CN105859318B - Staple fiber-SiC nano fiber enhancing carborundum porous ceramics material and preparation method thereof - Google Patents
Staple fiber-SiC nano fiber enhancing carborundum porous ceramics material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the preparation methods that staple fiber SiC nano fiber enhances carborundum porous ceramics material, enhance skeleton using chopped carbon fiber as three-dimensional, using activated carbon and phenolic resin as carbon source, it is heated to silicon fusing point or more in argon gas atmosphere and is reacted with silica flour.The present invention carries out porous silicon carbide ceramic using carbon fiber carbon SiClx nanofiber toughened and reinforced so that porous ceramics has higher bending strength, while also having certain fracture toughness.
Description
Technical field
The present invention relates to technology field of ceramic matrix composite material, especially staple fiber-SiC nano fiber enhancing carbonizations
Silicon porous ceramic film material and preparation method thereof.
Background technology
Porous ceramics is used as melting due to having many advantages, such as thermal shock resistance, chemical stability and anti-metal erosion
The filter of metal.Simultaneously due also to its, heat resistance low with the pressure loss, thermal shock resistance and oil smoke collecting efficiency height etc.
Characteristic makes it be widely used in a variety of applications in terms of Diesel soot collects filtering；In addition, not due to its surface usually bumps
Flat, there are a large amount of micropores, and when as catalyst carrier, this special microstructure significantly increases two phase-contact surfaces
It accumulates, while the time that higher thermal conductivity can make catalyst reach activation temperature needed for reaction greatly shortens.Therefore, silicon carbide is more
Hole ceramics also have broad prospects as catalyst carrier；On the other hand porosity, the aperture parameters due to porous ceramic film material
It can adjust as needed, or even obtain interconnected pore structure, this makes it become ideal skeletal tissue's substitute.
Currently, traditional porous ceramics preparation process mainly has addition pore creating material, foam impregnation, foaming and molten
Sol-gel.It from complex technical process and prepares for the aspect of performance of product, that there is gas cell distributions is equal for these methods
Even property is poor, and porosity is low, and article shape is restricted, and ingredient and density are not easy to control, simultaneously for ingredient requirement height, productivity
It is low, the shortcomings of processing performance is poor.Therefore, some special preparation methods are suggested, and mainly have cracking process, solid phase reaction sintering process
And gas phase reaction infiltration method etc..Wherein containing silicone resin cracking process refers to that high-molecular gel is made in organosilane precursor, abjection
The containing silicone resin that foam-like is obtained after organic solvent in gel is cracked to obtain the carbonization of foam-like after fully pre-oxidizing
Silicon ceramics；Solid phase reaction sintering process is to be molded foaming agent and Si powder and C powder after evenly mixing, by melting or vaporizing abjection hair
Infusion obtains foam-like ceramics after pyroreaction is sintered；Gas phase reaction infiltration method refer to silicon gas with porous carbon the system of reacting
Standby trepanning SiC material.
No matter taking any technique, the property of porous ceramics and its pore structure are closely related, Recent study person
The functional aspect such as pore-size distribution, porosity and liquid permeation rate is concentrated on to the research of porous ceramics.However, if wanting
Think so that porous ceramics has higher comprehensive performance, other than having excellent functional performance, it is also necessary to have preferable knot
Structure performance.The abatvoix that chemical industry system of Qinhua Univ., Beijing develops can reach 25% average attraction coefficient, but its bending resistance is strong
Degree only has 1.47MPa, this is but also the porous ceramics has that brittleness is larger, therefore is carried under the premise of assurance function
Its high mechanical property is the key that development high-performance porous ceramics.
Invention content
It is to significantly improve the structural behaviour of carborundum porous ceramics that the present invention, which needs the technical problem underlying solved, so that should
Class material has stronger comprehensive performance.To solve this technical problem, the present invention is proposed to be received by carbon fiber and silicon carbide
Rice fiber enhances carborundum porous ceramics material, wherein matrix silicon carbide ceramics mainly using silicon-carbon original position solid phase reaction come
It obtains, SiC nano fiber is then silicon-carbon gas phase reaction to generate.
