CN1176015C - Method of utilizing external force to crush, wash and purify slender carbon nanotube - Google Patents
Method of utilizing external force to crush, wash and purify slender carbon nanotube Download PDFInfo
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- CN1176015C CN1176015C CNB021174199A CN02117419A CN1176015C CN 1176015 C CN1176015 C CN 1176015C CN B021174199 A CNB021174199 A CN B021174199A CN 02117419 A CN02117419 A CN 02117419A CN 1176015 C CN1176015 C CN 1176015C
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Abstract
The present invention relates to a method for crushing, washing and purifying slender carbon nanometer tubes by external force, particularly relates to a slender carbon nanometer tube purifying physical method and a technique. The method comprises: external force crushing, liquid phase dispersion, sedimentation, filtration and washing. The slender carbon nanometer tubes have the characteristics of flexibility, abrasion resistance, and easy flocculating settling in a liquid phase, the present invention can efficiently remove large carbon fiber and large carbon nanometer tubes which are mixed in slender carbon nanometer tube samples, and simultaneously remove easily suspended impurities, such as nanometer carbon particles, small amorphous carbon, etc. The method does not damage the slender carbon nanometer tubes, and has the advantages of simple and convenient operation and high purification efficiency.
Description
Technical field
The present invention relates to a kind of method of purify slender carbon nanotube, relate to a kind of purify slender carbon nanotube technology, belong to technical field of novel materials.
Background technology
Carbon nanotube (Carbon Nanotubes is abbreviated as CNTs) structurally belongs to same class with " carbon fullerene (C60 etc.) ", all is (Sumio Iijima, Nature, 354 (1991) 56-58) that single carbon atom is assembled formation under certain condition.Because of its structure peculiar, carbon nanotube has many distinctive character, be hopeful to be used widely at aspects such as matrix material, molecule components and parts, support of the catalyst and nano electron devices, be the novel nano carbon material of a class (the Erik T.Thostenson et al. that causes height interest in recent years, Composites Science and Technology, 61 (2001) 1899-1912).
About the existing many research reports of the preparation of carbon nanotube, the prepared in laboratory method of comparative maturity mainly contains three kinds: arc discharge method, laser ablation method and catalystic pyrolysis.Yet the carbon nanotube that prepared in various methods goes out often and impurity such as carbon nano-particle, decolorizing carbon, graphite scrap, metallic particles mix." the poly-group of nanometer bed catalystic pyrolysis " (number of patent application: 011118349.7; PCT/CN02/00044) prepare the breakthrough of carbon nanotube technology in enormous quantities, for the applied research of this novel material provides favourable condition.Yet compare with other two kinds of preparation methods, though catalystic pyrolysis can obtain the thick product of high-purity relatively carbon nanotube, the caliber of its product common broad that distributes.Because it is close that catalystic pyrolysis prepares the manufacturing process of carbon nanotube technology and carbon fiber, in the mass preparation process, unavoidably have impurity such as carbon fiber and thick carbon nanotube when generating thin footpath carbon nanotube and generate.Because the existence of impurity makes the sign of carbon nanotube and application be subjected to very big obstruction.The removal of metallic particles is comparatively easy, and the metallic particles that is coated fully by carbon-coating can not removed with pickling, and the metal of Bao Fuing can be removed with high temperature fully.But the removal of carbon impurity is difficulty very.The existing method of removing non-tubular shape carbon in the thick product of carbon nanotube be divided into chemical method and physics method (people such as Hou Pengxiang, the plain technology of charcoal, 2001, No.4,30-33).Chemical process mainly is an oxidation style, comprises vapour phase oxidation process, liquid phase oxidation, intercalation oxidation style etc., and its grammar all is to utilize the rate of oxidation difference of different shape carbon.Because oxidation has destructiveness to carbon nanotube, and the rate of oxidation difference of various form carbon is limited, therefore if seek out high purity product, the sample loss of chemical oxidization method is bigger usually.Though only can reduce destruction to sample with conventional physical methods such as centrifugal, micro-filtration, stratographies, but be difficult to carbon nanotube is separated mutually fully with the carbon of other form, especially be difficult to separate the carbon nanotube and the carbon fiber of different tube diameters, therefore the purity of purifying is not high.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing external force to crush, wash and purify slender carbon nanotube,, also can remove easily suspended impurity such as tiny decolorizing carbon, nano carbon particle simultaneously in order to remove carbon fiber and thick carbon nanotube.
