CN105692584B - A kind of CNT ball of string and preparation method thereof - Google Patents
A kind of CNT ball of string and preparation method thereof Download PDFInfo
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- CN105692584B CN105692584B CN201610031119.4A CN201610031119A CN105692584B CN 105692584 B CN105692584 B CN 105692584B CN 201610031119 A CN201610031119 A CN 201610031119A CN 105692584 B CN105692584 B CN 105692584B
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention provides an a kind of CNT ball of string, and by single or more a diameter of 0.6 5nm, length, which is that 1mm 5m CNT is random, to be wound, and the tiling area of the CNT ball of string is in 0.001 10mm2Between, density is at 1 200CNTs/ μm.Preparation method includes:Catalyst is carried on into growth substrate to be placed in reactor, after being passed through mixed inert gas reducing catalyst, then mixed reaction gas is passed through and heats and overlength carbon nano pipe is prepared;Sound wave is added into reactor so that flexing winding occurs in the whirlpool that sound wave induces for overlength carbon nano pipe;10 20min, which change, to be passed through the mixed inert gas and stops conveying sound wave, is taken out after being cooled to less than 400 DEG C and is produced a CNT ball of string.CNT ball of string high density, large area and the chirality of the embodiment of the present invention unanimously, have widened the application field of CNT in itself.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular to an a kind of CNT ball of string and its preparation
Method.
Background technology
CNT is a kind of special carbon nanomaterial of the high length-diameter ratio with hollow tubular structure, be can be regarded as by two
Dimension graphene crimps forms in a certain direction, different rotation direction of principal axis cause the CNT to be formed have different optical activities with
Chiral parameter.It is near by its unique hollow tubular structure and excellent mechanics, calorifics, electrical and optical performance, CNT
The achievement to attract people's attention is achieved over a little years in ultracapacitor, lithium-sulfur cell, thin film transistor (TFT), rubber tyre etc., and
It is expected to substitute silicon to welcome the carbon-based integrated circuit epoch, the final dream for realizing manufacture high-performance carbon nanotube computer.It is but real
Existing CNT is to realize the controllable preparation of specific structure CNT in the important prerequisite that integrated circuit connection is applied.
IBM points out that requirement of the carbon-based integrated circuit of a new generation to carbon nano-tube material is semiconductor selectivity, the height for having ultra-high purity
Density and perfect structure, although being had made great progress in the last few years for the requirement of one-side material condition, want simultaneously
Realize this several explorations for requiring to also need to the longer time.
Structures shape property, in carbon nanotube growth process, CNT reality can all be reduced by any fault of construction occur
Border application performance.In numerous different types of CNTs, overlength carbon nano pipe has the perfect atomic structure of isotactic
And macro length, actual performance and the superperformance that CNT should have in theory are closest.Report at present most long
Overlength carbon nano pipe length can reach 55cm, and with perfect structure, isotactic and high semiconductor selectivity, but its is close
Degree but only has 2~3CNTs/100 μm, seriously limits its application in terms of extensive photoelectric device.Although pin in the last few years
There is remarkable progress to improving carbon nanotube density, as use " Troy " catalyst preparation goes out density is up to 130CNTs/ μm
Carbon nano pipe array, and by graphene or SiO2Nanosphere reduces catalyst coalescence, and it is close to improve overlength carbon nano pipe array
The methods of spending, but prepared carbon nano pipe array can not meet the requirement of high semiconductor selectivity and perfect structure.It is another
Aspect, by optimizing Catalyst Design, it is possible to achieve purity is prepared up to 92% chirality for the carbon nano pipe array of (12,6), but
It can not meet application conditions without semiconductor selectivity in terms of density and perfect structure.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide an a kind of CNT ball of string, the CNT ball of string high density, structure
It is perfect and chiral consistent, the application field of CNT in itself has been widened, has been had in micro-nano electronic device and field of photoelectric devices
There is great application potential.
The second object of the present invention is to provide a kind of preparation method of a CNT ball of string, and step is held in the mouth before and after methods described
Connect close, reasonable in design, simple and easy, operating condition is gentle, and involved material can be commercially available by market, and environmentally friendly nothing
Pollution, it can finally obtain a nanotube ball of string for chiral consistent, perfect structure, high density and overlength.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme:
The embodiments of the invention provide an a kind of CNT ball of string, and by single or more a diameter of 0.6-5nm, length is
1mm-5m CNT is random to be wound, and the tiling area of the CNT ball of string is in 0.001-10mm2Between, density
At 1-200CNTs/ μm.
