CN101962913B - Reversible electrochromism composite fiber and preparation method thereof - Google Patents
Reversible electrochromism composite fiber and preparation method thereof Download PDFInfo
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- CN101962913B CN101962913B CN2009100551925A CN200910055192A CN101962913B CN 101962913 B CN101962913 B CN 101962913B CN 2009100551925 A CN2009100551925 A CN 2009100551925A CN 200910055192 A CN200910055192 A CN 200910055192A CN 101962913 B CN101962913 B CN 101962913B
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Abstract
The invention belongs to the technical field of intelligent materials, relating to an electrochromism composite fiber. The composite fiber comprises a hollow carbon nano tube; polydiacetylene is formed in the carbon nano tube, when current is not led into the two ends of the composite fiber, the composite fiber presents the first color; when the current led into the composite fiber exceeds a critical value, the color of the composite fiber changes into the second color; and when the current led into the two ends of the composite fiber is turned off, the color restores into the first color. The preparation method of the composite fiber comprises the following steps: preparing a carbon nano tube erect column by a chemical vapor deposition method, and spinning into the carbon nano tube fiber; and dipping diyne monomer to the carbon nano tube fiber, and irradiating by utilizing ultraviolet rays, X-ray and gamma-ray to polymerize the diyne monomer into the carbon nano tube/polydiacetylene compound fiber. The electrochromic effect of the compound has repeat reversible comprehensive electrochromic performance, and has wide application potency and simple preparation method.
Description
Technical field
The present invention relates to the intellectual material technical field, particularly relate to a kind of complex fiber material and preparation method thereof with reversible electrochromic effect.
Background technology
Because along the delocalization effect of the pi-electron of main chain, conjugated polymer has good electricity and optical property, is applied in photoelectron and sensor aspect by broad research.For example; Gather diine (PDA) and can under different environmental stimulis, produce change color; Common stimulus comprises temperature, pH value, chemical reagent, stress and part effect, and typical change color is to become redness by blueness, and Application and Development is as the aberration sensor material.This change color is owing to the molecular conformation that under the stimulation of external condition, gathers diine changes.It exactly is exactly the polymer molecule more unordered (less copline) that the increase of the freedom of motion that gathers the diine side chain that causes of environmental stimuli makes the conjugation chain length reduce.It is enough about the research that gathers the new sensing function of diine, but as far as we know, also do not gather the report of diine variable color about current induced at present, and it is irreversible when gathering the diine variable color that several factors is induced.And under electric field action, induce the pure transformation that gathers the diine conformation is very difficult.Yet the variable color behavior that gathers diine of current induced can be applied in a lot of aspects, from Aero-Space to the miniaturized electronics etc.
An approach easily and effectively that addresses the above problem is exactly with gathering diine and other have the compound preparation nano composite material of material of excellent conductive performance.Wherein electric conductivity good one when feeding electric current, can produce enough electric fields induce be combined with each other gather the conformation change of diine molecule on nanoscale, perhaps the stack of this effect can macroscopic view go up the indication change in color.One of ideal material that satisfies this requirement is exactly CNT (CNT).We know that CNT has unique chemical structure and good electric conductivity.For example, the method through chemical vapour deposition (CVD) synthesizes the upright row of long CNT recently, and wherein the conductance of each root multi-walled carbon nano-tubes at room temperature can reach 104S/cm.These CNTs can be spun into macroscopic fiber and keep excellent electric conductivity simultaneously.Therefore, but the object of the invention is exactly to utilize carbon nano-fiber and gather the complex fiber material that diine prepares novel current induced variable color, with the needs of said application facet above satisfying.
Summary of the invention
The purpose of this invention is to provide a kind of electrochromism composite fibre and preparation method thereof, through will have electrochromic effect gather diine and to have a carbon nano-tube fibre of excellent conductive performance compound, obtain to repeat reversible electrochromism composite fibre.
