CN104021879B - Preparation method for carbon nanotube flexible transparent conductive thin film - Google Patents
Preparation method for carbon nanotube flexible transparent conductive thin film Download PDFInfo
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Abstract
A preparation method for a strong-adhesion-force carbon nanotube flexible transparent conductive thin film is characterized by carrying out pretreatment of nitric acid soaking, water washing and air drying in sequence on a polyethylene terephthalate (PET) base; and taking the PET which is subjected to the pretreatment as the base and spraying carbon nanotube solution to prepare the carbon nanotube flexible transparent conductive thin film FTCFs. The specific steps of spraying the carbon nanotube solution to prepare the carbon nanotube flexible transparent conductive thin film FTCFs are as follows: heating a heating plate placed with the PET to a pre-spraying temperature of 60-90 DEG C; spraying at a low speed for 10-20 times; then, raising the temperature to 100-130 DEG C; and spraying at a high speed for 30-50 times to prepare the FTCFs. With the preparation method, the adhesion force of SWCNTs on the PET can be effectively improved; an ultrasonic wave resonance method also provides an effective way for detecting the adhesion force of the FTCFs; and besides, the operation process is simple, no pollution is caused, the method is easy to realize, and the effect is obvious.
Description
Technical field
The present invention relates to a kind of preparation of the carbon nano tube flexible transparent conductive film of strong adhesive force, belong to nano material,
Display material, opto-electronic device, communication technique field.
Background technology
Ethylene glycol terephthalate (ethylene glycol terephthalate) is thin as a kind of carbon nano tube flexible electrically conducting transparent
The preferred flexible substrates of film, have light transmittance height, resistance to deformation, the advantages of flexible, thus obtain wide in electronic light emitting devices
General application.
CNT has good electric conductivity and pliability, carbon nano tube flexible transparent conductive film prepared therefrom
In electronic light emitting devices, solaode, the field such as liquid crystal display tool is widely used.Adopt spraying process with terephthaldehyde
Sour glycol ester prepares carbon nano tube flexible transparent conductive film for substrate, and speed is fast, and film surface is uniform, soft resistance to deformation, behaviour
Make simple and efficient.
However, directly carbon nano-tube solution is sprayed in ethylene glycol terephthalate substrate, its internal layer CNT
Not good in the suprabasil uniformity of ethylene glycol terephthalate, adhesive force is also than relatively low.Simultaneously as the restriction carbon of technology is received
Mitron is difficult to directly test in the suprabasil adhesive force of ethylene glycol terephthalate.
Content of the invention
It is an object of the invention to provide a kind of preparation method of carbon nano tube flexible transparent conductive film, the method operated
Journey is simple, pollution-free, easy to implement, effect obvious, can effectively improve attachment on ethylene glycol terephthalate for the swcnts
Power.
It is a further object of the present invention to provide the detection of above-mentioned carbon nano tube flexible transparent conductive film swcnts adhesive force
Method.
In order to solve the above problems, the technical scheme is that a kind of system of carbon nano tube flexible transparent conductive film
Preparation Method it is characterised in that: ethylene glycol terephthalate substrate is carried out successively with nitric acid dousing, the pre- place washed and dry
Reason, and carbon nano tube flexible transparent conductive film is obtained with this pretreated substrate spraying carbon nano-tube solution；Described spraying
Carbon nano-tube solution is obtained concretely comprising the following steps of carbon nano tube flexible transparent conductive film: will be placed with ethylene glycol terephthalate
Heater plate temperature be preliminarily sprayed to 60-90 DEG C, low speed sprays 10-20 time, then raises temperature to 100-130 DEG C, high-velocity spray
30-50 prepared carbon nano tube flexible transparent conductive film.
Described prepared carbon nano tube flexible transparent conductive film attachment force detection method is:
1. choose the flexible carbon nano tube thin film in 60%-90% for the light transmittance as ultrasound detection sample, supersonic frequency 30-
50khz, ultrasonic power 40-60w, and use manual time-keeping；
2. the flexible carbon nano tube thin-film ultrasonic detecting step with pretreatment ethylene glycol terephthalate as substrate:
A () vertically puts into the carbon nano tube flexible transparent conductive film after drying in the beaker filling deionized water；
B () starts ultrasonic washing unit, after ultrasonic stablizing, beaker is put in ultrasonic washing unit；
C () often ultrasonic 3-10s takes out whether observation carbon pipe comes off from ethylene glycol terephthalate substrate surface, until seeing
Till having observed partial exfoliation；
D () measures multigroup sample and takes time average, experimentation timing is simultaneously taken pictures to sample.
