CN103088648B - Preparation method for carbon fiber material with composite nano structure - Google Patents
Preparation method for carbon fiber material with composite nano structure Download PDFInfo
- Publication number
- CN103088648B CN103088648B CN201310028102.XA CN201310028102A CN103088648B CN 103088648 B CN103088648 B CN 103088648B CN 201310028102 A CN201310028102 A CN 201310028102A CN 103088648 B CN103088648 B CN 103088648B
- Authority
- CN
- China
- Prior art keywords
- gas
- carbon
- carbon cloth
- flow
- minutes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to a preparation method for a carbon fiber material with a composite nano structure. The preparation method comprises the following steps of: pretreating carbon fiber cloth, adhering a layer of thin iron film catalyst on the carbon fiber cloth by a liquid-phase method or a physical deposition method, in a chemical gas-phase reaction chamber, carrying out in-situ growth of carbon nanotubes on the carbon fiber cloth by using argon or nitrogen as a carrier gas, ethylene or acetylene gas as a carbon source gas, and hydrogen as a reducing gas, then carrying a gas containing titanium organism into the chemical gas-phase deposition reaction chamber through the carrier gas, growing titanium dioxide at the peripheries of the carbon nanotubes to form titanium dioxide nanoshells which wrap the carbon nanotubes, thus obtaining the carbon fiber material with the composite nano structure. The carbon fiber material obtained by the preparation method has the advantages of high mechanical strength, high thermal stability, good chemical inertness and high adsorption property, supernormal strength of carbon nanotubes, large length-diameter ratio, high thermal conductivity, good catalytic activity, high chemical stability, non-toxicity and super-hydrophilicity. The carbon fiber material with the composite nano structure can have important applications in photocatalysis, electrocatalysis and other aspects.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of composite nanostructure carbon fibre material.
Background technology
Carbon fiber is the micro crystal graphite material obtained through carbonization and graphitization processing by organic fiber.Carbon fiber has excellent mechanical property, and its proportion is less than 1/4 of steel, and carbon fiber resin composite material tensile strength is 7-9 times of steel, and tensile modulus of elasticity is also higher than steel.Carbon fiber also has unique chemical property, it be phosphorus content higher than 90% inorganic polymer fiber, its fatigue durability is good, specific heat and electric conductivity are between nonmetal and metal, and thermal coefficient of expansion is little, good corrosion resistance, the density of fiber is low, and X-ray transparent is good, and chemical stability is strong.So carbon fibre material is at present as protective materials, radiation resistance material, aviation and wide and electrode material, be widely used.
CNT is as monodimension nanometer material, lightweight, has many abnormal mechanics, calorifics, electricity and chemical property.CNT is because have huge specific surface, and the rejected region on its surface is with numerous active group, so CNT is also in order to make the composite of a lot of excellent performance.
Titanium dioxide nano material is the best catalysis material of current performance, has high catalytic activity, high stability.Nano titania material also shows great application prospect in fuel cell and photochemical breakdown water simultaneously, and the green energy resource for future solves and provides engineering feasibility.
But at present carbon fibre material and the nano combined mode of carbon all divides two steps to complete, and namely first grow CNT, then the dispersion liquid obtaining CNT in carbon nanotube dispersed to solution, utilize the carbon nano tube dispersion liquid after disperseing again with carbon fiber compound.The shortcoming of this preparation carbon fiber/carbon nanotube composite material and preparation method thereof is: (1) carbon nanotube dispersed is undesirable, is difficult to form single dispersing, so the excellent properties of CNT itself is not reflected after compound; (2) CNT first grows rear compound, be not growth in situ on carbon fiber, so the combination of the two is more weak, so the CNT after compound is easy to depart from carbon fiber.
Preparing the shortcoming of carbon fiber/carbon nanotube composite in order to overcome existing two step method, the invention provides a kind of method that in situ synthesis prepares composite nanostructure carbon fibre material.