For realizing above-mentioned purpose; The present invention utilizes the upright row spinning of CNT to process carbon nano-tube fibre; The multi-walled carbon nano-tubes that comprises hollow in the said carbon nano-tube fibre; The diine monomer is coated on said carbon nano-tube fibre, makes the diine monomer polymerization form through induction and gather diine, process carbon nano-tube/poly diine composite fibre.When electric current that said carbon nano-tube/poly diine composite fibre two ends do not import; It presents first kind of color; When the electric current that imports when said carbon nano-tube/poly diine composite fibre two ends surpasses a critical value; Its color change is second kind of color, and when current interruption that said carbon nano-tube/poly diine composite fibre two ends import, its color restoration is first kind of color.
The preparation method of said electrochromism composite fibre comprises that the upright row spinning of the CNT that utilizes chemical gaseous phase depositing process to make processes the step of carbon nano-tube fibre; Also comprise through carbon nano-tube fibre is soaked in the diine monomer solution of preset concentration; Carbon nano-tube fibre solvent flashing after order is soaked then and drying are coated on the diine monomer step of carbon nano-tube fibre; And employing ultraviolet ray, X ray or radiation gamma are induced the step that makes diine monomer polymerization formation carbon nano-tube/poly diine composite fibre.
The invention has the advantages that to have with the electrochromic effect of the carbon nano-tube/poly diine composite fibre of method for preparing and repeat reversible comprehensive discoloration, its application potential is extensive, and the preparation method is simple.
Description of drawings
Fig. 1 is the sketch map that utilizes the upright row of chemical vapour deposition technique synthesizing carbon nanotubes.
Fig. 2 a-2c is for being spun into the carbon nano tube structure sketch map of fiber.
Fig. 3 is the topochemical polymerization of diine molecule and gathers the sketch map of the change color of diine molecule.
Fig. 4 is the electron microscope picture that synthetic according to the method for the invention carbon nano-tube/poly diine composite fibre scans under different resolution.
Fig. 5 is conductance and the temperature relation and the transitive model conductance coordinate diagram of demonstration carbon nano-tube/poly diine composite fibre, wherein,
5a is the conductance of demonstration carbon nano-tube/poly diine composite fibre and the diagrammatic sketch of temperature relation;
5b is for showing the three-dimensional transitive model conductance coordinate diagram of carbon nano-tube/poly diine composite fibre;
5c is for showing the two-dimentional transitive model conductance coordinate diagram of carbon nano-tube/poly diine composite fibre;
5d is for showing the one dimension transitive model conductance coordinate diagram of carbon nano-tube/poly diine composite fibre.Fig. 6 is the sketch map of the experimental provision of the change color of observation carbon nano-tube/poly diine composite fibre when switching on.
The optical microscope photograph of variations in temperature when Fig. 7 is the energising of carbon nano-tube/poly diine composite fibre.
Fig. 8 is a carbon nano-tube/poly diine composite fibre stress-strain curve.
Fig. 9 is the ultraviolet-visible spectrogram of carbon nano-tube/poly diine composite fibre under the mechanical stress effect.
Figure 10 is the diagrammatic sketch of carbon nano-tube/poly diine composite fibre variable color under the mechanical friction effect.
Figure 11 is immersed in the ultraviolet-visible spectrogram in the different chemical reagent for carbon nano-tube/poly diine composite fibre.
The specific embodiment
Specify the principle of the present invention and the specific embodiment thereof below with reference to accompanying drawing.
As shown in Figure 1, pure carbon nano-tube fibre can be spun into by the synthetic upright row of CNT of chemical vapour deposition technique.Surface deposition one deck ferrous metal layer 20 of basalis 10 utilizes chemical vapour deposition technique (CVD) to grow the upright row of CNT (CNT) 30 on ferrous metal layer 20.Fig. 2 a-2c is for being spun into the carbon nano tube structure sketch map of fiber.The diameter of carbon nano-tube fibre can be controlled at 4-22 μ m, mainly by the initial carbon ribbon width decision of spinning process.Carbon ribbon is defined as a branch of CNT of when spinning process begins, from the upright row of CNT, pulling out.Transmission electron microscope figure (TEM, see Fig. 2 a) and high resolution transmission electron microscopy (seeing Fig. 2 b) shown that diameter is about many wall constructions of the CNT of 10nm.Fig. 2 c has shown the Raman spectrum of typical CNT, and its D band presents more weak peak at 1345cm-1 place, and its G is with the 1577cm-1 place to present stronger peak, and the report of this and other CNT is similar.
