CN107059129A - Co-precipitation and the preparation method of thermal evaporation techniques fabricated in situ taper SiC whiskers - Google Patents

Co-precipitation and the preparation method of thermal evaporation techniques fabricated in situ taper SiC whiskers Download PDF

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CN107059129A
CN107059129A CN201710217042.4A CN201710217042A CN107059129A CN 107059129 A CN107059129 A CN 107059129A CN 201710217042 A CN201710217042 A CN 201710217042A CN 107059129 A CN107059129 A CN 107059129A
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carbon
precast body
taper
carbon fiber
sic whiskers
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CN107059129B (en
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史小红
闫宁宁
杨莉
李贺军
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Wuxi Bozhi Composite Materials Co.,Ltd.
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Northwestern Polytechnical University
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/36—Carbides
    • 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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • 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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C04B35/83—Carbon fibres in a carbon matrix
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • 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
    • C04B2235/5276—Whiskers, spindles, needles or pins

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Inorganic Fibers (AREA)

Abstract

The present invention relates to a kind of preparation method of use co-precipitation+thermal evaporation techniques fabricated in situ taper SiC whiskers, one layer of carbon is deposited in carbon fiber precast body by CVI methods, precast body surface defect is filled up and sufficient reaction raw materials is provided；Secondly precast body is put into the urea liquid containing catalyst and impregnated, nanocatalyst is made in calcining, reduction；The sample for containing nanocatalyst is hung on equipped with silica flour and the mixed uniformly graphite jig inner tip position of carbon dust, afterwards by the heat treatment of certain temperature again, you can taper SiC whiskers are made.Preparation method of the present invention is simple, pollution-free and safety and stability, can effectively improve anti-aging capability, fracture toughness, creep resisting ability and the matrix of composite and the bond strength of reinforcement.It can be applied in carbon/carbon, carbon/pottery, magnesium-based and aluminum matrix composite, with good economic and social benefit.

Description

Co-precipitation and the preparation method of thermal evaporation techniques fabricated in situ taper SiC whiskers
Technical field
The invention belongs to being co-precipitated+thermal evaporation techniques prepare application of the taper whisker in technical field of composite materials, it is related to A kind of preparation method being co-precipitated with thermal evaporation techniques fabricated in situ taper SiC whiskers.
Background technology
Carbon/carbon compound material is a kind of aerospace field new structural material.Due to its height than by force, Gao Bimo, high lead The features such as heat, low bulk, excellent thermal shock resistance, it is widely applied in fields such as Aero-Space, military affairs, medicine, buildings. But carbon/carbon compound material is easily aoxidized in oxygen-containing atmosphere, and carbon/carbon compound material is big when being applied as Structural Engineering component It is in oxidizing atmosphere more, significantly reduces the service life of engineering component.With the development of new and high technology, it is desirable to carbon/carbon Composite must have preferable fracture toughness, creep-resistant property and more excellent heat resistance, thermal shock resistance and guarantor Hold complete aerodynamic configuration ability.Therefore, research carbon/carbon compound material anti-yaw damper, creep resistant and toughness reinforcing strengthen performance to this The development of material is most important.
Chemical coprecipitation technique is, by the material mixing of different chemical composition, to be added suitably in mixed liquor under solution state Precipitating reagent prepares presoma sediment, then sediment is dried or is calcined, so that corresponding powder granule is made.Thermal evaporation Technology refers to the workpiece or substrate of question response to be placed in graphite jig top, by steaming it heating of graphite jig bottom powder Getting angry and the technical process for being deposited on the concurrent biochemical reaction of workpiece or substrate surface.Pass through chemical coprecipitation technique and thermal evaporation Technology grows the nano material of specific morphology on precast body, to improving fracture of composite materials toughness, creep-resistant property, anti-oxidation Performance plays an important roll.The present invention prepares high-melting-point taper SiC whisker (sublimation temperatures using co-precipitation+thermal evaporation techniques 2700 DEG C), by the pinning effect of taper whisker, fracture toughness, creep-resistant property and the base of composite can be effectively improved The bond strength of body and reinforcement.
