CN102701185A - Method and device for orientating carbon nanotube - Google Patents
Method and device for orientating carbon nanotube Download PDFInfo
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- CN102701185A CN102701185A CN2012102068353A CN201210206835A CN102701185A CN 102701185 A CN102701185 A CN 102701185A CN 2012102068353 A CN2012102068353 A CN 2012102068353A CN 201210206835 A CN201210206835 A CN 201210206835A CN 102701185 A CN102701185 A CN 102701185A
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Abstract
The invention discloses a method for orientating a carbon nanotube. According to the method, an electric field device is arranged in the motion process of the carbon nanotube and the carbon nanotube is allowed to be orientated in the air before covering the surface of a matrix, so that the resistance in the orientation process of the carbon nanotube is smaller and the orientation degree is higher and further the voltage required by orientation is reduced; an electric field can be only applied to the front end of a spray gun or can be applied to the surrounding air of the matrix or can be simultaneously applied to the front end of the spray gun and the surrounding air of the matrix; and after the carbon nanotube is subjected to the orientation for two times, the orientation degree of the carbon nanotube is higher. Compared with the prior art, the method disclosed by the invention has the advantages that the orientation resistance of the carbon nanotube is reduced, high orientation degree is obtained and the orientation can be quickly realized on a large scale.
Description
Technical field
The present invention relates to a kind of method of material orientation, particularly a kind of method of carbon nanotube orientation.
Background technology
Carbon nanotube is compared unordered arrangement mode and more can be given full play to its effect if press the certain orientation ordered arrangement on matrix, more effectively significantly promotes matrix performances such as mechanics, calorifics or electromagnetism on assigned direction.
In the prior art, have about carbon nanotube in the liquid dispersant environment, through the directed report of modes such as electromagnetism or drawing.Chinese patent CN 200410009281.3 discloses a kind of method of controlling carbon nanotube orientation; The drips of solution that will contain carbon nanotube is on the prefabricated silicon substrate that electrode arranged; Require design electrode shape and structure according to the carbon nanotube orientations; On electrode, apply alternating-current,, realize that carbon nanotube is along the purpose of confirming that direction is arranged through the orientation of controlling alternating-electric field and the order that applies alternating-electric field.The orientation of carbon nanotube is in the drop that drips on silicon substrate, to accomplish in this patented process; To overcome the viscous resistance of liquid internal in the orientations process; Need apply very big outside tractive force, be difficult to realize the preparation of the material of big area carbon nanotube orientation.
Summary of the invention
The method that the object of the present invention is to provide a kind of carbon nanotube under the unconfinement state, to be orientated provides simultaneously and realizes the carbon nanotube unconfinement state device of orientation down.
The objective of the invention is to realize like this; Discharge carbon nanotube in a certain way and make it to be in the unconfinement state; The movement locus of the carbon nanotube of unconfinement state passes preset electric field arrangement; Through design electric field structure parameter, realize the coupling of unconfinement state carbon nanotube orientation time and run duration; Make the carbon nanotube of unconfinement state in moving process, under electric field action, accomplish the orientation rotation, when arriving the expection matrix surface, form oriented alignment, thereby realize the carbon nano-tube oriented purpose that covers matrix surface.
The carbon nanotube method for alignment that the present invention relates to is characterized in that: carbon nanotube is orientated under the unconfinement state, and operation steps comprises:
(1) according to carbon nanotube type and size, expection arrangement mode and delivery mode, coupling carbon nanotube orientation track and movement locus, the relative position of design electric field structure parameter, electrical parameter and carbon nanotube tripping gear, electric field and expection matrix;
(2) lay carbon nanotube tripping gear, electric field and expection matrix;
(3) electric field energising discharges carbon nanotube, and carbon nanotube is accomplished orientation under electric field action, cover the expection matrix surface, realizes the oriented alignment of carbon nanotube.
The method of the carbon nanotube orientation that the present invention relates to is characterized in that: for SWCN, and orientation strength of electric field 1.5 * 10
4V/m ~ 9 * 10
5V/m.
The method of the carbon nanotube orientation that the present invention relates to is characterized in that: for multi-walled carbon nano-tubes, and orientation strength of electric field 3.2 * 10
4V/m ~ 9 * 10
5V/m.
The method of the carbon nanotube orientation that the present invention relates to, it is characterized in that: described even carbon nanotube is scattered in the liquid.
The method of the carbon nanotube orientation that the present invention relates to, it is characterized in that: the carbon nanotube of stating discharges with dried forms.