The objective of the invention is to be achieved through the following technical solutions:
A kind of method of utilizing external force to crush, wash and purify slender carbon nanotube is characterized in that: this method comprises the steps;
(1) utilize the external force method with carbon fiber in the sample and thick carbon nanotube fragmentation;
(2) will in liquid phase, disperse through the crude samples that step (1) is handled, then suspended dispersed liquid is carried out sedimentation;
(3) filter to isolate settling and washing;
(4) repeating step (2), (3) through repeatedly dispersion-sedimentation, can obtain purify slender carbon nanotube.
External force method described in the above-mentioned steps can adopt grinds or ball milling method; If liquid phase adopts deionized water, then adding is a certain amount of in the external force fragmentation can strengthen the hydrophilic tensio-active agent of carbon nano tube surface, as: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyoxyethylene.In the liquid phase dispersion process, can adopt and stir or ultrasound-enhanced dispersion.
The present invention compares with the method for existing purifying carbon nano-tube, have the following advantages and beneficial effect: utilize the pliable and tough characteristics wear-resisting, easy flocculating settling in liquid phase of slender carbon nanotube, can effectively remove the thick carbon fiber and the thick carbon nanotube that mix in the slender carbon nanotube sample, also can remove easily suspended impurity such as nano carbon particle, decolorizing carbon simultaneously.This method is to the slender carbon nanotube not damaged, and is easy and simple to handle, the purification efficiency height.
We's ratio juris is to utilize the wear resistance of different diameter one dimension carbon material with suspension difference it to be separated.The wear resisting property of carbon fiber and thick carbon nanotube is poor, and methods such as mechanical mill can make its fragmentation.There are some researches show that Single Walled Carbon Nanotube has certain snappiness, brittle rupture can not take place in them under big stress.And thin footpath carbon nanotube diameter between carbon fiber and Single Walled Carbon Nanotube, also between Single Walled Carbon Nanotube and carbon fiber, mechanical mill is less to its damage for its snappiness and wear resisting property.The thin footpath carbon nanotube that length-to-diameter ratio is bigger is easy to twine agglomerating, and dispersing property is poor, at the easy flocculating settling of liquid phase; And easy dispersion of carbon fiber and impurity such as thick carbon nanotube fragment and nano carbon particle and stable suspersion are in liquid phase.Through sedimentation, the slender carbon nanotube product concentrates in sediment, and impurity carbon concentrates in liquid phase, thereby makes the two obtain separating.
Description of drawings
Fig. 1 is the schema of purify slender carbon nanotube of the present invention.
Fig. 2 is the electromicroscopic photograph of the embodiment of the invention 1 sample.
Fig. 2 a is the stereoscan photograph of sample before the embodiment of the invention 1 is ground.
Fig. 2 b is the stereoscan photograph that the embodiment of the invention 1 is ground the back sample.
Fig. 2 c is the transmission electron microscope photo of the embodiment of the invention 1 stable suspersion sample.
Fig. 3 is the electromicroscopic photograph of the embodiment of the invention 2 samples.
Fig. 3 a is the stereoscan photograph of sample before the embodiment of the invention 2 is ground.
Fig. 3 b is the transmission electron microscope photo of the embodiment of the invention 2 stable suspersion samples.
Fig. 3 c is the transmission electron microscope photo of the embodiment of the invention 2 flocculation deposited samples.
Fig. 4 is the electromicroscopic photograph of the embodiment of the invention 4 samples.
Embodiment
Further specify concrete enforcement of the present invention below in conjunction with embodiment and purification effect figure.The purpose that these embodiments are provided is to make full disclosure of the present invention, fully passes on thought of the present invention and implementation result to the those skilled in the art.Yet the present invention can implement by many different modes, not will be understood that operational condition and reagent that the present invention only is confined to here to be put down in writing.
When broken carbon fiber of external force and thick carbon nanotube,, in grinding or ball milling, can add the surface hydrophilicity that proper amount of surfactant strengthens carbon nanotube in order to strengthen crushing effect.For example Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, polyoxyethylene.