The pretreating process of described ethylene glycol terephthalate ethylene glycol terephthalate substrate is specifically according to following
Step is carried out:
1. original ethylene glycol terephthalate substrate is put in ethanol, super under 30-50khz, 50-200w power
Sound soaks 1-5h, is then placed in nitric acid being standing and soak for 1-5h；
2. the ethylene glycol terephthalate in taking out 1. puts into standing 1-3h in deionized water, removes p-phthalic acid
The nitric acid on glycol ester surface, and make ethylene glycol terephthalate surface that hydrolysis change to occur in water；
3. 2. standing in fume hood will be placed on to dry 10-15h by middle ethylene glycol terephthalate.
Described carbon nano-tube solution is by mass percentage, composed of the following components:
CNT 0.005%-0.05%
Dodecylbenzene sodium sulfonate 0.5%-5%
Deionized water 99.495%-94.95%
Said components total amount is 100%.
Described carbon nano-tube solution is prepared, and comprises the following steps:
1. carbon nanotube powder, the detergent alkylate of 0.5%-5% are weighed with the ratio of mass ratio 0.005%-0.05%
Sodium sulfonate, is dissolved in 50-200ml deionized water, under 50-100w power in ultrasonic cleaner, ultrasonic 1-3h, then exists again
Under 100-150w power in separating apparatus, ultrasonic 0.5-1h is obtained carbon pipe dispersion liquid；
2. by centrifugation 1-2h under the carbon pipe dispersion liquid 1000-5000rpm rotating speed of 1. step preparation, take upper strata centrifugal liquid
Cover set aside for use with preservative film in a small beaker.
Described carbon nanotube diameter is 0.8-3nm, length is 5-30 μm, purity is 60-99%.
The present invention has the advantage that and good effect:
1st, the present invention can improve it to carbon well by ethylene glycol terephthalate substrate surface is carried out with pretreatment
The affine performance of nanotube solution so that in spraying process CNT be more evenly distributed in ethylene glycol terephthalate
Substrate surface.
2nd, the present invention can table indirectly by carbon nano tube flexible transparent conductive film is carried out with adhesive force resonant ultrasound spectroscope
Levy the adhesive force size to CNT for the ethylene glycol terephthalate substrate.
3rd, operating process of the present invention is simply it is easy to implement, environmentally safe.
Brief description
Fig. 1 is the pretreatment of carbon nano tube flexible transparent conductive film and low pyrolytic coating process schematic；
Fig. 2 is the carbon nano tube flexible transparent conductive film attachment force detection method schematic diagram of strong adhesive force；
Fig. 3 is the carbon nano tube flexible transparent conductive film that different base and post processing mode obtain to be carried out with adhesive force surpass
Sound detection schematic diagram, wherein: Fig. 3-a is that washing ethylene glycol terephthalate washes carbon nano tube flexible electrically conducting transparent for substrate
Adhesive force ultrasonic tesint schematic diagram, Fig. 3-b is pretreatment ethylene glycol terephthalate is that substrate pickling CNT is soft
Property transparent conductive film adhesive force ultrasonic tesint schematic diagram；
Fig. 4 is the Raman spectrogram characterizing ultrasonic rear carbon nano tube flexible transparent conductive film different parts CNT.
Specific embodiment
First, as shown in Figure 1: a kind of preparation method of the carbon nano tube flexible transparent conductive film of strong adhesive force, including such as
Lower step:
1st, the pretreatment of ethylene glycol terephthalate ethylene glycol terephthalate substrate 1:
1. original ethylene glycol terephthalate substrate is put in ethanol, super under 30-50khz, 50-200w power
Sound soaks 1-5h, is then placed in being standing and soak for 1-5h in 2-12m nitric acid；
2. the ethylene glycol terephthalate in taking out 1. puts into standing 1-3h in deionized water, removes p-phthalic acid
The nitric acid on glycol ester surface, and make ethylene glycol terephthalate surface that hydrolysis change to occur in water；
3. 2. standing in fume hood will be placed on to dry 10-15h by middle ethylene glycol terephthalate.
