CN103061112B - Composite of carborundum and CNT and preparation method thereof - Google Patents
Composite of carborundum and CNT and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to composite of a kind of carborundum and CNT and preparation method thereof, take carbon nano-tube macroscopic body as precast body, chemical vapour deposition technique pyrolysis is adopted to contain silicon precursor by depositing SiC in CNT, prepare the composite of carborundum and CNT, the mass fraction of CNT is 0.5-90%.By selecting the various carbon nano-tube macroscopic bodies of CNT orientation and arrangement to be precast body, can obtain and there is the carborundum of high degree of dispersion, high volume content and various orientation arrangement and the composite of CNT; Can construct and prepare the carborundum of the different shape such as fiber and block and various yardstick and the composite of CNT by fiber preform design; Obtain the carborundum of multiple mechanics and electric property and the composite of CNT, be expected to as high-performance composite materials, conductive heat conducting material and functional material for fields such as Aero-Space, defence equipment and function material components.
Description
Technical field
The present invention relates to composite of a kind of carborundum and CNT and preparation method thereof, it is specifically precast body with carbon nano-tube macroscopic body, chemical vapour deposition technique pyrolysis is adopted to contain silicon precursor by depositing SiC in carbon nano-tube macroscopic body, prepare the composite of carborundum and CNT, belong to field of nanometer material technology.
Background technology
Composite material of silicon carbide has lightweight, high-strength, high tenacity, high temperature resistant, anti-thermal shock, Deng excellent mechanics and high-temperature behavior, and there is the physical property such as high connductivity, high heat conduction, be widely used in the high-tech sector such as Aero-Space, defence equipment, be also widely used in fields such as machinery, chemical industry, electronics industries.
CNT (CNT) has one-dimensional nano structure, high specific area, has the performances such as high strength, high-modulus, high tenacity and high connductivity, high-termal conductivity and electric field transmitted.The structure of these excellences, mechanics, physics and functional performance make CNT become the ideal material of Development of Novel high-performance, electric-conductivity heat-conductivity high composite and functional material.
CNT is carried out the performances such as the high specific area of complicated utilization CNT, high strength, high-modulus and high tenacity to mate with silicon carbide substrate form good interface cohesion as reinforcement and carborundum, there is little interfacial stress, be expected to obtain high-strength, shock resistance, high-performance fiber that is high temperature resistant and anti-thermal shock strengthens composite material of silicon carbide.
Utilize the one-dimensional nano structure of CNT uniqueness, high connductivity and high thermal conductivity, interconnective conduction and heat conduction network can be formed in silicon carbide substrate, realize composite carrying, be on active service and the Real-Time Monitoring of actual effect stress, development has the novel silicon carbide based composites of intelligent characteristic.
Chinese patent CN201010540199.9A discloses the silicon carbide fibre stereo fabric that a kind of growth in situ has CNT, this silicon carbide fibre stereo fabric forms primarily of silicon carbide fibre braiding, the even carbon nanotube of growth in situ is distributed in silicon carbide fibre surface, and CNT is wound in network structure mutually.Its preparation method comprises the following steps: first carry out preliminary treatment to silicon carbide fibre stereo fabric; Catalyst precursor vacuum impregnation-reducing process is adopted to load Ni-La-Al composite catalyst again; Finally carry out chemical vapour deposition (CVD), make growth in situ on silicon carbide fibre stereo fabric go out CNT.The method use catalyst, complex process, condition is comparatively harsh, and cost is higher.
The composite adopting chemical vapour deposition technique to prepare carborundum and CNT with the macroscopic body that CNT forms for precast body has no report.
Summary of the invention
The object of the present invention is to provide composite of a kind of carborundum and CNT and preparation method thereof.With the macroscopic body of CNT composition for precast body, chemical vapour deposition technique is adopted to prepare the composite of carborundum and CNT.Electrical heating can realize the composite of the efficient depositing SiC of Fast Heating for the preparation of carborundum and CNT as efficient local heating means.The present invention can prepare the composite of various content of carbon nanotubes and homodisperse carborundum and CNT.And CNT can be prepared there is the carborundum of unidirectional array and the various carborundum of CNT orientation of CNT and the composite of CNT.
Chemical vapour deposition technique can form uniform silicon carbide layer in carbon nano tube surface, there is the advantages such as the controlled and depositing silicon carbide of reaction is controlled, by controlling content and the thickness of the Parameter adjustable control carborundum such as depositing temperature, time and air pressure, these have the uniform carburized carborundum of silicon layer enveloped carbon nanometer tube structure and the composite of CNT and have high-strength, electric-conductivity heat-conductivity high and the performance such as anti-oxidant, are used for association area as high performance structures and functional material.
