CN104021879A - Preparation method for strong-adhesion-force carbon nanotube flexible transparent conductive thin film and adhesion force detection method - Google Patents
Preparation method for strong-adhesion-force carbon nanotube flexible transparent conductive thin film and adhesion force detection method 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 degrees; spraying at a low speed for 10-20 times; then, raising the temperature to 100-130 degrees; 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 preparation and the attachment force detection method thereof that the present invention relates to a kind of 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 (PET), as the preferred flexible substrates of a kind of carbon nano-tube flexible transparent conductive film, has light transmittance high, resistance to deformation, and the advantage such as flexible, thereby be used widely in electron luminescence device.
Carbon nano-tube has good electric conductivity and pliability, and carbon nano-tube flexible transparent conductive film prepared therefrom is at electron luminescence device, solar cell, and the fields such as liquid crystal display have extensive use.Adopt spraying process to prepare carbon nano-tube flexible transparent conductive film taking PET as substrate, speed is fast, film surface uniform, and soft resistance to deformation, simple and efficient to handle.
But, directly carbon nano-tube solution being sprayed in PET substrate, its internal layer carbon nano-tube is not good in the suprabasil uniformity of PET, and adhesive force is also lower.Meanwhile, because the restriction carbon nano-tube of technology is difficult to directly test at the suprabasil adhesive force of PET.
Summary of the invention
The object of this invention is to provide a kind of preparation method of carbon nano-tube flexible transparent conductive film of strong adhesive force, the method operating process is simple, pollution-free, easy to implement, successful, can effectively improve the adhesive force of SWCNTs on PET.
Another object of the present invention is to provide the detection method of above-mentioned carbon nano-tube flexible transparent conductive film SWCNTs adhesive force.
In order to address the above problem, technical scheme of the present invention is: a kind of preparation method of carbon nano-tube flexible transparent conductive film of strong adhesive force, it is characterized in that: the preliminary treatment that substrate is carried out nitric acid dousing successively, washed and dry to ethylene glycol terephthalate PET, and spraying carbon nano-tube solution makes carbon nano-tube flexible transparent conductive film FTCFs taking this pretreated PET as substrate; The concrete steps that described spraying carbon nano-tube solution makes carbon nano-tube flexible transparent conductive film FTCFs are: the heating plate that is placed with PET is heated to 60-90 DEG C of pre-spraying temperature, low speed spraying 10-20 time, be warming up to subsequently 100-130 DEG C, high-velocity spray makes FTCFs 30-50 time.
A carbon nano-tube flexible transparent conductive film attachment force detection method for strong adhesive force, is characterized in that: concrete steps are as follows:
1. choose light transmittance at the flexible carbon nano tube film of 60%-90% as ultrasound detection sample, supersonic frequency 30-50KHz, ultrasonic power 40-60W, and with manual time-keeping;
2. the flexible carbon nano tube thin-film ultrasonic detecting step taking preliminary treatment PET as substrate:
(a) the carbon nano-tube flexible transparent conductive film after drying is vertically put into the beaker that fills deionized water;
(b) start supersonic wave cleaning machine, after ultrasonic stablizing, beaker is put into supersonic wave cleaning machine;
(c) whether every ultrasonic 3-10s taking-up observation carbon pipe comes off from PET substrate surface, comes off until observed part;
(d) measure many group samples and get time average, experimentation timing is also taken pictures to sample.
The pretreating process of described ethylene glycol terephthalate PET substrate specifically carries out according to the following step:
1. original PET substrate is put in ethanol, ultrasonic immersion 1-5h under 30-50KHZ, 50-200W power, then puts in nitric acid and leaves standstill and soak 1-5h;
2. the PET in taking out 1. puts in deionized water and leaves standstill 1-3h, removes the nitric acid of pet sheet face, and makes pet sheet face that hydrolysis variation occur in water;
3. 2. middle PET is placed on the standing 10-15h that dries in fume hood.
Described carbon nano-tube solution is by mass percentage, composed of the following components:
Carbon nano-tube SWCNTs 0.005%-0.05%
Neopelex SDBS 0.5%-5%
Deionized water 99.495%-94.95%
Said components total amount is 100%.
Described carbon nano-tube solution preparation, comprises the following steps:
1. take carbon nano-tube SWCNTs powder with the ratio of mass ratio 0.005%-0.05%, the neopelex SDBS of 0.5%-5%, be dissolved in 50-200ml deionized water, ultrasonic 1-3h under 50-100W power in ultrasonic cleaner, and then in separating apparatus under 100-150W power ultrasonic 0.5-1h make carbon pipe dispersion liquid;
2. by centrifugation 1-2h under the carbon pipe dispersion liquid 1000-5000rpm rotating speed that 1. prepared by step, get upper strata centrifugate and cover set aside for use with preservative film in a small beaker.