The method of the carbon nanotube that the present invention relates to orientation is characterized in that: said carbon nanotube delivery mode be selected from injections, purging or freely scatter in a kind of.
The carbon nanotube aligning device that the present invention relates to is characterized in that: comprise carbon nanotube tripping gear and electric field arrangement, the movement locus of carbon nanotube passes electric field, and structure is shown in accompanying drawing 1.
The carbon nanotube aligning device that the present invention relates to is characterized in that: the relative position of described carbon nanotube tripping gear and electric field arrangement is fixed.
The carbon nanotube aligning device that the present invention relates to is characterized in that: described electric field arrangement is arranged at around the matrix and the tripping gear front end.
The carbon nanotube method for alignment that the present invention relates to, carbon nanotube are accomplished aerial orientation under the unconfinement state, the orientation resistance is little; Orientation effect is good, and efficient is high, and energy consumption is low; Be suitable for matrix surface carbon nanotube orientation, be specially adapted to big area matrix surface carbon nanotube orientation.
Description of drawings
What accompanying drawing 1 was represented is the synoptic diagram of the inventive method first embodiment
What accompanying drawing 2 was represented is the synoptic diagram of the inventive method second embodiment
What accompanying drawing 3 was represented is the synoptic diagram of the inventive method the 3rd embodiment
What accompanying drawing 4 was represented is the synoptic diagram of the inventive method the 4th embodiment
Wherein: 1-electrode, 2-spray gun, 3-matrix, the electric field pipeline section of 4-spray gun front end.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the technical scheme that the present invention relates to is further explained, but not as the restriction to technical scheme.
The carbon nanotube method for alignment that the present invention relates to is to let the carbon nanotube of unconfinement state under electric field action, in aerial completion orientation.Because suffered resistance is merely the air viscous resistance in the orientation rotation process; This reactive force is much smaller than the orientation reactive force of carbon nanotube in electric field; Therefore; In electric field,, just can achieve the orientation purpose as long as the difference of potential energy after the carbon nanotube orientation and initial potential energy surpasses the heat energy that its surrounding environment medium pedesis is produced.
The potential energy of carbon nanotube in electric field is expressed as:
The heat energy that the surrounding medium pedesis is produced can use
to represent.
Like this, the carbon nanotube of unconfinement state will be orientated rotation, must satisfy following formula:
Then the field minimum intensity that in electric field, is orientated of carbon nanotube can be expressed as:
Wherein,
is the potential energy of carbon nanotube in electric field; P is the moment of dipole of carbon nanotube in electric field; E is a strength of electric field;
is permittivity of vacuum;
is the axial volume polarization rate of carbon nanotube;
is carbon nanotube volume polarization rate perpendicular to axial direction;
be carbon nanotube axially and the angle of direction of an electric field;
is Boltzmann constant, and T is the T of medium.
Carbon nanotube is orientated rotation in electric field need the time, therefore, in electric field, accomplishes orientation for making carbon nanotube, and its residence time in electric field must be greater than the orientation rotation time.
The residence time of carbon nanotube in electric field depended on its release direction and mode, under the certain situation of delivery mode, obtains the short residence time(SRT) of carbon nanotube in electric field.
Carbon nanotube rotates required time and is calculated by following formula in electric field:
（5）
Wherein,
is air movement viscosity, and
is the pivoting friction coefficient.
Obtain minimum field strength and electric field relation of height by lacking
most; Confirmed the electric field height; Thereby obtain the field minimum intensity of this electric field height relatively; The minimum field strength that this minimum field strength and formula (4) are obtained is relatively got higher value as the field minimum intensity of this electric field height relatively in the inventive method; For purposes of the invention, field intensity is big more, and then the degree of orientation of carbon nanotube can be high more, and therefore, strength of electric field gets final product less than the breaking down field strength of air dielectric.For the electric field arrangement structure of the inventive method, when discharge be SWCN the time, institute's power taking intensity of field scope is 1.5 * 10
4V/m ~ 9 * 10
5V/m; When discharge be multi-walled carbon nano-tubes the time, institute's power taking intensity of field scope is 3.2 * 10
4V/m ~ 9 * 10
5V/m.
During release, carbon nanotube also can pass through device if exsiccant then both can discharge through the mode that purges or freely scatter, and discharges like spray gun.Preferably, before discharging, earlier carbon nanotube is scattered in the liquid, forms finely dispersed suspension-s with UW effect for some time, and then discharge through spray gun.In addition, the release direction of carbon nanotube can be any angle with direction of an electric field, only need guarantee that it can leave electric field and the rotation of completion orientation gets final product.