After fragmentation and liquid phase dispersion, thick carbon nanotube that length-to-diameter ratio is less and impurity such as carbon fiber fragments and nano carbon particle can be with monodispersed in stable condition being suspended in the liquid phase under the effect of tensio-active agent; Slender carbon nanotube then has very strong throwing out, easy flocculating settling under the condition of not having stirring and ultra-sonic dispersion.Sedimentation contains the suspended dispersed liquid of carbon nanotube crude samples, can adopt the method for gravity settling or centrifugal settling.Settling is mainly thin footpath carbon nanotube, can obtain highly purified slender carbon nanotube with washing after filtration.
Embodiment 1:
Present embodiment investigate external force to the crushing effect of carbon fiber and thick carbon nanotube with and the suspension property of fragment in liquid phase.The sample that uses is made by the poly-group of nanometer bed catalystic pyrolysis, mainly is made up of carbon fiber and thick carbon nanotube.In the 100mg sample, add the 25mg Sodium dodecylbenzene sulfonate, grind half an hour.Sample after grinding is placed the 25ml ionized water, under agitation condition, use ultrasonic wave sample to be disperseed 1500 rev/mins of mixing speed, ultrasound intensity 5W/ml, ultrasonic time 3 minutes.Obtain the suspension of sample behind the ultra-sonic dispersion.
Fig. 2 a is the stereoscan photograph of primary sample, wherein visible a large amount of thick carbon fibers.
Fig. 2 b therefrom can see many intercepted carbon fiber fragments for grinding the stereoscan photograph of back sample.Thick carbon fiber wear resisting property in this proof sample is relatively poor, can be broken in a large number through grinding.
Fig. 2 c is after leaving standstill 1 hour after disperseing, the transmission electron microscope photo of sample in the suspension.Fine impurities such as proof carbon fiber fragments, nano carbon particle, fine decolorizing carbon under Action of Surfactant, through can stable suspersion after the ultrasonic dispersing in deionized water.
Embodiment 2:
Embodiment 2～4 is purifying embodiment.The crude samples that uses is made by the poly-group of nanometer bed catalystic pyrolysis, wherein contains slender carbon nanotube, thick carbon nanotube and carbon fiber.In the 50mg crude samples, add the 10mg Sodium dodecylbenzene sulfonate, grind half an hour.Sample after grinding is placed the 25ml deionized water, under agitation condition, add ultrasonic wave and sample is disperseed 1800 rev/mins of mixing speed, ultrasound intensity 5W/ml, ultrasonic time 3 minutes.Obtain the suspension of sample behind the ultra-sonic dispersion.Suspension standing sedimentation 2 hours, the filtering separation settling is also used the 100ml deionized water wash.
Fig. 2 a is the stereoscan photograph of primary sample, impurity coexistences such as wherein visible slender carbon nanotube and thick carbon fiber.
Fig. 2 b is the transmission electron microscope photo that leaves standstill the back suspended sample, therefrom can see impurity such as the slender carbon nanotube of some high dispersing and a large amount of carbon fiber segment, nano carbon particle.
Fig. 2 c is the transmission electron microscope photo of flocculating settling sample, and wherein slender carbon nanotube purity increases than crude samples.Sample is without washing among the figure.
Embodiment 3:
Contain slender carbon nanotube, thick carbon nanotube and carbon fiber in the crude samples that uses.In the 440mg crude samples, add the 60mg polyoxyethylene, ground two hours.Sample after grinding is placed the 500ml deionized water, in the ultrasonic pond of SK2200H type, sample is disperseed ultrasonic time 30 minutes.Obtain the suspension of sample behind the ultra-sonic dispersion.Centrifugation sediment and suspension, 1000 rev/mins of rotating speeds, centrifugation time 20 minutes.
Electron microscopic observation proof slender carbon nanotube concentrates in sediment.
Embodiment 4:
Contain slender carbon nanotube, thick carbon nanotube and carbon fiber in the crude samples that uses.In the 200mg crude samples, add the 25mg sodium laurylsulfonate, ground one hour.Sample after grinding is placed the 500ml deionized water, 1900 rev/mins of mixing speed, ultrasonic power 5W, ultrasonic time 10 minutes.Obtain the suspension of sample behind the ultra-sonic dispersion.Centrifugal settling suspension, 2000 rev/mins of centrifugal rotational speeds.The filtering separation settling.Electron microscopic observation proof slender carbon nanotube concentrates in sediment.