Described carbon nano-tube diameter is that 0.8-3nm, length are that 5-30 μ m, purity are 60-99%.
The present invention has following advantage and good effect:
1, the present invention can improve its affine performance to carbon nano-tube solution well by PET substrate surface being carried out to preliminary treatment, makes carbon nano-tube in spraying process more be evenly distributed in PET substrate surface.
2, the present invention can characterize the adhesive force size of PET substrate to carbon nano-tube indirectly by carbon nano-tube flexible transparent conductive film being carried out to the detection of adhesive force ultrasonic resonance.
3, operating process of the present invention is simple, easy to implement, environmentally safe.
Brief description of the drawings
Fig. 1 is preliminary treatment and the low pyrolytic coating process schematic diagram of FTCFs;
Fig. 2 is the carbon nano-tube flexible transparent conductive film attachment force detection method schematic diagram of strong adhesive force;
Fig. 3 is that the FTCFs that different base and post processing mode are obtained carries out adhesive force ultrasound detection schematic diagram, wherein: Fig. 3-a is that washing PET is substrate washing FTCFs adhesive force ultrasonic tesint schematic diagram, and Fig. 3-b is that preliminary treatment PET is substrate pickling FTCFs adhesive force ultrasonic tesint schematic diagram;
Fig. 4 is the Raman spectrogram that characterizes ultrasonic rear FTCFs different parts carbon nano-tube.
Embodiment
One, as shown in Figure 1: a kind of preparation method of carbon nano-tube flexible transparent conductive film of strong adhesive force, comprises the steps:
1, the preliminary treatment of ethylene glycol terephthalate PET substrate 1:
1. original PET substrate is put in ethanol, ultrasonic immersion 1-5h under 30-50KHZ, 50-200W power, then puts in 2-12M nitric acid and leaves standstill and soak 1-5h;
2. the PET in taking out 1. puts in deionized water and leaves standstill 1-3h, removes the nitric acid of pet sheet face, and makes pet sheet face that hydrolysis variation occur in water;
3. 2. middle PET is placed on the standing 10-15h that dries in fume hood.
2, the preparation of carbon nano-tube solution for spraying:
1. take carbon nano-tube (SWCNTs) 2 powder with the ratio of mass ratio 0.005%, take neopelex (SDBS) 3 with the ratio of mass ratio 0.5%, be dissolved in 100ml deionized water, ultrasonic 1.5h under 100W power in ultrasonic cleaner, and then in separating apparatus ultrasonic 1h under 120W power.
2. by centrifugation 1h under the carbon pipe dispersion liquid 1000rpm rotating speed that 1. prepared by step, get upper strata centrifugate and cover set aside for use with preservative film in a small beaker.
Described carbon nano-tube 2 diameters are that 0.8-3nm, length are that 5-30 μ m, purity are 60-99%.
3, preparation carbon nano-tube flexible transparent conductive film FTCFs: the heating plate that is placed with PET is heated to 80 DEG C of pre-spraying temperatures, and low speed spraying 15 times, is warming up to 110 DEG C subsequently, and high-velocity spray makes FTCFs 30 times.
The carbon nano-tube flexible transparent conductive film FTCFs that just sprays preparation need be left standstill to 0.5-2h in deionized water, part is removed SDBS, then dry 0.5-1.5h, finally pickling 1-5h in 2-12M nitric acid at 60-100 DEG C of temperature, to remove the combination water of pet sheet face, make FTCFs sample.
Two, spraying is evenly sprayed in original PET substrate 4 and preliminary treatment PET substrate 1 by carbon nano-tube solution, makes corresponding FTCFs, respectively it is washed and pickling reprocessing, and above two kinds of FTCFs are carried out to the detection of adhesive force ultrasonic resonance.
Choose light transmittance at 80% flexible carbon nano tube film as ultrasound detection sample, supersonic frequency 45KHz, ultrasonic power 60W, and use manual time-keeping.
1, the flexible carbon nano tube film F TCFs adhesive force ultrasound detection step making taking preliminary treatment PET as substrate is as follows:
1. the carbon nano-tube flexible transparent conductive film after drying is vertically put into the beaker that fills deionized water.
2. start supersonic wave cleaning machine, after ultrasonic stablizing, beaker is put into supersonic wave cleaning machine.
3. whether every ultrasonic 5s taking-up observation carbon pipe comes off from PET substrate surface, comes off until observed part.
4. repeatedly measure many group samples and get time value.Experimentation timing is also taken pictures to sample.