The preparation method of staple fiber of the present invention-SiC nano fiber enhancing carborundum porous ceramics material, with the carbon that is chopped
Fiber is as three-dimensional enhancing skeleton, using activated carbon and phenolic resin as carbon source, be heated in argon gas atmosphere silicon fusing point or more with
Silica flour is reacted.
Carbon source is mainly derived from activated carbon powder and cracking carbon in reaction, and cracking carbon is obtained by phenolic resin Pintsch process,
During Pintsch process, polycondensation reaction will occur for phenolic resin, inside will produce tensile stress, there are a large amount of low-molecular materials to release,
So that occurring hole in material.
It is heated to silicon fusing point or more in argon gas atmosphere with silicon react including solid phase reaction and gas phase reaction, wherein solid
Phase reaction generates silicon carbide ceramics matrix, which is the process of a volume contraction.Volume contraction in reaction process can be made
At the appearance of material mesoporous gap, to further increase the porosity of material.And gas phase reaction then generates SiC nano fiber,
The SiC nano fiber of generation will cooperate with chopped carbon fiber, in crackle transmittance process, will by it is micro-/receive spike protein gene, bridge
Connect, nano net strengthen etc. absorb energy, the architectural characteristic of porous ceramics is improved with this.
The preparation method as a preferred technical solution, includes the following steps：
(1) silica flour and active powdered carbon mixing and ball milling are uniformly dispersed, as mixture；
(2) absolute ethyl alcohol and phenolic resin are prepared into solution according to mass ratio 1: 0.8, chopped carbon fiber and dispersion is added
Agent is added the mixture after being uniformly dispersed and is prepared into suspension, the suspension is shaken to dispersion in ultrasonic wave, does
It is dry, it is prepared into raw material crude green body；
(3) the raw material crude green body is subjected to first time curing process, is demoulded after compression moulding, the crude green body after demoulding is carried out
Second of curing process obtains precast body；
(4) precast body is placed in Vacuum graphite oven, is evacuated within 10Pa, be warming up to silicon fusing point or more, protected
Warm 30min postcoolings.
As a preferred technical solution, in step (1), the mass ratio of silica flour and active powdered carbon is 3~7: 1, most preferably 5
∶1.During silicon-carbon reaction, more remnants C, Si are had in most cases and is existed.At high temperature, remaining C directly affects material
Intensity, remain at 1350 DEG C to keep bending at room temperature and compressive strength without the porous ceramics of remnants C, and have remaining C's
The elevated temperature strength of porous ceramics is then decreased obviously.The presence of remnants Si phases can also make under the high temperature microstructure performance of material simultaneously
Drop, therefore the mass ratio of silicon phase and carbon phase is extremely important.In the reaction, if silica flour (Si) and activated carbon powder (C) to be allowed to occur
Reaction (Si+C=SiC) completely, then mass ratio is 2.33: 1.But the mass ratio that silica flour and activated carbon are chosen in the present invention is 3
~7: 1.Wherein the excessive purpose of silica flour is mainly based upon at following 2 points：First, which is phenolic resin, to be converted into cracking process
Carbon base body, therefore excessive silicon can react to generate silicon carbide substrate with carbon base body；Another aspect is silicon in high temperature ring
It can be evaporated under border, silicon steam will occur gas phase reaction with carbon during outflow and generate SiC nano fiber, therefore excessive
Silicon can guarantee gas phase reaction generation, to generate SiC nano fiber, through being calculated optimal proportion be 5: 1.
