CN102632026A - Preparation method of self-repairing conductive coating - Google Patents
Preparation method of self-repairing conductive coating Download PDFInfo
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- CN102632026A CN102632026A CN2012101405133A CN201210140513A CN102632026A CN 102632026 A CN102632026 A CN 102632026A CN 2012101405133 A CN2012101405133 A CN 2012101405133A CN 201210140513 A CN201210140513 A CN 201210140513A CN 102632026 A CN102632026 A CN 102632026A
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Abstract
The invention belongs to the technical field of preparation of a self-repairing coating, and particularly relates to a method for preparing a conductive coating with a self-repairing ability on a glass, quartz or plastic base in an arbitrary shape. The method comprises the steps of processing the base, preparing a coating solution, preparing a polymer coating, preparing a conductive layer and the like. The method disclosed by the invention is not limited by size and shape of the base, and is suitable for the base with a plane, a curve surface or an irregular surface. The prepared conductive coating has good flexibility and electrical conductivity and can repair scratches on the surface and damaged electrical conductivity under excitation of a solvent. The repairing process is fast; over 95% of the scratches can be repaired with excellent restoring effect, and the repairing process can be repeated for a plurality of times. The prepared conductive self-repairing coating has a plurality of potential applications, for example, the self-repairing coating is applied to a lead, a circuit and the like to increase the use stability of an electronic apparatus.
Description
Technical field
The invention belongs to the preparing technical field of selfreparing coating, particularly a kind of method that in arbitrary shape substrates such as glass, quartz, plastics, prepares conductive coating with self-reparing capability.
Background technology
In actual use, the surface of artificial material or inner can be owing to aging or surpass reason such as applied load and small slight crack occurs, and these slight cracks can enlarge along with the prolongation of service time gradually, finally cause the damage of whole material.In electronic instrument, this phenomenon is fatal.Because overtime use or receive external force collision and the slight crack that in lead or electronic component, produces can cause circuit breaker or component failure, finally cause the whole electronic instrument can't operate as normal.Usually, the electronic component that lost efficacy by the generation of slight crack of maintenance almost is that impossible, unique solution is changed exactly even need be changed the entire circuit plate sometimes, causes high maintenance cost.What nowadays artificial material can be spontaneous after sustaining damage perhaps no longer has been confined in the dreamlands such as film, novel in its mechanical performance of recovery and function under certain environmental stimuli; Through continuous effort, the self-repair function that scientists is successfully general with living nature has been incorporated in the artificial material., countlessly be full of creationary mentality of designing and be used to prepare self-repair material to utilizing reversible covalent bond or hydrogen bond from the initial loading of capsules renovation agent that utilizes.Self-repair function is incorporated in the artificial material, can effectively reduces the dependability of raw-material consumption, maintenance cost and material.Up to the present, being incorporated in the middle of super-hydrophobic and the corrosion-resistant coating of self-repair function success makes their function after sustaining damage, to recover fast.Yet, have the research of the self-repair material of high conductivity for preparation, but still be in the starting stage though its importance is self-evident.
Summary of the invention
The purpose of this invention is to provide a kind of preparation simply and easily and have the selfreparing coating of high conductive capability.This coating can be repaired impaired conductive capability fast under the stimulation in the external world.The present invention has double-decker, forms by having the polymer coating of under environmental stimuli, repairing the wound ability and the metal material layer with high conductivity.The inventive method does not receive substrate sizes, shape limits, and is all suitable to the substrate of plane, curved surface and irregular surface.Prepared conductive coating has good pliability and electric conductivity, and the cut and thereby the impaired electric conductivity on reparation that can be spontaneous under the exciting of solvent surface.Repair process is rapid, and recovery effects can reach more than 95%, and can repeatedly repeat.We have many potential application at the electric conductivity selfreparing coating of preparation, for example are applied to the stability in use that aspects such as lead, circuit increase electronic device.