2016, Australian University of Wollongong Xiang Li et al. were to quartz and graphite long-time ball milling and at 1600 DEG C Heat treatment obtains SiC whiskers.But whisker growth is disorderly and unsystematic, and a big chunk SiC is that occur in ceramic block form.Should Whisker growth is uneven and conversion is incomplete, makes it be difficult to apply in the industrial production.If by chemical coprecipitation technique and thermal evaporation Technology is combined, it is possible to achieve original position prepares high-melting-point taper SiC whiskers in the composite, reach raising composite it is each to The same sex, fracture toughness, the purpose of the bond strength of creep-resistant property and superhigh temperature anti-aging capability and matrix and reinforcement.
The content of the invention
The technical problem to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that a kind of co-precipitation is bored with thermal evaporation techniques fabricated in situ The preparation method of shape SiC whiskers.
Technical scheme
A kind of preparation method being co-precipitated with thermal evaporation techniques fabricated in situ taper SiC whiskers, it is characterised in that step is such as Under：
Step 1, the deposition carbon source layer in carbon fiber precast body：
Carbon fiber precast body is put into graphite jig folder and is loaded in CVI stoves, is opened after being vacuumized to furnace chamber Argon gas valve, is repeatedly rinsed；
Under argon gas protection, 800-1100 DEG C is warming up to by 4-5 DEG C/min of heating rate；The argon flow amount is 1500ml/min；
It is the constant temperature stage when temperature reaches 800-1100 DEG C, natural gas is passed through with 80L/h flow, while by Ar air-flow Amount is set to 1600ml/min, deposits 0.5-5h；
Then argon flow amount is adjusted to 1500ml/min, closes power supply, naturally cool to room temperature, completed in prefabricated carbon fiber Carbon source layer is deposited in body；
Step 2, coprecipitation prepare precast body-nanocatalyst system：The prefabricated carbon fiber of carbon source layer will be deposited Body is put into containing impregnating 8-12h in aluminum oxide, Nickelous nitrate hexahydrate, the urea liquid of ferrocene；120 DEG C of perseverances into reactor again Warm 2h；Then cool, take out carbon fiber precast body, be put into the insulating box that temperature is 200 DEG C and dry；
Hydrogen reducing is carried out in heat-treatment furnace：
The carbon fiber precast body that dried deposition has carbon source layer is loaded in heat-treatment furnace, furnace chamber is carried out to take out true Sky, opens argon gas valve, is repeatedly rinsed afterwards；
Then with 4-5 DEG C/min heating rate to 300-400 DEG C, argon gas protection, argon flow amount 100ml/min are passed through；
It is the constant temperature stage when temperature reaches 300-400 DEG C, opens hydrogen air valve, hydrogen flowing quantity is set to 150mL/min, Ar throughputs are set to 150ml/min simultaneously, 0.5-2h is reduced；
Argon flow amount is adjusted to 100ml/min, power supply is closed, naturally cools to room temperature；Obtain carbon fiber precast body-receive Rice catalyst system；
(Ni (the NO3)2·6H2O:Al2O3:Fe(C5H5)2:H2NCONH2Mol ratio be 1:1:1:5；
Step 3, thermal evaporation is carried out in high temperature sintering furnace, it is brilliant in carbon fiber precast body surface in situ growth taper SiC Palpus：
Carbon fiber precast body-nanocatalyst system is hung on into the graphite jig containing silica powder, silica flour and carbon dust Inner tip position, then graphite jig is fitted into high temperature sintering furnace, furnace chamber is vacuumized, argon gas is opened afterwards Valve, is repeatedly rinsed；
Temperature is raised to 1900-2200 DEG C with 4-7 DEG C/min heating rate, 0.5-2h is incubated, argon gas protection, argon is passed through Throughput 70-100ml/min, is made taper SiC whiskers；
The mol ratio of the silica powder, silica flour and carbon dust is 1:1:2.
Multiple rinse is three times.
The heat-treatment furnace uses BYQ BTF-1700C type horizontal type heat-treatment furnaces.
The high temperature sintering furnace uses ZGS-350 type high temperature sintering furnaces.
