CN108017413A - A kind of method for preparing SiC nanowire in C/SiC composite material surfaces - Google Patents
A kind of method for preparing SiC nanowire in C/SiC composite material surfaces Download PDFInfo
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- CN108017413A CN108017413A CN201610935892.3A CN201610935892A CN108017413A CN 108017413 A CN108017413 A CN 108017413A CN 201610935892 A CN201610935892 A CN 201610935892A CN 108017413 A CN108017413 A CN 108017413A
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- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 239000011204 carbon fibre-reinforced silicon carbide Substances 0.000 title claims abstract description 66
- 239000002070 nanowire Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000428 dust Substances 0.000 claims abstract description 18
- 238000005422 blasting Methods 0.000 claims abstract description 13
- 239000011812 mixed powder Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000010574 gas phase reaction Methods 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 25
- 239000010439 graphite Substances 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 230000037396 body weight Effects 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005498 polishing Methods 0.000 claims description 5
- 235000019786 weight gain Nutrition 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 12
- 239000000377 silicon dioxide Substances 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 7
- 238000005524 ceramic coating Methods 0.000 abstract description 4
- 230000003014 reinforcing effect Effects 0.000 abstract description 4
- 235000013312 flour Nutrition 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 48
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 43
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000005336 cracking Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- SICLLPHPVFCNTJ-UHFFFAOYSA-N 1,1,1',1'-tetramethyl-3,3'-spirobi[2h-indene]-5,5'-diol Chemical compound C12=CC(O)=CC=C2C(C)(C)CC11C2=CC(O)=CC=C2C(C)(C)C1 SICLLPHPVFCNTJ-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003517 fume Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- -1 on the other hand Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910021359 Chromium(II) silicide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
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- 238000001035 drying Methods 0.000 description 1
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- 230000005518 electrochemistry Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
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- 239000007792 gaseous phase Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000003701 mechanical milling Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5057—Carbides
- C04B41/5059—Silicon carbide
Abstract
The present invention provides a kind of method for preparing SiC nanowire in C/SiC composite material surfaces, comprises the following steps：First, the mixed powder for preparing silicon dioxide powder and carbon dust is spare, then blasting treatment is carried out to C/SiC composite samples, make its surface that there is certain roughness, then carbon source is introduced in sample surfaces using PIP techniques, finally, obtained sample is vacantly placed in above the mixture of silica flour and carbon dust, SiC nanowire is prepared in C/SiC composite material surfaces using chemical gas-phase reaction method, the present invention introduces carbon source in C/SiC composite material surfaces first and is successfully prepared SiC nanowire, solves the problems, such as the preparation in C/SiC composite material surface Strengthening and Toughening ceramic coating toughness reinforcing phases, and SiC nanowire can be generated largely, so that matrix surface is completely covered in SiC nanowire, preparation method of the present invention is simple, the use scope of C/SiC composite materials is widened.
Description
Technical field
The present invention relates to a kind of method for preparing SiC nanowire in C/SiC composite material surfaces, belongs to fibre reinforced pottery
Porcelain based composites field.
Background technology
Carbon fibre reinforced silicon carbide (C/SiC) composite material have high temperature resistant, low-density, high-performance and it is anti-oxidant etc. significantly
Advantage, is a kind of new thermal structure solar heat protection integrated material, can be widely applied to space flight, aviation, bullet train, advanced leads
The high-tech areas such as weapon, nuclear fusion energy source are played, the research temperature for C/SiC composite materials constantly heats up in recent years.In order to
C/SiC composite materials are applied to the use environment of temperature higher, it is necessary to solve the problems, such as the anti-oxidant of C/SiC composite materials.Mesh
Preceding most widely used pottery coating causes coating surface due to different from the thermal coefficient of expansion of C/SiC matrices of composite materials
With micro-crack, or even the stripping of coating and matrix, the intrusion for oxygen in air provides passage, so as to cause coating to lose
Protective effect to basis material.In order to reduce the generation of defect, it is necessary to coating structure is optimized, alleviate coating with
The mismatch problem of C/SiC matrices of composite material performances.