Carbon nano-tube/poly diine composite fibre according to the present invention is through directly diine monomer (like CH3 (CH2) 11C ≡ C-C ≡ C (CH2) 8COOH) being coated in above the CNT, and the diine monomer carries out topochemical polymerization under ultra violet lamp then.As shown in Figure 3, be blue behind the diine monomer polymerization, under environmental stimuli, to gather diine conjugated chain length and shorten, conformation changes, and demonstrates redness, and when removing environmental stimuli, gathering the diine conjugated chain possibly recover its length, makes color transition become original blueness.That Fig. 4 shows is SEM (SEM) figure of a carbon nano-tube/poly diine composite fibre, and its diameter evenly is 11 μ m vertically basically.Synthetic like this carbon nano-tube/poly diine composite fibre is blue, and is easy to observe with the naked eye.
Carbon nano-tube/poly diine composite fibre is because the orderly arrangement of its inner carbon nanotube has the conductance up to 102-103S/cm.Further studied the temperature dependency of carbon nano-tube/poly diine composite fibre conductance through the four point probe method.Shown in Fig. 5 a, conductance raises with temperature and improves, and has shown the characteristic of semiconductor behavior of carbon nano-tube/poly diine composite fibre.Two electrical conduction models are that range transition mechanism and tunnel transmission mechanism possibly be applicable to these composite fibres.According to previous reported method, the electronics transmission of carbon nano-tube/poly diine composite fibre more approaches three-dimensional transition mechanism, like Fig. 5 b.In other words, when feeding electric current, electronics can not be limited in the one dimension tunnel of CNT orientation.Opposite, electronics possibly transit to another site from a site, perhaps transits on another root CNT from a CNT.In addition, Fig. 5 c and 5d have shown two peacekeeping one dimension transitive model conductance coordinate diagram of carbon nano-tube/poly diine composite fibre respectively.Above-mentioned behavior is likely and is caused by CNT defective in the composite fibre.
Importantly, the energising of carbon nano-tube/poly diine composite fibre becomes redness from blueness rapidly later, and experimental provision shown in Figure 6 promptly is used for carbon nano-tube/poly diine composite fibre is switched on to observe its change in color.As shown in Figure 6; Carbon nano-tube/poly diine composite fibre of the present invention is fixed on the substrate of insulation, and glass is for example fixed with elargol at the composite fibre two ends and is connected lead; Can use gold thread, silver-colored line or copper cash etc., be connected with external power source again through lead.Before energising, composite fibre still is rendered as blueness, and after composite fibre was switched on, in being higher than the certain limit of critical electric current value, composite fibre became redness rapidly by blueness, and this variable color is reversible, promptly remove electric current after redness return to blueness.After continuing rising electric current to the second critical value, change color is irreversible, and after stopping to switch on, it is red that composite fibre keeps.Can induce diameter under the room temperature is that the minimum current of the fading of fiber of 11 μ m is 10mA.And, absolute value controlling carbon nanotube that can be through changing electric current/the gather invertibity of diine composite fibre variable color.For example, when electric current was lower than 30mA, blue was reversible to red transformation, and the variable color of this reversible ground can repeat many times continuously, and for example tens times, this Application in Sensing for reality is a key very.The percentage that the blueness that the variable color response is promptly calculated by ultraviolet-visible spectrum changes to redness, it is 0-0.3% that blueness is gathered diine, it is 10.9-11.4% that redness is gathered diine.In addition, the variable color behavior can be to the speed break-make response of electric current with 2 seconds, and promptly the blue fiber in energising back can become redness in 2 seconds, and red fiber just returns to blueness after removing electric current in 2 seconds.But, under the bigger function of current, this color transition is irreversible.
Several possible causes that the variable color of current induced composite fibre is arranged.When giving carbon nano-tube/poly diine composite fibre alive, thereby may cause change color by elevated temperature.But, following some facts should be got rid of the possibility of temperature-induced variable color.(1) gather diine and will reach about 56 ℃, and thermochromism is irreversible by the temperature that blueness becomes redness.(2) when giving the electric current of carbon nano-tube/poly diine composite fibre feeding 30mA, do not detect tangible temperature with infrared radiation thermometer and raise.(3) for further research electrochromism behavior, the outer surface that the benzophenone that we will be very thin (44 ℃ begin fusing) powder overlays on carbon nano-tube fibre obtains CNT/benzophenone composite fibre.The variation of composite fibre before and after the relatively more logical 30mA electric current under light microscope.Switching on did not all have to find to be close to the benzophenone fusing of fiber surface in one minute, and as shown in Figure 7, this is lower than 44 ℃ with regard to the temperature that shows carbon nano-tube fibre, and thermochromism will just can take place 56 ℃ even higher temperature.