Beneficial effect
A kind of preparation method being co-precipitated with thermal evaporation techniques fabricated in situ taper SiC whiskers proposed by the present invention, first One layer of carbon is deposited in carbon fiber precast body with isothermal chemical vapor infiltration (ICVI) method, secondly precast body is put into containing Ni+ Al+Fe(Ni(NO3)2·6H2O+Al2O3+Fe(C5H5)2) urea liquid in impregnate, calcining, reduction be made nanocatalyst；Again The sample for containing nanocatalyst is hung on equipped with silica flour and the mixed uniformly graphite jig inner tip position of carbon dust, it Afterwards by 2100 DEG C of heat treatments, you can taper SiC whiskers are made.SiC thermal coefficient of expansion and carbon are closest, and the whisker is in nail Less thermal stress is produced during bundle matrix；Taper SiC whiskers add the interface with matrix simultaneously so that composite breaks Split toughness raising.Therefore, taper SiC whiskers are activeness and quietness carbon/carbon, the ideal chose in carbon/ceramic composite material field.And taper SiC whiskers have high-melting-point, and high-temperature oxidation process produces SiO2Glassy layer, effectively packing crackle and can slow down further oxidation, Therefore the antioxygenic property of carbon/carbon compound material can be improved.In magnesium-based, aluminum matrix composite, taper SiC whiskers can have Effect ground pinning crystal boundary, prevents crystal grain from growing up, plays the purpose of crystal grain thinning.Therefore magnesium-based, aluminum matrix composite are greatly improved Intensity, toughness and creep resisting ability.
Invention preparation method is simple, pollution-free and safety and stability, can effectively improve composite material antioxidation ability, fracture The bond strength of toughness, creep resisting ability and matrix and reinforcement, at the same can be widely applied to carbon/carbon, carbon/pottery and magnesium-based, In aluminum matrix composite, with good economic and social benefit.
Brief description of the drawings
Fig. 1：Co-precipitation prepares the whisker modified composite technology flow charts of SiC with thermal evaporation techniques
Fig. 2：The scanning electron microscopy of the taper SiC whiskers of acquisition is combined with thermal evaporation techniques for chemical coprecipitation technique (SEM) figure；
(a) the SEM figures of carbon fiber surface；(b) catalyst surface SEM schemes；(c) the connected top SEM figures of taper SiC
Fig. 3：Taper SiC whisker EDS collection of illustrative plates
(a) EDS schemes on catalyst；(b) EDS schemes on whisker
Embodiment
In conjunction with embodiment, accompanying drawing, the invention will be further described：
The raw material that the present invention is used has：Nickelous nitrate hexahydrate, ferrocene, carbon felt (0.43-0.45g/cm3), carbon dust, oxidation Aluminium powder, silica powder, silica flour, methane, argon gas, hydrogen.The present invention uses equipment：ICVI stoves, pyrographite stove, heat-treatment furnace.
Concrete operation step is as follows：
(1) carbon source layer is deposited in carbon fiber precast body
1. carbon fiber precast body is put into graphite jig folder and is loaded in CVI stoves.Furnace chamber is vacuumized, afterwards Argon gas valve is opened, is rinsed.So 3 times repeatedly.
2. start-up temperature time control program, 800-1100 DEG C, 4-5 DEG C of heating rate/min, during heating are raised to by temperature Between be 4h, be passed through argon gas protection, argon flow amount 1500ml/min.
3. constant temperature stage.When temperature reaches 800-1100 DEG C, natural air valve is opened, gas discharge is set to 80L/h, Ar throughputs are set to 1600ml/min simultaneously, 0.5-5h is deposited.
4. natural gas air valve and flowmeter are closed, argon flow amount is adjusted to 1500ml/min, power supply is closed, naturally cools to Room temperature；Argon gas air valve and flowmeter are closed, experiment terminates.
(2) coprecipitation prepares precast body-nanocatalyst system
A. the carbon fiber precast body for having deposited carbon source layer is put into containing aluminum oxide, Nickelous nitrate hexahydrate, ferrocene Urea liquid (Ni (NO3)2·6H2O：Al2O3：Fe(C5H5)2：H2NCONH2Mol ratio be 1:1:1:5) dipping 8-12h in；Will Precast body and solution are poured into 120 DEG C of constant temperature 2h in reactor.Cooling, takes out precast body, is put into drying for one day in insulating box, perseverance Temperature of Warm Case is 200 DEG C, is down to room temperature sampling.