Embodiment 5:
The suspension high speed centrifugation of embodiment 2 is separated 10000 rev/mins of rotating speeds, 15 minutes time.Electron microscopic observation shows impurity such as being mainly carbon fiber segment, nano carbon particle in the centrifugate, and slender carbon nanotube content obviously descends; Contain impurity such as slender carbon nanotube and small amount of carbon fiber segment, nano carbon particle in the settling.The proof centrifugally operated can be strengthened the gathering sedimentation of slender carbon nanotube, thereby reduces the loss of elongated carbon pipe in the purge process, improves yield.
Embodiment 6:
Carry out continuously disperseing sedimentation operation for three times after the natural subsidence sample filtering separation with embodiment 2, the purity of Electron microscope showed slender carbon nanotube in the final settlement thing increases substantially, as shown in Figure 4.This proof multi-pass operations helps improving the purity of slender carbon nanotube.
Claims (5)
1. method of utilizing external force to crush, wash and purify slender carbon nanotube, it is characterized in that: this method comprises the steps:
(1) utilize the external force method with carbon fiber in the sample and thick carbon nanotube fragmentation;
(2) will in liquid phase, disperse through the crude samples that step (1) is handled, then suspended dispersed liquid is carried out sedimentation;
(3) filter to isolate settling and washing;
(4) repeating step (2), (3) obtain purify slender carbon nanotube.
2. it is characterized in that in accordance with the method for claim 1: the external force method described in the step (1) is for grinding or ball milling method.
3. in accordance with the method for claim 1, it is characterized in that: crude samples is scattered in the deionized water in above-mentioned steps (2), add in the external force fragmentation to strengthen the hydrophilic tensio-active agent of carbon nano tube surface in step (1).
4. it is characterized in that in accordance with the method for claim 3: described tensio-active agent is a kind of in Sodium dodecylbenzene sulfonate, sodium laurylsulfonate or the polyoxyethylene.
5. it is characterized in that in accordance with the method for claim 1: in described step (2), crude samples is adopted stirring or ultra-sonic dispersion in liquid phase.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021174199A CN1176015C (en) | 2002-04-19 | 2002-04-19 | Method of utilizing external force to crush, wash and purify slender carbon nanotube |
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| CN1176015C true CN1176015C (en) | 2004-11-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3676337B2 (en) * | 2002-10-23 | 2005-07-27 | 独立行政法人科学技術振興機構 | Gel-like composition comprising carbon nanotube and ionic liquid and method for producing the same |
| CN1314584C (en) * | 2005-06-17 | 2007-05-09 | 华东师范大学 | Process for preparing nanometer carbon particles |
| CN100386258C (en) * | 2006-06-23 | 2008-05-07 | 清华大学 | Aerogel carbon nanotube and its preparation method and application |
| CN101593699B (en) * | 2008-05-30 | 2010-11-10 | 清华大学 | Method for preparing thin film transistor |
| CN106513662B (en) * | 2016-10-31 | 2019-03-19 | 中国航空工业集团公司北京航空材料研究院 | A kind of quick shortization of carbon nanotube and evenly dispersed method in metal powder |
| CN109052372B (en) * | 2018-11-08 | 2022-08-12 | 武汉工程大学 | Method for preparing carbon nano tube dispersion liquid by means of solid phase stripping |
| CN109626360A (en) * | 2018-12-18 | 2019-04-16 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon nano tube dispersion liquid and products thereof and application |
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Assignee: CNano Technology Limited Assignor: Tsinghua University Contract fulfillment period: 2009.9.8 to 2022.4.18 Contract record no.: 2009990001200 Denomination of invention: Method of utilizing external force to crush, wash and purify slender carbon nanotube Granted publication date: 20041117 License type: Exclusive license Record date: 20091029 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.9.8 TO 2022.4.18; CHANGE OF CONTRACT Name of requester: BEIJING TIANNAI SCIENCE AND TECHNOLOGY CO., LTD. Effective date: 20091029 |
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