The change color of the carbon nano-tube/poly diine composite fibre of current induced more possibly be because the electric property of the uniqueness that interaction between CNT and the polymer and CNT provide.Carbon nano-tube/poly diine composite fibre shows the very high conductance of three-dimensional transition conduction, and just electronics transits on another root CNT from a CNT at fibrous inside.Therefore, have electric field between the adjacent carbons nanotube, electric field possibly cause the polarization that COOH group and conjugation on the diine side chain are gathered the diine main chain that gathers between the adjacent carbons nanotube.Above-mentioned polarization has reduced the delocalization effect that gathers pi-electron on the diine main chain, and the conjugation chain length shortens, and indicating fiber color, to change the variable color of inducing with other stimulations of having reported similar.The situation of less electric current, remove electric current after, gather the diine conformation and can return to original state, so variable color is reversible ground.Thereby to gather the recovery capability variable color of diine irreversible and big electric current possibly break ring.
Although the former polyurethane diine system of variable color response to mechanical stress has confirmed, could realize that this has just limited the application aspect sensing by very big percentage elongation.CNT is the firmest material that it is found that up to now, and carbon nano-tube fibre has very high mechanical strength (0.55GPa-0.65GPa), and high strength makes that gathering diine can ignore mechanics variable color under the situation of percentage elongation.Experiment confirm this hypothesis.The change color of carbon nano-tube/poly diine composite fibre under high tensile stress can be observed through ultraviolet-visible spectrum.Blue absworption peak appears at the scope of 600-700nm, and red absworption peak appears at the 500-600nm scope.Carbon nano-tube/poly diine composite fibre with 0.55GPa TENSILE STRENGTH, still blue during less than 0.48GPa in tensile stress. stress surpasses this point and becomes redness rapidly, and is as shown in Figure 8.If when stress reaches 0.48-0.51GPa, discharge stress rapidly, redness returns to blueness, that is to say, variable color is reversible ground.Because the TENSILE STRENGTH of composite fibre is 0.55GPa, we confirm the range of application of composite fibre at an easy rate through the change color under the tensile stress.
Carbon nano-tube/poly diine composite fibre can produce color response to a lot of other environmental stimulis, like mechanical friction, chemical reagent and organic vapor etc.What Fig. 9 showed is the uv-vis spectra of carbon nano-tube/poly diine composite fibre under the mechanical stress effect, and wherein curve a is the spectrogram that is rendered as blue synthetic composite fibre; Curve b is that composite fibre presents red spectrogram under the mechanical stress effect of 0.48GPa; Curve c removes stress is reverted to blue composite fibre afterwards by redness spectrogram.In addition, composite fibre can become redness from blueness in several seconds under the mechanical friction effect, referring to the sketch map of Figure 10.Similarly, when being heated to 56 ℃ or higher temperature, composite fibre also can just become redness by blueness in 1 minute.Composite fibre shows different responsiveness to different chemical reagent, sees Figure 11, and for example, at oxolane, N, in dinethylformamide, DMAC N,N and the 1-Methyl-2-Pyrrolidone, the composite fibre color changes fully; In styrene, methyl sulfoxide, benzene, toluene and methyl acrylate, the composite fibre color partly changes; And in water, methyl alcohol and ethanol, color does not change.Carbon nano-tube/poly diine composite fibre can also produce color response to organic vapor, for example oxolane and N, and dinethylformamide is seen Figure 12.In the oxolane atmosphere under room temperature, atmospheric pressure, composite fibre is changed to redness by blueness very soon, and transformation needs about 30 minutes ability to accomplish fully, because vapor diffusion needs the time to fibrous inside.Relative oxolane, composite fibre be to N, the response of dinethylformamide will be slowly many, about two days time.It should be noted that the change color that mechanical friction, chemical reagent and organic vapor are induced is irreversible.