SiC nanowire be it is a kind of there is height-oriented mono-crystlling fibre, crystal structure is similar with diamond, transgranular component
Homogeneous, chemical impurity is few, no grain boundary and defect is few, therefore has the property that and application field：(1) good electrochemistry
Stability, has huge application potential in high frequency, high-power and High Density Integration electronic device etc.；(2) high-melting-point, height
Specific strength, high elastic modulus, low thermal coefficient of expansion, excellent mechanical property and high-temperature oxidation resistance.Develop at present more
The preparation method of kind SiC nanowire, such as arc discharge method, chemical vapour deposition technique, Fabricated by Oxide-assisted Growth Mechanism method and template.
At present, there are the problems such as SiC nanowire is applied to solve ceramic base coating cracking by many people, patent application in the country
CN201110359635.7 with the two-step method that reaction-sintered and reaction in-situ are combined preparation Si-SiC complex phase ceramic matrixes
Upper preparation SiC nanowire and nanobelt, but this method simply prepares nanowire, nothing in ceramic matrix preparation process itself
Method is applied to prepare SiC nanowire in C/SiC composite material surfaces；Patent application CN201010142230.3 uses chemical gaseous phase
Deposition is prepared for SiC nanowire toughness reinforcing SiC-MoSi2-CrSi2Ceramic coating, by nanowire-toughened effect, reduces coating
Cracking trend, the composite material used in this method is C/C composite materials, uses it for the preparation of C/SiC composite material surfaces
During SiC nanowire, since C/SiC composite material surfaces are there are substantial amounts of SiC, when preparing SiC nanowire, generation is reacted
SiC nanowire is few, or even can not be reacted with raw material, so that the SiC nanowire for causing to prepare can not complete mulching composite
Surface；Patent application CN201210447597.5 SiC nanometers of in-situ preparations directly during C/SiC composite materials are prepared
Fiber, this method for being introduced directly into SiC nanowire in the base can not be applied to synthesize SiC in C/SiC composite material surfaces
Nano wire, must prepare nano wire while C/SiC composite materials are prepared using this method, cause cost high, uncomfortable
It is preferably commonly used.
To sum up, if SiC nanowire can be directly generated in C/SiC composite material surfaces, ceramics can on the one hand be improved
The toughness of coating, on the other hand, C/SiC composite materials are easily obtained, and solving can be extensive to the demands such as appointed condition, method
It is applied, expands the application range of C/SiC composite materials.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, proposes a kind of in C/SiC composite material surfaces preparation SiC
The method of nano wire, its technique is simple, and under conditions of no catalyst auxiliary, is prepared in C/SiC composite material surfaces
Substantial amounts of SiC nanowire, solves the problems, such as the toughness reinforcing of C/SiC composite material ceramic coatings.
The technical solution of the present invention is as follows：
A kind of method for preparing SiC nanowire in C/SiC composite material surfaces, is realized by following steps：
Silicon dioxide powder and carbon dust, be uniformly mixed to obtain powder by step 1, spare；
Step 2, by C/SiC composite materials carry out blasting treatment；
Composite material made from step 2, be impregnated in carbon source precursor by step 3, cure-crack, continues to repeat
The step, until composite material rate of body weight gain reaches 0.5%~1%；
Step 4, the powder for preparing step 1 are placed in graphite crucible, then the C/SiC composite materials that step 3 obtains are hanged
The top on powder surface in graphite crucible is hung over, using chemical gas-phase reaction method, you can largely give birth in C/SiC composite material surfaces
Into SiC nanowire.