Research to CNT in the prior art is with rapid changepl. never-ending changes and improvements that main research direction is the hand of CNT
Property structure, length and density etc., there is problems in that on the market also length, density and chiral knot can be taken into account
Preferably product comes out the indexs such as structure, therefore it is existing for how developing the consistent carbon nano-tube material of a kind of high density, chirality
There is research direction main in technology.Based on current present Research, the present invention provides an a kind of overlength carbon nano pipe ball of string, is to use
CNT with certain diameter and length requirement is wound by random, in situ can obtain high density, structure
A perfect, chiral consistent high semiconductor selectivity overlength carbon nano pipe ball of string, the advantages of its is notable are its highdensity performance, are
Any a product can not possibly compare in the prior art.Height can be realized simultaneously with the FET device of its making
Current density and high on-off ratio, there is great application potential in micro-nano electronic device and field of photoelectric devices.
The CNT ball of string of the present invention, it is to use the random winding of CNT with specific diameter and length
Formed, the diameter of CNT is needed between 0.6-5nm, and length is needed in 1mm-5m, if so when carrying out selection
Not within disclosed aspects, it is to be not likely to form this height with the present invention for length and diameter
A CNT ball of string for density performance, the parameters index for the CNT ball of string being additionally formed is also required in suitable model
In enclosing, tiling area is in 0.001-10mm2Between, density is at 1-200CNTs/ μm, and especially density highest can reach
200CNTs/ μm, compared to the density of CNT of the prior art, it fully belongs to high density product, although there is it to twine
Around do not have a systematicness, but its tiling is come, covered area can reach 10mm2As many as, just because of a CNT ball of string
With so excellent performance, therefore it also has broader practice field in application.
In the present invention, the diameter of every CNT is preferably 0.7-4nm, and length is preferably 1-5m, and diameter can be with
For 0.8nm, 3nm and 3.5nm etc., length can also be 2m, 3m, 4m and 4.5m etc..A CNT ball of string for formation is put down
Paving product is more excellent in 0.1-8mm2Between, density is more excellent between 100-150CNTs/ μm, and tiling area can also be 9mm2、
9.5mm2、8.5mm2、7mm2It can also be 190CNTs/ μm, 195CNTs/ μm, 198CNTs/ μm etc. Deng, density.
It is exactly chiral structure to also have an important parameter index for a CNT ball of string, and the carbon of the present invention is received
A mitron ball of string can reach purity 100%, to be passed through with consistent chiral structure, i.e., single chiral selectivity up to 100%
Rayleigh scattering characterizes the CNT ball of string and also can prove that it has chiral consistent structure, and the method that Rayleigh scattering characterizes
Itself can quickly, accurately distinguish different chiral CNTs, screening metallic carbon nanotubes and semiconductive carbon nano tube
Can directly judge the particular location that CNT chiral structure changes, thus its characterization result have it is very high accurate
Property.
The embodiment of the present invention additionally provides a kind of CNT ball of string its except providing an a kind of CNT ball of string
Middle a kind of preparation method, as long as the CNT ball of string product that certain other preparation methods of the prior art obtain the present invention is equal
Within the scope of the present invention.
The preparation method for this CNT ball of string that the present invention discloses mainly comprises the following steps:
(A) catalyst is carried on into growth substrate to be placed in reactor, is passed through the mixed inert gas of inert gas and hydrogen
After body reducing catalyst, then it is passed through the mixed reaction gas of carbon source and hydrogen and overlength carbon nano pipe is prepared in heating;
(B) sound wave is added into reactor so that flexing winding occurs in the whirlpool that sound wave induces for overlength carbon nano pipe,
Wherein described sound wave is by FREQUENCY CONTROL between 10 μ Hz-10kHz, and amplitude controlling is in 5mVpp-70VppElectric signal through electroacoustic turn
Change to be formed;
(C) 10-20min, which changes, is passed through the mixed inert gas and stops conveying sound wave, is taken out after being cooled to less than 400 DEG C
Produce a CNT ball of string.