Summary of the invention
The object of the invention is, a kind of preparation method of composite nanostructure carbon fibre material is provided, the method is realized by in-situ growing carbon nano tube on carbon cloth and nano titanium oxide, by carbon cloth first through preliminary treatment, then on carbon cloth, one deck iron thin film catalyst is adhered to by liquid phase method or physical deposition methods, by load, chemical gas phase reaction room put into by the carbon cloth of catalyst, carrier gas is done with argon gas or nitrogen, carbon-source gas is made with ethene or acetylene gas, hydrogen makes reducing gas, in-situ growing carbon nano tube on carbon cloth, to be brought in chemical vapor deposition reaction chamber by carrier gas containing the organic gas of titanium again, at CNT periphery growth titanium dioxide, form coated nano titania shell on the carbon nanotubes, obtain composite nanostructure carbon fibre material, the material obtained by method of the present invention possesses the high mechanical properties of carbon fiber, high heat stability performance, good chemical inertness and high absorption property, possesses the intensity that CNT is extraordinary simultaneously, huge draw ratio, high thermal conductivity, good catalytic activity, possesses again the chemical stability that nano titanium oxide is high, avirulence, Superhydrophilic, excellent photocatalysis performance.Therefore this composite nanostructure carbon fibre material can obtain important application in photocatalysis, electro-catalysis etc.
The preparation method of a kind of composite nanostructure carbon fibre material of the present invention, follows these steps to carry out:
A, carbon cloth carry out preliminary treatment: carbon cloth being put into concentration is in the sodium carbonate liquor of 20-40g/L, temperature is 60 DEG C, ultrasonic assistant cleans 30 minutes, by washed with de-ionized water, to carbon cloth be put in acetone soln again, ultrasonic assistant cleans 20 minutes, then in air atmosphere, by carbon cloth temperature 400 DEG C of heat treatments 30 minutes;
B, by liquid phase method, pretreated carbon cloth is put into the FeCl that concentration is 0.05-1.00mol/L
3flood in solution, obtain carbon cloth adhering to one deck Fe catalyst, then cleaned air is passed in vapour deposition indoor, temperature 450 DEG C to the Fe catalyst heat treatment that carbon cloth adheres to 15 minutes, then temperature is to 650-700 DEG C, and passing into flow is that the hydrogen of 30-100sccm carries out reductase 12-8 minutes;
Or pass through physical vaporous deposition, take purity as the Fe of 99.99% be target, by carbon cloth by magnetron sputtering or hot vapor deposition, the thickness of the Fe film that carbon cloth adheres to is 0.5-8nm, the carbon cloth that attached to Fe catalyst is directly sent into CVD chamber, be warming up to 600-700 DEG C with the heating rate of temperature 50 C/min, then passing into flow is that the hydrogen of 10-80sccm carries out reductase 12-8 minutes;
C, the carbon cloth obtained by liquid phase method or physical vaporous deposition in step b is passed through chemical gas-phase method, carrier gas is done with argon gas or nitrogen, carbon-source gas is made with ethene or acetylene gas, hydrogen makes reducing gas, reaction temperature is 600-700 DEG C, and the time is 1-30 minute in-situ growing carbon nano tube on carbon cloth;
D, pass through chemical gas-phase method, first do carrier gas with argon gas or nitrogen to rinse phase depositing reaction chamber, gas flow is 300-600sccm, washing time is 5-8 minute, do carrier gas with argon gas or nitrogen again, make titanium source gas with tetraisopropoxy titanium steam, reaction temperature is 300-720 DEG C, time is outside CNT, grow nano titania shell in 5-30 minute, can obtain composite nanostructure carbon fibre material.
In step c, argon gas or nitrogen make the flow of carrier gas is 50-500sccm, and the flow that ethene or acetylene gas make carbon-source gas is 20-200sccm, and the flow that hydrogen makes reducing gas is 5-50 sccm.
In steps d, argon gas or nitrogen make the flow of carrier gas is 50-300sccm, and the flow that tetraisopropoxy titanium steam makes titanium source gas is 10-250sccm.
