CN104926348B - It is a kind of to grow Si in 2D carbon felts internal in-situ3N4The method of nano wire - Google Patents
It is a kind of to grow Si in 2D carbon felts internal in-situ3N4The method of nano wire Download PDFInfo
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Abstract
The present invention relates to one kind grows Si in 2D carbon felts internal in-situ3N4The method of nano wire, the method for impregnating pyrolysis using presoma grow Si in carbon felt internal in-situ3N4Nano wire, overcomes the problem of traditional CVD method poor permeability in big thickness high density porous preform, realizes Si3N4Nano wire in integral prefabricated body by inside to surface homoepitaxial.In this method, the impact of the component ratio, dipping method and heat treatment process of presoma to experimental result is very big.By adjusting experiment parameter, the Si being evenly distributed can be obtained inside carbon felt3N4Nano wire, for being lifted, reinforced effects of the 2D carbon felts on multi-dimentional scale are highly beneficial.The inventive method, makes Si3N4Distribution density of the nano wire inside carbon felt is controllable, overcomes shortcoming of traditional CVD method in carbon felt growth inside nano wire poor permeability.This method has the advantages that low cost, cycle is short and easily realizes scale high efficiency production.
Description
Technical field
The invention belongs to growth in situ Si3N4The method of nano wire, and in particular to a kind of to grow in 2D carbon felts internal in-situ
Si3N4The method of nano wire.
Background technology
In recent years, the fast development of China's Aero-Space and science and techniques of defence, aero-engine such as of new generation, re-entry space vehicle
Deng further harsh requirement being proposed to the structure and performance of C/C composites, particularly with high-strength thin-walled, sharp
The demand of sharp shape and complicated integrated member is more urgent.However, as the 2D C/C composites commonly used are a kind of typical layers
Shape composite, in the tension of its Z-direction (stack direction), layer, the performance such as direction resistance to compression and shearing strength at intersection is very undesirable, and multidirectional
, as the fiber of edge and surface portion is cut off in its forming process, reinforced effects are significantly for braiding C/C composites
Degree weakens, and the component especially with sophisticated position can cause performance major injury or generation to collapse block, Jin Erwu because of fibre cutting
Method ensure thin-walled, sharp shape, complicated shape C/C composite elements under arms during size and stability.Document 1
“Song Q,Li K,Qi L,et al.The reinforcement and toughening of pyrocarbon-based
carbon/carbon composite by controlling carbon nanotube growth position in
carbon felt[J].Materials Science&Engineering A,2013,564(3):71-75. " propose a kind of logical
CVD is crossed in low-density (0.2g/cm3) carbon felt internal in-situ growth CNT, so as to C/C composite woods are improved on three dimension scale
The method of material mechanical property, result of study shows, by CNT is introduced inside low-density carbon felt, C/C composites
Obdurability is significantly increased.However, CNT in big thickness (such as>1mm) high density is (such as>0.4g/cm3) porous preform
Middle growth poor permeability, realizes CNT in the integral prefabricated body of big thickness high density by the equal of inside to surface by CVD
Even growth is extremely difficult.In addition, the relatively low intensity of CNT also limit its reinforced effects to C/C composites.
Ceramic nano line has higher mechanical strength, can be used to strengthen carbon-based, ceramic matric composite.Document 2 " Li K, Zhao K,
Wang Y.In-situ synthesis and growth mechanism of silicon nitride nanowires on
carbon fiber fabrics[J].Ceramics International,2014,40:15381-15389. " propose a kind of
In monolayer carbon cloth outer surface fabricated in situ Si3N4The method of nano wire, but using the technological parameter and method provided in document,
Cannot be in the uniform Si of carbon felt growth inside3N4Nano wire.
The content of the invention
Technical problem to be solved
In place of the deficiencies in the prior art, the present invention proposes a kind of in 2D carbon felts internal in-situ growth Si3N4Nanometer
The method of line, realizes that it is 0.1～0.6g/cm to be more than 1mm, density in thickness32D carbon felt internal in-situ homoepitaxial Si3N4Receive
The method of rice noodle.