Wherein in step (A), how to prepare overlength carbon nano pipe and itself disclosed in the prior art, need not go to live in the household of one's in-laws on getting married here
State, it is preferable that the single metal or metal alloy such as appropriate carbon nanotube growth catalysts Fe, Mo, Co, Cu, Ni, carbon nano tube growth
Catalyst is nano particle, and catalyst mode of loading is at least one of pressing, photoengraving, spin coating, evaporation and tube wall pre-deposition,
Hybrid reaction gas should be high-purity gas and sulfide<0.3 μ L/L, arsenide<0.3μL/L;Reaction temperature is 800-1200 DEG C
And make temperature fluctuation range<±1℃;Reaction whole process is permanent malleation, range of pressure fluctuations<±1Pa;Reaction gas flow is equal on section
The stably stratified flow of even distribution, Radial Perturbation<±3mm.
Emphasis place to be protected of the present invention is how using overlength carbon nano pipe to prepare a CNT ball of string, i.e., anti-
The later stage is answered, certain frequency, certain amplitude and the sound wave in direction are added from the entrance, the port of export or other positions of reactor, as long as
Sound wave can be delivered in reactor, so that sound wave is by reflection and travels to up to carbon nano tube growth area, make reactor
Middle laminar air flow forms Karman vortex streets under the sound wave effect, makes to be servo-actuated floating life under air-flow guide effect using the vortex street
Flexing winding occurs for long CNT, obtains a chiral consistent overlength carbon nano pipe ball of string, the carbon that the general vortex street is wound
Nanotube bending diameter is suitable with Kolmogorov minimums whirlpool size, in 10-20 microns.
Sound wave is that amplitude controlling is in 5mV by FREQUENCY CONTROL between 10 μ Hz-10kHzpp-70VppElectric signal through electroacoustic
What conversion was formed, more excellent, the frequency of electric signal can also be between 1-10kHz, and amplitude controlling is in 20-70VppBetween, such as
Frequency can also be 2kHz, 3kHz, 4kHz, 5kHz, and amplitude can also be 25Vpp、30Vpp、35Vpp、40VppDeng.Electroacoustic conversion one
As be achieved using converter, converter can select loudspeaker, siren, piezoelectric transducer and magnetostriction type
One of which in transducer, is concentrated after sound wave conversion during practical operation and amplified energy through amplitude transformer, the sound wave after amplification from
Reactor inlet, the port of export or other positions enter, and amplitude transformer is ultrasonic transformer or the attachment means with calibre-changeable feature.
In step (C), after conveying sound wave 10-20min in the reactor, CNT ball of string basic forming now can be with
Cooling is begun to cool down, because now the temperature of reactor is up to more than 900 DEG C, is changed to be passed through inertia by being passed through mixed reaction gas
Mixed gas, and stop conveying sound wave, the operation that now should be noted is that one is scheduled on while leading to inert mixed gas again
Stop conveying sound wave, because ablation phenomen can occur during cooling for a CNT ball of string, in order to avoid this phenomenon
Generation is protected, it is necessary to be passed through inert mixed gas, probably 0.5-2h can also be caused after protection gas is passed through for a period of time
The performance of a CNT ball of string stops adding sound wave again when more stable, and reaction stops, when the greenhouse cooling in reactor to 400
Taken out after below DEG C and produce a CNT ball of string, taken out sample and carry out subsequent characterizations.It should be noted that surpass when adding sound wave
Long CNT is yet constantly being grown, that is to say, that CNT is grown while flexing winding occurs.
A nanotube ball of string can be dipped in surfactant by the nanotube ball of string being prepared as further increased its density
In, such as ethylene glycol, glycerine, polyethylene glycol, ethanol.
Prior art is compared, and beneficial effects of the present invention are:
(1) a CNT ball of string of the invention, high density, perfect structure and chiral consistent, the advantages of its is notable, are high for it
The performance of density.High current density and high on-off ratio can be realized simultaneously with the FET device of its making, in micro-nano
Rice electronic device and field of photoelectric devices have great application potential;
(2) preparation method of a CNT ball of string of the invention, front and rear step linking is close, reasonable in design, simple and easy,
Operating condition is gentle, and involved material can be commercially available by market, and environment friendly and pollution-free, as long as in strict accordance with the present invention's
The progress of operating procedure step by step, the CNT ball of string prepared comply fully with the parameters standard of the present invention, have one
The chiral structure of cause.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described.
