, high frequency, also not even if above 1700 DEG C
It can crystallization and reduction quality.It also has very high hardness, the fat swollen coefficient of low-heat, high resistance and some photoluminescence performances.
Currently, domestic less to amorphous Si BCN ceramic research, compared with foreign countries, there is also there is a big difference.Amorphous state
The preparation of SiBCN ceramics is mainly based on polymer-derived method, mechanical alloying technique and hot pressing and sintering technique.Every kind of method has respectively
The characteristics of.Required temperature is low when being prepared using polymer-derived method, and can effectively avoid the harmful oxide sintering aid of addition leads to ceramics
Mechanical behavior under high temperature reduces；Precursor needed for can synthesizing in atomic level, obtains high-purity even tissue microstructure product.
But polymer-derived method also has its limitation.Such as generated time is long, low yield, process is complicated, and precursor is by air and moisture shadow
Sound is very big.The SiBCN material of polymer-derived method preparation at present is only applied on film, fiber and the lesser component of size, is limited
The preparation of SiBCN blocks of large material, thus it is also seldom to the report of its mechanical property.Mechanic Alloying Technology is still in just
Grade stage, various aspects are still not perfect, and to be walked there are also very long stretch.Hot pressed sintering although available ceramic of compact, but burn
It needs to carry out at high temperature when knot, and the time is long, the high requirements on the equipment, it is inefficient.Therefore, more efficient method is studied, is closed
Higher at yield, precursor more resistant to high temperature becomes the hot spot studied from now on.
In addition, amorphous ceramic is still in laboratory stage at present, primarily as block materials application, about continuous carbon fiber
The research that dimension impregnates polynary amorphous ceramic composite material is few.It is polynary amorphous that research process aspect, which needs the main problem solved,
The bond strength of phase and carbon fiber substrate.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of the C/SiC of resistance to ablation ceramic matric composite.
To achieve the goals above, the present invention provides the following technical scheme that
A kind of preparation method of resistance to ablation C/SiC ceramic matric composite, includes the following steps:
(1) porous C/C composite precast body is provided；
(2) precast body is prepared into C/SiC composite material；
(3) polysilazane, boron powder and solvent are mixed, the mass percentage of polysilazane in the mixture is 30-
40%, the mass percentage of boron powder in the mixture is 10-30%, stirs the mixture for uniformly, it is molten obtaining SiBCN presoma
Liquid；
(4) dipping solidification cracking is carried out to the composite material using SiBCN precursor solution, obtains the C/ of resistance to ablation
SiC ceramic based composites.
Preferably, the mass percentage of the boron powder is 20%.
Preferably, in step (3), the solvent be selected from chloroform, carbon tetrachloride, acetone, ethyl acetate, tetrahydrofuran,
Toluene, dimethylbenzene, dimethyl sulfoxide, chlorobenzene, dichloro-benzenes or trichloro-benzenes are any one or more of.
Preferably, providing density is 0.8~1.0g/cm3Porous C/C composite precast body.
Preferably, density is made in the precast body is 1.8~2.0g/cm3C/SiC composite material.
Preferably, in step (2), precursor dipping, solidification, cracking is carried out using Polycarbosilane solution, are prepared
C/SiC composite material；
If carrying out the primary dipping, solidification and cracking process is unable to reach density requirements, the dipping, solidification are repeated
With cracking process, until reach density requirements.
Preferably, in step (4), the dipping is vacuum impregnation, and vacuum degree is -0.1~-0.3MPa, and maceration extract does not have
Cross workpiece at least 10mm, 50~60min of dip time；
Solidified under 120-180 DEG C and air or inert atmosphere；And/or
It is cracked under 1400 DEG C or less and ammonia atmosphere.
Preferably, the dipping, the solidification and the cleavage step are repeated, the weight gain of material is made to be no more than 1%.
Preferably, carbon is deposited in the inside of carbon fiber precast body using chemical vapor infiltration, it is multiple obtains the porous C/C
Condensation material precast body.
