CN116262868B - Preparation method of high-transparency high-conductivity graphene nano indium silver-tarnish-resistant coating - Google Patents
Preparation method of high-transparency high-conductivity graphene nano indium silver-tarnish-resistant coating Download PDFInfo
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 120
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 112
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 239000011248 coating agent Substances 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012188 paraffin wax Substances 0.000 claims abstract description 132
- 239000002131 composite material Substances 0.000 claims abstract description 83
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229910052709 silver Inorganic materials 0.000 claims abstract description 72
- 239000004332 silver Substances 0.000 claims abstract description 72
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
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- 238000002844 melting Methods 0.000 claims abstract description 43
- 230000008018 melting Effects 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011889 copper foil Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 27
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
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- 238000004649 discoloration prevention Methods 0.000 description 7
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
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- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229960000846 camphor Drugs 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
-
- 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
- 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
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of coating materials, and discloses a preparation method of a high-transparency high-conductivity graphene nano indium silver-tarnish-resistant coating, which comprises the following steps: 1) Mixing oleylamine, indium acetate and paraffin, heating until paraffin is melted, and stirring for reaction to obtain a reaction mixture; 2) Heating and stirring the reaction mixture, stopping heating and continuing stirring to obtain a nano indium/paraffin composite material; 3) Heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material on the surface of the graphene/copper foil composite layer, heating and melting paraffin after paraffin is solidified, and rotating to prepare a film, and removing the copper foil to obtain the graphene/nano indium/paraffin composite film; 4) And (3) ultrasonically mixing the graphene/nano indium/paraffin composite film with ethanol, covering the surface of the silver matrix, volatilizing the ethanol, heating and melting paraffin, rotating to prepare a film, heating and melting nano indium, and removing impurities to obtain the coating. The silver-tarnish-resistant coating prepared by the method has high transparency and high conductivity, and the film base binding force of graphene and a silver matrix is high.
Description
Technical Field
The invention relates to the field of coating materials, in particular to a preparation method of a high-transparency high-conductivity graphene nano indium silver-tarnish-resistant coating.
Background
Silver, which is a noble metal, is widely used in the fields of jewelry, tableware, mirrors, electronics industry, etc. However, when the surface of the silver matrix is exposed to air, ag is formed on the surface of the silver matrix after being corroded by, for example, hydrogen sulfide, carbonyl sulfide, etc 2 S, the surface of the silver matrix loses luster, and a color change phenomenon occurs.
Currently, as for the anti-discoloration measures of silver, there are mainly anti-discoloration silver alloy, electroplating electroless plating surface treatment, preparation of self-assembled film on silver surface, and the like. The alloy technology has good effects on silver protection, discoloration prevention and the like, but the alloy composition has strict requirements and complex manufacturing process. The electroplating and chemical plating surface treatment has the problem of environmental pollution. The silver surface is used for preparing self-assembled films and the like, and the preparation process is simple, but the problems of poor thermal stability of a film layer, weak film base binding force and the like exist, and the conductivity of the silver surface is reduced, so that the silver surface cannot be applied in large-scale industrialization.
It can be seen that there is a need to develop a novel coating that can both prevent discoloration of the silver surface and increase the conductivity of the silver surface.
Graphene can be used as silver surface prevention due to its high transparency, excellent conductivity, chemical stability and mechanical propertiesA color-changing protective film. For example, ayhan et al [ Ayhan ME, kalita G, sharma S and Tanemura M, chemical vapor deposition of graphene on silver foil as a tarnish-resistant coating [ J ]]. Phys. Status Solidi RRL, 2013,7(12): 1076-1079.]Adopting chemical vapor deposition method, using camphor as carbon source, using Ar and H 2 In the mixed gas of (2), the graphene coating grows on the surface of the silver foil in situ. It was found that the silver surface not covered with the graphene film coating was rapidly blackened after contact with sulfur vapor, while the silver surface covered with the graphene film coating was not discolored. However, the chemical vapor deposition method is adopted to directly deposit the graphene coating on the silver surface, so that the equipment requirement is high and the mass production is difficult.