As a preferred technical solution, in step (2), dispersant is selected from methylcellulose, hydroxyethyl cellulose or carboxylic
At least one of sodium carboxymethylcellulose pyce.Three kinds of dispersants all have good peptizaiton to chopped carbon fiber.Wherein hydroxyl second
Base cellulose is more soluble in the polar group of water and chopped carbon fiber surface because containing more hydroxyl polar group in its structure
Hydrogen bond or bridging are formed, it is not only attractive between these " Nang Bao " to which chopped carbon fiber cladding is wherein formed " Nang Bao ", but also
There is repulsion, under ultrasonic wave or outer force effect, gravitation and repulsion interaction form and stablize relatively when the two reaches balance
Class colloidal dispersion system, at this time chopped carbon fiber in dispersant be in ideal dispersion state.Exist as a preferred technical solution,
In step (2), the mass ratio of mixture and phenolic resin is 0.5~2: 1；The volume (ml) of dispersant and phenolic resin quality
(g) than being 2: 1.In order to protect the integrality of chopped carbon fiber in the present invention, exhaustion layer is served as using phenolic resin cracking carbon,
It prevents damage of the liquid silicon to carbon fiber in high-temperature reaction process as possible with this, improves carbon fiber for carborundum porous ceramics material
Strengthening and toughening effect.And it can occur to react completely with excessive silicon in order to enable obtaining carbon base body after phenolic resin cracking
(being calculated with the carbon yield of phenolic resin 50%, optimal proportion is obtained with a mole reaction completely to calculate according to Si and C), obtains
The mass ratio for obtaining mixture and phenolic resin is 0.5~2: 1, and optimal is 1: 1.
The structural and functional and chopped carbon fiber distribution of fiber reinforcement porous ceramics has direct influence relationship.
It is uniformly distributed to obtain aperture size, the equally distributed porous ceramics of chopped carbon fiber.In technical solution of the present invention, it is added and divides
Powder prepares suspension, this makes in raw material crude green body chopped carbon fiber be in three-dimensional support frame, no lamination occur and point
It dissipates very uniformly, this dispersing mode improves the technological deficiency of chopped carbon fiber poor dispersion in general open report document.
As a preferred technical solution, in step (2), the length of the chopped carbon fiber is 1~2mm；It is described suspended
Chopped carbon fiber volume content is 5-20% in liquid.The wherein preferred polyacrylonitrile carbon fiber of chopped carbon fiber, for its modulus and
Intensity does not have particular/special requirement, and general purpose grade, high mould grade or high intensity level can be used.Length is 1~2mm, if fibre length is too short,
Fiber is weaker for the toughening enhancing effect of ceramic material；If length is too long, dispersibility cannot be guaranteed, structural behaviour
Stability is poor.The volume content of chopped carbon fiber is 5-20% in suspension, if carbon fiber volume content is relatively low, fiber pair
In the activeness and quietness effect unobvious of ceramic material；And carbon fiber volume content is higher, then carbon fiber disperses not in suspension
Uniformly, the comprehensive performance of final material can equally be reduced.Chopped carbon fiber volume content in the present invention is optimal with 12%.
As a preferred technical solution, in step (3), first time condition of cure is 150 DEG C of heat preservations 5h, pressure 0.5-
3MPa, second of condition of cure are 200 DEG C and keep the temperature for 24 hours.In technical solution of the present invention, solidification pressurization is carried out to raw material crude green body, with
This regulates and controls the pore-size distribution and density of porous ceramics.The different pressure, pressure range will be taken to be in the present invention
0.5-3MPa.If pressure is too small, porosity is too high, and bending strength and fracture toughness are too small；If pressure is excessive, porosity drop
Low, bending strength is higher, but fracture toughness is then smaller, is optimal with 2MPa.It demoulds, carries out after curing first time
On the one hand second of curing process, second solidification process can make the further crosslinking curing of green body, on the other hand can be with
Improve the carbon yield of phenolic resin.
As a preferred technical solution, in step (4), heating rate is not more than 5 DEG C/min in 900 DEG C, is higher than 900
DEG C when be higher than 5 DEG C/min.In technical solution of the present invention, phenolic resin fragmentation pathways and high-temperature reaction process are completed for a step, this
So that the manufacturing cycle of such material greatly shortens, but to obtain high performance carborundum porous ceramics, need to control
The rate of heat addition.Since the major cleavage section of phenolic resin is within 900 DEG C, in this warm area, it is anti-that polycondensation occurs for phenolic resin
It answers, inside generates tensile stress, and a large amount of low-molecular material releasings lead to hole occur.If heating rate is too fast, internal will be caused to answer
Power can not discharge in time, so that phenomena such as bulge, fragmentation occurs in green body, destroy the pore-size distribution of material, reduce material
Mechanical property.If heating rate is excessively slow, manufacturing cycle can be lengthened.It is highly preferred that with 5 DEG C/min liters in the step (4)
For temperature to 200 DEG C, 2 DEG C/min is warming up to 900 DEG C, and 1500 DEG C are warming up to 10 DEG C/min.