The preparation method of a kind of composite nanostructure carbon fibre material of the present invention, the advantage of the method is, CNT and nano titanium oxide all realize compound by growth in situ, do not connected by physical absorption, common surface large between CNT and carbon fiber, in conjunction with tight, the nano titania shell grown outside CNT, titanium dioxide is wherein greater than 95% from the ratio of institutional framework single crystal titanium dioxide point, only have is unbodied and titanium dioxide that is polycrystalline a little, in single crystal titanium dioxide, ratio shared by anatase structured titanium dioxide is greater than 90%, so farthest remain the advantage of respective material itself, the composite nanostructure carbon fibre material finally obtained is allowed to be the best performance.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the method that the present invention prepares composite nanostructure carbon fibre material is described in further detail, but the present invention is not only limited to the embodiment provided.
Embodiment 1
A, preliminary treatment is carried out to carbon cloth: it is in the sodium carbonate liquor of 30g/L that the biaxially carbon cloth of 100 × 100mm is put into concentration, be 60 DEG C by heating by electric cooker to solution temperature, ultrasonic assistant cleans 30 minutes, by washed with de-ionized water 2 times, put in acetone soln by carbon cloth again, ultrasonic assistant cleans 20 minutes, then in air atmosphere, carbon cloth is put in the tube furnace of both ends open, temperature 400 DEG C of heat treatments 30 minutes;
B, by liquid phase method, pretreated carbon cloth is put into the FeCl that concentration is 0.4 mol/L
3flood in solution, obtain carbon cloth adhering to one deck Fe catalyst, then in CVD chamber, cleaned air is passed into, temperature 450 DEG C to the Fe catalyst heat treatment that carbon cloth adheres to 15 minutes, then temperature to 650 DEG C, passing into flow is that the hydrogen of 60sccm carries out reduction 5 minutes;
C, the carbon cloth obtained by liquid phase method in step b is passed through chemical gas-phase method, be that 100sccm does carrier gas with the flow of argon gas, be that 50sccm gas makes carbon-source gas with the flow of acetylene, the flow of hydrogen is that 25sccm makes reducing gas, reaction temperature is 600 DEG C, and the time is 12 minutes in-situ growing carbon nano tubes on carbon cloth;
D, pass through chemical gas-phase method, first do carrier gas with argon gas to rinse phase depositing reaction chamber, gas flow is 600sccm, washing time is 5 minutes, object gets rid of other gas in reative cell, for growth of nano titanium dioxide provides clean environment, be that 120sccm does carrier gas with the flow of argon gas again, be that 18sccm makes titanium source gas with the flow of tetraisopropoxy titanium steam, reaction temperature is 480 DEG C, time is 16 minutes, nano titania shell is grown outside CNT, composite nanostructure carbon fibre material can be obtained, the wherein length average out to 750 μm of CNT, the thickness average out to 8nm of the nano titanium oxide shell of CNT periphery, anatase structured for monocrystalline.
Embodiment 2
A, carry out preliminary treatment to carbon cloth: it is in the sodium carbonate liquor of 20g/L that the three axial carbon fibres cloth of 120 × 120mm are put into concentration, be 60 DEG C by heating by electric cooker to solution temperature, ultrasonic assistant cleans 30 minutes, by washed with de-ionized water 2 times; Put in acetone soln by carbon cloth again, ultrasonic assistant cleans 20 minutes, then in air atmosphere, is put into by carbon cloth in the tube furnace of both ends open, temperature 400 DEG C of heat treatments 30 minutes;
B, pass through physical vaporous deposition, take purity as the Fe of 99.99% be target, by carbon cloth by hot vapor deposition, the thickness of the Fe film that carbon cloth adheres to is 5nm, the carbon cloth that attached to Fe catalyst is directly sent into CVD chamber, be warming up to 680 DEG C with the heating rate of temperature 50 C/min, then passing into flow is that the hydrogen of 80sccm carries out reductase 12 minute;
C, the carbon cloth obtained by physical vaporous deposition in step b is passed through chemical gas-phase method, be that 200sccm does carrier gas with the flow of nitrogen, be that 120sccm makes carbon-source gas with the flow of ethylene gas, the flow of hydrogen is that 50sccm makes reducing gas, reaction temperature is 700 DEG C, time is 15 minutes, in-situ growing carbon nano tube on carbon cloth;
D, pass through chemical gas-phase method, first do carrier gas with nitrogen to rinse phase depositing reaction chamber, gas flow is 300sccm, washing time is 8 minutes, object gets rid of other gas in reative cell, for growth of nano titanium dioxide provides clean environment, be that 200sccm does carrier gas with the flow of nitrogen again, be that 50sccm makes titanium source gas with the flow of tetraisopropoxy titanium steam, reaction temperature is 430 DEG C, time is outside CNT, grow nano titania shell in 12 minutes, composite nanostructure carbon fibre material can be obtained, the wherein length average out to 720 μm of CNT, the thickness average out to 5nm of the nano titanium oxide shell of CNT periphery, anatase structured for monocrystalline.
