CN104310371A - Method for growing carbon nano tube in situ on surface of fiber - Google Patents
Method for growing carbon nano tube in situ on surface of fiber Download PDFInfo
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- CN104310371A CN104310371A CN201410521138.6A CN201410521138A CN104310371A CN 104310371 A CN104310371 A CN 104310371A CN 201410521138 A CN201410521138 A CN 201410521138A CN 104310371 A CN104310371 A CN 104310371A
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Abstract
The invention provides a method for growing carbon nano tubes in situ on the surface of fiber. The method comprises the following steps: (1) pretreating the fiber, namely, treating the surface of the fiber by using a mixed liquid of concentrated sulfuric acid and hydrogen peroxide; (2) growing a catalyst in situ on the surface of the fiber; and (3) growing the carbon nano tubes on the surface of the fiber. As the fiber is pretreated by using the mixed liquid of concentrated sulfuric acid and hydrogen peroxide, the fiber surface which is relatively rough is provided, and the adhesion of the catalyst for preparing the carbon nano tubes is facilitated. Moreover, as the catalyst is uniformly adhered to the surface of the fiber by using a dipping method or a sol-gel method, the growth of the carbon nano tubes is facilitated. The dipping method or the sol-gel method is simple and feasible, easy to control, low in cost and beneficial for on-scale and in-batch production.
Description
Technical field
The present invention relates to the preparation field of carbon nanotube, relate more specifically to a kind of method of in-situ growing carbon nano tube on fiber.
Background technology
Carbon nanotube is suggested because of its large effective surface area, physical strength and thermal conductivity and electroconductibility its practicality in numerous applications.Having many in these application is all be particularly suitable for the carbon nanotube on fibre base plate of growing up.As when being longer than on fibre base plate, the characteristic of fibre base plate promotes by carbon nanotube.Such as, when carbon nanotube is grown up thereon, the physical strength of fibre base plate can be promoted, and fibre base plate can be changed into tool electroconductibility.At present, the preparation method preparing carbon nanotube mainly contains arc discharge method, the methods such as chemical Vapor deposition process.Wherein chemical Vapor deposition process is current most widely used preparation method, easily accomplishes scale production.In the process preparing carbon nanotube, catalyzer plays very important effect, and how catalyzer is simple, uniform, to be relatively firmly attached to fiber surface be that those skilled in the art manages to make great efforts to reach always.There is provided a kind of low cost, less energy-consumption, the method for preparing catalyst that preparation efficiency is high, and the preparation method being adapted at the carbon nanotube of industrial large-scale mass production is very necessary.
For improving carbon fiber surface activity, making catalyst precursor be easier to be attached to catalyst surface, pre-treatment being carried out to carbon fiber extremely important.Two-step approach is adopted to carry out pre-treatment in CN102351166A: 1) thermal treatment several hours under high temperature in a vacuum, by the tar removing of the sizing material on its surface and remnants; 2) adopt the method for strong acid treatment to increase the active group of carbon fiber, thus it is active to improve carbon fiber, reaches the object of the wettability increasing carbon fiber.But, with in strong acid treatment, can poisonous fume be produced.Need this to introduce specific facility and equipment, add technology difficulty and cost of investment.A kind of easy, efficient, nontoxic carbon fiber pre-treating process more will be conducive to industrialization scale operation carbon nanotube.
Summary of the invention
The object of the invention is to obtain a kind of method effectively directly preparing carbon nanotube at fiber surface.
The invention provides a kind of method of in-situ growing carbon nano tube on the fiber surface, described method comprises the steps:
1) pre-treatment is carried out to fiber, adopt the mixed solution of the vitriol oil and superoxol to process fiber surface;
2) at fiber surface growth in situ catalyzer;
3) at fiber surface carbon nano-tube.
According to the present invention, described filamentary material can be such as carbon fiber, organic fibre, glass fibre etc.
According to the present invention, described step 1) in, the vitriol oil is 3:1 with the ratio of superoxol, preferably, in aqueous hydrogen peroxide solution, the content of hydrogen peroxide is 1%-75% (mass/volume), preferred 10%-40% (mass/volume).The concentration of the described vitriol oil is 70%-98%, is preferably the vitriol oil of 98%.Described pre-treatment can provide coarse fiber surface, and it can deposit the catalyzer for the preparation of carbon nanotube.The preferably treatment time is 1-60 minute, more preferably 1-30 minute.