B. hydrogen reducing
Sample is carried out in BYQ BTF-1700C type horizontal type heat-treatment furnaces
1. carbon fiber precast body is loaded in horizontal type heat-treatment furnace.Furnace chamber is vacuumized, argon gas valve is opened afterwards, It is rinsed.So 3 times repeatedly.
2. start-up temperature time control program, is raised to 300-400 DEG C, 4-5 DEG C of heating rate/min is passed through argon gas by temperature Protection, argon flow amount 100ml/min.
3. constant temperature stage.When temperature reaches 300-400 DEG C, hydrogen air valve is opened, hydrogen flowing quantity is set to 150mL/ Min, while Ar throughputs are set into 150ml/min, reduces 0.5-2h.
4. hydrogen air valve and flowmeter are closed, argon flow amount is adjusted to 100ml/min, power supply is closed, naturally cools to room Temperature；It can obtain carbon fiber precast body-nanocatalyst system.
(4) thermal evaporation grows taper SiC whiskers in carbon fiber precast body surface in situ
Sample is carried out in ZGS-350 types high temperature sintering furnace (3000 DEG C).
1. sample hung on containing silica powder, silica flour and carbon dust to (mol ratio is 1:1:2) inside of graphite jig Graphite jig, is then fitted into high temperature sintering furnace by apical position, and furnace chamber is vacuumized, and argon gas valve is opened afterwards, carries out Rinse.So 3 times repeatedly.
2. start-up temperature time control program, 1900-2200 DEG C, 4-7 DEG C of heating rate/min, insulation are raised to by temperature 0.5-2h, is passed through argon gas protection, argon flow amount 70-100ml/min.
3. bolt down procedure, is down to room temperature naturally, sampling.
Embodiment 1
Take carbon felt (0.43-0.45g/cm3) cut, cut the sample for wearing into 10 × 10 × 10mm sizes and surfacing Product, sample is put into graphite jig folder and is loaded in CVI stoves.Furnace chamber is vacuumized, argon gas valve is opened afterwards, is carried out Rinse.So 3 times repeatedly；Start-up temperature time control program, 1000 DEG C, 4 DEG C/min of heating rate, during heating are raised to by temperature Between be 4h, be passed through argon gas protection, argon flow amount 1500ml/min；When temperature reaches 1000 DEG C, natural air valve is opened, will be natural Throughput is set to 80L/h, while Ar throughputs are set into 1600ml/min, deposits 1.5h；Natural gas air valve and flowmeter are closed, Argon flow amount is adjusted to 1500ml/min, power supply is closed, naturally cools to room temperature；Close argon gas air valve and flowmeter, experiment knot Beam.
By deposited carbon source layer carbon fiber precast body be put into containing aluminum oxide, Nickelous nitrate hexahydrate, ferrocene urine 8h is impregnated in plain solution；Precast body and solution are poured into 120 DEG C of constant temperature 2h in reactor.Cooling, takes out precast body, is put into perseverance Drying for one day in incubator, calorstat temperature is 200 DEG C, is down to room temperature sampling.
Carbon fiber precast body is loaded in horizontal type heat-treatment furnace.Furnace chamber is vacuumized, argon gas valve is opened afterwards, is entered Row is rinsed.So 3 times repeatedly；Start-up temperature time control program, is raised to 400 DEG C, 4-5 DEG C of heating rate/min is led to by temperature Enter argon gas protection, argon flow amount 100ml/min；When temperature reaches 400 DEG C, hydrogen air valve is opened, hydrogen flowing quantity is set to 150mL/min, while Ar throughputs are set into 150ml/min, reduces 1h；Hydrogen air valve and flowmeter are closed, by argon flow amount 100ml/min is adjusted to, power supply is closed, naturally cools to room temperature；It can obtain carbon fiber precast body-nanocatalyst system.