Embodiment 3
A, preliminary treatment is carried out to carbon cloth: it is in the sodium carbonate liquor of 40g/L that the biaxially carbon cloth of 100 × 100 mm is put into concentration, solution temperature is 60 DEG C, ultrasonic assistant cleans 30 minutes, by washed with de-ionized water 2 times, put in acetone soln by carbon cloth again, ultrasonic assistant cleans 20 minutes, then in air atmosphere, carbon cloth is put in the tube furnace of both ends open, temperature 400 DEG C of heat treatments 30 minutes;
B, pass through physical vaporous deposition, take purity as the Fe of 99.99% be target, carbon cloth is passed through magnetron sputtering deposition, the thickness of the Fe film that carbon cloth adheres to is 0.5 nm, the carbon cloth that attached to Fe catalyst is directly sent into CVD chamber, be warming up to 600 DEG C with the heating rate of temperature 50 C/min, then passing into flow is that the hydrogen of 10 sccm carries out reductase 12 minute;
C, the carbon cloth obtained by physical vaporous deposition in step b is passed through chemical gas-phase method, be that 50sccm does carrier gas with the flow of nitrogen, be that 20sccm makes carbon-source gas with the flow of ethylene gas, the flow of hydrogen is that 5sccm makes reducing gas, reaction temperature is 600 DEG C, and the time is 1 minute in-situ growing carbon nano tube on carbon cloth;
D, pass through chemical gas-phase method, first do carrier gas with argon gas to rinse phase depositing reaction chamber, gas flow is 600sccm, washing time is 6 minutes, object gets rid of other gas in reative cell, for growth of nano titanium dioxide provides clean environment, be that 50sccm does carrier gas with the flow of nitrogen, be that 10 sccm make titanium source gas with the flow of tetraisopropoxy titanium steam, reaction temperature is 300 DEG C, time is outside CNT, grow nano titania shell in 5 minutes, composite nanostructure carbon fibre material can be obtained, the wherein length average out to 50 μm of CNT, the thickness average out to 6nm of the nano titanium oxide shell of CNT periphery, anatase structured for monocrystalline.
Embodiment 4
A, preliminary treatment is carried out to carbon cloth: it is in the sodium carbonate liquor of 35g/L that carbon cloth is put into concentration by the three axial carbon fibres cloth of 120 × 120 mm, solution temperature is 60 DEG C, ultrasonic assistant cleans 30 minutes, by washed with de-ionized water, to carbon cloth be put in acetone soln again, ultrasonic assistant cleans 20 minutes, then in air atmosphere, carbon cloth is put in the tube furnace of both ends open, temperature 400 DEG C of heat treatments 30 minutes;
B, by liquid phase method, pretreated carbon cloth is put into the FeCl that concentration is 1.00 mol/L
3flood in solution, obtain carbon cloth adhering to one deck Fe catalyst, then cleaned air is passed in vapour deposition indoor, temperature 450 DEG C to the Fe catalyst heat treatment that carbon cloth adheres to 15 minutes, then temperature to 700 DEG C, passing into flow is that the hydrogen of 100sccm carries out reduction 8 minutes;
C, the carbon cloth obtained by liquid phase method in step b is passed through chemical gas-phase method, be that 500sccm does carrier gas with the flow of argon gas, be that 200 sccm make carbon-source gas with the flow of ethylene gas, the flow of hydrogen is that 50sccm makes reducing gas, reaction temperature is 700 DEG C, and the time is 30 minutes in-situ growing carbon nano tubes on carbon cloth;
D, pass through chemical gas-phase method, first do carrier gas with argon gas to rinse phase depositing reaction chamber, gas flow is 600 sccm, washing time is 7 minutes, object gets rid of other gas in reative cell, for growth of nano titanium dioxide provides clean environment, be that 300 sccm do carrier gas with the flow of argon gas, titanium source gas is made with flow 250 sccm of tetraisopropoxy titanium steam, reaction temperature is 720 DEG C, time is outside CNT, grow nano titania shell in 30 minutes, composite nanostructure carbon fibre material can be obtained, the wherein length average out to 920 μm of CNT, the thickness average out to 25nm of the nano titanium oxide shell of CNT periphery, anatase structured for monocrystalline.