Fig. 1 is that the SEM for the overlength carbon nano pipe that the preparation method of the embodiment of the present invention one obtains characterizes collection of illustrative plates;
Fig. 2 is that the Rayleigh for the overlength carbon nano pipe that the preparation method of the embodiment of the present invention one obtains characterizes collection of illustrative plates;
Fig. 3 is the apparatus structure schematic diagram used in the preparation method of the embodiment of the present invention one, wherein, 1 is for providing
The function signal generator of electric signal;2 be the substrate for growing CNT;3 be urging for catalytic growth CNT
Agent;4 be the amplitude transformer for converging acoustic wave energy;5 be the converter for converting electrical signals to acoustic vibration;6 be
The different shape CNT of the lower substrate surface buoyant growth of sound wave interference;7 be the mixed of the carbon sources that are passed through of course of reaction and hydrogen
Close reacting gas;
Fig. 4 is the ESEM for the different shape CNT ball of string that the preparation method of the embodiment of the present invention one obtains
(SEM) collection of illustrative plates is characterized;
Fig. 5 is the Raman scattering characterize data figure for the CNT ball of string that the preparation method of the embodiment of the present invention two obtains
Table;
Fig. 6 is the Rayleigh scattering characterize data figure for the CNT ball of string that the preparation method of the embodiment of the present invention three obtains
Table.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
1) will be by being pressed with 0.1mol/L FeCl3The silicon chip substrate of the ethanol solution of catalyst is placed on substrate or quartz boat
In, it is placed in furnace reactor;
2) 200sccm argon gas and the mixed inert gas (Ar of hydrogen are passed through into reactor:H2=1:2, v/v) as guarantor
Shield property gas, and start to warm up, after temperature rises to 900-1010 DEG C, constant temperature 20min.The stage of reaction is subsequently entered, is passed through
180sccm methane and hydrogen hybrid reaction gas (H2:CH4=2:1, v/v), start overlength carbon nano pipe and prepare reaction, reaction time
10min-2h, obtained single overlength carbon nano pipe Sample Scan Electronic Speculum characterization result is as shown in figure 1, Rayleigh characterizes collection of illustrative plates as schemed
Shown in 2, a diameter of 0.6-5nm for length standard, after testing CNT, length 1mm-5m of picture lower right corner mark;
3) when the reaction later stage, sound wave is added into reactor, sound wave is formed by electro-acoustic conversion device, electro-acoustic conversion device
Build as shown in figure 3,1 is the function signal generator for providing electric signal, 2 be the substrate for growing CNT, 3
It is the amplitude transformer for converging acoustic wave energy for the catalyst for catalytic growth CNT, 4,5 be for electric signal to be turned
The converter of acoustic vibration is changed to, 6 be the different shape CNT of the substrate surface buoyant growth under sound wave interference, and 7 be anti-
Answer carbon source that process is passed through and the mixed reaction gas of hydrogen.Wherein, connected between 1 and 5 by a double fastener line wire, cumulative
It is closely sealed using silica gel or other adhesive sticker viscosity between device and converter.The FREQUENCY CONTROL of electric signal between 10 μ Hz-10kHz,
Amplitude controlling is in 5mVpp-70Vpp, the sound wave of certain frequency and amplitude is exported by the port of export of amplitude transformer, from the entrance of reactor
Carbon nano tube growth area is traveled to, compresses reaction gas flow, the single overlength carbon for making to be servo-actuated buoyant growth under air-flow guide effect is received
Flexing winding occurs for mitron, obtains an overlength carbon nano pipe ball of string;Wherein, sound wave is continuous sine wave, and converter is loudspeaker;
4) the mixed inert gas (Ar of the argon gas for being passed through 200sccm and hydrogen is changed after 10-20min:H2=1:2, v/v) to prevent
Blocking pipe is ablated in temperature-fall period, simultaneously closes off sound wave generating device, after temperature is down to below 400 DEG C, takes out sample and enters
Row subsequent characterizations, as shown in Figure 4, and length of carbon nanotube is longer for characterization result, and the CNT ball of string density of formation is higher,
Area is bigger, and its area is up to 0.001-10mm after testing2Between, density has consistent chiral knot at 1-200CNTs/ μm
Structure.