The composite of carborundum provided by the invention and CNT is with CNT and contains silicon precursor for raw material, in electrical heating precipitation equipment, carbon nano-tube macroscopic body is precast body, by chemical vapor deposition pyrolytic containing silicon precursor, by depositing SiC in carbon nano-tube macroscopic body, form the carborundum of different content of carbon nanotubes and carbon nanotube architecture and the composite of CNT.The mass fraction of CNT can be 0.5-90%.Alternatively, the mass fraction of CNT can be 5-85%,
Described CNT is Single Walled Carbon Nanotube, double-walled carbon nano-tube, the mixture of one or more of multi-walled carbon nano-tubes.
Described carbon nano-tube macroscopic body is the precast body that carbon nano-tube fibre or carbon nano-tube fibre are formed.
Described contains the mixing of one or more that silicon precursor is methylchlorosilane, methyl-monosilane, silicon-containing compound or carbon compound mixture.
Described depositing SiC temperature used is 1000-1200 oC.
The carrier gas used of described depositing SiC is the mixing of one or more in hydrogen, argon gas, nitrogen.
Described depositing SiC air pressure used is 10-101 kPa.
The step that the concrete preparation method of composite of carborundum provided by the invention and CNT comprises:
Carbon nano-tube fibre is processed into according to a conventional method and determines that the carbon nano-tube macroscopic body of shape is as precast body, precast body to be placed in electrical heating precipitation equipment between two electrodes, logical argon gas 1-2 h gets rid of the air in quartz ampoule, opening power, voltage is set to 15-22 V, to precast body electrified regulation, control preform temperatures 900-1400 oC, adopt hydrogen, argon gas, nitrogen is carrier gas (flow 20-40 sccm), preferred argon gas, quartz ampoule will be loaded into containing silicon precursor, air pressure in quartz ampoule is 1-101 kPa, silicon precursor pyrolysis by depositing SiC in precast body, sedimentation time is 15-45 min, power-off is stopped the supple of gas or steam, naturally cool to room temperature.
The step that the concrete preparation method of composite of carborundum provided by the invention and CNT comprises:
Carbon nano-tube fibre is processed into according to a conventional method the precast body determining shape, precast body to be placed in electrical heating precipitation equipment between two electrodes, logical argon gas 1-2 h gets rid of the air in quartz ampoule, opening power, voltage is set to 15-19 V, to precast body electrified regulation, control preform temperatures 1000-1100 oC, employing argon gas is carrier gas (flow 20-40 sccm), trichloromethyl silane is loaded into quartz ampoule, air pressure in quartz ampoule is 30-101 kPa, pyrolysis, by depositing SiC in precast body, sedimentation time is 15-35 min, power-off is stopped the supple of gas or steam, naturally cool to room temperature.
The present invention utilizes carbon nano-tube macroscopic body for precast body, by carrying out the braiding of various orientation to carbon nano-tube fibre, form the carbon nano-tube macroscopic body of different carbon nanotube architecture, there is various content of carbon nanotubes, the composite of specific orientation and homodisperse carborundum and CNT by chemical vapor deposition of silicon carbide preparation.
Composite of carborundum provided by the invention and CNT and preparation method thereof, adopt chemical vapour deposition technique can form uniform silicon carbide layer in carbon nano tube surface, there is the advantages such as the controlled and depositing silicon carbide of reaction is controlled, by controlling content and the thickness of the Parameter adjustable control carborundum such as depositing temperature, time and air pressure, electrical heating can realize the efficient depositing SiC of Fast Heating as efficient local heating means.Thus the composite of various content of carbon nanotubes and homodisperse carborundum and CNT can be prepared.And CNT can be prepared there is the carborundum of unidirectional array and the various carborundum of CNT orientation of CNT and the composite of CNT.The present invention prepares the composite of carborundum and CNT.These have the uniform carburized carborundum of silicon layer enveloped carbon nanometer tube structure and the composite of CNT and have high-strength, electric-conductivity heat-conductivity high and the performance such as anti-oxidant, can be used as high performance structures conductive heat conducting material and functional material, for association area, be expected to especially as high-performance composite materials, for fields such as Aero-Space, defence equipment and function material components.
Accompanying drawing explanation
Fig. 1 is electrical heating precipitation equipment schematic diagram of the present invention.
Fig. 2 is the optical photograph of example 1 electrical heating carbon nano-tube fibre precast body.
Fig. 3 is the surface sweeping electromicroscopic photograph of example 1 carborundum and carbon nano tube compound material.
Fig. 4 is the surface sweeping electromicroscopic photograph of example 1 carborundum and carbon nano tube compound material.
Fig. 5 is the high magnification stereoscan photograph of example 1 carborundum and carbon nano tube compound material.
Fig. 6 is the infared spectrum of example 1 carborundum and carbon nano tube compound material.
Fig. 7 is the Raman collection of illustrative plates of example 1 carborundum and carbon nano tube compound material.