The C/SiC composite materials select conventional C/SiC composite materials, described for the ease of the introducing of follow-up carbon source
The porosity of holding one's breath of C/SiC composite materials is preferably more than 15%；
The concrete operations of the step 1 are：In mass ratio 1~2：1 weighing silicon dioxide powder and carbon dust are mixed to get mixing
Powder, then in mass ratio 0.3~0.5：1 weighs the mixed powder and absolute ethyl alcohol and is mixed in the ball mill, and mixing 4~
After 6h, be put into fume hood 24~48h of standing, be then placed in baking oven keep the temperature it is spare；
In the step 1, the ratio of silicon dioxide powder and carbon dust is 1~2：1, the reason is that：Carbon powder content is excessive can pairing
Microscopic appearance into product SiO has tremendous influence, there's almost no a nanometer wire；Dioxide-containing silica is excessive, can to react
Raw material can not react completely, and Product formation rate is low and causes the wasting of resources；The mixed proportion of mixed powder and absolute ethyl alcohol for 0.3~
0.5：1, the reason is that：Mechanical milling process requires suspension concentration cannot be excessive, and concentration is excessive, causes raw material mixing scattered uneven,
In addition, suspension concentration concentration can not be too small, the concentration too small time for then increasing the volatilization of later stage ethanol, production efficiency is reduced；
Further, the particle diameter of the silicon dioxide powder is 1~2 μm, purity 99%；The particle diameter of carbon dust is 0.5~2 μm,
Purity is 99%；If silicon dioxide powder and carbon dust particle diameter are too big, Ball-milling Time is caused to be grown, both undercompoundings, particle diameter is too
It is small, then difficulties in dispersion；
In the step 2, the C/SiC composite materials are by sanding and polishing, cleaning and the C/SiC of drying composite woods
Material；
Further, the technology that the blasting treatment is known in the art, such as blasting treatment its erosion particle can use
The white fused alumina sand that about 150 μm of size, used medium can be N2, impact velocity is 60~90m/s, and angle of attack is 45~90 °, sandblasting
Time is 10~30min；
Carbon source precursor in the step 3 selects the conventional resin for being capable of providing carbon source, such as common ammonia phenolic aldehyde
Any of resin, boron bakelite resin or furane resins, use ammonia phenolic aldehyde and boron phenolic solution, its matter during infiltration pyrolysis
It can be 40%~50% to measure fraction, and furane resins can be used directly；
In the step 3, dipping, the condition for curing and cracking are techniques well knowns, can be according to needs of production
Make choice, for example, dipping can first pass through vacuum impregnation, then carry out impregnating by pressure；Condition of cure can be cure under pressure, Gu
It can be 1.5~2.2MPa to change pressure；Cracking reaction can carry out in vacuum high-temperature resistance furnace, and condition can be：With 2~3 DEG C/
The speed of min is warming up to 200 DEG C ± 2 DEG C, keeps the temperature 2h~2.5h, 600 DEG C ± 5 are warming up to the speed of 0.2~0.4 DEG C/min
DEG C, 2h~3h is kept the temperature, then 1000 DEG C ± 10 DEG C are warming up to the speed of 0.1~0.15 DEG C/min, keep the temperature 3~5h；
Further, the step 3, which obtains composite material rate of body weight gain, must reach 0.5%~1%, this is because, weightening is too
Low, then matrix surface can not be completely covered in the SiC nanowire that C/SiC composite material surfaces carbon content can not enough to prepare；Increase
Weight is too high, then the carbon source of C/SiC composite material surfaces can not participate in reacting completely, reduces SiC nanowire and basis material
With reference to power；
In the step 4, sample is specifically bundled using carbon fiber and is suspended on the top on powder surface in graphite crucible, is made
The exposed largest surface area in reaction atmosphere of sample is obtained, may be such that the SiC nanowire that composite material surface is synthesized is covered substantially
Lid is complete；
Further, in the step 4, powder thickness is the 1/5~1/3 of graphite crucible depth；
Further, in the step 4, technology that the chemical gas-phase reaction method is known in the art, it reacts bar
Part can make choice according to needs of production；
For example, the chemical gas phase reaction can carry out in accordance with the following steps：Graphite crucible is put into high-temperature atmosphere sintering
In stove, vacuum is set to reach -0.1MPa ± -0.01MPa, fidelity sky 30min ± 5min after vacuumizing 30min ± 2min, then
Inert gas is passed through to normal pressure, furnace temperature is risen to 1000 DEG C ± 5 DEG C from room temperature with the programming rate of 2~3 DEG C/min, then with 1~2
DEG C/programming rate of min rises to 1400~1600 DEG C, keep the temperature 2~4h；It is then turned off power supply cooled to room temperature, whole mistake
Lead to inert gas shielding in journey；
In the step 1, oven temperature can be 60 DEG C~80 DEG C；
The step 3 and 4 carries out in an inert atmosphere, and inert gas used is argon gas.