The staple fiber prepared the present invention also provides the above method-SiC nano fiber enhances the curved of carborundum porous ceramics
Qu Qiangdu is 5-10MPa, fracture toughness 250-500Pam1/2, porosity 50-70%.The present invention prepares porous ceramics
Reinforced phase is the three-dimensional enhancing skeleton of chopped carbon fiber and SiC nano fiber, using micro-nano multi-scale technology activeness and quietness carbon
SiClx porous ceramics, this receives the different advantages of micro-meter scale and nanoscale reinforced phase to a certain extent, and makes up it not
Foot so that the performance of porous material is more superior and stablizes.The bending strength of carborundum porous ceramics material is 5- in the present invention
10MPa, this is than generally disclosing the high of report.It is about 250- simultaneously also by unilateral gap beam method test fracture toughness
500Pa·m1/2, and for the fracture toughness of porous ceramic film material, open report rarely found at present.
Invention effect
The present invention carries out porous silicon carbide ceramic using carbon fiber-SiC nano fiber toughened and reinforced so that porous
Ceramics have higher bending strength (5-10MPa), while also having certain fracture toughness (250-500Pam1/2)。
The heating rate that the present invention passes through the different warm areas of control so that one step of cracking and silicon-carbon reaction in-situ of phenolic resin
It completes, greatly reduces the manufacturing cycle of such material.
The present invention is discharged with small molecule to there is tensile stress in phenolic resin cracking process and generates porous structure, while is high
The lower silicon-carbon reaction of temperature is reacted for volume contraction, this makes the porosity of porous ceramics further increase.
Carbon source is provided using cracking carbon base body and activated carbon in the present invention, wherein carbon base body can reduce liquid silicon for enhancing
The corrosion damage of phase carbon fiber protects the integrality of carbon fiber, so that it has been given full play to carbon fiber and makes pottery for porous silicon carbide
The toughened and reinforced effect of porcelain.
Carbon pasc reaction of the present invention is solid phase reaction and gas phase reaction, and carbonization is also generated while generating silicon carbide ceramics matrix
The generation of silicon nanofiber, nanofiber will play certain effect in nano-scale to the strengthening and toughening of porous ceramic film material.
The present invention utilizes dispersant, carbon fiber and reaction powder is prepared suspension, this makes carbon fiber at evenly dispersed
Three-dimensional enhancing skeleton, to avoid the occurrence of lamination, solve the fiber occurred in common technology means disperse it is bad
Technological deficiency.
Description of the drawings
Fig. 1 is the optics electron microscope of raw material crude green body in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of prepared carborundum porous ceramics material in embodiment 1；
Fig. 3 is the load-displacement curves figure that carborundum porous ceramics material is prepared in embodiment 1.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail, but the following examples are only the preferable embodiment of the present invention,
Scope of protection of the present invention is not limited thereto, technology model of any one skilled in the art in present disclosure
In enclosing, it is subject to equivalent substitution or change according to the technical scheme of the invention and its inventive conception, should all covers the guarantor in the present invention
Within the scope of shield.
Embodiment 1：The preparation method of staple fiber-SiC nano fiber enhancing carborundum porous ceramics material, including under
State step：
(1) by 7g silica flours and 2g activity powdered carbon (Aladdin reagent) mixing and ball milling, ball milling parameter 150r/min, when ball milling
Between be 24 hours, be uniformly dispersed after crucible is ground after ball milling.(2) phenolic resin for weighing about 5g, is added the anhydrous of about 6.25g
Ethyl alcohol is configured to solution, be added in the melt 10ml hydroxyethyl cellulose (present invention to the mixing speed of dispersant and
Mixing time is not construed as limiting), the chopped carbon fiber of 0.6g is added, the length of chopped carbon fiber is about 1mm.2.5g is added later
The mixture obtained in step (1) is prepared into suspension, and chopped carbon fiber volume content is 6% in the suspension.It will be above-mentioned
Device shakes dispersion in ultrasonic wave, and then drying about for 24 hours, prepares raw material crude green body in room temperature environment.