Preferably, the carbon fiber precast body pierces lamination laminated cloth felt using needle, more preferably uses density for 0.4-
0.5g/cm3Needle pierce lamination laminated cloth felt
Beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
Using organic precursor as raw material dipping continuous carbon fibre knitted body, (preferably needle pierces lamination laminated cloth to the present invention
Felt), by constantly infiltration pyrolysis, realize the densification of composite material, selection polysilazane+boron powder is raw material.
The present invention impregnates superhigh temperature phase amorphous Si BCN by introducing continuous fiber knitted body, on continuous carbon fibre surface
Ceramics protect matrix, obtain the composite material with greater density while improving and weaving matrix superhigh temperature performance, can
To substantially improve its mechanical behavior under high temperature, to solve the brittleness problems with the polynary ceramics of non crystalline structure, its application is expanded
Range.
By showing to prepare boundary layer in carbon fiber, and by introducing B element while preparing SiC matrix, to establish
The chemical bonding of amorphous phase and matrix, to improve the bond strength of polynary amorphous phase and carbon fiber substrate.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation method of the C/SiC of resistance to ablation ceramic matric composite, which includes such as
Lower step:
(1) porous C/C composite precast body is provided, preferably density is 0.8~1.0g/cm3It (can be within the scope of this
Any number, for example, can be 0.8g/cm3、0.9g/cm3、1.0g/cm3) porous C/C composite precast body.
The present invention can use CVI density carbon fiber precast body, and carbon fiber precast body is placed in chemical vapor deposition stove, benefit
Chemical deposition is carried out to green body with CVI technique, carbon-source gas diffuses into carbon fiber precast body after cracking in low vacuum environment
It in hole, and is deposited on hole wall, obtains porous C/C composite precast body.Thickening technology can be using propylene as carbon-source gas, nitrogen
Gas is carrier gas, and depositing temperature can be 800~1100 DEG C, can be any number within the scope of this, for example, can for 800 DEG C,
850℃,900℃,950℃,1000℃,1050℃,1100℃.In this step, carbon fiber precast body used is preferably needle
Lamination laminated cloth felt is pierced, more preferably density is 0.4-0.5g/cm3Needle pierce lamination laminated cloth felt.
(2) precast body is prepared into C/SiC composite material, being preferably made density is 1.8~2.0g/cm3(can be
Any number within the scope of this, for example, can be 1.8g/cm3、1.9g/cm3、2.0g/cm3) C/SiC composite material.At this
In step, the present invention carries out precursor dipping, solidification, cracking using Polycarbosilane solution, and the C/SiC composite wood is prepared
Material.If carrying out the primary dipping, solidification and cracking process is unable to reach density requirements, need to repeat the dipping, solidification
With cracking process, until reach density requirements.Used Polycarbosilane solution includes Polycarbosilane and solvent, and the solvent can
To use chloroform, carbon tetrachloride, acetone, ethyl acetate, tetrahydrofuran, toluene, dimethylbenzene, dimethyl sulfoxide, chlorobenzene, dichloro-benzenes
Or trichloro-benzenes is any one or more of.The concentration of present invention Polycarbosilane solution used in the step can be 60-70%,
I.e. the mass percentage of Polycarbosilane in the solution is 60-70%, can be any number within the scope of this, for example, can be with
It is 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%.
For dipping, solidification and the cracking technology in the step, the prior art can be referred to, the present invention no longer carries out it
It is described in detail.
(3) polysilazane, boron powder and solvent are mixed, mixture is stirred uniformly, it is molten to obtain SiBCN presoma
Liquid.
The solute of SiBCN precursor solution is polysilazane, and wherein polysilazane can be dry with various polarity or nonpolarity
Solvent is diluted, but sensitive to water, alcohols solvent, and hydrolysis or alcoholysis reaction easily occurs, and keeps product rotten, so the step can
To use chloroform, carbon tetrachloride, acetone, ethyl acetate, tetrahydrofuran, toluene, dimethylbenzene, dimethyl sulfoxide, chlorobenzene, dichloro-benzenes
Or any one or more of solvent as precursor solution of trichloro-benzenes.In addition, polysilazane should also be avoided contact acid, alkali etc.
Proton type substance.The present invention preferably adjusts the mass percentage of the polysilazane in SiBCN precursor solution in 30-40%
Within the scope of this, can choose any number within the scope of this in operation, for example, can for 30%, 31%, 32%,
33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%.