Claims (1)
1. a preparation method for composite nanostructure carbon fibre material, is characterized in that following these steps to carry out:
A, carbon cloth carry out preliminary treatment: carbon cloth being put into concentration is in the sodium carbonate liquor of 20-40g/L, temperature is 60 DEG C, ultrasonic assistant cleans 30 minutes, by washed with de-ionized water, to carbon cloth be put in acetone soln again, ultrasonic assistant cleans 20 minutes, then in air atmosphere, by carbon cloth temperature 400 DEG C of heat treatments 30 minutes;
B, by liquid phase method, pretreated carbon cloth is put into the FeCl that concentration is 0.05-1.00mol/L
3flood in solution, obtain carbon cloth adhering to one deck Fe catalyst, then cleaned air is passed in vapour deposition indoor, temperature 450 DEG C to the Fe catalyst heat treatment that carbon cloth adheres to 15 minutes, then temperature is to 650-700 DEG C, and passing into flow is that the hydrogen of 30-100sccm carries out reductase 12-8 minutes;
Or pass through physical vaporous deposition, take purity as the Fe of 99.99% be target, by carbon cloth by magnetron sputtering or hot vapor deposition, the thickness of the Fe film that carbon cloth adheres to is 0.5-8nm, the carbon cloth that attached to Fe catalyst is directly sent into CVD chamber, be warming up to 600-700 DEG C with the heating rate of temperature 50 C/min, then passing into flow is that the hydrogen of 10-80sccm carries out reductase 12-8 minutes;
C, the carbon cloth obtained by liquid phase method or physical vaporous deposition in step b is passed through chemical gas-phase method, carrier gas is done with argon gas or nitrogen, carbon-source gas is made with ethene or acetylene gas, hydrogen makes reducing gas, reaction temperature is 600-700 DEG C, time is 1-30 minute in-situ growing carbon nano tube on carbon cloth, wherein argon gas or nitrogen make the flow of carrier gas is 50-500sccm, the flow that ethene or acetylene gas make carbon-source gas is 20-200 sccm, and the flow that hydrogen makes reducing gas is 5-50sccm;
D, pass through chemical gas-phase method, first do carrier gas with argon gas or nitrogen to rinse phase depositing reaction chamber, gas flow is 300-600sccm, washing time is 5-8 minute, be 50-300sccm with the flow that argon gas or nitrogen do carrier gas again, the flow making titanium source gas with tetraisopropoxy titanium steam is 10-250 sccm, and reaction temperature is 300-720 DEG C, time is outside CNT, grow nano titania shell in 5-30 minute, can obtain composite nanostructure carbon fibre material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310028102.XA CN103088648B (en) | 2013-01-25 | 2013-01-25 | Preparation method for carbon fiber material with composite nano structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310028102.XA CN103088648B (en) | 2013-01-25 | 2013-01-25 | Preparation method for carbon fiber material with composite nano structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103088648A CN103088648A (en) | 2013-05-08 |
| CN103088648B true CN103088648B (en) | 2015-01-07 |
Family
ID=48201743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310028102.XA Expired - Fee Related CN103088648B (en) | 2013-01-25 | 2013-01-25 | Preparation method for carbon fiber material with composite nano structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103088648B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104291313A (en) * | 2014-09-26 | 2015-01-21 | 青岛科技大学 | Preparation method of nano carbon fiber |
| CN104862948B (en) * | 2015-04-28 | 2017-01-25 | 武汉纺织大学 | Production method of color carbon fibers |
| CN105107509A (en) * | 2015-09-08 | 2015-12-02 | 徐金富 | Flexible loading type carbon fiber loaded CoB catalyst and preparation method thereof |