The present invention reaction principle be：
First, after C/SiC composite materials being carried out blasting treatment, the roughness of material surface can be increased, improve and introduce
The combination power of carbon source and C/SiC matrices of composite materials；Secondly, by the process of dipping-curing-cracking in C/SiC composite materials
Surface introduce carbon source, control rate of body weight gain for 0.5~1% when it is proper；Finally closed using chemical gas-phase reaction method in material surface
Into SiC nanowire.
SiO2(s)+C(s)→SiO(g)+CO(g) （1）
SiO(g)+3CO(g)→SiC(s)+2CO2(g) （2）
SiO(g)+2C(s)→SiC(s)+CO(g) （3）
C(s)+CO2(g)→2CO(g) （4）
In this process, according to maximum energy criterion, react (1) first in reacting furnace, that is, titanium dioxide
Silicon and carbon dust, which react, generates gaseous silica, and gaseous silica is diffused into inside graphite, with one in graphite
Carbonoxide, which reacts, generates carborundum, that is, reaction (2)；When the concentration of carborundum reaches degree of supersaturation, i.e. generation is brilliant
Grain, because the matrix of grain growth at this time is C/SiC matrices of composite materials surface, and silica gas and carbon monoxide are dispersed in
In graphite, so when carborundum grain continues to generate, silicon carbide nanometer line is just formed, simultaneously because composite material surface has
A large amount of carbon sources and carbon source possessed by itself, silica and above-mentioned carbon source react, such as formula（3）It is shown, i.e., multiple
Condensation material surface forms a large amount of uniform silicon carbide nanometer lines, and simultaneous reactions (3) are also the reaction (2) of generation silicon carbide nanometer line
Carbon monoxide needed for providing, furthermore, it is also possible to which there are formula（4）Shown reaction, i.e. carbon dust may be with formula（2）Generation
Carbon dioxide reaction, is further formula（2）Carbon monoxide is provided；And comprehensive analysis formula (1)~(4), the chemistry of SiO2 and C
The ratio between stoichiometric number is 1：3, i.e., as m (SiO2)/m (C)=5/3, reaction raw materials react completely, therefore it is required that titanium dioxide in raw material
The mass ratio of silicon and carbon dust is 1~2：1, it is too high or too low all to have certain influence on reaction product.
The present invention compared with prior art the characteristics of and beneficial effect：
1st, the present invention introduces carbon source in C/SiC composite material surfaces and is successfully prepared SiC nanowire, solves in C/
The preparation problem of SiC ceramic matrix composite material surface toughening ceramic coating toughness reinforcing phase, wherein, blasting treatment is introduced in preparation process, is increased
The big roughness of C/SiC composite materials, improves carbon source and the combination power of C/SiC matrices of composite materials, and then can strengthen system
Standby SiC nanowire and the combination power of C/SiC matrices of composite materials, prevent SiC nanowire from coming off from matrix surface；
2nd, ratio, the particle diameter of the invention by controlling silicon dioxide powder and carbon dust, silicon dioxide powder-carbon dust mixed powder and second
The ratio of alcohol, and powder thickness in graphite crucible so that the product yield of generation is high, raw material reaction is abundant, avoids resource
Waste, improve production efficiency；
3rd, the present invention is by measuring the rate of body weight gain of C/SiC composite materials and then stringent control C/SiC composite material surfaces
Carbon source content, makes the carbon source of C/SiC composite material surfaces substantially completely participate in reacting, largely generates SiC nanowire so that SiC
Matrix surface is completely covered in nano wire, and the SiC nanowire synthesized is linear nano wire, basic without floccule, top
There is no bead, diameter distribution is homogeneous；
4th, preparation method of the present invention is simple, has widened the use scope of C/SiC composite materials.