Sample hangs on containing silica powder, silica flour and carbon dust to (mol ratio is 1:1:2) the inside top of graphite jig Graphite jig, is then fitted into high temperature sintering furnace by end position, and furnace chamber is vacuumized, and argon gas valve is opened afterwards, is rushed Wash.So 3 times repeatedly；Start-up temperature time control program, 2100 DEG C, 4-7 DEG C of heating rate/min, insulation are raised to by temperature 0.5-2h, is passed through argon gas protection, argon flow amount 100ml/min；Bolt down procedure, is down to room temperature naturally, sampling.
Embodiment 2
Take carbon felt (0.43-0.45g/cm3) cut, cut the sample for wearing into 10 × 10 × 10mm sizes rule and surfacing Product, sample is put into graphite jig folder and is loaded in CVI stoves.Furnace chamber is vacuumized, argon gas valve is opened afterwards, is carried out Rinse.So 3 times repeatedly；Start-up temperature time control program, 1000 DEG C, 4 DEG C/min of heating rate, during heating are raised to by temperature Between be 4h, be passed through argon gas protection, argon flow amount 1500ml/min；When temperature reaches 1000 DEG C, natural air valve is opened, will be natural Throughput is set to 80L/h, while Ar throughputs are set into 1600ml/min, deposits 3h；Natural gas air valve and flowmeter are closed, will Argon flow amount is adjusted to 1500ml/min, closes power supply, naturally cools to room temperature；Argon gas air valve and flowmeter are closed, experiment terminates.
By deposited carbon source layer carbon fiber precast body be put into containing aluminum oxide, Nickelous nitrate hexahydrate, ferrocene urine 12h is impregnated in plain solution；Precast body and solution are poured into 120 DEG C of constant temperature 2h in reactor.Cooling, takes out precast body, is put into Drying for one day in insulating box, calorstat temperature is 200 DEG C, is down to room temperature sampling.
Carbon fiber precast body is loaded in horizontal type heat-treatment furnace.Furnace chamber is vacuumized, argon gas valve is opened afterwards, is entered Row is rinsed.So 3 times repeatedly；Start-up temperature time control program, is raised to 400 DEG C, 4-5 DEG C of heating rate/min is led to by temperature Enter argon gas protection, argon flow amount 100ml/min；When temperature reaches 400 DEG C, hydrogen air valve is opened, hydrogen flowing quantity is set to 150mL/min, while Ar throughputs are set into 150ml/min, reductase 12 h；Hydrogen air valve and flowmeter are closed, by argon flow amount 100ml/min is adjusted to, power supply is closed, naturally cools to room temperature；It can obtain carbon fiber precast body-nanocatalyst system.
Sample hangs on containing silica powder, silica flour and carbon dust to (mol ratio is 1:1:2) the inside top of graphite jig Graphite jig, is then fitted into high temperature sintering furnace by end position, and furnace chamber is vacuumized, and argon gas valve is opened afterwards, is rushed Wash.So 3 times repeatedly；Start-up temperature time control program, 2100 DEG C, 4-7 DEG C of heating rate/min, insulation are raised to by temperature 0.5-2h, is passed through argon gas protection, argon flow amount 100ml/min；Bolt down procedure, is down to room temperature naturally, sampling.
Ferrocene in all implementation examples>98%, Nickelous nitrate hexahydrate>98%, Al2O3>99%, carbon dust>99%, silica flour> 99%, silica powder>99%, Ar>99.999%, H2>99.999%, CH4>99.9%.
Present invention incorporates the process advantage of distinct methods, superhigh temperature whisker morphology is largely enriched, for carrying Anti-aging capability, fracture toughness, creep resisting ability and the matrix of high composite and the bond strength of reinforcement have certain Progressive meaning.SiC thermal coefficient of expansion and carbon are closest, and the whisker produces less thermal stress during pinning matrix； Meanwhile, taper SiC whiskers add its interface with matrix so that fracture of composite materials toughness is improved.Therefore, taper SiC is brilliant It must be the ideal chose of activeness and quietness carbon/carbon, carbon/ceramic composite material etc..And taper SiC whiskers have high-melting-point, high-temperature oxydation Process produces SiO2Glassy layer, effectively packing crackle and can slow down oxidation, therefore can improve the anti-oxidant of carbon/carbon compound material Performance.In magnesium-based, aluminum matrix composite, taper SiC whiskers can effectively pinning crystal boundary, prevent crystal grain from growing up, play thin Change the purpose of crystal grain.Therefore, SiC whiskers are greatly improved magnesium-based, the intensity of aluminum matrix composite, toughness and creep resistant energy Power.Preparation method of the present invention is simple, pollution-free and safety and stability, can effectively improve anti-aging capability, the fracture of composite The bond strength of toughness, creep resisting ability and matrix and reinforcement, can be applied to carbon/carbon, carbon/pottery, magnesium-based and aluminium base multiple In condensation material, with good economic and social benefit.