The boron powder ratio being added in the SiBCN precursor solution is 10-30%, can choose the model in operation
Enclose interior any number, for example, can for 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%,
20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, most preferably 20%.Inventor exists
It is found in research process, when the boron powder excessive concentration in SiBCN precursor solution, boron powder is easily collected on material surface, drop
Low SiBCN precursor solution enters the channel of material internal, influences efficiency of densification, while also reducing the density of final material.
The concentration of boron powder is too low, extends material manufacturing cycle.Based on this discovery, the present invention is by the boron powder of SiBCN precursor solution
Mass percentage preferably adjust in 10-30% within the scope of this.
In the subsequent infiltration pyrolysis stage, SiBCN precursor solution preferably (can be within the scope of this at 120-180 DEG C
Any number, for example, can be 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165
DEG C, 170 DEG C, 175 DEG C, 180 DEG C) under the conditions of realize crosslinking curing, solidification may be selected to carry out under air or inert atmosphere.In addition to
Outside this curing method, hydrosilylation can also be carried out using platinum catalyst, it (can be within the scope of this at 80-100 DEG C
Any number, for example, can be 80 DEG C, 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C) under the conditions of realize solidification, curing time view solidification temperature
Depending on degree and catalyst amount, generally 2-5h can be any number within the scope of this, for example, can for 2h, 3h, 4h,
5h。
Solidfied material is first converted into amorphous ceramics through Pintsch process, and finally obtains crystalline ceramics.1400 DEG C the following are
Amorphous products, 1400 DEG C or more start to crystallize.Ceramic product composition and cracking atmosphere have substantial connection, nitrogen or argon gas situation
It is down SiC and SiBCN；It is mainly SiBCN under ammonia atmosphere；It is mainly SiOCN under air conditions.Based on this, the present invention is at this
Cracking condition in the cracking process of step is 1400 DEG C or less and carries out under ammonia atmosphere.
(4) dipping solidification cracking is carried out to the composite material using SiBCN precursor solution, obtains the C/ of resistance to ablation
SiC ceramic based composites.
The dipping is vacuum impregnation, and vacuum degree is -0.1~-0.3MPa, and maceration extract did not had workpiece at least 10mm, is impregnated
50~60min of time.
As it was noted above, it is preferred that realizing crosslinking curing under the conditions of 120-180 DEG C, solidification may be selected in air condition of cure
Or it is carried out under inert atmosphere.Other than this curing method, hydrosilylation can also be carried out using platinum catalyst, in 80-
Under the conditions of 100 DEG C realize solidification, curing time depending on solidification temperature and catalyst amount, generally 2-5h.
Cracking condition is preferably 1400 DEG C or less and carries out under ammonia atmosphere.
In this step, the dipping, the solidification and the cleavage step are repeated, the weight gain of material is made to be no more than 1%.
It is the embodiment that the present invention enumerates below.
Embodiment 1
(1) chemical deposition is carried out to green body using CVI technique, obtains porous C/C composite precast body, deposition to density
For 0.8g/cm3, for thickening technology using propylene as carbon-source gas, nitrogen is carrier gas, and depositing temperature is 900 DEG C.
(2) precursor dipping, solidification, cracking are carried out using Polycarbosilane solution, C/SiC composite material is prepared, into
The more round infiltration pyrolysis of row, it is 1.8g/cm that density, which is prepared,3C/SiC composite material.
(3) using chloroform as solvent, polysilazane is added and boron powder, accounting of the polysilazane in mixed solution are
35wt%, accounting of the boron powder in mixed solution are 20wt%.It stirs evenly, obtains SiBCN precursor solution.
(4) precursor solution obtained above is utilized, dipping solidification is carried out to C/SiC composite material made from step (2)
Cracking.Dipping is vacuum impregnation, and vacuum degree is -0.1MPa, and maceration extract did not had workpiece at least 10mm, dip time 50min.Solidification
It is carried out under the conditions of 140 DEG C, under inert atmosphere, curing time 3h.Cracking carries out under 1300 DEG C, ammonia atmosphere, is cracked into
Amorphous products.Repeated impregnations crack process, until composite material increases weight less than 1%.