The solution of polymethyl methacrylate (PMMA) dissolved in organic solvents such as diethyl ether is spin-coated on the surface of a graphene/copper foil composite layer, the cured polymethyl methacrylate (PMMA) is used as a graphene supporting layer, copper foil is removed by etching liquid, and then the polymethyl methacrylate/graphene composite layer is obtained. Although the above method greatly improves the binding force of graphene and silver surface, the conductivity of silver surface is impaired because polymethyl methacrylate with low conductivity is not removed.
Indium (In) is a group IIIA element, is a low melting point metal having a tetragonal crystal structure, has a silver-white luster, and is used for preventing silver from discoloring by plating metal indium on silver. For example, the patent application No. ZL201310139110.1 discloses a method for preventing silver from discoloring by electroplating indium metal on silver, while preventing silver from discoloring, and improving the conductivity of the coating.
In view of this, if the graphene/nano indium composite film is covered on the surface of the silver matrix, and then the graphene and the silver matrix are welded by heating and melting the indium nanoparticles, it is expected that the film-based binding force of the graphene and the silver matrix is remarkably improved while the high-transparency and high-conductivity silver discoloration prevention coating is obtained. However, no relevant report has been made in the prior art.
Disclosure of Invention
The invention provides a preparation method of a high-transparency high-conductivity graphene nano-indium silver-discoloration prevention coating.
The specific technical scheme of the invention is as follows: the preparation method of the high-transparency high-conductivity graphene nano indium silver-tarnish-resistant coating comprises the following steps:
(1) The oleylamine, the indium acetate and the paraffin are mixed, heated until the paraffin is melted, and continuously stirred for reaction, so that a reaction mixture is obtained.
(2) And heating and stirring the reaction mixture under an inert atmosphere, stopping heating, and continuing stirring to obtain the nano indium/paraffin composite material.
(3) Heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material on the surface of the graphene/copper foil composite layer, transferring the cured paraffin onto a rotary gumming machine, heating and melting the paraffin, rotating to prepare a film, and etching and removing the copper foil by using ferric chloride solution to obtain the graphene/nano indium/paraffin composite film;
(4) Cleaning the graphene/nano indium/paraffin composite film, then ultrasonically mixing the cleaned graphene/nano indium/paraffin composite film with ethanol, covering the surface of a silver matrix, volatilizing the ethanol to obtain a silver matrix with the surface covered with the graphene/nano indium/paraffin composite coating, transferring the silver matrix to a rotary gumming machine, heating and melting paraffin, rotating to prepare a film, and heating and melting nano indium to weld the graphene and the silver matrix; and removing impurities by using an organic solvent to obtain the coating. According to the invention, indium acetate is skillfully used as an indium source, molten liquid paraffin is used as a heating solvent, oleylamine is used as a dispersion stabilizer, and the indium acetate is decomposed by heating in a hot wax bath under an inert atmosphere, so that the nano indium/paraffin composite material is obtained. When the nano indium is prepared, the nano indium is uniformly dispersed in the paraffin matrix by utilizing the electrostatic steric hindrance stabilizing effect and the steric hindrance effect of the oleylamine, and the preparation of the nano indium and nano indium/paraffin composite material is completed simultaneously, so that the oxidation reaction of metal nano particles in the air can be effectively avoided, and the collecting and storing links of the nano particles are omitted. On the basis, the paraffin has the characteristics of simple and stable chemical structure and high thermal expansion coefficient, is used as a supporting layer for graphene transfer, and solves the problems of pollution and wrinkling of the supporting layer of graphene.