Technical scheme
It is a kind of to grow Si in 2D carbon felts internal in-situ3N4The method of nano wire, it is characterised in that step is as follows：
Step 1, pretreatment 2D carbon felts：2D carbon felts are cleaned by ultrasonic using dehydrated alcohol, are dried or is dried in being subsequently placed in air
Dry in case；
Step 2, in 2D carbon felts load ferrocene catalyst：Carbon felt is impregnated with the dimethylbenzene supersaturated solution of ferrocene,
Dry in drying baker after taking-up；The mass fraction of the ferrocene is about 15%；
Step 3：In 2D carbon felts immersion mixed solution prepared by step 2, impregnate in being put into vacuum impregnation case, until mixing
Dimethylbenzene in solution is drained；The mixed solution is by polysilazane that volume fraction is 10%～18% and dimethylbenzene magnetic
Power stirs to form mixed solution；
Step 4：2D carbon felts after step 3 is processed are placed in heat treatment in horizontal pipe furnace：With the programming rate of 6 DEG C/min
1450 DEG C～1650 DEG C are risen to by room temperature, after 4～6h of insulation, power supply is closed；High Purity Nitrogen is passed through always in whole heat treatment process
Gas, 600 DEG C before, and nitrogen flow rate is 50cm3/ min, overpressure are 1atm；In the gentle insulating process of liter afterwards, nitrogen stream
Speed control is in 150～200cm3/ min, opens vacuum pump, and controls overpressure for 0.5～0.7atm；After closing power supply, nitrogen
Gas velocity is adjusted to 50cm3/ min, and close vacuum pump so that overpressure is 1atm；By being cooled to after room temperature in carbon felt
Portion obtains the Si being evenly distributed3N4Nano wire.
The density of the 2D carbon felts is 0.1～0.6g/cm3。
The thickness of the 2D carbon felts is 1mm～50mm.
Step 1 dehydrated alcohol is cleaned by ultrasonic 2D carbon felts twice, each 15min.
The purity of the high pure nitrogen is 99.999%.
The purity of the ferrocene is pure for analysis.
The purity of the dimethylbenzene is pure for analysis.
The polysilazane is commercialization Si-C-N ceramic forerunners, and english name is polyureasilazane, referred to as
PSN-2。
Beneficial effect
It is proposed by the present invention a kind of in 2D carbon felts internal in-situ growth Si3N4The method of nano wire, using presoma dipping-
The method of pyrolysis, grows Si in carbon felt internal in-situ3N4Nano wire, overcomes traditional CVD method pre- in big thickness high density porous
In body processed, the problem of poor permeability, realizes Si3N4Nano wire in integral prefabricated body by inside to surface homoepitaxial.This
In method, the impact of the component ratio, dipping method and heat treatment process of presoma to experimental result is very big.By adjusting experiment
Parameter, can obtain the Si being evenly distributed inside carbon felt3N4Nano wire, for lifting enhancing of the 2D carbon felts on multi-dimentional scale
Effect is highly beneficial.
The inventive method, makes Si3N4Distribution density of the nano wire inside carbon felt is controllable, overcomes traditional CVD method in carbon
The shortcoming of felt growth inside nano wire poor permeability.This method has low cost, cycle is short and easily realizes that scale high efficiency is given birth to
The advantage of product.
Description of the drawings
Fig. 1：Si inside carbon felt prepared by embodiment 33N4The SEM figures of nano wire；
Fig. 2：Carbon felt surface Si prepared by embodiment 33N4The SEM figures of nano wire；
Fig. 3：The XRD figure of the nano wire prepared by embodiment 3.
Specific embodiment
In conjunction with embodiment, accompanying drawing, the invention will be further described：
Embodiment one：
1) by density be 0.2g/cm32D carbon felts be processed into size be 40mm × 30mm × 10mm cuboid, in ethanol
It is cleaned by ultrasonic in solution twice, each 15min；
2) the loading ferrocene catalyst in 2D carbon felts：With the dimethylbenzene supersaturated solution (quality of ferrocene of ferrocene
Fraction is about 15%) dipping carbon felt 1h, is dried after taking-up in drying baker；
3) polysilazane is diluted with dimethylbenzene：The volume fraction for preparing polysilazane is 10% polysilazane and dimethylbenzene
Mixed solution, magnetic agitation 1h；
4), in the mixed solution of the carbon felt immersion step 3 for preparing step 2, impregnate in being put into rapidly vacuum impregnation case, directly
Dimethylbenzene into mixed solution is blotted；
5) carbon felt in step 4 is placed in into heat treatment in horizontal pipe furnace：Risen to by room temperature with the programming rate of 6 DEG C/min
1450 DEG C, after insulation 4h, close power supply.High pure nitrogen is passed through always in whole heat treatment process, and 600 DEG C before, nitrogen flow rate
For 50cm3/ min, overpressure are 1atm；In the gentle insulating process of liter afterwards, nitrogen flow rate is controlled in 150cm3/ min, beats
Vacuum pump is opened, and overpressure is controlled for 0.7atm；After closing power supply, nitrogen flow rate is adjusted to 50cm3/ min, and close vacuum
Pump so that overpressure is 1atm；The Si of homoepitaxial is obtained by after being cooled to room temperature inside carbon felt3N4Nano wire.