Embodiment 2
1) will be by being pressed with 0.1mol/L FeCl3The silicon chip substrate of the ethanol solution of catalyst is placed on substrate or quartz boat
In, it is placed in furnace reactor;
2) 200sccm argon gas and the mixed inert gas (Ar of hydrogen are passed through into reactor:H2=1:2, v/v) as guarantor
Shield property gas, and start to warm up, after temperature rises to 900-1010 DEG C, constant temperature 20min.The stage of reaction is subsequently entered, is passed through
180sccm methane and hydrogen hybrid reaction gas (H2:CH4=2:1, v/v), start overlength carbon nano pipe and prepare reaction, reaction time
10min-2h, obtained overlength carbon nano pipe, after testing a diameter of 0.7-4nm, length 1-5m;
3) when the reaction later stage, sound wave is added into reactor, sound wave is formed by electro-acoustic conversion device, electro-acoustic conversion device
Built using the building method of embodiment 1.The FREQUENCY CONTROL of electric signal is between 1-10kHz, and amplitude controlling is in 20-
70Vpp, the sound wave of certain frequency and amplitude is exported by the port of export of amplitude transformer, CNT life is traveled to from the outlet of reactor
Long area, reaction gas flow is compressed, make more CNTs for being servo-actuated buoyant growth under air-flow guide effect that flexing winding occur, obtain
An overlength carbon nano pipe ball of string;Wherein, sound wave is the sawtooth waveforms of interruption, and converter is piezoelectric transducer;
4) gaseous mixture (Ar of the argon gas for being passed through 200sccm and hydrogen is changed after 10-20min:H2=1:2, v/v) to prevent blocking
Pipe is ablated in temperature-fall period, and sound wave generating device is closed after 1h, after temperature is down to below 400 DEG C, takes out sample and is dipped in second
To increase its density in glycol, subsequent characterizations are then carried out, Fig. 5 is four on the CNT ball of string sample obtained to embodiment 2
Individual diverse location carries out the data image result of Raman sign.The characteristic peak of CNT is located at 1500-1600cm-1, referred to as G
Peak, displacement is in 1200-1400cm-1Characteristic peak be referred to as D peaks, the ratio of general conventional D peaks and G peaks peak intensity reflects carbon nanometer
Tubular construction defect level, ratio is bigger, and defect level is higher.CNT is can be seen that from the Raman peaks data result in Fig. 5
Diverse location is in 1200-1400cm on a ball of string-1Place does not have D peaks nearly all, illustrates that a prepared CNT ball of string has perfection
Structure, it is chiral consistent.On the other hand, the peak shape at typically conventional G peaks represents the metallicity and semiconductive of CNT, semiconductor
The G peaks of property CNT are sharp, and the G peak stretchings of metallic carbon nanotubes, and prepared carbon is may determine that from the peak shape in Fig. 5
A nanotube ball of string is semiconductive, and its area is up to 0.1-8mm after testing2Between, density has one at 100-150CNTs/ μm
The chiral structure of cause.