Preparation method's of the present invention step is following:
The processing of substrate: the typical substrate that the present invention uses is silicon chip, quartz and plastic sheet.For silicon chip and quartz substrate, at first, substrate is cleaned by polarity of solvent with several kinds of different solvents of polarity successively from small to large, as cleaning with toluene, acetone, chloroform, ethanol and distilled water successively; Then, through volume ratio be 3: 7 H again
2O
2And H
2SO
4Mixed solution handle can be so that the surface of substrate has one deck silicon hydroxyl; At the bottom of plastic base, utilize the second alcohol and water alternately to wash the grease that removes the surface;
1. the preparation of coating solution: with two kinds of polyelectrolyte formation complex solutions soluble in water that have negative electrical charge, the concentration of two kinds of electronegative polyelectrolyte is respectively 1.0～10.0mg/mL in this complex solution; Again cationic polymer is dissolved in the deionized water, is prepared into the solution that concentration is 1.0～10.0mg/mL;
2. the preparation of polymer coating: the substrate that will handle alternately is immersed in two kinds of prepared solution of step 1 each 3～20 minutes, after each the immersion deionized water rinsing is taken out and use in substrate, thus the preparation of the layer assembly film of completion one-period; Repeat said process, thus utilize laminated assembling technology to prepare in the substrate to have can stimulation in external condition the polymer coating of reparation surface scratch down, the thickness of this coating is 10～100 μ m.
3. the preparation of conductive layer: (concentration is the polymer-coated surface that 1～20mg/mL) method through spraying deposits to step 2 preparation, and quantity for spray is 1～60mL/cm will to be dispersed with the ethanolic solution of metal nanometer line
2, metal nanometer line tangles each other and forms the conductive layer of thickness between 0.1～10 μ m after the solvent evaporates, and the polymer coating below it is combined together to form the conductive coating that under extraneous incentive condition, has self-repair function.Deposition through the control metal nanometer line can be regulated and control the transmitance and the electric conductivity of selfreparing conductive coating.
The polyelectrolyte that has negative electrical charge of the present invention is polyacrylic acid (molecular weight 100000～800000), Sodium Hyaluronate (molecular weight 400000～1000000) or kayexalate (molecular weight 50000～100000) etc.;
The used cationic polymer of the present invention is poly dimethyl diallyl amine hydrochlorate, polypropylene amine or polymine;
Environmental stimuli condition required for the present invention is to drip common solvents such as toluene, n-hexane, deionized water on impaired conductive coating surface;
The used metal nanometer line of the present invention is gold, silver or copper nano-wire, and diameter is at 20～500nm, and length is between 5～60 μ m.
Compared with prior art, the invention has the advantages that:
1. technology is simple, and raw material is easy to get, and cost is low;
Coating electric conductivity high;
3. it is simple to repair conditions needed;
4. selfreparing speed is fast, and repairing effect reaches more than 95%.
5. through regulating the deposition of metal nanometer line, can obtain transparent selfreparing conductive coating.
Description of drawings
The field emission scanning electron microscope figure of the conduction selfreparing coating of Fig. 1: embodiment 1 preparation;
The optical photograph of the conduction selfreparing coating of Fig. 2: embodiment 1 preparation;
The repair process photo of the conduction selfreparing coating of Fig. 3: embodiment 1 preparation;
The superficial cut of the electric selfreparing coating of Fig. 4: embodiment 1 preparation is (a) and the field emission scanning electron microscope figure that repairs back (b) before reparation;
The optical photograph (a) of the electrically conducting transparent selfreparing coating of Fig. 5: embodiment 2 preparations; The superficial cut of embodiment 2 gained electrically conducting transparent selfreparing coatings is (b) and the field emission scanning electron microscope figure that repairs back (c) before reparation;
The specific embodiment
Below in conjunction with embodiment the present invention is further described:
Field emission scanning electron microscope figure is obtained by XL30 ESEM FEG type field emission scanning electron microscope.
The sheet resistance of conductive coating utilizes four probe method to measure, and the instrument model is RTS-8.
Embodiment 1:
(1) processing of substrate:
The PET plastic sheet is cleaned the back drying for standby with the second alcohol and water.
(2) preparation of solution:
The kayexalate (molecular weight 70000) of 2g polyacrylic acid (molecular weight 100000) and 1g is dissolved in the 100mL deionized water, and dissolving evenly back is for use.3g poly dimethyl diallyl amine hydrochlorate is dissolved in the 100mL deionized water, dissolving evenly back is for use again.
(3) preparation of polymer coating:
The substrate that step 1 was handled alternately is immersed in two kinds of prepared solution of step 2 each 10 minutes, after each the immersion deionized water rinsing is taken out and use in substrate, thus the preparation of the layer assembly film of completion one-period; Repeat 50 cycles of said process, thus utilize laminated assembling technology to prepare in the substrate to have can stimulation in external condition the polymer coating of reparation surface scratch down, the thickness of this coating is 58 μ m;
(4) preparation of conductive layer:
With concentration is that 4mg/mL, length are that 15 μ m, diameter are the ethanolic solution of the copper nano-wire of 120nm deposits in the step 3 preparation through the aerial spraying method polymer-coated surface; Spraying process uses the SATA board spray gun be connected on the air compressor to carry out; Spraying process pressure is controlled at 2bar; Spray distance is 15cm, and the solution spraying amount that control sprays on the polymer coating is 50mL/cm
2Can each other to tangle and form thickness be the conductive layer of 1 μ m to copper nano-wire after the solvent evaporates, is combined together to form the conductive coating (seeing accompanying drawing 1) with self-healing properties with the polymer coating of lower floor.
Conduction selfreparing coating through said method system has excellent conducting performance, and its surface film resistance has only 0.38 Ω/sq, and this coating has good pliability, and shown in accompanying drawing 2, this coating can withstand very big bending, is 8.1mm in curvature
-1And it is not chipping.We test the conduction repair ability of this coating subsequently, and for the ease of observing more intuitively, we connect in circuit and have advanced a light emitting diode (LED) bulb.In order to guarantee that the LED bulb remains on certain brightness, the voltage of voltage-stabilized power supply is fixed on 3.0V in the whole experiment.We use the surface of streaking whole conductive coating that scalpel is exerted oneself subsequently, and then the LED bulb extinguishes immediately, thereby explain that whole nano silver wire layer is caused circuit breaker (accompanying drawing 3-2) in two by scalpel.We drip the conduction reparation function that several deionized waters activate coating to the wound subsequently.Shown in accompanying drawing 3-3, the interior LED lamp in several seconds that deionized water is added drop-wise to behind the wound is just bright once more, has been connected in together again though brightness is divided into to have between the two-part nano silver wire layer partly not as good as explanation before.Along with the prolongation of repair time, the brightness of LED lamp increases gradually, and the brightness of LED bulb had both returned to coating and has been scratched degree (accompanying drawing 3-4～Fig. 3-5) before after about 3 minutes.At last, utilize the nitrogen deionized water that the wound is residual to dry up, whole repair process finishes.Utilizing the four probe method measurement is 0.42 Ω/sq across the film resistor of the wound of the reparation of coating, and repairing effect reaches more than 95%.
We utilize SEM that the cut before and after repairing is observed, and shown in accompanying drawing 4a, the cut that is cut by scalpel is deep to substrate, and its width is 48 μ m.Under the exciting of deionized water; Polymer coating generation swelling below the copper nano-wire layer makes the wound face of cut both sides contact, and drives the cut nano silver wire layer on upper strata simultaneously; Make it and overlap on together (accompanying drawing 4b) again, make that impaired electric conductivity obtains repairing.
Embodiment 2:
(1) processing of substrate:
The PET plastic sheet is cleaned the back drying for standby with the second alcohol and water;
(2) preparation of solution:
1g Sodium Polyacrylate (molecular weight 450000) and 7g Sodium Hyaluronate (molecular weight 800000) are dissolved in the 100mL deionized water, and dissolving evenly back is for use.The 6g polymine is dissolved in the 100mL deionized water, dissolving evenly back is for use again.
(3) preparation of polymer coating:
The substrate that step 1 was handled alternately is immersed in two kinds of prepared solution of step 2 each 10 minutes, after each the immersion deionized water rinsing is taken out and use in substrate, thus the preparation of the layer assembly film of completion one-period; Repeat 30 cycles of said process, thus utilize in the substrate laminated assembling technology preparation have can stimulation in external condition the polymer coating of reparation surface scratch down, the thickness of this coating is 42 μ m.
(4) preparation of conductive layer:
With concentration be 3.3mg/mL, to be dispersed with diameter be that 200nm, length are the polymer-coated surface that the method for silver nanowire ethanolic solution through aerial spraying of 20 μ m deposits to preparation in the step 3; Spraying process uses the SATA board spray gun be connected on the air compressor to carry out; Spraying process pressure is controlled at 2bar; Spray distance is 15cm, and the solution spraying amount that control sprays on the polymer coating is 5mL/cm
2Nano silver wire can each other tangle and form conductive layer after the solvent evaporates, and this nano silver wire conductive layer thickness is 200nm, combines with the polymer coating of lower floor and forms the transparent conducting coating (seeing accompanying drawing 5a) with self-healing properties.This coated film resistance is 7 Ω/sq, and mean transmissivity is 56% and has electric conductivity self-reparing capability (accompanying drawing 5b, c) equally that the film resistor across the wound after repairing rises to 14 Ω/sq.
Claims (9)
- But 1. the preparation method of a selfreparing conductive coating, its step is following:1) preparation of coating solution: with two kinds of polyelectrolyte formation complex solutions soluble in water that have negative electrical charge, the concentration of two kinds of electronegative polyelectrolyte is respectively 1.0～10.0mg/mL in this complex solution; Again cationic polymer is dissolved in the deionized water, is prepared into the solution that concentration is 1.0～10.0mg/mL;2) preparation of polymer coating: the substrate that will handle alternately is immersed in two kinds of prepared solution of step 1) each 3～20 minutes, after each the immersion deionized water rinsing is taken out and use in substrate, thus the preparation of the layer assembly film of completion one-period; Repeat said process, thus utilize laminated assembling technology to prepare in the substrate to have can stimulation in external condition the polymer coating of reparation surface scratch down, the thickness of this coating is 10～100 μ m;3) preparation of conductive layer: with concentration be 1～20mg/mL, the ethanolic solution that is dispersed with metal nanometer line deposits to step 2 through the method for spraying) polymer-coated surface of preparation; Metal nanometer line tangles each other and forms the conductive layer of thickness between 0.1～10 μ m after the solvent evaporates, and the polymer coating below it is combined together to form the conductive coating that under extraneous incentive condition, has self-repair function.
- 2. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 1 is characterized in that: substrate is silicon chip, quartz and plastic sheet.
- 3. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 2 is characterized in that: at first, silicon chip or quartz substrate are cleaned with toluene, acetone, chloroform, ethanol and distilled water successively; Then, through volume ratio be 3: 7 H again 2O 2And H 2SO 4Mixed solution handle.
- 4. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 2 is characterized in that: the processing at the bottom of the plastic base is to utilize the second alcohol and water alternately to wash the grease that removes the surface plastic sheet.
- 5. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 1 is characterized in that: the polyelectrolyte that has negative electrical charge is polyacrylic acid, Sodium Hyaluronate or kayexalate.
- 6. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 6; It is characterized in that: polyacrylic molecular weight is 100000～800000; The molecular weight of Sodium Hyaluronate is 400000～1000000, and the molecular weight of kayexalate is 50000～100000.
- 7. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 1 is characterized in that: cationic polymer is poly dimethyl diallyl amine hydrochlorate, polypropylene amine or polymine.
- 8. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 1 is characterized in that: the environmental stimuli condition is for dripping toluene, n-hexane or deionized water on impaired conductive coating surface.
- 9. but the preparation method of a kind of selfreparing conductive coating as claimed in claim 1 is characterized in that: metal nanometer line is gold, silver or copper nano-wire, and the diameter of nano wire is 20～500nm, and length is 5～60 μ m.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9308616B2 (en) | 2013-01-21 | 2016-04-12 | Innovative Finishes LLC | Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device |
| CN105669046A (en) * | 2014-11-21 | 2016-06-15 | 东华大学 | Fluorescent enhancement nano thin film and preparation method thereof |
| CN106969860A (en) * | 2017-05-01 | 2017-07-21 | 苏州科技大学 | Intelligent Magnetic driving selfreparing flexible pressure-sensitive sensor and preparation method thereof |
| CN111704894A (en) * | 2020-06-04 | 2020-09-25 | 东华大学 | Assembling preparation method of efficient solar heating surface |
| CN112038061A (en) * | 2020-09-08 | 2020-12-04 | 国网上海市电力公司 | High overload capacity distribution transformer |
| CN112054176A (en) * | 2020-09-10 | 2020-12-08 | 北京航空航天大学 | Self-repairing lithium ion battery anode material and preparation method thereof |
| CN112941960A (en) * | 2021-01-26 | 2021-06-11 | 中国科学院合肥物质科学研究院 | Preparation method of high-uniformity silver nanowire-based conductive paper |
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| CN102087885A (en) * | 2009-12-08 | 2011-06-08 | 中国科学院福建物质结构研究所 | Planar silver nanowire transparent conductive thin film and preparation method thereof |
| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
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2012
- 2012-05-08 CN CN2012101405133A patent/CN102632026A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102087885A (en) * | 2009-12-08 | 2011-06-08 | 中国科学院福建物质结构研究所 | Planar silver nanowire transparent conductive thin film and preparation method thereof |
| CN102319662A (en) * | 2011-09-26 | 2012-01-18 | 吉林大学 | Method for preparing self-repairing polyelectrolyte coating based on layer-by-layer assembly technology |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9308616B2 (en) | 2013-01-21 | 2016-04-12 | Innovative Finishes LLC | Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device |
| CN105669046A (en) * | 2014-11-21 | 2016-06-15 | 东华大学 | Fluorescent enhancement nano thin film and preparation method thereof |
| CN105669046B (en) * | 2014-11-21 | 2019-06-04 | 东华大学 | A kind of fluorescence enhancement nano thin-film and preparation method thereof |
| CN106969860A (en) * | 2017-05-01 | 2017-07-21 | 苏州科技大学 | Intelligent Magnetic driving selfreparing flexible pressure-sensitive sensor and preparation method thereof |
| CN106969860B (en) * | 2017-05-01 | 2019-10-11 | 苏州科技大学 | A kind of preparation method of intelligence Magnetic driving selfreparing flexible pressure-sensitive sensor |
| CN111704894A (en) * | 2020-06-04 | 2020-09-25 | 东华大学 | Assembling preparation method of efficient solar heating surface |
| CN111704894B (en) * | 2020-06-04 | 2021-07-20 | 东华大学 | Assembling preparation method of efficient solar heating surface |
| CN112038061A (en) * | 2020-09-08 | 2020-12-04 | 国网上海市电力公司 | High overload capacity distribution transformer |
| CN112054176A (en) * | 2020-09-10 | 2020-12-08 | 北京航空航天大学 | Self-repairing lithium ion battery anode material and preparation method thereof |
| CN112941960A (en) * | 2021-01-26 | 2021-06-11 | 中国科学院合肥物质科学研究院 | Preparation method of high-uniformity silver nanowire-based conductive paper |
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Application publication date: 20120815 |