And (3) heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material onto the surface of the graphene/copper foil composite layer, transferring the obtained composite film to a rotary gumming machine after paraffin is solidified at room temperature, heating and melting the paraffin again, and then rotating to prepare a film, so that the thickness of the nano indium/paraffin film is controlled. And finally, removing the copper foil by using ferric chloride solution as etching solution to obtain the graphene/nano indium/paraffin composite film. Further, cleaning the graphene/nano indium/paraffin composite film with deionized water, placing the cleaned graphene/nano indium/paraffin composite film in ethanol, ultrasonically mixing the cleaned graphene/nano indium/paraffin composite film and the dried graphene/nano indium/paraffin composite film to form a film, covering the film on the surface of a silver matrix, volatilizing the ethanol, transferring the silver matrix with the graphene/nano indium/paraffin composite coating on the surface to a rotary gumming machine, heating again to melt paraffin, rotating to form a film, and then continuously heating to melt nano indium so as to weld the graphene and the silver matrix; and removing impurities such as paraffin, oleylamine and the like by using an organic solvent to obtain the graphene/nano indium silver-discoloration prevention coating with high transparency and high conductivity.
Preferably, in the step (1), the dosage ratio of oleylamine to indium acetate to paraffin is 2-4 g: 2-4 g: 45-60 g.
According to the invention, the oleylamine is used as a dispersion stabilizer, so that the growth of indium nanocrystals can be inhibited, and more importantly, the steric hindrance force of the oleylamine to the indium nanocrystals is larger than the attractive force between the indium nanocrystals by adjusting the dosage ratio of the oleylamine to the indium acetate to the paraffin, so that the indium nanocrystals are stably dispersed in the liquid paraffin without further polymerization growth.
Preferably, in the step (1), the paraffin wax is a single melting point paraffin wax or a mixed paraffin wax compounded by a plurality of single melting point paraffin waxes, and the melting point is 48-50 ℃.
Preferably, in the step (1), the heating temperature is 10-15 ℃ higher than the melting point of paraffin.
Preferably, in the step (1), the continuous stirring reaction is carried out for 2-3 hours at 200-300 rpm.
Preferably, in the step (2), the heating and stirring are performed by heating to 230-250 ℃ and stirring for 3-4 hours at 300-500 rpm.
Preferably, in the step (2), the continuous stirring is performed at 300-500 rpm for 1-2 hours.
Preferably, in the step (3), the graphene/copper foil composite layer includes a copper foil and 1-5 layers of graphene grown on the surface of the copper foil.
Preferably, in the step (3), the concentration of the ferric chloride solution is 0.8-1.2 mol/L, and the etching time is 40-50 minutes.
Preferably, in the step 3), the rotating speed of the rotary glue spreader is 800-1200 rpm, the rotary glue spreader rotates for 1-3 minutes, and the thickness of the nano indium/paraffin film is controlled to be 15-25 micrometers.
Preferably, in the step 4), the rotation speed of the rotary glue spreader is 2500-3500 rpm, and the rotary glue spreader rotates for 1-3 minutes.
Preferably, in the step (4), the temperature is raised to 157-165 ℃.
Preferably, in step (4), the organic solvent is n-hexane.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, indium acetate is skillfully used as an indium source, molten liquid paraffin is used as a heating solvent, oleylamine is used as a dispersion stabilizer, and the indium acetate is decomposed by heating in a hot wax bath under an inert atmosphere, so that the nano indium/paraffin composite material is obtained. When the nano indium is prepared, the nano indium is uniformly dispersed in the paraffin matrix by utilizing the electrostatic steric hindrance stabilizing effect and the steric hindrance effect of the oleylamine, and the preparation of the nano indium and nano indium/paraffin composite material is completed simultaneously, so that the oxidation reaction of metal nano particles in the air can be effectively avoided, and the collecting and storing links of the nano particles are omitted.
(2) According to the invention, by utilizing the characteristics of simple and stable chemical structure and high thermal expansion coefficient of paraffin, the nano indium/paraffin composite material is selected as a support layer for graphene transfer, and meanwhile, the problems of pollution and wrinkling of the support layer of graphene are solved.