Embodiment 3
1) will be by being pressed with 0.1mol/L FeCl3The silicon chip substrate of the ethanol solution of catalyst is placed on substrate or quartz boat
In, it is placed in furnace reactor;
2) 200sccm argon gas and the mixed inert gas (Ar of hydrogen are passed through into reactor:H2=1:2, v/v) as guarantor
Shield property gas, and start to warm up, after temperature rises to 1000 DEG C, constant temperature 20min.The stage of reaction is subsequently entered, is passed through 180sccm
Methane and hydrogen hybrid reaction gas (H2:CH4=2:1, v/v), start overlength carbon nano pipe and prepare reaction, reaction time 10min-
2h, obtained overlength carbon nano pipe, after testing a diameter of 5nm, length 5m;
3) when the reaction later stage, sound wave is added into reactor, sound wave is formed by electro-acoustic conversion device, electro-acoustic conversion device
Built using the building method of embodiment 1.The FREQUENCY CONTROL of electric signal is between 1-10kHz, and amplitude controlling is in 20-
70Vpp, the sound wave of certain frequency and amplitude is exported by the port of export of amplitude transformer, CNT life is traveled to from the outlet of reactor
Long area, reaction gas flow is compressed, make the CNT for being servo-actuated buoyant growth under air-flow guide effect that flexing winding occur, obtain overlength
A CNT ball of string;Wherein, sound wave is the square wave of interruption, and converter is magnetostriction transducer;
4) the mixed inert gas (Ar of the argon gas for being passed through 200sccm and hydrogen is changed after 10-20min:H2=1:2, v/v) to prevent
Blocking pipe is ablated in temperature-fall period, and sound wave generating device is closed after 30min, after temperature is down to below 400 DEG C, takes out sample
It is dipped in glycerine to strengthen its density, then carries out subsequent characterizations, Fig. 6 is the CNT ball of string sample obtained to embodiment 3
Upper four diverse locations carry out the data image result of Rayleigh sign.Rayleigh characterize can intuitively judge chiral structure whether one
Cause, if diverse location chiral structure is consistent, identical peak shape and peak position are had on Rayleigh peak figure picture.Obtained from Fig. 6
Rayleigh peak view data sees, the peak shape of four diverse locations and peak position are essentially identical, illustrate there is consistent chiral structure, pass through
Detection, its area is up to 9mm2, density is at 190CNTs/ μm.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (11)
- A 1. a kind of CNT ball of string, it is characterised in that by single or more a diameter of 0.6-5nm, length is 1mm-5m carbon Nanotube is random to be wound, and the tiling area of the CNT ball of string is in 0.001-10mm2Between, density is in 1- 200CNTs/μm;The preparation method of a CNT ball of string includes:(A) catalyst is carried on into growth substrate to be placed in reactor, is passed through the mixed inert gas of inert gas and hydrogen also After raw catalyst, then it is passed through the mixed reaction gas of carbon source and hydrogen and overlength carbon nano pipe is prepared in heating;(B) sound wave is added into reactor so that flexing winding occurs in the whirlpool that sound wave induces for overlength carbon nano pipe, wherein The sound wave is by FREQUENCY CONTROL between 10 μ Hz-10kHz, and amplitude controlling is in 5mVpp-70VppElectric signal through electroacoustic change shape Into;(C) 10-20min, which changes, is passed through the mixed inert gas and stops conveying sound wave, takes out and produces after being cooled to less than 400 DEG C A CNT ball of string.
- An a kind of 2. CNT ball of string according to claim 1, it is characterised in that a diameter of 0.7- of every CNT 4nm, length 1-5m.
- An a kind of 3. CNT ball of string according to claim 1, it is characterised in that the flat spreading part of the CNT ball of string Product is in 0.1-8mm2Between, density is at 100-150CNTs/ μm.
- 4. a kind of CNT ball of string according to claim any one of 1-3, it is characterised in that the CNT ball of string has There is consistent chiral structure.
- A 5. CNT ball of string according to claim 1, it is characterised in that in the step (B), the sound wave is continuous Or the one of which in the sine wave of interruption, sawtooth waveforms, square wave.
- A 6. CNT ball of string according to claim 5, it is characterised in that in the step (B), the sound wave is continuous Or interruption sine wave.
- A 7. CNT ball of string according to claim 1, it is characterised in that in the step (B), realized using converter Electroacoustic is changed, and the converter is wherein one in loudspeaker, siren, piezoelectric transducer and magnetostriction transducer Kind.
- A 8. CNT ball of string according to claim 7, it is characterised in that in the step (B), through poly- after electroacoustic conversion Can device concentration simultaneously amplified energy, then sound wave is added into reactor.
- A 9. CNT ball of string according to claim 1, it is characterised in that in the step (B), the frequency control of electric signal System is between 1-10kHz, and amplitude controlling is in 20-70VppBetween.
- A 10. CNT ball of string according to claim 1, it is characterised in that in the step (C), change and be passed through described mix After closing inert gas, stop adding sound wave again by 0.5-2h.
- A 11. CNT ball of string according to claim 1, it is characterised in that in the step (C), by what is be prepared A nanotube ball of string is soaked in surfactant to increase the density of a nanotube ball of string, and the surfactant is ethylene glycol, sweet One of which in oil, polyethylene glycol, ethanol.
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