(3) raw material crude green body is placed in graphite jig, which is placed on temperature and pressure machine, with 5 DEG C/min's
Heating rate is heated to 150 DEG C, and heat preservation 5h carries out first time curing process, and the pressure in solidification process is 0.5MPa.Solidification knot
Demoulding is handled after beam, which is placed in Muffle furnace, and at 200 DEG C, heat preservation carries out second of curing process for 24 hours.
(4) sample that second of solidification terminates is positioned in graphite crucible, which is placed on vacuum graphite
It in stove, is first evacuated within 10Pa, then is heated, heating process is：With 5 DEG C/min to 200 DEG C, then with 2 DEG C/min
900 DEG C are warming up to, then 1500 DEG C are warming up to 5 DEG C/min, keeps the temperature furnace cooling after 30min.
Embodiment 2：
Compared with Example 1, silica flour, active powdered carbon, the addition of phenolic resin and dispersant are constant, uniquely for the present embodiment
What is changed is the addition of chopped carbon fiber, and chopped carbon fiber quality is that 1.2g (divide in suspension by volume in this embodiment
12%) number is.
Embodiment 3：
Compared with Example 1, silica flour, active powdered carbon, the addition of phenolic resin and dispersant are constant, uniquely for the present embodiment
Variation be chopped carbon fiber addition, carbon fiber quality is that (volume fraction in suspension is 2g in this embodiment
18%).
Embodiment 4：
The present embodiment compared with Example 1, chopped carbon fiber, active powdered carbon, phenolic resin and dispersant addition not
Become, the silica flour quality uniquely changed, silica flour quality is 10g in this embodiment.
Embodiment 5：
The present embodiment compared with Example 1, chopped carbon fiber, active powdered carbon, phenolic resin and dispersant addition not
Become, the silica flour quality uniquely changed, silica flour quality is 13g in this embodiment.
Embodiment 6：
The present embodiment compared with Example 1, the addition of chopped carbon fiber, silica flour, active powdered carbon, phenolic resin and dispersant
Measure constant, the pressure when first time uniquely changed cures.Pressure is 1MPa in the present embodiment.
Embodiment 7：
The present embodiment compared with Example 1, the addition of chopped carbon fiber, silica flour, active powdered carbon, phenolic resin and dispersant
Measure constant, the pressure when first time uniquely changed cures.Pressure is 2MPa in the present embodiment.
Embodiment 8：
The present embodiment compared with Example 1, the addition of chopped carbon fiber, silica flour, active powdered carbon, phenolic resin and dispersant
Measure constant, the pressure when first time uniquely changed cures.Pressure is 4MPa in the present embodiment.
Embodiment 9：
Compared with Example 1, what is uniquely changed is the type of dispersant, the dispersant used in the present embodiment to the present embodiment
For methylcellulose
Embodiment 10：
Compared with Example 1, what is uniquely changed is the type of dispersant, the dispersant used in the present embodiment to the present embodiment
For sodium carboxymethylcellulose
The dispersing uniformity of the chopped carbon fiber in crude green body in embodiment 1 is observed with light microscope, such as Fig. 1 institutes
Show, it can be seen that prepare suspension by dispersant, chopped carbon fiber does not occur in the crude green body obtained after concussion dispersion is dry
Layering, dispersion are more uniform.
The microscopic appearance of ceramic porous material with flying-spot microscope to being prepared in embodiment 1 is observed (such as Fig. 2 institutes
Show), contain more hole in material by can be seen that in Fig. 2 (a), while can significantly find out that carbon fiber acts as three-dimensional
Enhance skeleton, dispersion is more uniform, while also filling up silicon carbide ceramics matrix between the fibers.The picture is further amplified,
As shown in Fig. 2 (b), can be more obvious find out that the integrality of carbon fiber surface is preferable, this shows during silicon-carbon reaction,
Liquid silicon is smaller for the corrosion damage of carbon fiber surface, and fiber maintains a preferable integrality, while it is also seen that fine
Dimension is combined weaker with basal body interface, this is but also the porous ceramics with higher bending strength and fracture toughness, while also may be used
To find out that material internal is scattered with aperture not of uniform size.The picture is further amplified, as shown in Fig. 2 (c), it can be seen that micron
Scale carbon fiber surface grows many SiC nano fibers, these SiC nano fibers can be by extracting, bridging
Energy absorption is carried out, so that the porous ceramic film material has higher mechanical property.