(3) According to the invention, the graphene and the silver matrix are welded by heating and melting indium nano particles, so that the film-based binding force of the graphene and the silver matrix is remarkably improved while the high-transparency and high-conductivity silver-discoloration-preventing coating is obtained.
Drawings
FIG. 1 is an XRD spectrum of a nano-indium/paraffin composite material in example 1;
FIG. 2 is a TEM photograph of nano indium in example 1;
FIG. 3 is a graph showing the comparison of the resistance values of the silver matrix with the graphene/nano-indium composite coating coated on the surface and the pure silver matrix in example 1;
fig. 4 is a graph showing the anti-discoloration performance test of the graphene/nano-indium coating-containing silver matrix and the pure silver matrix of example 1.
Detailed Description
The invention is further described below with reference to examples.
General examples
The preparation method of the high-transparency high-conductivity graphene nano indium silver-tarnish-resistant coating comprises the following steps:
(1) The mass ratio is 2-4 g: 2-4 g: 45-60 g of oleylamine, indium acetate and paraffin are mixed, heated until the paraffin is melted (10-15 ℃ higher than the melting point of the paraffin), and continuously stirred for reaction for 2-3 hours at 200-300 rpm to obtain a reaction mixture.
Preferably, the paraffin is paraffin with a single melting point or mixed paraffin compounded by a plurality of paraffin with single melting point, and the melting point is 48-50 ℃.
(2) And heating the reaction mixture at 230-250 ℃ in an inert atmosphere, stirring for 3-4 hours at 300-500 rpm, stopping heating, and continuously stirring for 1-2 hours at 300-500 rpm to obtain the nano indium/paraffin composite material.
(3) Heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material on the surface of the graphene/copper foil composite layer, transferring the cured paraffin onto a rotary gumming machine, heating and melting the paraffin, and rotating at a rotating speed of 800-1200 rpm for film preparation for 1-3 minutes, wherein the thickness of the nano indium/paraffin film is controlled to be 15-25 micrometers. Etching with 0.8-1.2 mol/L ferric chloride solution for 40-50 minutes to remove copper foil, and obtaining the graphene/nano indium/paraffin composite film;
preferably, the graphene/copper foil composite layer comprises a copper foil and 1-5 layers of graphene grown on the surface of the copper foil.
(4) Cleaning the graphene/nano indium/paraffin composite film, then ultrasonically mixing the cleaned graphene/nano indium/paraffin composite film with ethanol, covering the surface of a silver matrix, volatilizing the ethanol to obtain a silver matrix with the surface covered with the graphene/nano indium/paraffin composite coating, transferring the silver matrix onto a rotary gumming machine, heating and melting paraffin, rotationally preparing a film at a rotating speed of 2500-3500 rpm for 1-3 minutes, and heating to 157-165 ℃ to melt nano indium so as to weld the graphene and the silver matrix; removing impurities such as paraffin and oleylamine with organic solvent (preferably n-hexane) to obtain the coating.
Example 1
(1) 2g of oleylamine, 2g of indium acetate and 45g of paraffin wax (melting point 48-50 ℃ C.) were mixed, and the mixture was heated to 62 ℃ C. And stirred continuously at a stirring speed of 200 rpm for 2 hours to obtain a reaction mixture.
(2) Heating the reaction mixture in the step (1) to 230 ℃ under the protection of nitrogen, stirring for 3 hours at 300 revolutions per minute, then stopping heating, continuing stirring for 1 hour at 300 revolutions per minute, and obtaining the nano indium/paraffin composite material.
(3) Heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material on the surface of a graphene/copper foil composite layer (3 layers of graphene are grown on the surface of the copper foil in situ), transferring the cured paraffin onto a rotary gumming machine at room temperature, heating and melting the paraffin, and rotationally preparing a film for 2 minutes at a rotating speed of 1000 revolutions per minute, wherein the thickness of the nano indium/paraffin film is controlled to be 20 microns. And then etching with 1.0mol/L ferric chloride solution for 45 minutes to remove the copper foil, thus obtaining the graphene/nano indium/paraffin composite film.