According to the present invention, described step 2) in, at fiber surface growth in situ granules of catalyst, namely first use pickling process or sol-gel method that catalyst precursor is attached to fiber surface, reduced again afterwards.
Described catalyst precursor can be the transition metal salt of any d-district transition metal.Described salt form comprises acetate, nitrate etc.Nonrestrictive exemplary transition metal such as, Ni, Fe, Co, Mo, Cu, Pt, Au and Ag.
According to the present invention, described step 2) in, in described pickling process, by fiber impregnation in the solution of catalyst precursor, preferred concentration is 0.05-3mM, described solvent such as water, ethanol etc.; Preferably, the fiber after dipping is carried out drying, such as dry at 80-120 DEG C.
According to the present invention, described step 2) in, in described sol-gel method, be dissolved in solvent by described catalyst precursor, and add appropriate ammoniacal liquor, form colloidal sol, described solvent is preferably ethylene glycol monomethyl ether ethylene glycol, glycerol etc.In a preferred embodiment, the hydrochlorate containing nickel (Ni) element is dissolved in ethylene glycol monomethyl ether, and adds proper ammonia, obtain transparent colloidal sol.
According to the present invention, described step 2) in, described reduction step can pass into hydrogen at a certain temperature and reduce, and the hydrogen and the nitrogen that preferably pass into certain volume ratio reduce, described temperature such as 400-600 DEG C.
According to the present invention, described step 3) in, at a certain temperature, pass into carbon-source gas carbon nano-tube.As known in the art, under suitable reaction conditions, multiple carbon compound is suitable for as nano-carbon precursor.It can be suitable be selected from carbon monoxide (CO), aliphatics and aromatic hydrocarbons and its oxidized derivatives one or more.The example of non-aromatic hydrocarbon has ethene, acetylene, propylene, ethane, propane etc.Usually preferably the short chain containing no more than 4 carbon atoms saturated or unsaturated hydrocarbons, optimal ethylene or acetylene.Aromatic hydrocarbons preferably contains 6-20 carbon atom aromatic hydrocarbon, if the derivative of benzene, naphthalene or its alkyl replacement is as toluene, dimethylbenzene, isopropyl benzene or ethylbenzene.The example of oxygenated hydrocarbon has alcohol (such as methyl alcohol), aldehyde (as formaldehyde or acetaldehyde) or ketone (such as acetone), or its mixture.Described temperature of reaction depends on carbonaceous gas type and other reaction conditions of use, as catalyst type, flow velocity etc.Preferred temperature of reaction is 400-1000 DEG C, such as 500-900 DEG C, such as 600-800 DEG C, such as 650-750 DEG C.Described temperature is preferably 600-800 DEG C.
The present invention's superiority is compared to existing technology:
1) the present invention adopts the mixed solution of the vitriol oil and superoxol to carry out pretreatment of fiber, provides more coarse fiber surface, is beneficial to the attachment of the catalyzer for the preparation of carbon nanotube.The mixing solutions of the vitriol oil and superoxol has controlled strong oxidizing property, can make the uniform roughness of processbearing astrocyte.And due to the strong oxidizing property of this mixed solution, the high temperature heat treatment step in carbon fiber pre-treatment in prior art can be saved, pre-treatment is reduced to a step.Compared with conventional strong oxidizing property acid solution chloroazotic acid (concentrated nitric acid: vitriol oil 3:1 or concentrated nitric acid: concentrated hydrochloric acid 3:1), the preparation of the vitriol oil and superoxol and deposit easy.Only oxygen is discharged in the pretreatment process of present method; and nitrogen dioxide gas, nitrogen tetroxide, hydrogen chloride gas etc. that in chloroazotic acid process, a large amount of generation is poisonous; therefore; in pretreatment process of the present invention; do not need other special protection facilities and equipment protect personnel and process poisonous fume, method provided by the invention is a kind of eco-friendly Green Chemistry method.
2) use pickling process or sol-gel method that catalyzer is attached to fiber surface uniformly, be more conducive to the growth of carbon nanotube.Pickling process wherein or sol-gel method method simple, easily control, cost is low, is conducive to big area, production in enormous quantities.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of carbon fiber surface before and after the pre-treatment of carbon fiber in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the carbon nanotube of preparation in embodiment 1.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
1) pre-treatment
Carbon cloth is put into the mixed solution (vitriol oil: hydrogen peroxide=3: 1) of the hydrogen peroxide of the vitriol oil and 30% (mass/volume) of 98%, process 30min, in distilled water, at least three times are cleaned, drying two hours at 80 DEG C after taking-up.As can be seen from Figure 1, not pretreated carbon fiber surface is very flat, and pretreated carbon fiber surface then has a lot of groove.