Fig. 2 (c) is the displacement-load curves of ceramic porous material prepared by embodiment 1, it can be seen that the porous ceramics exists
It is not brittle fracture when fracture, but at pseudoplastic behavior fracture mode, this should be that Fiber Bridge has occurred in crackle transmittance process
The processes such as connection, extraction absorb energy to failure, to cause porous material that plastic behavior is presented.
The percent opening of all embodiments and mechanical property in the present invention are tested, as shown in table 1.
Enhance silicon carbide from can be seen that the staple fiber-SiC nano fiber prepared in the present invention in embodiment 1-10
The density of porous ceramic film material is in 1.7-2.1g/cm3, porosity is between 50-70%, bending strength 5-10MPa；Fracture
Toughness is 250-500Pam1/2。
From embodiment 1-3 it is found that improving the percent by volume of carbon fiber in carborundum porous ceramics material, composite material
Density is basically unchanged, and the porosity has and slightly rises, while bending strength reduces, and the reduction of bending strength is mainly due to stomata
The increased reason of rate, and with the increase of fiber volume fraction, the fracture toughness of material also improves.
From embodiment 1,4,5 it is found that keeping the content of fiber C, the quality of silica flour is improved, density rises, while trepanning
Rate is held essentially constant, and bending strength has apparent rising, and fracture toughness is then decreased obviously.In example 4, silicon-carbon quality
Than for complete reaction ratio, remaining silicon is compared small in final composite material, for apparent without finding in the observation of microscopic appearance
Remaining silicon distributed mutually.But room temperature flexural intensity and fracture toughness do not show apparent advantage in the embodiment.This
Be due under room temperature state, the influence of the presence of remaining silicon phase for material mechanical performance be not clearly, and according to
Open source literature reports that remaining silicon mutually mainly influences the high temperature heat structure and structure stability of porous ceramics, therefore, in the embodiment
Mechanical behavior under high temperature be better than other embodiment.
From embodiment 1,6,7,8 it is found that the method for the present invention is conducive to the porosity of regulation and control porous ceramics, with to raw material crude green body
The porosity of the continuous increase of pressure, porous body reduces, while the bending strength of porous ceramic film material increases, and fracture toughness is then bright
It is aobvious to decline.
From embodiment 1,9,10 it is found that used in the present invention three kinds of dispersants (methylcellulose, hydroxyethyl cellulose or
Sodium carboxymethylcellulose) preferable dispersion effect is all had for chopped carbon fiber, therefore for the physical property of porous material
The influence of (density and percent opening) and mechanical property (bending strength and fracture toughness) is not obvious.Therefore dispersant in the present invention
Selected from least one of methylcellulose, hydroxyethyl cellulose or sodium carboxymethylcellulose.
Claims (6)
1. the preparation method of staple fiber-SiC nano fiber enhancing carborundum porous ceramics material, which is characterized in that be chopped
Carbon fiber is heated to silicon fusing point or more using activated carbon and phenolic resin as carbon source as three-dimensional enhancing skeleton in argon gas atmosphere
It is reacted with silica flour；
The preparation method includes the following steps：
(1) silica flour and active powdered carbon mixing and ball milling are uniformly dispersed, as mixture；
(2) by absolute ethyl alcohol and phenolic resin according to mass ratio 1:0.8 prepares solution, and chopped carbon fiber and dispersant is added, point
The mixture is added after dissipating uniformly and is prepared into suspension, the suspension is shaken to dispersion in ultrasonic wave, it is dry, it prepares
Obtain raw material crude green body；
(3) the raw material crude green body is subjected to first time curing process, is demoulded after compression moulding, the crude green body after demoulding is carried out second
Secondary curing process obtains precast body；
(4) precast body is placed in Vacuum graphite oven, is evacuated within 10Pa, be warming up to silicon fusing point or more, kept the temperature
30min postcoolings；
In the step (1), the mass ratio of silica flour and active powdered carbon is 3~7:1；
In the step (2), the mass ratio of mixture and phenolic resin is 0.5~2:1；The volume of dispersant and phenolic resin matter
Amount is than being 2:1；
In the step (4), to be warming up to 200 DEG C with 5 DEG C/min, 2 DEG C/min is warming up to 900 DEG C, 10 DEG C/min for the heating
It is warming up to 1500 DEG C.