Detailed description of the invention
Be further described below in conjunction with embodiment, but do not limit the scope of the invention with this:
Fig. 1 electrical heating precipitation equipment schematic diagram, wherein, 1 flowmeter; 2 switches; 3 containing silicon precursor; 4 quartz ampoules; 5 carbon nano-tube macroscopic bodies; 6 graphite electrodes; 7 wires; 8 polytetrafluoro flanges.
Electrical heating precipitation equipment is made up of reactor, power supply and pipeline.Reactor is that quartz ampoule 4 two ends polytetrafluoro flange 8 seals, and two graphite electrodes 6 are installed at middle part, and for fixing carbon nano-tube macroscopic body 5 and on-load voltage, electrode connects outside voltage stabilization and current stabilization dc source.Carrier gas flux is regulated by flowmeter 1.For monitoring temperature in the middle part of infrared radiation thermometer Signal reception window aligned carbon nanotubes macroscopic body 5.
Prepare according to the chemical gaseous phase spin processes of patent CN101665997A report for the preparation of carborundum and carbon nano tube compound material carbon nano-tube fibre used.Being 4 cm(diameter ~ 150 μm by about 40 and length) carbon nano-tube fibre forward twists composition depositing silicon carbide precast body (carbon nano-tube macroscopic body) used, and precast body is rod shape.In the quartz ampoule 4 precast body being sandwiched in electrical heating precipitation equipment between two graphite electrodes 6, logical argon gas (160 sccm) 2 h gets rid of the air in quartz ampoule, opening power (YH-1718-5, voltage stabilization and current stabilization dc source, Beijing great Hua company) voltage is set to 19 V, to precast body electrified regulation, use infrared radiation thermometer (Raytek-Raynger-3i, range 600-3000 oC, Lei Tai company of the U.S.) thermometric, infrared radiation thermometer display preform temperatures reaches 1100 oC, accompanying drawing 2 is electrical heating precast body optical photographs when reaching depositing temperature, adopt argon gas (40 sccm), as carrier gas, trichloromethyl silane is loaded into quartz ampoule 4, air pressure in quartz ampoule 4 is 101 kPa, trichloromethyl silane pyrolysis by depositing SiC in precast body, deposit 15 min, power-off is stopped the supple of gas or steam, naturally cool to room temperature, the composite of obtained carborundum and CNT.Weigh quality before and after preform deposition, composite carbon nanotube mass mark is 90%.Composite material surface pattern is observed, material surface dense uniform, as accompanying drawing 3 with ESEM (SEM, TDCLS-4800, Toshiba Corp).High magnification observe composite cross section, have a large amount of depositing SiC in tube bank and interbank, as accompanying drawing 4.Observe composite inner, nanometer silicon carbide uniform particles is distributed in CNT interfascicular, diameter 100-120 nm, and also coated carborundum on carbon nano-tube bundle, as accompanying drawing 5.Infrared spectrum (Bio-Rad FTS 6000,400-4000 cm
-1, Beijing Rayleigh Analytical Instrument Co., Ltd) and COMPOSITE MATERIALS is at 780 cm
-1there is Si-C characteristic peak at place, shows that SiC has deposited to precast body, as accompanying drawing 6.Raman spectrum (DXR, laser 532 nm, 100-3500 cm
-1, the U.S.) and COMPOSITE MATERIALS is at 813 cm
-1there is SiC characteristic peak at place, further demonstrate that the existence of SiC, as accompanying drawing 7.
Embodiment 2:
Adopt the method that example 1 is identical, turn down voltage, make depositing temperature 1100 oC be reduced to the composite that 1050 oC obtain carborundum and CNT.It is 0.81 g/cm that drainage records composite density
3.
Embodiment 3:
Adopt the method that example 1 is identical, sedimentation time 15 min is extended for the composite that 35 min obtain carborundum and CNT.Weigh quality before and after preform deposition, composite carbon nanotube mass mark is 85%.
Embodiment 4:
Adopt the method that example 1 is identical, turn down voltage, make depositing temperature 1100 oC be reduced to the composite that 1000 oC obtain carborundum and CNT.
Embodiment 5:
Adopt the method that embodiment 1 is identical, carrier gas argon gas is changed into the composite of the obtained carborundum of hydrogen (20 sccm) and CNT.In composite, carborundum evenly wraps up carbon nano-tube bundle.
Embodiment 6:
Adopt the method that embodiment 5 is identical, turn down voltage, make depositing temperature 1100 oC be reduced to the composite that 1050 oC obtain carborundum and CNT.
Embodiment 7:
Adopt the method that embodiment 1 is identical, quartz ampoule internal gas pressure 101 kPa is reduced to the composite that 30 kPa obtain carborundum and CNT.