According to principle of the present invention, the method for preparing carbon nano-tube/poly diine composite fibre comprises following main step:
At first, be to prepare carbon nano-tube fibre according to existing technology, for example be spun into composite fibre through the synthetic upright row of CNT of chemical vapour deposition technique, detailed process is omitted at this.
Following step is that the diine monomer is coated on the carbon nano-tube fibre that spinning processes.In this step, a kind of preferred implementation is that carbon nano-tube fibre is immersed in the diine monomer solution, treats that the diine monomer penetrates in the multi-walled carbon nano-tubes hollow structure of composite fibre, takes out at the fiber that soaks into to make solvent evaporates make its drying again.Concrete processing procedure comprises: at first the diine monomer is dissolved in the solvent, is made into certain density solution; Then pure carbon nano-tube fibre is immersed in certain hour in the diine monomer solution, again fiber is taken out, at room temperature solvent flashing.The fiber of handling is placed on certain hour in the fume hood, and solvent volatilizees fully, and fiber parches.The carbon nano-tube fibre of doing is the black that shows CNT.
At synthesis step, the carbon nano-tube fibre that will soak diine solution is at room temperature shone by ultraviolet light, makes the diine monomer polymerization that is coated on the fiber.Polymerization time does not wait from 10 minutes by 2 hours, depends on the diameter of fiber.After the polymerization, carbon nano-tube/poly diine composite fibre is rendered as blue or orange.The composite fibre two ends that the diine polymerization is later are fixed, and with elargol the fiber two ends are connected with lead, and lead can link to each other with current source.Feed to surpass the electric current of a certain critical value, composite fibre becomes redness or brown at short notice, remove an electric current after, composite fibre returns to original blue or orange very soon.And this reversible electrochromism can repeat many times.
Instantiation one:
With monomer CH
3(CH
2)
11C ≡ C-C ≡ C (CH
2)
8COOH is dissolved in the oxolane, is made into the diine monomer solution of 10mg/ml.Be that the carbon nano-tube fibre of 11 μ m was immersed in the diine monomer solution 10 minutes with diameter then, solvent flashing at room temperature after the taking-up.Be placed on fume hood interior 24 hours.Use wavelength to shine 1 hour apart from fiber 17cm, make the diine monomer polymerization on the fiber, obtain blue carbon nano-tube/poly diine composite fibre as the uviol lamp of 254nm.Get a section fibre and be fixed on the glass substrate, two ends are linked together with elargol and gold thread.Gold thread is connected with current source, feeds electric current.Constantly increase current value, electric current is during less than 10mA, and composite fibre does not have significant change.Electric current greater than 10mA during less than 30mA in 2 seconds composite fibre become redness, remove electric current, composite fibre returned to original blueness again in 2 seconds.Electric current greater than 30mA after, blue composite fibre becomes redness very soon, removes after the electric current, can not be returned to blueness, still keeps red.Between the 10-30mA electric current, repeat electric current of make-and-break and make the composite fibre color that repeatedly reversible variation take place, the number of times of repetition is 14 times.
Instantiation two:
With monomer HOOC (CH
2)
8C ≡ C-C ≡ C (CH
2)
8COOH is dissolved in the oxolane, is made into the diine monomer solution of 10mg/ml.Be that the carbon nano-tube fibre of 11 μ m was immersed in the diine monomer solution 30 minutes with diameter then, solvent flashing at room temperature after the taking-up.Be placed on fume hood interior 24 hours.Use wavelength to shine 1.5 hours apart from fiber 17cm, make the diine monomer polymerization on the fiber, obtain blue carbon nano-tube/poly diine composite fibre equally as the uviol lamp of 254nm.Get a section fibre and be fixed on the glass substrate, two ends are linked together with elargol and gold thread.Gold thread is connected with current source, feeds electric current.Constantly increase current value, electric current is during less than 10mA, and composite fibre does not have significant change.Electric current greater than 10mA during less than 30mA in 2 seconds composite fibre become redness, remove electric current, composite fibre returned to original blueness again in 2 seconds.Between electric current 10-30mA, repeat the energising outage, make the composite fibre color produce repeatedly reversible variation, number of repetition is 15 times.Electric current greater than 30mA after, blue composite fibre becomes redness very soon, removes after the electric current, still keeps red.