Brief description of the drawings
Fig. 1-3 is the SEM figures of the C/SiC composite material surface SiC nanowires prepared by the present invention
Embodiment
Following implementation is the description of the invention, rather than is limited the scope of the invention.
Embodiment 1
1. prepared by raw material：Take silicon dioxide powder, carbon dust in mass ratio 1：1 weighs, and mixed powder and absolute ethyl alcohol are pressed quality
Than 0.5：1 mixes, and after mixing 4h in planetary ball mill, is put into fume hood and stands 24h, be then placed in baking oven
60 DEG C of insulation 8h are spare；
2. will be cleaned after C/SiC composite material sanding and polishings, it is put into baking oven and dries；
3. blasting treatment：Sample made from step 2 is subjected to blasting treatment；
4. infiltration pyrolysis：Sample made from step 3 is impregnated in ammonia phenolic resin, is soaked by vacuum impregnation and pressurization
Stain, then carries out pressure-cure, and then sample is placed in vacuum high-temperature resistance furnace and carries out cracking carbonization under an ar atmosphere；
5. powder prepared by step 1 is put into graphite crucible, make that its powder thickness is graphite crucible depth 1/5, then
The top on powder surface in graphite crucible is suspended on after the C/SiC composite samples that step 4 is handled are bundled with carbon fiber；Will
Graphite crucible is put into high-temperature atmosphere sintering furnace, vacuum is reached -0.1MPa, fidelity sky 30min after vacuumizing 30min, so
After be passed through argon gas to normal pressure, furnace temperature is risen to by 1000 DEG C, then the heating with 1 DEG C/min from room temperature with the programming rate of 3 DEG C/min
Speed rises to 1400 DEG C, keeps the temperature 4h；Power supply cooled to room temperature is then turned off, argon gas protection is led in whole process.
C/SiC composite material surface SiC nanowires prepared by the present embodiment SEM figure as shown in Figure 1,
It will be seen from figure 1 that product is made of substantial amounts of SiC nanowire, the SiC nanowire of synthesis is linear nanometer
Line, without floccule, the reaction of this explanation carbon and silica is thorough, causes to give birth to there is no carbon deficiency in carbothermic reduction process
Into cotton-shaped carborundum, in addition, bead is not present in the SiC nanowire top largely synthesized, that is to say, that the life of SiC nanowire
Length follows gas phase-solid phase (VS) mechanism, and the wire diameter distribution of synthesis is homogeneous, and diameter is about 100~200nm, and length is about
For tens microns.
Embodiment 2
1. prepared by raw material：Take silicon dioxide powder, carbon dust in mass ratio 5：3 weigh, and mixed powder and absolute ethyl alcohol are pressed quality
Than 0.5：1 mixes, and after mixing 4h in planetary ball mill, is put into fume hood and stands 24h, be then placed in baking oven
60 DEG C of insulation 8h are spare；
2. will be cleaned after C/SiC composite material sanding and polishings, it is put into baking oven and dries；
3. blasting treatment：Sample made from step 2 is subjected to blasting treatment；
4. infiltration pyrolysis：Sample made from step 3 is impregnated in ammonia phenolic resin, is soaked by vacuum impregnation and pressurization
Stain, then carries out pressure-cure, and then sample is placed in vacuum high-temperature resistance furnace and carries out cracking carbonization under an ar atmosphere；
5. powder prepared by step 1 is put into graphite crucible, make that its powder thickness is graphite crucible depth 1/5, then
The top on powder surface in graphite crucible is suspended on after the C/SiC composite samples that step 4 is handled are bundled with carbon fiber；Will
Graphite crucible is put into high-temperature atmosphere sintering furnace, vacuum is reached -0.1MPa, fidelity sky 30min after vacuumizing 30min, so
After be passed through argon gas to normal pressure, furnace temperature is risen to by 1000 DEG C, then the heating with 1 DEG C/min from room temperature with the programming rate of 3 DEG C/min
Speed rises to 1500 DEG C, keeps the temperature 4h；Power supply cooled to room temperature is then turned off, argon gas protection is led in whole process.