Embodiment two：
1) by density be 0.48g/cm32D carbon felts be processed into size be 40mm × 30mm × 10mm cuboid, in wine
It is cleaned by ultrasonic in smart solution twice, each 15min；
2) the loading ferrocene catalyst in 2D carbon felts：With the dimethylbenzene supersaturated solution (quality of ferrocene of ferrocene
Fraction is about 15%) dipping carbon felt 1h, is dried after taking-up in drying baker；
3) polysilazane is diluted with dimethylbenzene：The volume fraction for preparing polysilazane is 15% polysilazane and dimethylbenzene
Mixed solution, magnetic agitation 1h；
4), in the mixed solution of the carbon felt immersion step 3 for preparing step 2, impregnate in being put into rapidly vacuum impregnation case, directly
Dimethylbenzene into mixed solution is blotted；
5) carbon felt in step 4 is placed in into heat treatment in horizontal pipe furnace：Risen to by room temperature with the programming rate of 6 DEG C/min
1550 DEG C, after insulation 5h, close power supply.High pure nitrogen is passed through always in whole heat treatment process, and 600 DEG C before, nitrogen flow rate
For 50cm3/ min, overpressure are 1atm；In the gentle insulating process of liter afterwards, nitrogen flow rate is controlled in 170cm3/ min, beats
Vacuum pump is opened, and overpressure is controlled for 0.6atm；After closing power supply, nitrogen flow rate is adjusted to 50cm3/ min, and close vacuum
Pump so that overpressure is 1atm；The Si of homoepitaxial is obtained by after being cooled to room temperature inside carbon felt3N4Nano wire.
Embodiment three：
1) by density be 0.45g/cm32D carbon felts be processed into size be 40mm × 30mm × 10mm cuboid, in wine
It is cleaned by ultrasonic in smart solution twice, each 15min；
2) the loading ferrocene catalyst in 2D carbon felts：With the dimethylbenzene supersaturated solution (quality of ferrocene of ferrocene
Fraction is about 15%) dipping carbon felt, and 1h is dried after taking-up in drying baker；
3) polysilazane is diluted with dimethylbenzene：The volume fraction for preparing polysilazane is 18% polysilazane and dimethylbenzene
Mixed solution, magnetic agitation 1h；
4), in the mixed solution of the carbon felt immersion step 3 for preparing step 2, impregnate in being put into rapidly vacuum impregnation case, directly
Dimethylbenzene into mixed solution is blotted；
Carbon felt in step 4 is placed in into heat treatment in horizontal pipe furnace：Risen to by room temperature with the programming rate of 6 DEG C/min
1650 DEG C, after insulation 6h, close power supply.High pure nitrogen is passed through always in whole heat treatment process, and 600 DEG C before, nitrogen flow rate
For 50cm3/ min, overpressure are 1atm；In the gentle insulating process of liter afterwards, nitrogen flow rate is controlled in 200cm3/ min, beats
Vacuum pump is opened, and overpressure is controlled for 0.5atm；After closing power supply, nitrogen flow rate is adjusted to 50cm3/ min, and close vacuum
Pump so that overpressure is 1atm；The Si of homoepitaxial is obtained by after being cooled to room temperature inside carbon felt3N4Nano wire.