(4) Cleaning the graphene/nano indium/paraffin composite film, then ultrasonically mixing the cleaned graphene/nano indium/paraffin composite film with ethanol, covering the surface of a silver matrix, volatilizing the ethanol to obtain a silver matrix with the surface covered with the graphene/nano indium/paraffin composite coating, transferring the silver matrix onto a rotary gumming machine, heating and melting paraffin, rotationally preparing a film for 2 minutes at a rotating speed of 3000 rpm, and heating to 160 ℃ to melt nano indium so as to weld the graphene and the silver matrix; and removing impurities such as paraffin, oleylamine and the like by using n-hexane to obtain the graphene/nano indium silver-discoloration prevention coating with high transparency and high conductivity.
Performance testing and characterization
Fig. 1 is an XRD curve of the nano indium/paraffin composite material prepared in example 1. As can be seen from the figure, the 2 theta angle positions of the diffraction peaks of the product are 22.01 ° and 24.17 ° corresponding to the (110) and (0014) crystal planes of paraffin wax, respectively, and the 2 theta angles of the diffraction peaks are 32.95 °, 36.31 °, 39.26 ° and 56.54 ° corresponding to the (101), (002), (110) and (200) crystal planes of indium, respectively, indicating that the product obtained after the reaction consists of paraffin wax and indium, and the diffraction peak intensity of indium is weaker compared with that of paraffin wax, because the indium content is lower in the composite material.
Fig. 2 is a TEM photograph of nano indium in example 1. And (3) loading a small amount of thermal decomposition products into a centrifuge tube, adding n-hexane for dissolution, repeatedly centrifuging and washing for 4 times, dispersing by ultrasonic, dropping a proper amount of suspension liquid on a copper mesh, drying under an infrared lamp, and then placing into a transmission electron microscope stage for observation. As can be seen, the average particle size of the indium particles was about 20nm, and the dispersion was relatively uniform.
Fig. 3 is the sheet resistance of the pure silver matrix and the silver matrix with the graphene/nano-indium composite coating on the surface in example 1. The surface square resistance of the pure silver matrix is measured to be 32 m minus/sq by adopting a double-electrical-measurement four-probe tester, and the surface square resistance of the silver matrix with the graphene/nano-indium composite coating covered on the surface is 36 m minus/sq, and the comparative analysis shows that the influence on the surface square resistance of the silver matrix is small after the graphene/nano-indium composite coating is covered on the surface of the silver matrix, so that the high conductivity of the silver matrix is effectively maintained.
Fig. 4 test of discoloration resistance of the silver matrix (a) and the pure silver matrix (b) of example 1, which were surface-coated with graphene/nano-indium composite coating. Na is mixed with 2 S powder is added into deionized water to prepare a solution with the concentration of 0.001mol/L, the solution is respectively dripped on the surfaces of the two samples by using a rubber head dropper, and the silver matrix with the surface covered by the graphene/nano indium composite coating does not change color obviously after 2 hours, but is arranged on a pure silver matrixDripping Na 2 The black spots appear at the S position, which indicates that the graphene/nano indium composite coating can effectively prevent the oxidative discoloration of the silver matrix.
Example 2
(1) 3g of oleylamine, 3g of indium acetate and 55g of paraffin wax (melting point 48-50 ℃ C.) were mixed, and the mixture was heated to 62 ℃ C. And stirred continuously at a stirring speed of 250 rpm for 3 hours to obtain a reaction mixture.
(2) Heating the reaction mixture in the step (1) to 250 ℃ under the protection of nitrogen, stirring for 4 hours at 400 rpm, then stopping heating, continuing stirring for 2 hours at 400 rpm, and obtaining the nano indium/paraffin composite material.