C/SiC composite material surface SiC nanowires prepared by the present embodiment SEM figure as shown in Fig. 2,
Compared to Figure 1, the diameter of the SiC nanowire of generation smaller, draw ratio bigger at 1500 DEG C.
Embodiment 3
1. prepared by raw material：Take silicon dioxide powder, carbon dust in mass ratio 2：1 weighs, and mixed powder and absolute ethyl alcohol are pressed quality
Than 0.5：1 mixes, and after mixing 4h in planetary ball mill, is put into fume hood and stands 24h, be then placed in baking oven
60 DEG C of insulation 8h are spare；
2. will be cleaned after C/SiC composite material sanding and polishings, it is put into baking oven and dries；
3. blasting treatment：Sample made from step 2 is subjected to blasting treatment；
4. infiltration pyrolysis：Sample made from step 3 is impregnated in ammonia phenolic resin, is soaked by vacuum impregnation and pressurization
Stain, then carries out pressure-cure, and then sample is placed in vacuum high-temperature resistance furnace and carries out cracking carbonization under an ar atmosphere；
5. powder prepared by step 1 is put into graphite crucible, make that its powder thickness is graphite crucible depth 1/5, then
The top on powder surface in graphite crucible is suspended on after the C/SiC composite samples that step 4 is handled are bundled with carbon fiber；Will
Graphite crucible is put into high-temperature atmosphere sintering furnace, vacuum is reached -0.1MPa, fidelity sky 30min after vacuumizing 30min, so
After be passed through argon gas to normal pressure, furnace temperature is risen to by 1000 DEG C, then the heating with 1 DEG C/min from room temperature with the programming rate of 3 DEG C/min
Speed rises to 1600 DEG C, keeps the temperature 4h；Power supply cooled to room temperature is then turned off, argon gas protection is led in whole process.
C/SiC composite material surface SiC nanowires prepared by the present embodiment SEM figure as shown in figure 3,
Compared with Fig. 1 and Fig. 2, the diameter of SiC nanowire prepared by 1600 DEG C of whens is maximum, and draw ratio is minimum.
Unspecified part of the present invention is known to the skilled person technology.
Claims (10)
- A kind of 1. method for preparing SiC nanowire in C/SiC composite material surfaces, it is characterised in that comprise the following steps：Silicon dioxide powder and carbon dust, be uniformly mixed to obtain powder by step 1, spare；Step 2, by C/SiC composite materials carry out blasting treatment；Composite material made from step 2, be impregnated in carbon source precursor by step 3, cure-crack, and continues to repeat the step Suddenly, until composite material rate of body weight gain reaches 0.5%~1%；Step 4, the powder for preparing step 1 are placed in graphite crucible, then the C/SiC composite materials that step 3 obtains are suspended on The top on powder surface in graphite crucible, using chemical gas-phase reaction method, you can largely generated in C/SiC composite material surfaces SiC nanowire.
- 2. according to the method described in claim 1, it is characterized in that, the mass ratio of the silicon dioxide powder and carbon dust is 1~2： 1。
- 3. according to the method described in claim 1, it is characterized in that, in the step 1, first silicon dioxide powder and carbon dust are carried out Mixed powder is mixed to get, then mixed powder carries out ball milling mixing with absolute ethyl alcohol again and obtains powder.
- 4. according to the method described in claim 3, it is characterized in that, the mass ratio of the mixed powder and absolute ethyl alcohol for 0.3~ 0.5：1.
- 5. according to the method described in claim 1, it is characterized in that, in the step 2, the C/SiC composite materials are process The composite material that sanding and polishing is crossed.