2) preparation of catalyzer
By Fe (NO
3)
39H
2o is dissolved in the Fe (NO that compound concentration in ethanol is 100mM
3)
3solution; Then by step 1) pretreated carbon cloth puts into this solution and soaks 2h.The carbon cloth processed is placed in silica tube, heats under inert gas atmosphere; After temperature is elevated to 700 DEG C, is incubated half an hour, passes into 200sccm hydrogen.
3) carbon fiber surface carbon nano-tube
Remain on 700 DEG C again, pass into 50sccm acetylene, keep quartzy intraductal pressure to be several KPa; Close gas after 30min, silica tube drops to room temperature in the protection of rare gas element.
Fig. 2 is the scanning electron microscope (SEM) photograph of preparation-obtained carbon nanotube.
Embodiment 2
1) pre-treatment
Carbon cloth is put into the mixed solution (vitriol oil: hydrogen peroxide=3: 1) of the hydrogen peroxide of the vitriol oil and 30% (mass/volume) of 98%, process 30min, in distilled water, at least three times are cleaned, drying two hours at 80 DEG C after taking-up.
2) preparation of catalyzer
With 2M Ni (NO
3)
2solution and ethylene glycol monomethyl ether prepare colloidal sol, and add proper ammonia, high-speed stirring 6 hours, and rear sealing and standing obtained transparent colloidal sol after 10 hours.Adopt dip-coating method that colloidal sol is coated in pretreated fiber surface equably, described pull rate is 8cm/ minute.Wet film is repeated impregnations lift after 100 DEG C of thermal treatment, and lift number of times is 3 times.Be placed in the chamber of chemical gas-phase deposition system by scribbling containing the fiber of Ni elemental sols, start to heat up, target temperature is 500 DEG C, passes into reducing gas hydrogen, and the hold-time is 10 minutes.
3) carbon fiber surface carbon nano-tube
By described step 2) in furnace temperature continue to rise to 700 DEG C, pass into methane and nitrogen simultaneously.Methane: nitrogen ratios is 2: 5.Control the closed degree of vacuum butterfly valve, guarantee that the air pressure of whole reaction process is at about 400Pa; React after 30 minutes, grow complete.Stop gas passing into, be cooled to less than 100 DEG C.
Claims (9)
1. a method for in-situ growing carbon nano tube on the fiber surface, comprises the steps:
1) pre-treatment is carried out to fiber, adopt the mixed solution of the vitriol oil and superoxol to process fiber surface;
2) at fiber surface growth in situ catalyzer;
3) at fiber surface carbon nano-tube.
2. the method for claim 1, wherein described filamentary material is carbon fiber, organic fibre or glass fibre.
3. the method for claim 1, wherein step 1) in, the vitriol oil is 3:1 with the ratio of superoxol, preferably, in aqueous hydrogen peroxide solution, the content of hydrogen peroxide is 1%-75% (mass/volume), preferred 10%-40% (mass/volume); The concentration of the described vitriol oil is 70%-98%, is preferably the vitriol oil of 98%.The preferably treatment time is 1-60 minute, more preferably 1-30 minute.
4. the method for claim 1, wherein step 2) in, at fiber surface growth in situ granules of catalyst, namely first use pickling process or sol-gel method that catalyst precursor is attached to fiber surface, reduced again afterwards.
Described catalyst precursor can be the transition metal salt of any d-district transition metal.Described salt form comprises acetate, nitrate etc.Nonrestrictive exemplary transition metal such as, Ni, Fe, Co, Mo, Cu, Pt, Au and Ag.
5. method as claimed in claim 4, in described pickling process, by fiber impregnation in the solution of catalyst precursor, preferred concentration is 0.05-3mM, described solvent such as water, ethanol etc.; Preferably, the fiber after dipping is carried out drying, such as dry at 80-120 DEG C.