Claims (4)

1. a kind of preparation method being co-precipitated with thermal evaporation techniques fabricated in situ taper SiC whiskers, it is characterised in that step is as follows：
Step 1, the deposition carbon source layer in carbon fiber precast body：
Carbon fiber precast body is put into graphite jig folder and is loaded in CVI stoves, argon gas is opened after being vacuumized to furnace chamber Valve, is repeatedly rinsed；
Under argon gas protection, 800-1100 DEG C is warming up to by 4-5 DEG C/min of heating rate；The argon flow amount is 1500ml/ min；
It is the constant temperature stage when temperature reaches 800-1100 DEG C, natural gas is passed through with 80L/h flow, while Ar throughputs are set For 1600ml/min, 0.5-5h is deposited；
Then argon flow amount is adjusted to 1500ml/min, closes power supply, naturally cool to room temperature, completed in carbon fiber precast body Deposit carbon source layer；
Step 2, coprecipitation prepare precast body-nanocatalyst system：The carbon fiber precast body for having deposited carbon source layer is put Enter containing impregnating 8-12h in aluminum oxide, Nickelous nitrate hexahydrate, the urea liquid of ferrocene；120 DEG C of constant temperature into reactor again 2h；Then cool, take out carbon fiber precast body, be put into the insulating box that temperature is 200 DEG C and dry；
Hydrogen reducing is carried out in heat-treatment furnace：
The carbon fiber precast body that dried deposition has carbon source layer is loaded in heat-treatment furnace, furnace chamber is vacuumized, it Argon gas valve is opened afterwards, is repeatedly rinsed；
Then with 4-5 DEG C/min heating rate to 300-400 DEG C, argon gas protection, argon flow amount 100ml/min are passed through；
It is the constant temperature stage when temperature reaches 300-400 DEG C, opens hydrogen air valve, hydrogen flowing quantity is set to 150mL/min, simultaneously Ar throughputs are set to 150ml/min, 0.5-2h is reduced；
Argon flow amount is adjusted to 100ml/min, power supply is closed, naturally cools to room temperature；Carbon fiber precast body-nanometer is obtained to urge Agent system；
(Ni (the NO3)2·6H2O:Al2O3:Fe(C5H5)2:H2NCONH2Mol ratio be 1:1:1:5；
Step 3, thermal evaporation is carried out in high temperature sintering furnace, taper SiC whiskers are grown in carbon fiber precast body surface in situ：
Carbon fiber precast body-nanocatalyst system is hung in the graphite jig containing silica powder, silica flour and carbon dust Graphite jig, is then fitted into high temperature sintering furnace by portion's apical position, and furnace chamber is vacuumized, and argon gas valve is opened afterwards, is entered Row is repeatedly rinsed；
Temperature is raised to 1900-2200 DEG C with 4-7 DEG C/min heating rate, 0.5-2h is incubated, argon gas protection, argon gas stream is passed through 70-100ml/min is measured, taper SiC whiskers are made；
The mol ratio of the silica powder, silica flour and carbon dust is 1:1:2.
2. the preparation method with thermal evaporation techniques fabricated in situ taper SiC whiskers, its feature are co-precipitated according to claim 1 It is：Multiple rinse is three times.
3. the preparation method with thermal evaporation techniques fabricated in situ taper SiC whiskers, its feature are co-precipitated according to claim 1 It is：The heat-treatment furnace uses BYQ BTF-1700C type horizontal type heat-treatment furnaces.
4. the preparation method with thermal evaporation techniques fabricated in situ taper SiC whiskers, its feature are co-precipitated according to claim 1 It is：The high temperature sintering furnace uses 3000 DEG C of ZGS-350 types high temperature sintering furnace.
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