2nd, the preparation of spraying carbon nano-tube solution:
1. CNT (swcnts) 2 powder is weighed with the ratio of mass ratio 0.005%, with the ratio of mass ratio 0.5%
Weigh dodecylbenzene sodium sulfonate (sdbs) 3, be dissolved in 100ml deionized water, super under 100w power in ultrasonic cleaner
Sound 1.5h, then ultrasonic 1h under 120w power in separating apparatus again.
2. by centrifugation 1h under the carbon pipe dispersion liquid 1000rpm rotating speed of 1. step preparation, take upper strata centrifugal liquid little in one
Set aside for use is covered with preservative film in beaker.
The a diameter of 0.8-3nm of described CNT 2, length are 5-30 μm, purity is 60-99%.
3rd, prepare carbon nano tube flexible transparent conductive film carbon nano tube flexible transparent conductive film: terephthaldehyde will be placed with
The heater plate of sour glycol ester is preliminarily sprayed temperature to 80 DEG C, and low speed sprays 15 times, then raises temperature to 110 DEG C, high-velocity spray
30 prepared carbon nano tube flexible transparent conductive films.
The carbon nano tube flexible transparent conductive film carbon nano tube flexible transparent conductive film of firm spraying preparation need to gone
0.5-2h is stood, part removes sdbs, then 0.5-1.5h is dried at a temperature of 60-100 DEG C, finally in 2-12m in ionized water
Pickling 1-5h in nitric acid, to remove the combination water on ethylene glycol terephthalate surface, makes carbon nano tube flexible electrically conducting transparent
Film sample.
2nd, by spraying with carbon nano-tube solution even application in original ethylene glycol terephthalate substrate 4 and pretreatment
In ethylene glycol terephthalate substrate 1, be obtained corresponding carbon nano tube flexible transparent conductive film, respectively it is carried out washing and
Pickling post processing, and adhesive force resonant ultrasound spectroscope is carried out to both the above carbon nano tube flexible transparent conductive film.
The flexible carbon nano tube thin film choosing light transmittance 80% as ultrasound detection sample, supersonic frequency 45khz, ultrasonic
Power 60w, and use manual time-keeping.
1st, the flexible carbon nano tube flexible transparent conductive film being obtained for substrate with pretreatment ethylene glycol terephthalate
Adhesive force ultrasound detection step is as follows:
1. the carbon nano tube flexible transparent conductive film after drying vertically is put in the beaker filling deionized water.
2. start ultrasonic washing unit, after ultrasonic stablizing, beaker is put in ultrasonic washing unit.
3. often ultrasonic 5s takes out and observes whether carbon pipe comes off from ethylene glycol terephthalate substrate surface, until observing
Till having partial exfoliation.
4. repeatedly measure multigroup sample and take time value.Experimentation timing is simultaneously taken pictures to sample.
2nd, to wash the carbon nano tube flexible transparent conductive film adhesive force that ethylene glycol terephthalate is obtained for substrate
Ultrasound detection step repeats above-mentioned 1. 2. 3. 4. step.
As shown in Figure 2,3: both adhesive force ultrasonic characterization:
Carbon nano tube flexible transparent conductive film s with washing and pretreatment ethylene glycol terephthalate as substrate is entered
The ultrasonic time timing that comes off of row CNT swcnts, can compare adhesive force indirectly by the time length that more each comes off big
Little.By the carbon nanometer to ultrasonic carbon nano tube flexible transparent conductive film various location in front and back for the raman spectroscope
Pipe does Raman spectrum, can detect the change of the change carbon nano tube structure performance with carbon nano-tube film thickness.
Claims (6)
1. a kind of preparation method of carbon nano tube flexible transparent conductive film it is characterised in that: to ethylene glycol terephthalate
Substrate carries out nitric acid dousing, the pretreatment washed and dry successively, and sprays carbon nano-tube solution with this pretreated substrate
Prepared carbon nano tube flexible transparent conductive film；Described spraying carbon nano-tube solution is obtained carbon nano tube flexible transparent conductive film
Concretely comprise the following steps: temperature is preliminarily sprayed being placed with the heater plate of ethylene glycol terephthalate to 60-90 DEG C, low speed sprays
10-20 time, then raise temperature to 100-130 DEG C, 30-50 prepared carbon nano tube flexible transparent conductive film of high-velocity spray.