| CN108625159A (en) * | 2017-03-24 | 2018-10-09 | 山东大学 | Device and method for carbon cloth surface homoepitaxial carbon nanotube |
| CN108360250A (en) * | 2018-02-05 | 2018-08-03 | 天津大学 | A kind of preparation method of carbon nano-tube in situ modified carbon fiber reinforced resin based structures-damp composite material |
| CN109092245B (en) * | 2018-08-24 | 2020-12-22 | 华南理工大学 | Diatomite-loaded carbon nanotube adsorbent and preparation method thereof |
| CN111389365B (en) * | 2020-04-16 | 2022-11-25 | 郑州大学 | Carbon nanotube/titanium dioxide composite film and preparation method and application thereof |
| CN111900423A (en) * | 2020-06-29 | 2020-11-06 | 华南理工大学 | Flexible air electrode, flexible metal-air battery and wearable electronic equipment |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005026430A1 (en) * | 2003-09-16 | 2005-03-24 | Showa Denko K. K. | Composite of vapor grown carbon fiber and inorganic fine particle and use thereof |
| CN1695797A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing photocatalyst of titanium dioxide carried by active carbon |
| CN1736585A (en) * | 2005-07-18 | 2006-02-22 | 华东理工大学 | Nano carbon fiber/graphite felt compound catalytic material and preparation process thereof |
| CN1877774A (en) * | 2005-06-03 | 2006-12-13 | 北京汉纳源纳米科技有限公司 | Linear nano carbon tube composite-field emission source and method for preparing same and dedicated device therefor |
| CA2779493A1 (en) * | 2009-12-01 | 2011-06-30 | Applied Nanostructured Solutions, Llc | Metal matrix composite materials containing carbon nanotube-infused fiber materials and methods for production thereof |
| CN102553531A (en) * | 2012-01-13 | 2012-07-11 | 同济大学 | Preparation method of multiporous carbonaceous adsorbing material with micro-nano composite structure |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8951632B2 (en) * | 2007-01-03 | 2015-02-10 | Applied Nanostructured Solutions, Llc | CNT-infused carbon fiber materials and process therefor |
| US8158217B2 (en) * | 2007-01-03 | 2012-04-17 | Applied Nanostructured Solutions, Llc | CNT-infused fiber and method therefor |
| US9725314B2 (en) * | 2008-03-03 | 2017-08-08 | Performancy Polymer Solutions, Inc. | Continuous process for the production of carbon nanofiber reinforced continuous fiber preforms and composites made therefrom |
| FR2952631B1 (en) * | 2009-11-13 | 2012-01-13 | Commissariat Energie Atomique | PROCESS FOR PRODUCING CARBON NANOTUBES ON A SUBSTRATE |
| WO2012019819A1 (en) * | 2010-08-13 | 2012-02-16 | Huntsman Advanced Materials (Switzerland) Gmbh | Process to grow carbon nanotubes onto fibers |
| JP2012046369A (en) * | 2010-08-26 | 2012-03-08 | Sunstar Engineering Inc | Carbon fiber-reinforced carbon composite material and method for manufacturing the same |
| US8815341B2 (en) * | 2010-09-22 | 2014-08-26 | Applied Nanostructured Solutions, Llc | Carbon fiber substrates having carbon nanotubes grown thereon and processes for production thereof |
| CN102634873A (en) * | 2012-04-18 | 2012-08-15 | 江南大学 | Nano titanium dioxide coated carbon nanotube reinforced carbon nanofiber and preparation method thereof |
-
2013
- 2013-01-25 CN CN201310028102.XA patent/CN103088648B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005026430A1 (en) * | 2003-09-16 | 2005-03-24 | Showa Denko K. K. | Composite of vapor grown carbon fiber and inorganic fine particle and use thereof |
| CN1695797A (en) * | 2005-03-15 | 2005-11-16 | 浙江大学 | Method for preparing photocatalyst of titanium dioxide carried by active carbon |
| CN1877774A (en) * | 2005-06-03 | 2006-12-13 | 北京汉纳源纳米科技有限公司 | Linear nano carbon tube composite-field emission source and method for preparing same and dedicated device therefor |
| CN1736585A (en) * | 2005-07-18 | 2006-02-22 | 华东理工大学 | Nano carbon fiber/graphite felt compound catalytic material and preparation process thereof |