2, repeat above-mentioned 1. 2. 3. 4. step to wash the thin FTCFs adhesive force of carbon nano-tube flexible and transparent conductive ultrasound detection step that PET makes as substrate.
As shown in Figure 2,3: both adhesive force ultrasonic characterization:
To carrying out the ultrasonic time timing that comes off of SWCNTs taking washing and preliminary treatment PET as the FTCFs of substrate, by coming off more separately, time length can compare adhesive force size indirectly.By Raman spectroscope, the carbon nano-tube at FTCFs diverse location place, ultrasonic front and back is done to Raman spectrum, can detect the variation with the variation carbon nano tube structure performance of carbon nano-tube film thickness.
Claims (6)
1. the preparation method of the carbon nano-tube flexible transparent conductive film of a strong adhesive force, it is characterized in that: the preliminary treatment that substrate is carried out nitric acid dousing successively, washed and dry to ethylene glycol terephthalate PET, and spraying carbon nano-tube solution makes carbon nano-tube flexible transparent conductive film FTCFs taking this pretreated PET as substrate; The concrete steps that described spraying carbon nano-tube solution makes carbon nano-tube flexible transparent conductive film FTCFs are: the heating plate that is placed with PET is heated to 60-90 DEG C of pre-spraying temperature, low speed spraying 10-20 time, be warming up to subsequently 100-130 DEG C, high-velocity spray makes FTCFs 30-50 time.
2. a carbon nano-tube flexible transparent conductive film attachment force detection method for strong adhesive force according to claim 1, is characterized in that: concrete steps are as follows:
1. choose light transmittance at the flexible carbon nano tube film of 60%-90% as ultrasound detection sample, supersonic frequency 30-50KHz, ultrasonic power 40-60W, and with manual time-keeping;
2. the flexible carbon nano tube thin-film ultrasonic detecting step taking preliminary treatment PET as substrate:
(a) the carbon nano-tube flexible transparent conductive film after drying is vertically put into the beaker that fills deionized water;
(b) start supersonic wave cleaning machine, after ultrasonic stablizing, beaker is put into supersonic wave cleaning machine;
(c) whether every ultrasonic 3-10s taking-up observation carbon pipe comes off from PET substrate surface, comes off until observed part;
(d) measure many group samples and get time average, experimentation timing is also taken pictures to sample.
3. the preparation method of the carbon nano-tube flexible transparent conductive film of strong adhesive force according to claim 1, is characterized in that: the pretreating process of described ethylene glycol terephthalate PET substrate specifically carries out according to the following step:
1. original PET substrate is put in ethanol, ultrasonic immersion 1-5h under 30-50KHZ, 50-200W power, then puts in nitric acid and leaves standstill and soak 1-5h;
2. the PET in taking out 1. puts in deionized water and leaves standstill 1-3h, removes the nitric acid of pet sheet face, and makes pet sheet face that hydrolysis variation occur in water;
3. 2. middle PET is placed on the standing 10-15h that dries in fume hood.
4. the preparation method of the carbon nano-tube flexible transparent conductive film of strong adhesive force according to claim 1, is characterized in that: described carbon nano-tube solution is by mass percentage, composed of the following components:
Carbon nano-tube SWCNTs 0.005%-0.05%
Neopelex SDBS 0.5%-5%
Deionized water 99.495%-94.95%
Said components total amount is 100%.
5. according to the preparation method of the carbon nano-tube flexible transparent conductive film of the strong adhesive force described in claim 1 or 4, it is characterized in that: described carbon nano-tube solution preparation, comprises the following steps:
1. take carbon nano-tube SWCNTs powder with the ratio of mass ratio 0.005%-0.05%, the neopelex SDBS of 0.5%-5%, be dissolved in 50-200ml deionized water, ultrasonic 1-3h under 50-100W power in ultrasonic cleaner, and then in separating apparatus under 100-150W power ultrasonic 0.5-1h make carbon pipe dispersion liquid;
2. by centrifugation 1-2h under the carbon pipe dispersion liquid 1000-5000rpm rotating speed that 1. prepared by step, get upper strata centrifugate and cover set aside for use with preservative film in a small beaker.
6. the preparation method of the carbon nano-tube flexible transparent conductive film of strong adhesive force according to claim 4, is characterized in that: described carbon nano-tube SWCNTs diameter is that 0.8-3nm, length are that 5-30 μ m, purity are 60-99%.
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| CN106353404A (en) * | 2016-08-10 | 2017-01-25 | 上海交通大学 | Test specimen and method applicable to testing material constants of film by aid of ultrasonic resonance spectrum processes |
| 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 |
| CN113458072A (en) * | 2021-07-06 | 2021-10-01 | 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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| 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 |
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