- 6. according to the method described in claim 1, it is characterized in that, the particle diameter of the silicon dioxide powder be 1~2 μm, the carbon The particle diameter of powder is 0.5~2 μm.
- 7. according to the method described in claim 1, it is characterized in that, in the step 4, carbon fiber is specifically used to composite material Bundled and be suspended on the top on powder surface in graphite crucible.
- 8. according to the method described in claim 1, it is characterized in that, in the step 4, the powder thickness is deep for graphite crucible The 1/5~1/3 of degree.
- 9. according to the method described in claim 1, it is characterized in that, the carbon source precursor is selected from ammonia phenolic resin, boron phenolic Any of resin or furane resins.
- 10. according to the method described in claim 1, it is characterized in that, the step 3 and 4 carries out in an inert atmosphere.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912316A (en) * | 2019-01-07 | 2019-06-21 | 南京航空航天大学 | A kind of preparation method of the nanowire-toughened coating of C/SiC composite material surface |
| CN110818417A (en) * | 2019-11-18 | 2020-02-21 | 武汉科技大学 | Carbon-silicon carbide porous filter for purifying air and preparation method thereof |
| CN111172625A (en) * | 2020-01-21 | 2020-05-19 | 西安稀有金属材料研究院有限公司 | Method for connecting silicon carbide nanowires |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102126859A (en) * | 2011-03-03 | 2011-07-20 | 西北工业大学 | Method for preparing bamboo-shaped SiC nanowire-toughened HfC ceramic |
| US20120133088A1 (en) * | 2009-02-19 | 2012-05-31 | Rhoads Randy L | Large refractory article and method for making |
| CN102491331A (en) * | 2011-11-15 | 2012-06-13 | 西北工业大学 | Method for preparing SiC nanometre wires and nanometre belts |
| CN102745998A (en) * | 2012-06-21 | 2012-10-24 | 西北工业大学 | Preparation method for anti-oxidant silica-based ceramic coating with wide temperature range for carbon/carbon composite |
| CN104876621A (en) * | 2015-05-07 | 2015-09-02 | 陕西科技大学 | C/SiC porous composite ceramic with bionic structure and preparation method of C/SiC porous composite ceramic |
-
2016
- 2016-11-01 CN CN201610935892.3A patent/CN108017413A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120133088A1 (en) * | 2009-02-19 | 2012-05-31 | Rhoads Randy L | Large refractory article and method for making |
| CN102126859A (en) * | 2011-03-03 | 2011-07-20 | 西北工业大学 | Method for preparing bamboo-shaped SiC nanowire-toughened HfC ceramic |
| CN102491331A (en) * | 2011-11-15 | 2012-06-13 | 西北工业大学 | Method for preparing SiC nanometre wires and nanometre belts |
| CN102745998A (en) * | 2012-06-21 | 2012-10-24 | 西北工业大学 | Preparation method for anti-oxidant silica-based ceramic coating with wide temperature range for carbon/carbon composite |
| CN104876621A (en) * | 2015-05-07 | 2015-09-02 | 陕西科技大学 | C/SiC porous composite ceramic with bionic structure and preparation method of C/SiC porous composite ceramic |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912316A (en) * | 2019-01-07 | 2019-06-21 | 南京航空航天大学 | A kind of preparation method of the nanowire-toughened coating of C/SiC composite material surface |
| CN110818417A (en) * | 2019-11-18 | 2020-02-21 | 武汉科技大学 | Carbon-silicon carbide porous filter for purifying air and preparation method thereof |
| CN110818417B (en) * | 2019-11-18 | 2021-08-03 | 武汉科技大学 | Carbon-silicon carbide porous filter for purifying air and preparation method thereof |
| CN111172625A (en) * | 2020-01-21 | 2020-05-19 | 西安稀有金属材料研究院有限公司 | Method for connecting silicon carbide nanowires |
| CN111172625B (en) * | 2020-01-21 | 2022-03-04 | 西安稀有金属材料研究院有限公司 | Method for connecting silicon carbide nanowires |
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