(5) gained exemplar is processed into test bars, carries out the test of performance.
Embodiment 2 to 4
It is substantially the same that the preparation method is the same as that of Example 1, the difference is that:
For embodiment 2, in step (2), more round infiltration pyrolysis are carried out, it is 1.9g/cm that density, which is prepared,3Pottery
Porcelain based composites.
For embodiment 3, in step (2), more round infiltration pyrolysis are carried out, it is 2.0g/cm that density, which is prepared,3Pottery
Porcelain based composites.
For embodiment 4, in step (2), more round infiltration pyrolysis are carried out, it is 2.5g/cm that density, which is prepared,3Pottery
Porcelain based composites.
The testing result of test bars is as shown in table 1.
Table 1
The test result of comparative example 1 to 4, inventors have found that with the increase of C/SiC composite density, finally
The mechanical property of composite material is also become better and better.Inventor speculates this is because relatively compact C/SiC composite material can be very
Fiber and boundary layer are protected well, to enhance mechanical property.When C/SiC composite density is excessive, theoretically composite material
Mechanical property can be more preferable.But inventors have found that this, which is equivalent to, leads to final material when C/SiC composite density is excessive
In SiBCN amorphous ceramic ratio accounting it is lower, cause the chemical bonding degree of amorphous phase and matrix to die down, so that finally
The mechanical property of material will appear the degree of decline instead.In addition, inventor also found, with C/SiC composite density
Increase, the ablation resistance of final material also enhances therewith, this shows that the compactness of C/SiC composite material plays a crucial role, i.e.,
Keep the SiBCN amorphous ceramic accounting in final material at this time lower and lower, but the ablation resistance of material is influenced less, it is fine and close
The preferable matrix of property still ensures that the ablation resistance of material.But when C/SiC composite density is excessive, due to final material
In SiBCN amorphous ceramic ratio accounting it is too low, along with mechanical property it is also bad, will affect its long-time high temperature antioxygen instead
Change effect.Based on this, the present invention is during the preparation process preferably by SiC matrix density domination in 1.8~2.0g/cm3.Embodiment 5
To embodiment 7
It is substantially the same that the preparation method is the same as that of Example 1, the difference is that:
For embodiment 5, in step (2), the boron powder ratio being added into solution is 20%.
For embodiment 6, in step (2), the boron powder ratio being added into solution is 30%.
For embodiment 7, in step (2), the boron powder ratio being added into solution is 40%.
The testing result of test bars is as shown in table 2.
Table 2
From Table 2, it can be seen that material has the resistance to temperature area of opposite wide area, resistance to ablation with the increase of boron powder ratio
Performance is become better and better, and mechanical property is also become better and better.This is because with the increase of boron powder, the chemical bonding of amorphous phase and matrix
Intensity is become better and better, to be integrally improved the mechanical property of material.Again because amorphous phase accounting after Pintsch process compared with
Greatly, boron nitride oxidation resistance temperature also has good lubricity up to 900 DEG C at high temperature, is a kind of excellent high-temp solid
Lubricant, chemical property are stablized, and are all in chemical inertness to almost all of molten metal, and energy high temperature resistant is to 2000 DEG C, to mention
The high ablation resistance of material.But when the adding too much of boron powder, the mechanical property of final material reduces instead.This be because
It is easily collected on material surface for boron powder at this time, the channel that SiBCN precursor solution enters material internal is reduced, influences to densify
Efficiency and effect, so as to cause the mechanical properties decrease of material.When boron powder additive amount is excessive, the ablation resistance of final material
Do not significantly improve.Inventor speculates, since the densification degree of material is affected, under the density of final material occurs
Drop, to affect the ablation resistance of material to a certain extent, even if amorphous phase accounting is slightly higher than before at this time, can not yet
Significantly improve its ablation resistance.