Embodiment 8:
Adopt the method that embodiment 1 is identical, quartz ampoule internal gas pressure 101 kPa is reduced to the composite that 10 kPa obtain carborundum and CNT.
Embodiment 9:
Adopt the method that embodiment 5 is identical, quartz ampoule internal gas pressure 101 kPa is reduced to the composite that 30 kPa obtain carborundum and CNT.
Embodiment 10:
Adopt the method that embodiment 1 is identical, precast body is changed into the composite fibre that carbon nano-tube fibre obtains carborundum and CNT.Carborundum evenly wraps up carbon nano-tube fibre.
Embodiment 11:
Adopt the method that embodiment 10 is identical, carrier gas argon gas is changed into the composite fibre of the obtained carborundum of hydrogen and CNT.
Embodiment 12:
Adopt the method that embodiment 10 is identical, quartz ampoule internal gas pressure 101 kPa is reduced to the composite fibre that 30 kPa obtain carborundum and CNT.
Embodiment 13:
Adopt the method that embodiment 10 is identical, quartz ampoule internal gas pressure 101 kPa is reduced to the composite fibre that 5 kPa obtain carborundum and CNT.
Claims (1)
1. a preparation method for the composite of carborundum and CNT, is characterized in that the step comprised:
Be 4 cm by 40 and length, diameter is that the carbon nano-tube fibre of 150 μm forward twists composition depositing silicon carbide precast body used, i.e. carbon nano-tube macroscopic body, and precast body is rod shape, in quartz ampoule precast body being sandwiched in electrical heating precipitation equipment between two graphite electrodes, logical 160 sccm argon gas 2 h get rid of the air in quartz ampoule, opening power, voltage is set to 19 V, to precast body electrified regulation, use infrared radiation thermometer thermometric, infrared radiation thermometer display preform temperatures reaches 1100 oC, adopt the argon gas of 40 sccm, as carrier gas, trichloromethyl silane is loaded into quartz ampoule, air pressure in quartz ampoule is 101 kPa, trichloromethyl silane pyrolysis by depositing SiC in precast body, deposit 15 min, power-off is stopped the supple of gas or steam, naturally cool to room temperature, the composite of obtained carborundum and CNT,
Wherein, electrical heating precipitation equipment is made up of reactor, power supply and pipeline, and reactor is quartz ampoule two ends polytetrafluoro flange seals, and two graphite electrodes are installed at middle part, for fixing carbon nano-tube macroscopic body and on-load voltage, electrode connects outside voltage stabilization and current stabilization dc source; Carrier gas flux is regulated by flowmeter; For monitoring temperature in the middle part of infrared radiation thermometer Signal reception window aligned carbon nanotubes macroscopic body.
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| CN103911597B (en) * | 2014-04-22 | 2017-01-25 | 武汉理工大学 | Preparation method of silicon carbide film |
| CN105693263B (en) * | 2016-01-14 | 2018-04-06 | 西北工业大学 | A kind of preparation method of CNT multidimensional braiding precast body ceramic matric composite |
| CN105970185B (en) * | 2016-04-22 | 2018-05-08 | 太仓派欧技术咨询服务有限公司 | A kind of preparation method of carbon nanotubes-SiC films |
| CN106631079B (en) * | 2016-12-19 | 2019-04-16 | 中国人民解放军国防科学技术大学 | Carbon nanotube composite material of silicon carbide and preparation method thereof |
| CN108863434A (en) * | 2017-05-09 | 2018-11-23 | 天津大学 | A kind of high-content carbon nanotube enhancing PRECURSOR-DERIVED CERAMICS composite material and preparation method |
| CN108977795B (en) * | 2017-05-31 | 2021-01-12 | 中国科学院金属研究所 | Device and method for preparing silicon carbide coating by using electric coupling chemical vapor deposition method |
| CN107311685B (en) * | 2017-06-23 | 2020-05-12 | 西北工业大学 | Preparation method for in-situ synthesis of refractory metal carbide nanowires by electrophoresis and thermal evaporation technology |
| CN108598377B (en) * | 2018-01-26 | 2020-05-12 | 河北工业大学 | Preparation method of sulfur-silicon carbide doped carbon nanotube material |
| CN110950323A (en) * | 2019-12-19 | 2020-04-03 | 湖南德智新材料有限公司 | Carbon nanotube-silicon carbide nanowire composite material and preparation method thereof |
| CN113896559B (en) * | 2021-11-19 | 2023-04-28 | 山东建筑大学 | Silicon carbide/carbon nano tube composite material and preparation method thereof |
| CN114436660A (en) * | 2022-02-22 | 2022-05-06 | 合肥工业大学 | Preparation method of carbon nano tube-ceramic composite membrane |
| CN115709996A (en) * | 2022-11-05 | 2023-02-24 | 西北工业大学 | Preparation method of SiC micron tube macroscopic body |
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