Claims (8)
1. one kind grows Si in 2D carbon felts internal in-situ3N4The method of nano wire, it is characterised in that step is as follows：
Step 1, pretreatment 2D carbon felts：Using dehydrated alcohol be cleaned by ultrasonic 2D carbon felts, dry in being subsequently placed in air or baking oven in
Drying；
Step 2, in 2D carbon felts load ferrocene catalyst：With the dimethylbenzene supersaturated solution dipping carbon felt of ferrocene, take out
Dry in drying baker afterwards；The mass fraction of the ferrocene is 15%；
Step 3：In 2D carbon felts immersion mixed solution prepared by step 2, impregnate in being put into vacuum impregnation case, until mixed solution
In dimethylbenzene drained；The mixed solution is to stir polysilazane that volume fraction is 10%～18% and dimethylbenzene magnetic force
Mix to form mixed solution；
Step 4：2D carbon felts after step 3 is processed are placed in heat treatment in horizontal pipe furnace：With the programming rate of 6 DEG C/min by room
Temperature rise closes power supply to 1450 DEG C～1650 DEG C after 4～6h of insulation；High pure nitrogen is passed through always in whole heat treatment process,
600 DEG C before, and nitrogen flow rate is 50cm3/ min, overpressure are 1atm；In the gentle insulating process of liter afterwards, nitrogen flow rate
Control is in 150～200cm3/ min, opens vacuum pump, and controls overpressure for 0.5～0.7atm；After closing power supply, nitrogen
Flow velocity is adjusted to 50cm3/ min, and close vacuum pump so that overpressure is 1atm；By being cooled to after room temperature inside carbon felt
Obtain the Si being evenly distributed3N4Nano wire.
2. Si is grown in 2D carbon felts internal in-situ according to claim 13N4The method of nano wire, it is characterised in that：The 2D
The density of carbon felt is 0.1～0.6g/cm3。
3. Si is grown in 2D carbon felts internal in-situ according to claim 13N4The method of nano wire, it is characterised in that：The 2D
The thickness of carbon felt is 1mm～50mm.
4. Si is grown in 2D carbon felts internal in-situ according to claim 13N4The method of nano wire, it is characterised in that：The step
Rapid 1 dehydrated alcohol is cleaned by ultrasonic 2D carbon felts twice, each 15min.
5. Si is grown in 2D carbon felts internal in-situ according to claim 13N4The method of nano wire, it is characterised in that：The height
The purity of pure nitrogen gas is 99.999%.
6. Si is grown in 2D carbon felts internal in-situ according to claim 13N4The method of nano wire, it is characterised in that：Described two
The purity of luxuriant ferrum is pure for analysis.
7. Si is grown in 2D carbon felts internal in-situ according to claim 13N4The method of nano wire, it is characterised in that：Described two
The purity of toluene is pure for analysis.
8. Si is grown in 2D carbon felts internal in-situ according to claim 13N4The method of nano wire, it is characterised in that：It is described poly-
Silazane is commercialization Si-C-N ceramic forerunners, and english name is polyureasilazane, abbreviation PSN-2.
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| CN106602072B (en) * | 2016-12-20 | 2019-04-23 | 西北工业大学 | A kind of preparation method of high-energy density, high power density lithium ion battery |
| CN108640700B (en) * | 2018-05-14 | 2021-04-02 | 西北工业大学 | Si3N4Surface modification method of nanowire |
| CN108751197B (en) * | 2018-07-30 | 2021-10-22 | 西北工业大学 | Method for preparing 3D carbide nanowire array in situ by precursor impregnation cracking and magnetic pulling method |
| CN111205100B (en) * | 2020-03-02 | 2022-06-07 | 西北工业大学 | Method for in-situ growth of silicon carbide nanowire by non-catalytic precursor impregnation pyrolysis method |
| CN115093239B (en) * | 2022-06-05 | 2023-03-31 | 西北工业大学 | Paper with hydrophobic and fireproof performances and preparation method thereof |
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| CN101550600A (en) * | 2009-04-22 | 2009-10-07 | 中国地质大学（北京） | A method to prepare a high-purity high-density monocrystalline silicon nitride nano array |
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Patent Citations (2)
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| CN101550600A (en) * | 2009-04-22 | 2009-10-07 | 中国地质大学（北京） | A method to prepare a high-purity high-density monocrystalline silicon nitride nano array |
| CN102148161A (en) * | 2011-01-19 | 2011-08-10 | 青岛大学 | Method for preparing P-type Si3N4 nano wire field effect transistor |
Non-Patent Citations (2)
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| "In-situ synthesis and growth mechanism of silicon nitride nanowires on carbon fiber fabrics";Kaiyuan Li et al.;《Ceramics International》;20140529;第40卷;第15381-15389页 * |
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Effective date of registration: 20221103 Address after: No. 25, Yangbei Road, Luoshe Town, Huishan District, Wuxi City, Jiangsu Province, 214154 Patentee after: Wuxi Bozhi Composite Materials Co.,Ltd. Address before: 710072 No. 127 Youyi West Road, Shaanxi, Xi'an Patentee before: Northwestern Polytechnical University |