Instantiation three:
With monomer HOCH
2C ≡ C-C ≡ CCH
2OH is dissolved in the oxolane, is made into the diine monomer solution of 10mg/ml.Be that the carbon nano-tube fibre of 11 μ m was immersed in the diine monomer solution 20 minutes with diameter then, solvent flashing at room temperature after the taking-up.Be placed on fume hood interior 24 hours.Use wavelength to shine 2 hours apart from fiber 17cm, make the diine monomer polymerization on the fiber, obtain orange carbon nano-tube/poly diine composite fibre as the uviol lamp of 254nm.Get a section fibre and be fixed on the glass substrate, two ends are linked together with elargol and gold thread.Gold thread is connected with current source, feeds electric current.Constantly increase current value, electric current is during less than 10mA, and composite fibre does not have significant change.Electric current greater than 10mA during less than 30mA in 2 seconds composite fibre become brown, remove electric current, composite fibre returns to original orange again in 2 seconds.Between electric current 10-30mA, repeat the energising outage, make the composite fibre color produce repeatedly reversible variation, number of repetition is 16 times.Electric current greater than 30mA after, blue composite fibre becomes redness very soon, removes after the electric current, still keeps brown.
In sum, the synthetic carbon nano-tube/poly diine composite fibre of polymerization can reversible and promptly change color under the function of current according to the present invention.These composite fibres are used a lot of aspects such as sensor in position.
Claims (7)
1. a composite fibre is characterized in that said composite fibre comprises the hollow carbon nanotube, and polymerization formation gathers diine in this CNT; When said composite fibre two ends do not import electric current; It presents first kind of color, and when the electric current that imports when said composite fibre two ends surpassed a critical value, its color change was second kind of color; And when current interruption that said composite fibre two ends import, its color restoration is first kind of color.
2. composite fibre according to claim 1, said CNT are multi-walled carbon nano-tubes.
3. composite fibre according to claim 2, the diameter of said CNT are 6nm to 15nm, and length is 200 μ m to 800 μ m.
4. composite fibre according to claim 1, the diameter of said composite fibre are 4 μ m to 22 μ m.
5. method for preparing the described composite fibre of claim 1 comprises step:
-upright row the spinning of CNT that utilizes chemical gaseous phase depositing process to make forms carbon nano-tube fibre; It is characterized in that this method also comprises step:
-the diine monomer is coated on said carbon nano-tube fibre; And
The diine monomer polymerization that-order is coated on the carbon nano-tube fibre forms carbon nano-tube/poly diine composite fibre.
6. composite fibre preparation method according to claim 5 is characterized in that said the diine monomer being coated on carbon nano-tube fibre through following step:
-carbon nano-tube fibre is soaked in the diine monomer solution of preset concentration;
Carbon nano-tube fibre solvent flashing after-order is soaked and drying, and the diine monomer in the solution is resided in the hollow carbon nanotube of carbon nano-tube fibre.
7. composite fibre preparation method according to claim 6 is characterized in that the step of said diine monomer polymerization adopts ultraviolet ray, X ray or radiation gamma to induce.
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| CN102086593B (en) * | 2009-12-04 | 2012-08-01 | 复旦大学 | Method for preparing carbon nano tube composite fibers with excellent performance |
| CN102190747B (en) * | 2011-04-19 | 2013-04-10 | 复旦大学 | Magnetochromic polydiyne/ferroferric oxide composite material as well as preparation method and application thereof |
| CN102618254B (en) * | 2012-03-16 | 2014-12-31 | 苏州大学 | Electrochromic composite material and preparation method thereof |
| CN104910566B (en) * | 2015-06-03 | 2017-06-06 | 东华大学 | A kind of preparation method of polymer masterbatch and fiber with moisture absorption coloring function |
| CN109750364B (en) * | 2019-03-19 | 2021-03-16 | 青岛大学 | Process for preparing hollow fiber based on electrostrictive material |
| CN113106570B (en) * | 2021-03-16 | 2022-11-11 | 南通纺织丝绸产业技术研究院 | Composite electrochromic material and preparation method and application thereof |
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