Inventor also found, when settled density and identical SiC matrix density, with the infiltration pyrolysis of SiBCN solution, most
The resistance to ablation of the high composite material of whole density (referring to the density for solidifying material after cracking using SiBCN precursor solution repeated impregnations)
Ability enhancing, this is it can be appreciated that dipping is secondary this is because the amorphous phase ceramics generated under high temperature have very strong resistance to ablation horizontal
Number is more, and the amount that it is generated is bigger.When temperature is low is higher than 1600 DEG C, SiC matrix plays protective effect to fiber, under high temperature
The SiO of generation2With certain viscosity, the gap of material surface has been filled up.When temperature is more than 2000 DEG C, the amorphous phase of generation
Play superhigh temperature antioxidation.
But this does not represent the density of final material, and the higher the better, other than application environment requires " lightweight ", dipping
The problem of amorphous phase that number is excessively also easy to appear in material is unevenly distributed, finished product control are bad.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of preparation method of the C/SiC of resistance to ablation ceramic matric composite, which comprises the steps of:
(1) porous C/C composite precast body is provided；
(2) precast body is prepared into C/SiC composite material；
(3) polysilazane, boron powder and solvent are mixed, the mass percentage of polysilazane in the mixture is 30-40%, boron
The mass percentage of powder in the mixture is 10-30%, stirs the mixture for uniformly, obtaining SiBCN precursor solution；
(4) dipping solidification cracking is carried out to the composite material using SiBCN precursor solution, obtains the C/SiC of resistance to ablation
Ceramic matric composite.
2. preparation method according to claim 1, which is characterized in that
The mass percentage of the boron powder is 20%.
3. preparation method according to claim 1, which is characterized in that
In step (3), the solvent be selected from chloroform, carbon tetrachloride, acetone, ethyl acetate, tetrahydrofuran, toluene, dimethylbenzene,
Dimethyl sulfoxide, chlorobenzene, dichloro-benzenes or trichloro-benzenes are any one or more of.
4. preparation method according to claim 1, which is characterized in that
Offer density is 0.8~1.0g/cm3Porous C/C composite precast body.
5. preparation method according to claim 1, which is characterized in that it is 1.8~2.0g/ that density, which is made, in the precast body
cm3C/SiC composite material.
6. preparation method according to any one of claims 1 to 5, which is characterized in that
In step (2), precursor dipping, solidification, cracking are carried out using Polycarbosilane solution, C/SiC composite wood is prepared
Material；
If carrying out the primary dipping, solidification and cracking process is unable to reach density requirements,
The dipping, solidification and cracking process are then repeated, until reaching density requirements.
7. preparation method according to any one of claims 1 to 6, which is characterized in that
In step (4), the dipping is vacuum impregnation, and vacuum degree is -0.1~-0.3MPa, and maceration extract did not had workpiece at least
10mm, 50~60min of dip time；
Solidified under 120-180 DEG C and air or inert atmosphere；And/or
It is cracked under 1400 DEG C or less and ammonia atmosphere.
8. preparation method according to claim 7, which is characterized in that
The dipping, the solidification and the cleavage step are repeated, the weight gain of material is made to be no more than 1%.
9. preparation method according to any one of claims 1 to 8, which is characterized in that
Carbon is deposited in the inside of carbon fiber precast body using chemical vapor infiltration, it is prefabricated to obtain the porous C/C composite
Body.