2. according to the method described in claim 1, it is characterized in that, in the step (2), dispersant be selected from methylcellulose,
At least one of hydroxyethyl cellulose or sodium carboxymethylcellulose.
3. according to the method described in claim 1, it is characterized in that, in the step (2), the length of the chopped carbon fiber is
1~2mm；Chopped carbon fiber volume content is 5-20% in the suspension.
4. according to the method described in claim 1, it is characterized in that, in the step (3), first time condition of cure is 150 DEG C
Keep the temperature 5h, pressure 0.5-3MPa；Second of condition of cure is 200 DEG C and keeps the temperature for 24 hours.
5. according to the method described in claim 1, it is characterized in that, in the step (4), heating rate is little in 900 DEG C
In 5 DEG C/min, it is higher than 5 DEG C/min when being higher than 900 DEG C.
6. staple fiber prepared by claim 1-5 any one the methods-SiC nano fiber enhancing silicon carbide porous pottery
Porcelain, which is characterized in that the bending strength of the porous ceramics is 5-10MPa；Fracture toughness is 250-500Pam1/2；Porosity
For 50-70%.
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| CN106478121A (en) * | 2016-09-30 | 2017-03-08 | 巩义市泛锐熠辉复合材料有限公司 | A kind of preparation method of carbon fiber toughened silicon carbide wood ceramics |
| CN107010979B (en) * | 2017-04-25 | 2020-08-04 | 宁波欧翔精细陶瓷技术有限公司 | Preparation method of novel carbon fiber reinforced silicon carbide composite material |
| CN107935614B (en) * | 2017-11-30 | 2020-09-15 | 北京天宜上佳高新材料股份有限公司 | Carbon-ceramic composite material and preparation method thereof |
| CN112010654B (en) * | 2020-09-11 | 2022-04-29 | 航天特种材料及工艺技术研究所 | Fiber-reinforced silicon nitride composite material and preparation method thereof |
| CN113158491B (en) * | 2021-05-14 | 2023-09-12 | 南京工程学院 | Method and device for judging breaking strength limit of ceramic special-shaped micropore, computer equipment and storage medium |
| CN113773094B (en) * | 2021-09-30 | 2023-12-22 | 中国航发北京航空材料研究院 | Treatment method of silicon powder for melt siliconizing |
| CN114804903B (en) * | 2022-06-30 | 2022-10-21 | 北京绿清科技有限公司 | Production method of optical ceramic-based mold |
| CN115493455B (en) * | 2022-09-27 | 2023-09-22 | 江苏领瑞新材料科技有限公司 | Preparation method of high-strength fiber material with bulletproof function |
| CN115872758B (en) * | 2022-12-16 | 2024-03-29 | 西安交通大学 | BJ3DP printed reaction sintering silicon carbide ceramic and preparation method thereof |
| CN116727214A (en) * | 2023-06-14 | 2023-09-12 | 湖南搏盛天弘新材料技术有限公司 | Silicon carbide coating on surface of carbon fiber thermal insulation material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013026168A1 (en) * | 2011-08-24 | 2013-02-28 | Polyvalor, Société En Commandite | Porous sic ceramic and method for the fabrication thereof |
| CN102976756A (en) * | 2012-04-19 | 2013-03-20 | 安徽众星新材料有限公司 | Continuous carbon fiber reinforced C-SiC binary base composite material and preparation method thereof |
Family Cites Families (1)
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013026168A1 (en) * | 2011-08-24 | 2013-02-28 | Polyvalor, Société En Commandite | Porous sic ceramic and method for the fabrication thereof |
| CN102976756A (en) * | 2012-04-19 | 2013-03-20 | 安徽众星新材料有限公司 | Continuous carbon fiber reinforced C-SiC binary base composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Mechanical, structural and oxidation resistance enhancement of carbon foam by in situ grown SiC nanowires;Hui Mei et al.;《Ceramics International》;20151210(第42期);第4723–4733页 * |
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