2. carbon nano tube flexible transparent conductive film according to claim 1 preparation method it is characterised in that: described system
The carbon nano tube flexible transparent conductive film attachment force detection method obtaining is:
1. choose the flexible carbon nano tube thin film in 60%-90% for the light transmittance as ultrasound detection sample, supersonic frequency 30-
50khz, ultrasonic power 40-60w, and use manual time-keeping；
2. the flexible carbon nano tube thin-film ultrasonic detecting step with pretreatment ethylene glycol terephthalate as substrate:
A () vertically puts into the carbon nano tube flexible transparent conductive film after drying in the beaker filling deionized water；
B () starts ultrasonic washing unit, after ultrasonic stablizing, beaker is put in ultrasonic washing unit；
C () often ultrasonic 3-10s takes out whether observation carbon pipe comes off from ethylene glycol terephthalate substrate surface, until observing
Till having partial exfoliation；
D () measures multigroup sample and takes time average, experimentation timing is simultaneously taken pictures to sample.
3. carbon nano tube flexible transparent conductive film according to claim 1 preparation method it is characterised in that: described right
The pretreating process of PET substrate is specifically carried out according to the following step:
1. original ethylene glycol terephthalate substrate is put in ethanol, ultrasonic leaching under 30-50khz, 50-200w power
Bubble 1-5h, is then placed in nitric acid being standing and soak for 1-5h；
2. the ethylene glycol terephthalate in taking out 1. puts into standing 1-3h in deionized water, removes p-phthalic acid second two
The nitric acid on alcohol ester surface, and make ethylene glycol terephthalate surface that hydrolysis change to occur in water；
3. 2. standing in fume hood will be placed on to dry 10-15h by middle ethylene glycol terephthalate.
4. carbon nano tube flexible transparent conductive film according to claim 1 preparation method it is characterised in that: described carbon
Nanotube solution is by mass percentage, composed of the following components:
CNT 0.005%-0.05%
Dodecylbenzene sodium sulfonate 0.5%-5%
Deionized water 99.495%-94.95%
Said components total amount is 100%.
5. the carbon nano tube flexible transparent conductive film according to claim 1 or 4 preparation method it is characterised in that: institute
State carbon nano-tube solution to prepare, comprise the following steps:
1. carbon nanotube powder, the DBSA of 0.5%-5% are weighed with the ratio of mass ratio 0.005%-0.05%
Sodium, is dissolved in 50-200ml deionized water, ultrasonic 1-3h under 50-100w power in ultrasonic cleaner, then again in dispersion
Under 100-150w power in instrument, ultrasonic 0.5-1h is obtained carbon pipe dispersion liquid；
2. by centrifugation 1-2h under the carbon pipe dispersion liquid 1000-5000rpm rotating speed of 1. step preparation, take upper strata centrifugal liquid in one
Set aside for use is covered with preservative film in small beaker.
6. carbon nano tube flexible transparent conductive film according to claim 4 preparation method it is characterised in that: described carbon
Tube diameters are 0.8-3nm, length is 5-30 μm, purity is 60-99%.
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| CN106353404B (en) * | 2016-08-10 | 2019-10-08 | 上海交通大学 | The test method of the sample of thin-film material constant is surveyed suitable for ultrasonic resonance spectrometry |
| CN107197551A (en) * | 2017-07-06 | 2017-09-22 | 天津工业大学 | A kind of thin film heater and preparation method thereof |
| CN109421081A (en) * | 2017-09-01 | 2019-03-05 | 淮安信息职业技术学院 | A kind of method of production for the intelligent power-assisting robot system carried based on heavy duty |
| CN111044453A (en) * | 2019-12-27 | 2020-04-21 | 浙江锋源氢能科技有限公司 | Method for measuring binding force of coating on surface of substrate |
| CN113458072B (en) * | 2021-07-06 | 2022-01-18 | 广东固特超声股份有限公司 | Intelligent terminal controlled ultrasonic cleaning method and cleaning machine for glasses |
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Effective date of registration: 20210129 Address after: 300382 A1-5, workshop D19, East District, No.1 Xuefu West Road, Xiqing Xuefu Industrial Zone, Xiqing District, Tianjin Patentee after: Carbon Star Technology (Tianjin) Co.,Ltd. Address before: No. 399 Bingshui Road, Xiqing District, Tianjin, Tianjin Patentee before: TIANJIN POLYTECHNIC University |