| CA2779493A1 (en) * | 2009-12-01 | 2011-06-30 | Applied Nanostructured Solutions, Llc | Metal matrix composite materials containing carbon nanotube-infused fiber materials and methods for production thereof |
| CN102553531A (en) * | 2012-01-13 | 2012-07-11 | 同济大学 | Preparation method of multiporous carbonaceous adsorbing material with micro-nano composite structure |
Non-Patent Citations (3)
| Title |
|---|
| Activity of TIO2 deposited by the CVD method on ammoxidized surface of a carbonaceous material in hydrogenation of styrene;L Wachowski;《reaction kinetics and catalysis letters》;20070630;第91卷(第1期);第93-99页 * |
| Gas phase synthesis and field emission properitise of 3D aligned double walled carbon nanotube/anatase hybrid architectures;Ravi K. Joshi;《Nanoscal》;20110630;第3卷(第8期);摘要、第3259页左栏第2段、右栏第1-2段、第3260页左栏第2段 * |
| 常压化学气相沉积法制备二氧化钛薄膜的沉积工艺及薄膜均匀性;庞世红;《硅酸盐学报》;20100131;第38卷(第1期);第64-67页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103088648A (en) | 2013-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103088648B (en) | Preparation method for carbon fiber material with composite nano structure | |
| Han et al. | Flame synthesis of superhydrophilic carbon nanotubes/Ni foam decorated with Fe2O3 nanoparticles for water purification via solar steam generation | |
| Hosono et al. | Synthesis of a perpendicular TiO2 nanosheet film with the superhydrophilic property without UV irradiation | |
| He et al. | Iron catalysts for the growth of carbon nanofibers: Fe, Fe3C or both? | |
| Zangmeister | Preparation and evaluation of graphite oxide reduced at 220 C | |
| Delzeit et al. | Multiwalled carbon nanotubes by chemical vapor deposition using multilayered metal catalysts | |
| CN104150459B (en) | Chemical method synthesizing carbon nanotubes/titanium dioxide composite porous fillers | |
| CN104909363B (en) | A kind of preparation method of meshed nano structure material with carbon element | |
| Fang et al. | Construction of carbon nanorods supported hydrothermal carbon and carbon fiber from waste biomass straw for high strength supercapacitor | |
| CN103436854B (en) | The preparation method of a kind of Graphene and carbon nano tube compound material | |
| CN102923686A (en) | Graphene/carbon nanotube composite material preparation method | |
| Du et al. | Particle− wire− tube mechanism for carbon nanotube evolution | |
| CN110182788A (en) | A kind of device and method of high yield preparation carbon nanotube | |
| CN103569992A (en) | Preparation method of carbon nanotube | |
| TWI403413B (en) | Hydrophilic-hydrophobic transformable composite film and the method of fabricating the same | |
| CN103724043B (en) | High thermal conductivity C/C composite and preparation method | |
| CN103979528B (en) | One step prepares the method for super-elasticity carbon nanotube/amorphous carbon composite all-carbon sponge | |
| Wu et al. | One-step synthesis of hierarchical metal oxide nanosheet/carbon nanotube composites by chemical vapor deposition | |
| CN103643217A (en) | Method for preparing self-supporting graphite porous amorphous carbon thin film | |
| CN102658153B (en) | Preparation method of copper substrate surface growth fullerene doped porous carbon nanofibers | |
| CN113149115A (en) | Multistage heterostructure membrane for photo-thermal seawater desalination and preparation method | |
| Wang et al. | Research on adhesion strength and optical properties of SiC films obtained via RF magnetron sputtering | |
| Fei et al. | Bonding TiO2 array on carbon fabric for outstanding mechanical and wear resistance of carbon fabric/phenolic composite | |
| Cui et al. | Synthesis of carbon nanocoils on substrates made of plant fibers | |
| CN101786597A (en) | TiO2 nuclear shell structure nano rod array coated with carbon bed and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150107 Termination date: 20190125 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |