CN115491070A - Preparation method and application of electric-conductive and heat-conductive coating - Google Patents
Preparation method and application of electric-conductive and heat-conductive coating Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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Abstract
The invention discloses a preparation method and application of an electric-conductive heat-conductive coating, wherein a nano carbon material is added into ultrapure water, and ultrasonic treatment is carried out under the condition of ice-water bath to obtain a nano carbon material dispersion liquid; adding a tannin-based dispersing agent into the nano carbon material dispersion liquid, uniformly mixing and stirring, carrying out ultrasonic treatment, adjusting the pH value to 5-9, carrying out ultrasonic treatment in an ice-water bath, pouring the mixed liquid into a sample bottle after the ultrasonic treatment is finished, thus obtaining the stable electric and heat conducting paint, soaking the pretreated silicon-based material in the paint, and forming an electric and heat conducting coating on the surface of the silicon-based material; the invention uses the tannic acid dispersing agent, tannic acid is a non-toxic and water-soluble natural polyphenol, has rich side chains, can interact with nano conjugation, interacts with other interfaces simultaneously, further plays a role of bridging molecules, draws the nano material to different interfaces to finally construct a coating, has wider use conditions, and can be popularized and used in the field of nano materials.
Description
Technical Field
The invention relates to a preparation method and application of an electric-conductive and heat-conductive coating, and relates to the technical field of nano carbon materials.
Background
In recent years, scholars at home and abroad develop preparation methods of various nano material coatings, which are generally divided into two types: chemical vapor deposition and aqueous assembly. The temperature of the preparation process of the chemical deposition method is too high (above 800 ℃), the requirement on a carbon coating loaded substrate is high, the preparation process environment is harsh, and the method is only limited to graphite derived carbon materials; the water phase assembling method comprises the following steps: electrophoretic deposition method, vacuum filtration method, coating film method, and water phase self-assembly deposition method. The electrophoretic deposition method is suitable for polyaniline which is a material with polar groups, and can damage the carbon conjugate structure due to the introduction of a carbon nano tube or a pure graphene covalent bond, reduce the performance of the carbon material and have high requirement on the cleanness of the surface of a matrix; the coating method has low material utilization rate and lacks strong interaction between the coating and the substrate; the vacuum filtration method consumes time and energy, only the carbon material film can be obtained after filtration, and the fixation to the substrate needs another method. The method is a water-phase self-assembly deposition method, the carbon material is transferred and fixed by utilizing the interaction between a matrix and the nano carbon material, the final coating structure is easy to regulate and control, but in the aspect of solving the problem of hydrophilicity of the carbon material, if covalent bond modification is introduced, the performance of the carbon material is influenced.
Therefore, a proper transfer and immobilization factor is introduced to interact with the nano carbon material through non-covalent bonds to construct a water-dispersible ligand, and then the transfer and immobilization factor on the surface of the ligand interacts with the matrix, so that the carbon material coating is constructed on the premise of keeping the original performance and nano scale of the carbon material, and the application development of the nano carbon conjugated material is promoted.
Disclosure of Invention
The invention provides a preparation method and application of an electric-conductive and heat-conductive coating, and the specific technical scheme is as follows:
a preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding a nano carbon material into ultrapure water, and placing the ultrapure water in an ultrasonic cell crusher for ultrasonic treatment under the condition of ice-water bath to obtain a nano carbon material dispersion liquid;
(2) Adding a tannic acid based dispersing agent into the nano carbon material dispersion liquid, uniformly mixing and stirring, putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 20-60 minutes, adjusting the pH to 5-9 by using 0.1-1 mol/L hydrochloric acid or sodium hydroxide solution, putting the mixture into an ice water bath, performing ultrasonic treatment by using an ultrasonic crusher, and pouring the mixed solution into a sample bottle after the ultrasonic treatment is finished and standing the mixed solution for a period of time to obtain the stable electric and heat conducting coating.
The nano carbon material in the step (1) is a nano conjugated carbon material such as graphene, a carbon nano tube, polyaniline and the like, and the concentration of the nano carbon material dispersion liquid is 0.5-8g/L.
The ultrasonic treatment process of the step (1) and the step (2) is the same, the power is 500-1000W, the ultrasonic treatment lasts for 3 seconds, the interval is 3 seconds, and the total ultrasonic treatment time is 10-30 minutes.
The mass ratio of the nano-carbon material in the nano-carbon material dispersion liquid in the step (2) to the tannic acid in the tannic acid based dispersant is 1.1-2.
The tannic acid based dispersing agent in the step (2) is tannic acid, a tannic acid/trivalent metal ion solution or a tetramethylammonium chloride/tannic acid solution; wherein the molar ratio of the tannic acid to the trivalent metal ions in the tannic acid/trivalent metal ion solution is 2-3; the tetramethylammonium chloride/tannic acid solution is obtained by mixing quaternary ammonium salt and tannic acid at a molar ratio of 0.1-1.
The invention also provides application of the electric-conduction heat-conduction coating, and particularly relates to application of the electric-conduction heat-conduction coating as a surface coating of a silicon-based material.
The silicon substrate material is polydimethylsiloxane, mica sheet, quartz glass and the like; the Piranha solution is obtained by mixing hydrogen peroxide and concentrated sulfuric acid with the mass fraction of 98% according to the volume ratio of v/v = 3/7; the pretreating agent is an anhydrous toluene solution containing 5% volume fraction of 3-aminopropyltriethoxysilane.
The invention has the advantages that:
(1) The tannic acid used in the invention is a natural product, is nontoxic and easily soluble in water, and exists in pulp, bark and leaves of a plurality of plants; silicon-based material Polydimethylsiloxane (PDMS), a hydrophobic organic silicon material, is nontoxic and tasteless, has high transparency, physiological inertia and good chemical stability; PDMS and curing agent are mixed according to a certain proportion, and the mixture is heated for a period of time at room temperature or a little to obtain the elastomer, or hard substrates such as mica sheets, quartz glass and the like can be used.
(2) According to the invention, the tannic acid/carbon material dispersion liquid is coated on the modified silicon substrate material by adopting a self-assembly technology, the prepared coating has good stability and is not easy to fall off, under an electron microscope, the carbon nano tubes, the graphene and the polyaniline are gathered and stacked on the silicon substrate material in respective nano-size shapes, and no obvious limit exists between the materials, which indicates that strong interaction exists between the three dispersion materials and the silicon substrate material, so that the tannic acid/carbon material is tightly bonded on the modified silicon substrate material.
(3) The dispersing agent used in the invention is tannin, tannin/trivalent metal ions and quaternary ammonium salt/tannin, and the ligand formed by trivalent metal and tannin has more branched structures than tannin, has larger pi-pi stacking effect with the nano carbon material, and the formed dispersion liquid has smaller particle size and is more tightly combined with a substrate. Since the bond energy of cation-pi interactions is greater than that of pi-pi stacking interactions, introduction of an interaction between carbon conjugated systems that is stronger than pi-pi stacking interactions results in a more stable ligand structure, so addition of unused types of organic cations, such as quaternary ammonium salts, can result in more stable dispersions and more compact coating structures.
Drawings
FIG. 1 is an infrared spectrum of PDMS before and after modification;
FIG. 2 is an SEM image of the surface and cross-section of the PDMS coating of example 1 (left: surface, right: cross-section);
FIG. 3 is an SEM image of the surface and cross-section of the PDMS coating of example 4 (left: surface, right: cross-section);
FIG. 4 is an SEM image of the surface and cross-section of the PDMS coating of example 7 (left: surface, right: cross-section);
FIG. 5 is a graph of the coating conductivity and resistance change of tannic acid/graphene dispersion on PDMS (a: coating conductivity, b: test apparatus, c: resistance change);
FIG. 6 is an infrared thermographic plot of temperature as a function of time for PDMS after the coating was built and pure PDMS without the built coating at 40 ℃ (left: pure PDMS without the built coating, right: PDMS after the built coating);
FIG. 7 is an infrared thermographic plot of temperature as a function of time for PDMS after the coating was built and pure PDMS after the coating was not built at 80 deg.C (left: pure PDMS without the built coating, right: PDMS after the built coating).
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding the nano carbon material graphene into ultrapure water, placing the ultrapure water into an ultrasonic cell crusher under the condition of ice water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 500W, the ultrasonic treatment is carried out for 3 seconds at intervals, and the total ultrasonic treatment time is 30 minutes, so as to obtain nano carbon material dispersion liquid with the concentration of 0.5 g/L;
(2) Adding tannic acid into the nano carbon material dispersion liquid, wherein the mass ratio of the nano carbon material to the tannic acid in the nano carbon material dispersion liquid is 1.
The preparation method comprises the steps of treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then treating the PDMS in a pretreating agent (the pretreating agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, and taking out the PDMS to obtain the stable graphene coating.
FIG. 1 is an IR chart of PDMS of example 1 after treatment with a pretreatment agent, analyzed from the FT-IR chart, showing the appearance of an absorption peak at 1586cm-1 by-NH 2, indicating-NH of 3-Aminopropyltriethoxysilane (ATES) in the pretreatment agent 2 Groups were successfully introduced to the PDMS surface.
Example 2
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding the nano carbon material graphene into ultrapure water, placing the ultrapure water into an ultrasonic cell crusher under the condition of ice water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 800W, the ultrasonic treatment is carried out for 3 seconds at intervals, and the total ultrasonic treatment time is 20 minutes, so as to obtain a nano carbon material dispersion liquid with the concentration of 1 g/L;
(2) Adding a tannin/trivalent metal ion solution into the nano carbon material dispersion liquid, wherein the molar ratio of the tannin to the trivalent metal ions in the tannin/trivalent metal ion solution is 2; the mass ratio of the nano carbon material to the tannin in the nano carbon material dispersion liquid is 1.
The preparation method comprises the steps of treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then treating the PDMS in a pretreating agent (the pretreating agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, and taking out the PDMS to obtain the stable graphene coating.
Example 3
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding the nano carbon material graphene into ultrapure water, placing the ultrapure water into an ultrasonic cell crusher under the condition of ice water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 1000W, the ultrasonic treatment is carried out for 3 seconds at intervals of 3 seconds, and the total ultrasonic treatment time is 10 minutes, so as to obtain a nano carbon material dispersion liquid with the concentration of 8 g/L;
(2) Adding tetramethylammonium chloride/tannic acid solution into the nano-carbon material dispersion liquid, wherein the tetramethylammonium chloride/tannic acid solution is obtained by mixing quaternary ammonium salt and tannic acid at a molar ratio of 0.5, the mass ratio of the nano-carbon material to the tannic acid in the nano-carbon material dispersion liquid is 1.
The preparation method comprises the steps of treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then treating the PDMS in a pretreating agent (the pretreating agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, and taking out the PDMS to obtain the stable graphene coating.
Example 4
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding carbon nano-tubes into ultrapure water, placing the ultrapure water in an ultrasonic cell crusher under the condition of ice-water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 500W, the ultrasonic treatment is carried out for 3 seconds at intervals, and the total ultrasonic treatment time is 30 minutes, so as to obtain carbon nano-tube dispersion liquid with the concentration of 0.5 g/L;
(2) Adding tannic acid into the nano-carbon material dispersion liquid, wherein the mass ratio of the nano-carbon material to the tannic acid in the nano-carbon material dispersion liquid is 1:0.1, uniformly mixing and stirring, putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 20 minutes, adjusting the pH to 5 by using 0.1mol/L hydrochloric acid or sodium hydroxide solution, putting the mixture into an ultrasonic cell crusher for ultrasonic treatment under the condition of ice-water bath, wherein the ultrasonic treatment power is 500W, the ultrasonic treatment time is 3 seconds, the ultrasonic treatment interval is 3 seconds, the total ultrasonic treatment time is 0 minute, and pouring the mixed solution into a sample bottle to stand for a period of time after the ultrasonic treatment is finished, so that the stable electric and heat conducting coating is obtained.
Putting PDMS into a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for treatment for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, putting the PDMS into a pretreatment agent (the pretreatment agent is an anhydrous toluene solution containing 5% volume fraction of 3-aminopropyltriethoxysilane), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, putting the PDMS into a dispersion liquid, standing the dispersion liquid for 24h, and taking out the PDMS to obtain the stable carbon nanotube coating.
Example 5
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding carbon nano-tubes into ultrapure water, placing the ultrapure water in an ultrasonic cell crusher under the condition of ice-water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 800W, the ultrasonic treatment is carried out for 3 seconds at intervals of 3 seconds, and the total ultrasonic treatment time is 15 minutes, so as to obtain carbon nano-tube dispersion liquid with the concentration of 8 g/L;
(2) Adding a tannin/trivalent metal ion solution into the nano-carbon material dispersion liquid, wherein the molar ratio of tannin to trivalent metal ions in the tannin/trivalent metal ion solution is 3; the mass ratio of the nano carbon material to the tannin in the nano carbon material dispersion liquid is 1.5, the mixture is uniformly stirred and then placed in an ultrasonic cleaner for ultrasonic treatment for 30 minutes, 0.5mol/L hydrochloric acid or sodium hydroxide solution is used for adjusting the pH value to 7, the mixture is placed in an ultrasonic cell crusher for ultrasonic treatment under the condition of ice water bath, the ultrasonic treatment power is 800W, the ultrasonic treatment is carried out for 3 seconds at intervals, the total ultrasonic treatment time is 20 minutes, and after the ultrasonic treatment is finished, the mixed liquid is poured into a sample bottle and stands for a period of time, so that the stable electric and heat conducting coating is obtained.
And (2) treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then placing the PDMS in a pretreatment agent (the pretreatment agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume fraction), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, and taking out the PDMS to obtain the stable carbon nanotube coating.
Example 6
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding carbon nanotubes of a nano carbon material into ultrapure water, placing the ultrapure water in an ultrasonic cell crusher under the condition of ice-water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 1000W, the ultrasonic treatment is carried out for 3 seconds at intervals of 3 seconds, and the total ultrasonic treatment time is 10 minutes, so as to obtain a carbon nanotube dispersion liquid with the concentration of 2 g/L;
(2) Adding tetramethylammonium chloride/tannic acid solution into the nano-carbon material dispersion liquid, wherein the tetramethylammonium chloride/tannic acid solution is obtained by mixing quaternary ammonium salt and tannic acid at a molar ratio of 0.1, the mass ratio of the nano-carbon material to the tannic acid in the nano-carbon material dispersion liquid is 1.
The preparation method comprises the following steps of (1) treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then placing the PDMS in a pretreating agent (the pretreating agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume fraction), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, taking out the PDMS, and obtaining a stable carbon nanotube coating on the surface of the PDMS.
Example 7
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding the polyaniline in the nano carbon material into ultrapure water, placing the ultrapure water in an ultrasonic cell crusher under the condition of ice water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 500W, the ultrasonic treatment is carried out for 3 seconds at intervals, and the total ultrasonic treatment time is 30 minutes, so as to obtain the nano carbon material dispersion liquid with the concentration of 8 g/L;
(2) Adding tannic acid into the nano-carbon material dispersion liquid, wherein the mass ratio of the nano-carbon material to the tannic acid in the nano-carbon material dispersion liquid is 1:0.1, uniformly mixing and stirring, putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 20 minutes, adjusting the pH to 5 by using 0.1mol/L hydrochloric acid or sodium hydroxide solution, putting the mixture into an ultrasonic cell crusher for ultrasonic treatment under the condition of ice-water bath, wherein the ultrasonic treatment power is 500W, the ultrasonic treatment time is 3 seconds, the ultrasonic treatment interval is 3 seconds, the total ultrasonic treatment time is 30 minutes, and pouring the mixed solution into a sample bottle for standing for a period of time after the ultrasonic treatment is finished, thus obtaining the stable electric and heat conducting paint.
The preparation method comprises the steps of treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then treating the PDMS in a pretreating agent (the pretreating agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, taking out the PDMS, and obtaining a stable polyaniline coating on the surface of the PDMS.
Example 8
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding nano carbon material polyaniline into ultrapure water, placing the ultrapure water into an ultrasonic cell crusher under the condition of ice water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 700W, the ultrasonic treatment is carried out for 3 seconds at intervals, and the total ultrasonic treatment time is 15 minutes, so as to obtain nano carbon material dispersion liquid with the concentration of 0.5 g/L;
(2) Adding a tannin/trivalent metal ion solution into a nano carbon material dispersion liquid, wherein the molar ratio of tannin to trivalent metal ions in the tannin/trivalent metal ion solution is 2.5, the mass ratio of nano carbon materials to tannin in the nano carbon material dispersion liquid is 1.
The preparation method comprises the steps of treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then treating the PDMS in a pretreating agent (the pretreating agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, taking out the PDMS, and obtaining a stable polyaniline coating on the surface of the PDMS.
Example 9
A preparation method of an electric and heat conducting coating comprises the following steps:
(1) Adding the polyaniline in the nano carbon material into ultrapure water, placing the ultrapure water in an ultrasonic cell crusher under the condition of ice water bath for ultrasonic treatment, wherein the ultrasonic treatment power is 1000W, the ultrasonic treatment is carried out for 3 seconds at intervals, and the total ultrasonic treatment time is 10 minutes, so as to obtain nano carbon material dispersion liquid with the concentration of 3 g/L;
(2) Adding tetramethylammonium chloride/tannic acid solution into the nano-carbon material dispersion liquid, wherein the tetramethylammonium chloride/tannic acid solution is obtained by mixing quaternary ammonium salt and tannic acid at a molar ratio of 1.
The preparation method comprises the steps of treating PDMS in a Piranha solution (hydrogen peroxide: concentrated sulfuric acid, v/v = 3/7) at 90 ℃ for 5min, taking out the PDMS, cleaning the PDMS with a large amount of ultrapure water, drying the PDMS by blowing with nitrogen, then treating the PDMS in a pretreating agent (the pretreating agent is an anhydrous toluene solution containing 5% of 3-aminopropyltriethoxysilane by volume), treating the PDMS at 80 ℃ for 12h, cleaning the modified PDMS with anhydrous toluene and anhydrous ethanol, drying the PDMS by blowing with nitrogen, placing the PDMS in a dispersion liquid, standing the dispersion liquid for 24h, taking out the PDMS, and obtaining a stable polyaniline tube coating on the surface of the PDMS.
The SEM images of PDMS after coating of examples 1, 4, and 7 are shown in fig. 2, 3, and 4, and it can be seen from the images that the carbon nanotubes are stacked in a single stripe shape, the stripe-shaped carbon nanotubes and PMDS are clearly divided into upper and lower layers on the cross-sectional view of SEM, and the same result is obtained from the coating images of graphene and polyaniline, which indicates that the conjugated carbon material is assembled into a film on the modified PDMS in nano-uniform particles and aggregates, and has strong interaction with the PDMS.
The coatings prepared in example 1 were tested for electrical and thermal conductivity:
as shown in fig. 5, a coating is formed on the surface of the pretreated PDMS by the coating of example 1, the PDMS after the coating is formed is connected to a closed current loop, a Light Emitting Diode (LED) indicator emits white light, the coating is bent toward one side, and the LED light is turned on to indicate that the resistance is changed, and the resistance change curve shows normalization under certain strain, which occurs: under the action of no pressure, huge resistance is generated among graphene sheets in the coating through larger gaps and thousands of gaps, so that the current is prevented from passing through the graphene sheets.
The PDMS before and after coating is placed on a heating plate at the same time, the thermal conductivity difference is tested, the brighter the color is, the higher the temperature is, as shown in FIGS. 6 and 7, at the same time point, the coating is built on the surface of the pretreated PDMS by using the coating of example 1, the heat conduction speed of the PDMS after the coating is built from the heating plate to the room temperature environment is higher than that of the pure PDMS without the coating built, the temperature of the two PDMS is increased along with the increase of time at the same temperature of the heating plate, and finally the same temperature is reached, the difference is more obvious under the condition that the heating time is shorter, the heat conduction of the PDMS after the coating is built is fast, and the thermal conductivity of the PDMS is proved to be increased by the tannic acid/graphene dispersion liquid coating.
According to the invention, the coordination effect of metal ions is utilized by the tannic acid/trivalent metal ions, the number of tannic acid monomers and the branching degree are increased, and the tannic acid is not modified, so that more branched chains and the nano carbon material have pi-pi accumulation effect and have tighter effect with a substrate; tetramethylammonium chloride/tannic acid solutions utilize small organic cations with typical structures because the bond energy of cation-pi interactions is greater than the bond energy of pi-pi stacking, introducing cation-pi interactions in two carbon conjugated systems results in more stable dispersed ligands and a better smoothness of the coating formed on the substrate.
Claims (10)
1. The preparation method of the electric-conduction heat-conduction coating is characterized by comprising the following steps of:
(1) Adding a nano carbon material into ultrapure water, and performing ultrasonic treatment in an ice water bath to obtain a nano carbon material dispersion liquid;
(2) Adding a tannin-based dispersing agent into the nano carbon material dispersion liquid, uniformly mixing and stirring, carrying out ultrasonic treatment in an ultrasonic cleaning machine for 20-60 minutes, adjusting the pH value to 5-9, and carrying out ultrasonic treatment in an ice water bath to obtain the stable electric and heat conducting paint.
2. The method for preparing an electrically and thermally conductive coating according to claim 1, wherein the nanocarbon material in step (1) is graphene, carbon nanotubes or polyaniline, and the concentration of the nanocarbon material dispersion is 0.5 to 8g/L.
3. The preparation method of the electrically and thermally conductive coating according to claim 1, wherein the ultrasonic treatment process in the step (1) and the step (2) are the same, the power of the ultrasonic cell crusher is 500-1000W, the ultrasonic treatment is performed for 3 seconds at intervals of 3 seconds, and the total ultrasonic treatment time is 10-30 minutes.
4. The method for preparing the electrically and thermally conductive coating material as claimed in claim 1, wherein the mass ratio of the nanocarbon material in the nanocarbon material dispersion liquid and the tannic acid in the tannic acid-based dispersant in the step (2) is 1.
5. The method for preparing an electrically and thermally conductive coating material as claimed in claim 1, wherein the tannin based dispersant of step (2) is tannin, a tannin/trivalent metal ion solution or tetramethylammonium chloride/tannin solution.
6. The method for preparing the electrically and thermally conductive coating as claimed in claim 5, wherein the molar ratio of tannic acid to trivalent metal ions in the tannic acid/trivalent metal ion solution is 2 to 1, and the trivalent metal ion source is ferric chloride hexahydrate; the tetramethylammonium chloride/tannic acid solution is obtained by mixing quaternary ammonium salt and tannic acid at a molar ratio of 0.1-1.
7. The application of the electric and heat conductive coating as claimed in claim 1, wherein the electric and heat conductive coating is formed on the surface of the silicon-based material by firstly immersing the silicon-based material in Piranha solution at 90 ℃ for 5min, then treating the silicon-based material in a pretreatment agent at 80 ℃ for 12h, cleaning the silicon-based material with anhydrous toluene and anhydrous ethanol, drying the silicon-based material by blowing with nitrogen, and then immersing the silicon-based material in the coating for 24 h.
8. The use of the electrically and thermally conductive coating according to claim 7, wherein the silicon substrate material is polydimethylsiloxane, mica flakes or quartz glass.
9. The application of the electrically and thermally conductive coating as claimed in claim 7, wherein the Piranha solution is prepared by mixing hydrogen peroxide and 98% by mass of concentrated sulfuric acid at a volume ratio v/v = 3/7.
10. The application of the electric and heat conductive paint as claimed in claim 7, wherein the pretreating agent is an anhydrous toluene solution containing 5% volume fraction of 3-aminopropyltriethoxysilane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049925A (en) * | 2007-03-29 | 2007-10-10 | 浙江大学 | Method for preparing suspension liquid of steady Nano carbon tube by using tannic acid |
| CN103553353A (en) * | 2013-11-08 | 2014-02-05 | 东莞南玻太阳能玻璃有限公司 | Method for pretreating glass substrate and method for manufacturing solar cell packaging glass by using glass substrate |
| CN113817343A (en) * | 2021-09-27 | 2021-12-21 | 昆明理工大学 | Dispersing method of nano carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049925A (en) * | 2007-03-29 | 2007-10-10 | 浙江大学 | Method for preparing suspension liquid of steady Nano carbon tube by using tannic acid |
| CN103553353A (en) * | 2013-11-08 | 2014-02-05 | 东莞南玻太阳能玻璃有限公司 | Method for pretreating glass substrate and method for manufacturing solar cell packaging glass by using glass substrate |
| CN113817343A (en) * | 2021-09-27 | 2021-12-21 | 昆明理工大学 | Dispersing method of nano carbon material |
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