10. preparation method according to any one of claims 1 to 9, which is characterized in that
The carbon fiber precast body pierces lamination laminated cloth felt using needle, more preferably uses density for 0.4-0.5g/cm3Needle thorn
Lamination laminated cloth felt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910725957.5A CN110423119B (en) | 2019-08-07 | 2019-08-07 | Preparation method of ablation-resistant C/SiC ceramic matrix composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910725957.5A CN110423119B (en) | 2019-08-07 | 2019-08-07 | Preparation method of ablation-resistant C/SiC ceramic matrix composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110423119A true CN110423119A (en) | 2019-11-08 |
| CN110423119B CN110423119B (en) | 2020-09-01 |
Family
ID=68414625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910725957.5A Active CN110423119B (en) | 2019-08-07 | 2019-08-07 | Preparation method of ablation-resistant C/SiC ceramic matrix composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110423119B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157671A (en) * | 2020-01-17 | 2020-05-15 | 南京航空航天大学 | Method for simulating ablation morphology of ceramic matrix composite material in high-temperature gas environment |
| CN111704467A (en) * | 2020-05-20 | 2020-09-25 | 深圳市科思飞科技有限公司 | Organic ceramic precursor and ceramic product |
| CN111848219A (en) * | 2020-07-13 | 2020-10-30 | 航天特种材料及工艺技术研究所 | Method for improving performance of ceramic-based composite material prepared by RMI process and prepared ceramic-based composite material |
| CN111943726A (en) * | 2020-08-11 | 2020-11-17 | 航天特种材料及工艺技术研究所 | High-performance C/SiBCN composite material and preparation method and application thereof |
| CN112299865A (en) * | 2020-11-19 | 2021-02-02 | 航天特种材料及工艺技术研究所 | Modified C/SiC composite material and preparation method thereof |
| CN113735590A (en) * | 2021-09-29 | 2021-12-03 | 北京理工大学 | Preparation method and product of high-temperature-resistant electromagnetic wave-absorbing ceramic matrix composite material |
| CN113979784A (en) * | 2020-11-23 | 2022-01-28 | 航天特种材料及工艺技术研究所 | High-density ceramic matrix composite and preparation method thereof |
| CN115180983A (en) * | 2022-08-01 | 2022-10-14 | 航天特种材料及工艺技术研究所 | High-entropy ceramic modification method of ceramic matrix composite and high-entropy modified composite prepared by same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101215154A (en) * | 2008-01-18 | 2008-07-09 | 天津大学 | Carbon content controllable silicon-containing ceramic and preparing method thereof |
| US20090130446A1 (en) * | 2007-07-17 | 2009-05-21 | Schmidt Wayde R | High temperature refractory coatings for ceramic substrates |
| US20090264273A1 (en) * | 2005-01-24 | 2009-10-22 | Riedell James A | Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component |
| CN103102179A (en) * | 2013-01-06 | 2013-05-15 | 西北工业大学 | Method for preventing carbon/carbon-base or ceramic-base composite fastener from loosening |
| CN107935614A (en) * | 2017-11-30 | 2018-04-20 | 北京天宜上佳新材料股份有限公司 | Carbon ceramic composite material and preparation method thereof |
| CN110041089A (en) * | 2019-04-16 | 2019-07-23 | 西安航空制动科技有限公司 | A kind of carbon/ceramic friction material and preparation method thereof |
-
2019
- 2019-08-07 CN CN201910725957.5A patent/CN110423119B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090264273A1 (en) * | 2005-01-24 | 2009-10-22 | Riedell James A | Ceramic material suitable for repair of a space vehicle component in a microgravity and vacuum environment, method of making same, and method of repairing a space vehicle component |
| US20090130446A1 (en) * | 2007-07-17 | 2009-05-21 | Schmidt Wayde R | High temperature refractory coatings for ceramic substrates |
| CN101215154A (en) * | 2008-01-18 | 2008-07-09 | 天津大学 | Carbon content controllable silicon-containing ceramic and preparing method thereof |
| CN103102179A (en) * | 2013-01-06 | 2013-05-15 | 西北工业大学 | Method for preventing carbon/carbon-base or ceramic-base composite fastener from loosening |
| CN107935614A (en) * | 2017-11-30 | 2018-04-20 | 北京天宜上佳新材料股份有限公司 | Carbon ceramic composite material and preparation method thereof |
| CN110041089A (en) * | 2019-04-16 | 2019-07-23 | 西安航空制动科技有限公司 | A kind of carbon/ceramic friction material and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111157671A (en) * | 2020-01-17 | 2020-05-15 | 南京航空航天大学 | Method for simulating ablation morphology of ceramic matrix composite material in high-temperature gas environment |