6. method as claimed in claim 4, in described sol-gel method, is dissolved in described catalyst precursor in solvent, and adds appropriate ammoniacal liquor, and form colloidal sol, described solvent is preferably ethylene glycol monomethyl ether ethylene glycol, glycerol etc.In a preferred embodiment, the hydrochlorate containing nickel (Ni) element is dissolved in ethylene glycol monomethyl ether, and adds proper ammonia, obtain transparent colloidal sol.
7. method as claimed in claim 4, described reduction step can pass into hydrogen at a certain temperature and reduce, and the hydrogen and the nitrogen that preferably pass into certain volume ratio reduce, described temperature such as 400-600 DEG C.
8. the method for claim 1, wherein said step 3) in, at a certain temperature, pass into carbon-source gas carbon nano-tube.
9. method as claimed in claim 8, described carbon-source gas can be selected from carbon monoxide (CO), aliphatics and aromatic hydrocarbons and its oxidized derivatives one or more.The example of non-aromatic hydrocarbon has ethene, acetylene, propylene, ethane, propane etc.Usually preferably the short chain containing no more than 4 carbon atoms saturated or unsaturated hydrocarbons, optimal ethylene or acetylene.Aromatic hydrocarbons preferably contains 6-20 carbon atom aromatic hydrocarbon, if the derivative of benzene, naphthalene or its alkyl replacement is as toluene, dimethylbenzene, isopropyl benzene or ethylbenzene.The example of oxygenated hydrocarbon has alcohol (such as methyl alcohol), aldehyde (as formaldehyde or acetaldehyde) or ketone (such as acetone), or its mixture.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532548A (en) * | 2015-01-29 | 2015-04-22 | 中国兵器工业集团第五三研究所 | In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface |
| CN105645393A (en) * | 2016-01-14 | 2016-06-08 | 山东科技大学 | Preparing method for in-situ growth of graphene on graphite fibers |
| CN106390766A (en) * | 2016-09-23 | 2017-02-15 | 天津工业大学 | Imitated-mucociliary-structure filtering material having self-cleaning function |
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN112608156A (en) * | 2020-12-29 | 2021-04-06 | 黑龙江冠瓷科技有限公司 | Preparation method of micro-nano mixed SiC chopped fibers |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021817A (en) * | 2010-11-11 | 2011-04-20 | 中国人民解放军国防科学技术大学 | Silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, composite material and preparation method thereof |
| CN102351166A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Method for directly growing carbon nanotube on surface of carbon fiber |
-
2014
- 2014-09-30 CN CN201410521138.6A patent/CN104310371A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021817A (en) * | 2010-11-11 | 2011-04-20 | 中国人民解放军国防科学技术大学 | Silicon carbide fiber solid fabric for in-situ growing carbon nano tubes, composite material and preparation method thereof |
| CN102351166A (en) * | 2011-06-30 | 2012-02-15 | 中国科学院上海硅酸盐研究所 | Method for directly growing carbon nanotube on surface of carbon fiber |
Non-Patent Citations (1)
| Title |
|---|
| 朱弘: "功能性层状双氢氧化物/聚合物纳米复合材料", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104532548A (en) * | 2015-01-29 | 2015-04-22 | 中国兵器工业集团第五三研究所 | In-situ growth method for carbon nano tubes (CNTs) on carbon fiber surface |
| CN105645393A (en) * | 2016-01-14 | 2016-06-08 | 山东科技大学 | Preparing method for in-situ growth of graphene on graphite fibers |
| CN105645393B (en) * | 2016-01-14 | 2017-12-01 | 山东科技大学 | A kind of preparation method of the growth in situ graphene on graphite fibre |
| CN106390766A (en) * | 2016-09-23 | 2017-02-15 | 天津工业大学 | Imitated-mucociliary-structure filtering material having self-cleaning function |
| CN106390766B (en) * | 2016-09-23 | 2019-03-05 | 天津工业大学 | A kind of imitative nasal cavity ciliary structures filtering material with self-cleaning function |
| CN109750492A (en) * | 2018-12-20 | 2019-05-14 | 山东大学 | A kind of surface treatment method of carbon cloth surfaces homoepitaxial carbon nanotube early period |
| CN112608156A (en) * | 2020-12-29 | 2021-04-06 | 黑龙江冠瓷科技有限公司 | Preparation method of micro-nano mixed SiC chopped fibers |
| CN112608156B (en) * | 2020-12-29 | 2021-12-03 | 内蒙古海特华材科技有限公司 | Preparation method of micro-nano mixed SiC chopped fibers |
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