Used in the present invention spray gun can be selected common spray gun for use; Also can select for use spray nozzle front end that the spray gun of electric field arrangement is installed, when selecting the latter for use, as long as the electric field arrangement of spray gun front end can be realized the object of the invention; Then can not be used in matrix installing electrodes on every side, thereby simplify the operation flow process; Certainly, both at the spray gun front end electric field arrangement is installed, around matrix during installing electrodes, carbon nanotube can experience twice electric field orientation before arriving matrix surface, thereby improved the degree of orientation of carbon nanotube again.
After carbon nanotube completion orientation is rotated away from electric field, cover the matrix surface that is provided with in advance.
Embodiment one
In winding shaping process, 90 ° on the wide glass fiber bundle of 30cm surface of the multi-walled carbon nano-tubes of external diameter 3.79nm, internal diameter 2nm, long 30 μ m are arranged and are elaborated for example first embodiment to the carbon nanotube method for alignment that the present invention relates to.
Electric field arrangement is set.At the 50cm place, glue groove the place ahead that fills the resol glue; The fibrous bundle surface vertically is provided with the metal electrode 1 of a pair of wide 8cm, high 10cm, and is as shown in Figure 1, and the spacing of two metal electrodes 1 is 31cm; Parallel with fiber bundle direction, electrode 1 lower surface is apart from the surperficial 5cm of fibrous bundle.
Choose the carbon nanotube tripping gear.The carbon nanotube tripping gear of selecting for use in the inventive method is a V-3 type spray gun 2, and its nozzle diameter is 0.5mm, and top hole pressure is 0.3MPa.
The preparation carbon nano tube suspension.Carbon nanotube is scattered in the aqueous solution, uses power to be the UW effect of 200w 2 hours then, make it to form the carbon nanotube weight content and be 0.1% suspension-s.
After ready, the suspension-s that is dispersed with carbon nanotube is packed in spray gun 2 storage tanks.Before discharging suspension-s with spray gun 2, earlier metal electrode 1 being applied frequency is that 5MHz, voltage are 9.92 kilovolts alternating-current.Discharge carbon nano tube suspension, and let glass fiber bundle slowly move forward under external force.The liquid drop movement that discharges in the metal electrode 1 after, wherein induced charge appears in carbon nano tube surface, drive carbon nanotube drop is orientated rotation under the electrical forces effect.
When discharging the suspension-s of carbon nanotubes, release direction is preferably vertical with direction of an electric field.
For covering more multizone, said spray gun 2 preferred immobilization are on device with letting even carbon nanotube, and it is at the uniform velocity mobile before and after the direction of an electric field by instrument control.Said metal electrode 1 more preferably is placed on the device with the relatively-stationary mode in position with spray gun 2; At the uniform velocity mobile by its edge of instrument control perpendicular to the direction of continuous glass fibre bundle; Can dwindle the distance of 1 at two electrodes so greatly, apply voltage of alternating current in the above thereby reduce, for example; The distance that two electrodes are 1 is 5cm, and it is applied 1.6 kilovolts of voltage of alternating current.
Through behind the electric field orientation, the drop that is dispersed with carbon nanotube covers the glass fiber bundle surface that is soaked with the resol glue, and along with the curing of resol glue is fixed on the glass fiber bundle surface.
As a kind of improvement of the present invention, used spray gun 2 also can be provided with electric field pipeline section 4 at its front end in the present embodiment, and this electric field pipeline section 4 is made up of with the flat segments of long 5cm, internal diameter 4cm the taper pipeline section of cone angle 150 degree.Flat segments is made up of relative curved metal electrode in both sides and the insulating material around it of long 4cm, radian 2/3 π, and it is that 5MHZ, voltage are 1.28 kilovolts alternating-current that this electric field pipeline section 4 is applied frequency.Like this, carbon nanotube can be at first carry out orientation first time in the electric field that spray gun 2 front end electric field pipeline sections 4 form, and then moves to and carry out in the electric field that is formed by metal electrode 1 being orientated the second time, thereby effectively improves the degree of orientation of carbon nanotube.
Embodiment 2
Be that with the difference of embodiment 1 it is 310,000 volts of voltage of alternating current of 5MHz that metal electrode has been applied frequency, it is 4.5 ten thousand volts of voltage of alternating current of 5MHz that spray gun front end electric field pipeline section has been applied frequency.
Embodiment 3
Be that with the difference of embodiment 1 it is 50,000 volts of voltage of alternating current of 5MHz that metal electrode has been applied frequency, it is 1.5 ten thousand volts of voltage of alternating current of 5MHz that spray gun front end electric field pipeline section has been applied frequency.
Embodiment 4
With the SWCN of external diameter 2nm, long 5 μ m on prepreg 90 ° arrange that to be example be elaborated to second embodiment of the carbon nanotube method for alignment that the present invention relates to.
Electric field arrangement is set.The prepreg of fixed placement one 30cm * 50cm on table plane is installed one group of metal electrode 1 in the rear and front end of this prepreg, as shown in Figure 2; This metal electrode 1 is in a certain angle with the prepreg plane; Preferred 30 °-60 ° of this angle, its design width is 52cm, highly is 5cm; The spacing of two electrodes 1 is 31cm, and its lowest position of this metal electrode 1 is apart from prepreg upper surface 5cm.
Choose the carbon nanotube tripping gear.The carbon nanotube tripping gear of selecting for use in the inventive method is the same with embodiment 1, also is V-3 type spray gun 2, and its nozzle diameter is 0.5mm, and top hole pressure is 0.3MPa.
The preparation carbon nano tube suspension.Carbon nanotube is scattered in the chloroform, uses power to be the UW effect of 200w 2 hours then, making it to form concentration is the finely dispersed suspension-s of 0.1mg/ml.
After preparation work is accomplished, the chloroform suspension-s that is dispersed with carbon nanotube is packed in spray gun 2 storage tanks.Discharge before the suspension-s, earlier metal electrode 1 being applied frequency is that 5MHz, voltage are 27.9 ten thousand volts alternating-current.Discharge carbon nano tube suspension, let liquid drop movement in the electric field of metal electrode 1 formation, be orientated rotation.
When discharging the chloroform suspension-s of carbon nanotubes, release direction is preferably vertical with direction of an electric field.
For covering more multizone, said spray gun 2 preferred immobilization are on device with letting even carbon nanotube, and it is at the uniform velocity mobile before and after the direction of an electric field by instrument control.Said metal electrode 1 more preferably is placed on the device with the relatively-stationary mode in position with spray gun 2; At the uniform velocity mobile by its edge of instrument control perpendicular to the direction of continuous glass fibre bundle; Can dwindle the distance of 1 at two electrodes so greatly, apply voltage of alternating current in the above thereby reduce.
Through behind the electric field orientation, the drop that is dispersed with carbon nanotube covers the prepreg surface, after the chloroform volatilization, along with the curing of glue is fixed on the prepreg surface.
The same with embodiment 1, also can electric field pipeline section 4 be set in the present embodiment at spray gun 2 front ends, it is applied 4.5 ten thousand volts of voltage of alternating current that frequency is 5MHz, make carbon nanotube carry out the secondary orientation, improve the degree of orientation of carbon nanotube.
Embodiment 5
Be with embodiment 2 differences, around prepreg, metal electrode 1 be not set in the present embodiment, only rely on the orientation of the electric field pipeline section 4 realization carbon nanotubes of spray gun 2 front ends to rotate.
At first, the electric field pipeline section 4 of spray gun 2 front ends being applied frequency is that 5MHZ, voltage are 1.8 kilovolts alternating-current.
Then; Let spray gun 2 nozzles with at the uniform velocity mobile, discharge suspension-s in the moving process perpendicular to the direction on prepreg surface, as shown in Figure 3; SWCN is orientated in the electric field of spray gun front end; Cover the prepreg surface behind the electric field orientation, the chloroform volatilization, SWCN is fixed on the prepreg with the curing of resin.
Embodiment 6
Being example on the prepreg surface with the dried carbon nanotube tube bank vertical arranged of external diameter 2nm, long 8 μ m is elaborated to the 4th embodiment of the carbon nanotube method for alignment that the present invention relates to.
Electric field arrangement is set.In 30cm * 50cm * 6cm prepreg top and bottom surface pair of metal electrodes 1 is installed, as shown in Figure 4, the design width of this metal electrode 1 is 50cm, highly is 30cm, and the distance that two metal electrodes are 1 is 50cm, and lower electrode is close to the prepreg lower surface.
After ready, metal electrode 1 is applied 7.5 kilovolts of voltage of alternating current that frequency is 5MHz.In electric field, discharge the tube bank of dried carbon nanotube with the free mode of scattering then, carbon nanotube is finally fallen on the prepreg surface with vertical mode after accomplishing orientation along direction of an electric field.
Certainly, the dried carbon nanotube in the present embodiment can also be discharged in the electric field with the mode of purging or lance ejection.
Claims (9)
1. the method for carbon nanotube orientation, step comprises:
(1) according to carbon nanotube type and size, expection arrangement mode and delivery mode; Coupling carbon nanotube orientation track and movement locus, the relative position of design electric field structure parameter, electrical parameter and carbon nanotube tripping gear, electric field and expection matrix (3);
(2) lay carbon nanotube tripping gear, electric field and expection matrix (3);
(3) electric field energising discharges carbon nanotube, and carbon nanotube is accomplished orientation under electric field action, covers expection matrix (3) surface, realizes the oriented alignment of carbon nanotube.
2. according to the method for the said carbon nanotube orientation of claim 1, it is characterized in that: for SWCN, its orientation strength of electric field scope is 1.5 * 10
4V/m ~ 9 * 10
5V/m.
3. according to the method for the said carbon nanotube orientation of claim 1, it is characterized in that: for multi-walled carbon nano-tubes, its orientation strength of electric field scope is 3.2 * 10
4V/m ~ 9 * 10
5V/m.
4. according to the method for each said carbon nanotube orientation of claim 1 to 3, it is characterized in that: described even carbon nanotube is scattered in the liquid.
5. according to the method for each said carbon nanotube orientation of claim 1 to 3, it is characterized in that: described carbon nanotube discharges with dried forms.
6. according to the method for the said carbon nanotube of claim 5 orientation, it is characterized in that: described carbon nanotube delivery mode be selected from injections, purging or freely scatter in a kind of.
7. aligning device of realizing the said carbon nanotube method for alignment of claim 1, it is characterized in that: comprise carbon nanotube tripping gear and electric field arrangement, the movement locus of carbon nanotube that said tripping gear discharges passes said electric field arrangement.
8. aligning device according to claim 7 is characterized in that: the relative position of described carbon nanotube tripping gear and electric field arrangement is fixed.
9. according to claim 7 or 8 each described aligning devices, it is characterized in that: described electric field arrangement comprises and is arranged at said expection matrix (3) metal electrode (1) on every side and the electric field pipeline section (4) that is arranged on the tripping gear front end.
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| CN103358563A (en) * | 2013-07-25 | 2013-10-23 | 中国兵器工业集团第五三研究所 | Winding formed carbon nanotube reinforced composite forming method and apparatus |
| CN103818877A (en) * | 2013-12-19 | 2014-05-28 | 中国兵器工业集团第五三研究所 | Method and device for orientating carbon nano tube by means of moving |
| CN104513486A (en) * | 2013-10-01 | 2015-04-15 | 三星Sdi株式会社 | Conductive thermoplastic resin composition |
| CN104724670A (en) * | 2014-09-03 | 2015-06-24 | 青岛科技大学 | Manufacturing method of composite material of doped aligned carbon nanotubes |
| CN106115661A (en) * | 2016-06-20 | 2016-11-16 | 青岛科技大学 | A kind of collection device of nanotube dispersion |
| CN108609434A (en) * | 2018-03-26 | 2018-10-02 | 苏州捷迪纳米科技有限公司 | Collection device and preparation system |
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| CN103358563B (en) * | 2013-07-25 | 2016-03-23 | 中国兵器工业集团第五三研究所 | A kind of Wrapping formed Carbon Nanotubes Reinforced Composites forming method |
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| CN108609434A (en) * | 2018-03-26 | 2018-10-02 | 苏州捷迪纳米科技有限公司 | Collection device and preparation system |
| CN113825720A (en) * | 2019-04-24 | 2021-12-21 | 卡纳图有限公司 | Apparatus and method for directional deposition |
| CN113825720B (en) * | 2019-04-24 | 2022-12-27 | 卡纳图有限公司 | Apparatus and method for directional deposition |
| CN112652819A (en) * | 2020-09-07 | 2021-04-13 | 上海大学 | Mold and method for preparing polymer composite solid electrolyte by electric field induced orientation |
| CN112606566A (en) * | 2020-12-15 | 2021-04-06 | Tcl华星光电技术有限公司 | Ink-jet printing nozzle, preparation method of quantum rod polarizing film and display panel |
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Application publication date: 20121003 |