| CN111704467A (en) * | 2020-05-20 | 2020-09-25 | 深圳市科思飞科技有限公司 | Organic ceramic precursor and ceramic product |
| CN111704467B (en) * | 2020-05-20 | 2022-04-29 | 深圳市科思飞科技有限公司 | Organic ceramic precursor and ceramic product |
| CN111848219A (en) * | 2020-07-13 | 2020-10-30 | 航天特种材料及工艺技术研究所 | Method for improving performance of ceramic-based composite material prepared by RMI process and prepared ceramic-based composite material |
| CN111943726A (en) * | 2020-08-11 | 2020-11-17 | 航天特种材料及工艺技术研究所 | High-performance C/SiBCN composite material and preparation method and application thereof |
| CN111943726B (en) * | 2020-08-11 | 2022-10-04 | 航天特种材料及工艺技术研究所 | High-performance C/SiBCN composite material and preparation method and application thereof |
| CN112299865A (en) * | 2020-11-19 | 2021-02-02 | 航天特种材料及工艺技术研究所 | Modified C/SiC composite material and preparation method thereof |
| CN113979784A (en) * | 2020-11-23 | 2022-01-28 | 航天特种材料及工艺技术研究所 | High-density ceramic matrix composite and preparation method thereof |
| CN113735590A (en) * | 2021-09-29 | 2021-12-03 | 北京理工大学 | Preparation method and product of high-temperature-resistant electromagnetic wave-absorbing ceramic matrix composite material |
| CN115180983A (en) * | 2022-08-01 | 2022-10-14 | 航天特种材料及工艺技术研究所 | High-entropy ceramic modification method of ceramic matrix composite and high-entropy modified composite prepared by same |
| CN115180983B (en) * | 2022-08-01 | 2023-03-10 | 航天特种材料及工艺技术研究所 | High-entropy ceramic modification method of ceramic matrix composite and high-entropy modified composite prepared by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110423119B (en) | 2020-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110423119A (en) | A kind of preparation method of resistance to ablation C/SiC ceramic matric composite | |
| CN100355700C (en) | Method for preparing silicon carbide fiber reinforced silicon carbide composite material | |
| CN105541334B (en) | Silicon carbide-based composite foamed ceramic of perforated muscle structure and preparation method thereof | |
| CN110256082B (en) | Method for preparing single crystal silicon carbide nanofiber/silicon carbide ceramic matrix composite material by reaction sintering | |
| JP4647370B2 (en) | Fiber-reinforced silicon carbide composite material and method for producing the same | |
| CN103708846B (en) | Preparation method of C/C-SiC composite material | |
| CN101863665A (en) | Method for preparing self-healing anti-oxidation functional fiber reinforced ceramic matrix composite material | |
| CN107556011A (en) | SiCf/ SiC ceramic matrix composite material and preparation method thereof | |
| CN110627514A (en) | C/SiC-HfB2Composite material and preparation method thereof | |
| CN108191447A (en) | A kind of preparation method of the anti-oxidant C/C-ZrC of resistance to ablation carbon ceramic composite material | |
| CN104030715A (en) | Preparation method of Cf/BN-SiC composite material | |
| CN110002890A (en) | A kind of Cf/ HfC-SiC ultra-temperature ceramic-based composite material and preparation method thereof | |
| CN110668839A (en) | Low-cost high-strength carbon fiber reinforced silicon carbide composite material and preparation method thereof | |
| CN114621020B (en) | Carbon-ceramic composite structure and preparation method thereof | |
| CN108129156A (en) | A kind of carbon ceramic composite material and its precursor impregnation preparation method | |
| CN114573357A (en) | SiC nanowire reinforced SiC ceramic matrix composite and preparation method thereof | |
| CN112299865A (en) | Modified C/SiC composite material and preparation method thereof | |
| CN108083832A (en) | A kind of high efficiency, low cost near clean shaping preparation method of C/C-HfC composite materials | |
| CN115677370A (en) | Preparation method of carbon-ceramic brake material | |
| CN108752038A (en) | It is a kind of with can be thermally cured Polycarbosilane preparation foam silicon carbide ceramics | |
| CN112374901B (en) | Ablation-resistant modified C/SiC composite material and preparation method thereof | |
| JP4641845B2 (en) | Coated porous structure and method for producing coated porous structure | |
| CN108191460A (en) | The method for preparing C/SiC composite materials | |
| CN108395256B (en) | A kind of preparation method of dense form richness carbon PRECURSOR-DERIVED CERAMICS | |
| CN110451969A (en) | Carbon fiber-zirconium carbide composite material and preparation method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |