CN117229703A - Conductive coating and preparation method and application thereof - Google Patents
Conductive coating and preparation method and application thereof Download PDFInfo
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- CN117229703A CN117229703A CN202311256644.2A CN202311256644A CN117229703A CN 117229703 A CN117229703 A CN 117229703A CN 202311256644 A CN202311256644 A CN 202311256644A CN 117229703 A CN117229703 A CN 117229703A
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- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 156
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 78
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 73
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 claims abstract description 43
- 239000004814 polyurethane Substances 0.000 claims abstract description 43
- 239000002270 dispersing agent Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 18
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- 239000011231 conductive filler Substances 0.000 abstract description 9
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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Abstract
The invention discloses a conductive coating and a preparation method and application thereof. The preparation method of the invention comprises the following steps: mixing waterborne polyurethane with graphene and a graphene dispersing agent to obtain a dispersing liquid; mixing the dispersion liquid with the carbon nano tube and the carbon nano tube dispersing agent to obtain a conductive coating; the total mass of the graphene and the carbon nano tube is 0.5-2.0wt% of the mass of the aqueous polyurethane. According to the invention, the carbon nano tube and the graphene with excellent conductivity and stability are used as the conductive filler, and the carbon conductive fillers with different shapes can generate interaction and synergistic effects, so that on one hand, the conductive network in the matrix can be perfected; on the other hand, the corrosion resistance of the material is improved to a certain extent; the water-based polyurethane with strong corrosion resistance can further improve the corrosion resistance of the material; the aggregation of graphene and carbon nanotubes can be avoided by adopting the sequence of stepwise feeding, the dispersion performance is improved, the content of graphene and carbon nanotubes is controlled, and the conductivity and corrosion resistance of the material are further improved.
Description
Technical Field
The invention belongs to the technical field of conductive paint, and particularly relates to a conductive paint, a preparation method and application thereof.
Background
The grounding device is an important component in the grounding system, connects the power system with the ground, plays roles in providing fault current, a lightning current discharging channel, stable potential and the like, and is a guarantee for ensuring the safe operation of the power system and the safety of personnel. The grounding device is mainly composed of copper, and can seriously suffer electrochemical corrosion under the action of air, moisture and various salts to influence the normal operation of a power grid because the grounding device is in long-term service in a humid or corrosive gas and acid-base soil environment.
At present, the anti-corrosion agent of the grounding device is prepared by adopting conductive anti-corrosion paint, compounding conductive filler graphene and matrix resin to prepare the conductive anti-corrosion paint, and then coating the conductive anti-corrosion paint on the surface of a grounding material, wherein the graphene belongs to a lamellar structure, and when the conductive paint is applied as a conductive medium, a lamellar structure is easy to form, in the lamellar structure, non-conductive resin is mixed between the graphene and the graphene, and the resins are equivalent to a capacitor, so that the graphene is difficult to form a conductive network in the coating, and the conductivity of the whole conductive coating is poor; in addition, graphene has small chemical activity, small acting force with a resin matrix and poor compatibility, so that the prepared conductive composite material has uneven conductivity, poor adhesion with a base material and easy falling off, thereby influencing the conductivity and corrosion resistance.
Therefore, how to improve the conductivity and corrosion resistance of the coating becomes a challenge in the art.
Disclosure of Invention
The invention aims to provide a conductive coating, and a preparation method and application thereof. The conductive coating prepared by the preparation method provided by the invention has excellent conductivity and corrosion resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a conductive coating, which comprises the following steps:
(1) Mixing waterborne polyurethane with graphene and a graphene dispersing agent to obtain a dispersing liquid;
(2) Mixing the dispersion liquid obtained in the step (1) with carbon nanotubes and a carbon nanotube dispersing agent to obtain a conductive coating;
the total mass of the graphene in the step (1) and the carbon nano tube in the step (2) is 0.5-2.0wt% of the mass of the aqueous polyurethane in the step (1).
Preferably, the solid content of the aqueous polyurethane in the step (1) is 29-31%, and the specific gravity of the aqueous polyurethane is 1.04-1.08 g cm -3 The pH value of the aqueous polyurethane is 6-9.
Preferably, the number of layers of graphene in the step (1) is less than 30.
Preferably, the mixing in step (1) is performed under stirring.
Preferably, the stirring time is 15-20 min, and the stirring rotating speed is 500-800 r/min.
Preferably, in the step (2), the outer diameter of the carbon nanotube is 4-6 mm, and the length of the carbon nanotube is 0.5-2 μm.
Preferably, the mass ratio of the graphene in the step (1) to the carbon nanotubes in the step (2) is 1:1.
preferably, the total mass of the graphene in the step (1) and the carbon nano tube in the step (2) is 1.0-1.5 wt% of the mass of the aqueous polyurethane in the step (1).
The invention also provides the conductive coating prepared by the preparation method.
The invention also provides application of the conductive coating in a grounding material.
According to the invention, the carbon nano tube and the graphene with excellent conductivity and stability are used as the conductive filler, and the carbon conductive fillers with different shapes can generate interaction and synergistic effects, so that on one hand, the conductive network in the matrix can be perfected; on the other hand, the corrosion resistance of the material can be improved to a certain extent; the water-based polyurethane with strong corrosion resistance can further improve the corrosion resistance of the material; the aggregation of graphene and carbon nanotubes can be avoided to the greatest extent by adopting the sequence of step feeding, the dispersion performance is improved, and the content of the graphene and the carbon nanotubes is controlled, so that the conductivity and the corrosion resistance of the material are further improved. Experimental results show that when the addition amount of CNTs (carbon nanotubes) and GE (graphene) is 2wt% of the mass of the aqueous polyurethane, the self-corrosion potential of the conductive coating is-0.493V, and the resistivity is remarkably reduced to 0.144×10 -1 Ω·cm。
Drawings
FIG. 1 is a graph showing the macroscopic morphology of the surface of the conductive coating prepared in comparative application example 2 and application examples 1 to 4 in the embodiment of the present invention;
FIG. 2 is a graph showing the electrokinetic polarization of the coatings prepared in comparative application example 1 and application examples 1 to 4 in the embodiment of the present invention.
Detailed Description
The invention provides a preparation method of a conductive coating, which comprises the following steps:
(1) Mixing waterborne polyurethane with graphene and a graphene dispersing agent to obtain a dispersing liquid;
(2) Mixing the dispersion liquid obtained in the step (1) with carbon nanotubes and a carbon nanotube dispersing agent to obtain a conductive coating;
the total mass of the graphene in the step (1) and the carbon nano tube in the step (2) is 0.5-2.0wt% of the mass of the aqueous polyurethane in the step (1).
According to the invention, aqueous polyurethane is mixed with graphene and a graphene dispersing agent to obtain a dispersion liquid.
In the present invention, the solid content of the aqueous polyurethane is preferably 29 to 31%, more preferably30%; the specific gravity of the aqueous polyurethane is preferably 1.04-1.08 g cm -3 More preferably 1.04 to 1.06g cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The pH value of the aqueous polyurethane is preferably 6-9; the aqueous polyurethane is preferably produced by Anhui An Dahua Taai New Material Co.Ltd. In the invention, the aqueous polyurethane has excellent adhesive force to metal, glass and the like, excellent water resistance, solvent resistance, compatibility with strong acid and alkali solutions, electrolyte resistance and semitransparent appearance, and can improve the adhesive force and corrosion resistance of the coating.
In the invention, the number of layers of the graphene is preferably less than 30 layers; the sheet diameter thickness of the graphene is preferably 10nm; the graphene is preferably 5 μm in size; the graphene is preferably produced in the middle-age nanometer. In the invention, the graphene is a conductive filler, and can generate interaction and synergistic effect with the carbon nano tube, so that on one hand, the conductive network in the matrix can be perfected; on the other hand, the corrosion resistance of the material can be improved to a certain extent.
In the invention, the graphene dispersing agent is preferably a special dispersing agent for nano-produced graphene in the middle-family age; the model of the graphene dispersing agent is preferably 7782-42-5. In the invention, the graphene dispersing agent is used for improving the dispersibility of graphene.
In the present invention, the mass of the graphene dispersing agent is preferably 36 to 200% of the mass of graphene, more preferably 36 to 100%, and even more preferably 36 to 60%.
In the invention, the operation of mixing the aqueous polyurethane with the graphene and the graphene dispersing agent is preferably to sequentially add the graphene and the graphene dispersing agent into the aqueous polyurethane. According to the invention, the dispersibility of graphene in the waterborne polyurethane can be further improved by controlling the mixing operation, so that the conductivity of the material is improved.
In the invention, the mixing of the aqueous polyurethane with the graphene and the graphene dispersing agent is preferably performed under stirring conditions; the stirring time is preferably 15 to 20min, more preferably 16 to 18min; the stirring speed is preferably 500-800 r/min. The invention can further improve the dispersion degree of the raw materials by controlling the stirring process parameters.
After the dispersion liquid is obtained, the dispersion liquid is mixed with the carbon nano tube and the carbon nano tube dispersing agent to obtain the conductive coating. The invention adopts the sequence of step feeding, can avoid the agglomeration of graphene and carbon nano tubes to the greatest extent, and improves the dispersion performance.
In the present invention, the outer diameter of the carbon nanotube is preferably 4 to 6mm; the length of the carbon nano tube is preferably 0.5-2 mu m; the carbon nanotubes are preferably produced in the middle-age nanometer. In the invention, the carbon nano tube is used as conductive filler, can generate interaction and synergistic effect with graphene, and can perfect a conductive network in a matrix on one hand; on the other hand, the corrosion resistance of the material can be improved to a certain extent.
In the invention, the carbon nanotube dispersing agent is preferably a special dispersing agent for carbon nanotubes produced in the middle-age nanometer; the type of the carbon nanotube dispersing agent is preferably TNWDIS. In the present invention, the carbon nanotube dispersing agent can improve the dispersibility of carbon nanotubes.
In the invention, the total mass of the graphene and the carbon nano tube is 0.5-2.0 wt% of the mass of the waterborne polyurethane, and is preferably 1.0-1.5 wt%; the mass ratio of the graphene to the carbon nano tube is preferably 1:1. according to the invention, the content of graphene and carbon nano tubes is controlled, so that the conductivity and corrosion resistance of the material are further improved.
In the present invention, the mass of the carbon nanotube dispersing agent is preferably 36 to 200% by mass of the carbon nanotubes, more preferably 36 to 100%, and even more preferably 36 to 60%.
In the present invention, the operation of mixing the dispersion with the carbon nanotubes and the carbon nanotube dispersing agent is preferably to sequentially add the carbon nanotubes and the carbon nanotube dispersing agent to the dispersion.
In the present invention, the mixing of the dispersion with the carbon nanotubes and the carbon nanotube dispersing agent is preferably sequentially performed with stirring and ultrasound; the stirring time is preferably 20 to 30min, more preferably 20 to 25min; the rotation speed of stirring is preferably 800-1000 r/min; the time of the ultrasonic treatment is preferably 20 to 30 minutes. The present invention is not particularly limited to the operation of the ultrasonic wave, and may employ an operation well known to those skilled in the art. The invention can further improve the dispersion degree of the raw materials by controlling the stirring process parameters.
According to the invention, the carbon nano tube and the graphene with excellent conductivity and stability are used as the conductive filler, and the carbon conductive fillers with different shapes can generate interaction and synergistic effects, so that on one hand, the conductive network in the matrix can be perfected; on the other hand, the corrosion resistance of the material can be improved to a certain extent; the water-based polyurethane with strong corrosion resistance can further improve the corrosion resistance of the material; the aggregation of graphene and carbon nanotubes can be avoided to the greatest extent by adopting the sequence of step feeding, the dispersion performance is improved, and the content of the graphene and the carbon nanotubes is controlled, so that the conductivity and the corrosion resistance of the material are further improved.
The invention adopts the filling type conductive paint to paint on the grounding material, ensures the corrosion resistance and has good conductivity, and prolongs the service life of the grounding material. The high polymer in the conductive coating is selected from nontoxic, solvent-free, volatile, water-based polyurethane (WPU) with strong corrosion resistance and easy solidification, the filled conductive medium is selected from carbon substances, and the carbon nano tube and the graphene have excellent conductivity and stability, so that the carbon conductive materials with two different shapes can produce mutual promotion and synergistic effect, and on one hand, the conductive network in the matrix can be perfected; on the other hand, the corrosion resistance of the grounding material can be improved to a certain extent.
The invention also provides the conductive coating prepared by the preparation method.
The conductive coating provided by the invention has excellent conductivity and corrosion resistance.
The invention also provides application of the conductive coating in a grounding material.
In the invention, the conductive coating is preferably applied in the grounding material by coating the conductive coating on a substrate, and then sequentially drying and curing to obtain the conductive coating.
The material of the substrate is not particularly limited, and the substrate may be judged according to common knowledge.
The present invention is not particularly limited to the coating operation, and may employ an operation well known to those skilled in the art.
In the present invention, the drying temperature is preferably room temperature; the drying time is preferably 12 hours; the curing temperature is preferably 70-80 ℃; the curing time is preferably 3-4 hours; the thickness of the conductive coating is preferably 40 to 50 μm, more preferably 45 μm.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the conductive coating comprises the following steps:
(1) Sequentially adding graphene and a graphene dispersing agent into the waterborne polyurethane, and stirring and mixing to obtain a dispersion liquid; wherein the solid content of the aqueous polyurethane is 30 percent and the specific gravity is 1.05g cm -3 The pH value is 8; the aqueous polyurethane is produced by Anhui An Dahua Taai New Material Co., ltd; the number of layers of the graphene is less than 30, the sheet diameter thickness is 10nm, and the size is 5 mu m; graphene is produced in nanometer mode in the middle age; the graphene dispersing agent is a special dispersing agent for nano-produced graphene in the middle-family age, and the mass of the dispersing agent is 36wt% of that of the graphene; stirring time is 20min, and stirring rotating speed is 700r/min;
(2) Adding carbon nano tubes and carbon nano tube dispersing agents into the dispersion liquid in sequence, and stirring and ultrasonic treatment are carried out in sequence to obtain the conductive coating; wherein the outer diameter of the carbon nano tube is 4-6 mm, and the length is 0.5-2 mu m; carbon nanotubes are produced in the middle age of nanometer; the carbon nanotube dispersing agent is a dispersing agent special for carbon nanotubes produced in the middle-family era, and the mass of the dispersing agent is 36wt% of the mass of the carbon nanotubes; the total mass of the graphene and the carbon nano tube is 0.5wt% of the mass of the waterborne polyurethane; the mass ratio of graphene to carbon nano tube is 1:1, a step of; stirring time is 30min, and rotating speed is 1000r/min; the time of the ultrasound was 30min.
Example 2
The total mass of graphene and carbon nanotubes was modified to 1.0wt% of the mass of the aqueous polyurethane on the basis of example 1, with the other conditions unchanged.
Example 3
The total mass of graphene and carbon nanotubes was modified to 1.5wt% of the mass of the aqueous polyurethane on the basis of example 1, with the other conditions unchanged.
Example 4
The total mass of graphene and carbon nanotubes was modified to 2.0wt% of the mass of the aqueous polyurethane on the basis of example 1, with the other conditions unchanged.
Comparative example 1
Waterborne polyurethane (i.e., only the waterborne polyurethane of example 1 was used)
Application examples 1 to 4
The conductive coatings prepared in examples 1 to 4 were brushed onto the surface of a steel substrate using a general Mao Shuatu brush, respectively, and then dried at room temperature for 12 hours, and then cured in an oven at 70 ℃ for 3 hours, to obtain a conductive coating having a thickness of 45 μm.
Comparative application example 1
The aqueous polyurethane of comparative example 1 was brushed on the surface of a steel substrate using a general Mao Shuatu brush, then dried at room temperature for 12 hours, and then cured in an oven at 70 ℃ for 3 hours to obtain a coating layer having a thickness of 45 μm.
Comparative application example 2
Steel matrix (i.e. uncoated steel matrix of application example 1)
Comparative application example 2 the macroscopic morphology of the surface of the conductive coating prepared in application examples 1 to 4 is shown in figure 1.
Corrosion resistance test:
the coatings prepared in comparative application example 1 and application examples 1 to 4 were immersed in 3.5% nacl solution (kept at room temperature) prior to electrochemical testing. The test system is a three-electrode system, the auxiliary electrode is a Pt electrode, the reference electrode is a saturated calomel electrode, and the working electrode is a coating sample. The open circuit potential of the coating sample is tested by using an electrochemical workstation, and after the open circuit potential of the system is stabilized, the electrokinetic potential polarization curve of the tested coating is shown in figure 2.
The self-corrosion potential is an important thermodynamic parameter for evaluating the corrosion tendency of a material, and the greater the self-corrosion potential, the greater the difficulty of corrosion of the material. The self-corrosion potential of the conductive coating prepared according to comparative application example 1 and application examples 1 to 4 in 3.5% NaCl solution was obtained according to FIG. 2, as shown in Table 1.
TABLE 1 self-corrosion potential of coating in 3.5% NaCl solution
| Total mass/wt% of graphene and carbon nanotubes | Ecorr(V) | |
| Comparative application example 1 | 0 | -0.687 |
| Application example 1 | 0.5 | -0.585 |
| Application example 2 | 1.0 | -0.543 |
| Application example 3 | 1.5 | -0.516 |
| Application example 4 | 2.0 | -0.493 |
As can be seen from table 1, as the content of carbon nanotubes and graphene in the coating layer was increased, the self-corrosion potential was gradually increased, and when the addition amount was 2wt%, the self-corrosion potential of the conductive coating layer was-0.493V, and the corrosion resistance was improved as compared with the increase of 0.194V without the coating layer.
Conductivity test:
the resistivity of the conductive coatings of comparative application example 1 and application examples 1 to 4 is shown in table 2.
Table 2 comparative resistivity of conductive coatings of application example 1 and application examples 1 to 4
| Total mass/wt% of graphene and carbon nanotubes | Resistivity (Ω cm) | |
| Comparative application example 1 | 0 | Insulation of |
| Application example 1 | 0.5 | 4.8×10 -1 |
| Application example 2 | 1.0 | 3.5×10 -1 |
| Application example 3 | 1.5 | 1.6×10 -1 |
| Application example 4 | 2.0 | 0.14×10 -1 |
As can be seen from Table 1, the resistivity of the conductive coating containing 2wt% was significantly reduced to 0.14X10 -1 Omega cm, it can be seen that the conductivity of the coating increases after the addition of carbon nanotubes and graphene.
Therefore, the corrosion resistance and the conductivity of the coating can be obviously improved by adding the carbon nano tube and the graphene into the waterborne polyurethane.
From the above examples and comparative examples, the conductive coating prepared by the preparation method provided by the invention has excellent conductivity and corrosion resistance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the conductive coating is characterized by comprising the following steps:
(1) Mixing waterborne polyurethane with graphene and a graphene dispersing agent to obtain a dispersing liquid;
(2) Mixing the dispersion liquid obtained in the step (1) with carbon nanotubes and a carbon nanotube dispersing agent to obtain a conductive coating;
the total mass of the graphene in the step (1) and the carbon nano tube in the step (2) is 0.5-2.0wt% of the mass of the aqueous polyurethane in the step (1).
2. The process according to claim 1, wherein the aqueous polyurethane in the step (1) has a solid content of 29 to 31%, and the aqueous polyurethane has a specific gravity of 1.04 to 1.08g cm -3 The pH value of the aqueous polyurethane is 6-9.
3. The method according to claim 1, wherein the number of graphene layers in step (1) is less than 30.
4. The method according to claim 1, wherein the mixing in step (1) is performed under stirring.
5. The method according to claim 4, wherein the stirring time is 15 to 20min and the stirring rotation speed is 500 to 800r/min.
6. The method according to claim 1, wherein the outer diameter of the carbon nanotubes in the step (2) is 4 to 6mm, and the length of the carbon nanotubes is 0.5 to 2 μm.
7. The preparation method according to claim 1, wherein the mass ratio of the graphene in the step (1) to the carbon nanotubes in the step (2) is 1:1.
8. the preparation method according to claim 1, wherein the total mass of the graphene in the step (1) and the carbon nanotubes in the step (2) is 1.0 to 1.5wt% of the mass of the aqueous polyurethane in the step (1).
9. The electroconductive coating prepared by the preparation method of any one of claims 1 to 8.
10. Use of the conductive coating of claim 9 in a grounding material.
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