(3) Heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material on the surface of a graphene/copper foil composite layer (1 layer of graphene grows on the surface of the copper foil in situ), transferring the cured paraffin onto a rotary gumming machine at room temperature, heating and melting the paraffin, and rotating at a rotating speed of 800 rpm for film preparation for 3 minutes, wherein the thickness of the nano indium/paraffin film is controlled to be 25 micrometers. And then etching with 1.0mol/L ferric chloride solution for 45 minutes to remove the copper foil, thus obtaining the graphene/nano indium/paraffin composite film.
(4) Cleaning the graphene/nano indium/paraffin composite film, then ultrasonically mixing the cleaned graphene/nano indium/paraffin composite film with ethanol, covering the surface of a silver matrix, volatilizing the ethanol to obtain a silver matrix with the surface covered with the graphene/nano indium/paraffin composite coating, transferring the silver matrix onto a rotary gumming machine, heating and melting paraffin, rotating at a rotating speed of 2500 rpm for film making for 3 minutes, and heating to 160 ℃ to melt nano indium so as to weld the graphene and the silver matrix; and removing impurities such as paraffin, oleylamine and the like by using n-hexane to obtain the graphene/nano indium silver-discoloration prevention coating with high transparency and high conductivity.
Example 3
(1) 4g of oleylamine, 4g of indium acetate and 60g of paraffin wax (melting point 48-50 ℃ C.) were mixed, heated to 62 ℃ C., and continuously stirred at a stirring speed of 300 rpm for 3 hours to obtain a reaction mixture.
(2) Heating the reaction mixture in the step (1) to 250 ℃ under the protection of nitrogen, stirring for 4 hours at 500 revolutions per minute, then stopping heating, continuing stirring for 2 hours at 500 revolutions per minute, and obtaining the nano indium/paraffin composite material.
(3) Heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material on the surface of a graphene/copper foil composite layer (5 layers of graphene are grown on the surface of the copper foil in situ), transferring the cured paraffin onto a rotary gumming machine at room temperature, heating and melting the paraffin, and rotationally preparing a film for 1 minute at a rotating speed of 1200 revolutions per minute, wherein the thickness of the nano indium/paraffin film is controlled to be 15 microns. And then etching with 1.0mol/L ferric chloride solution for 45 minutes to remove the copper foil, thus obtaining the graphene/nano indium/paraffin composite film.
(4) Cleaning the graphene/nano indium/paraffin composite film, then ultrasonically mixing the cleaned graphene/nano indium/paraffin composite film with ethanol, covering the surface of a silver matrix, volatilizing the ethanol to obtain a silver matrix with the surface covered with the graphene/nano indium/paraffin composite coating, transferring the silver matrix onto a rotary gumming machine, heating and melting paraffin, rotationally preparing a film for 1 minute at a rotating speed of 3500 revolutions per minute, and heating to 160 ℃ to melt nano indium so as to weld the graphene and the silver matrix; and removing impurities such as paraffin, oleylamine and the like by using n-hexane to obtain the graphene/nano indium silver-discoloration prevention coating with high transparency and high conductivity.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the high-transparency high-conductivity graphene nano indium silver-tarnish-resistant coating is characterized by comprising the following steps of:
1) Mixing oleylamine, indium acetate and paraffin, heating and melting the paraffin, and stirring for reaction to obtain a reaction mixture;
2) Heating and stirring the reaction mixture under an inert atmosphere, stopping heating and continuing stirring to obtain a nano indium/paraffin composite material;
3) Heating and melting the nano indium/paraffin composite material, dripping the nano indium/paraffin composite material on the surface of the graphene/copper foil composite layer, transferring the cured paraffin onto a rotary gumming machine, heating and melting the paraffin, rotating to prepare a film, and etching and removing the copper foil by using ferric chloride solution to obtain the graphene/nano indium/paraffin composite film;
4) Ultrasonically mixing the graphene/nano indium/paraffin composite film with ethanol, covering the surface of a silver matrix, volatilizing the ethanol, transferring to a rotary gumming machine, heating to melt paraffin, rotating to prepare a film, and heating to melt nano indium to weld the graphene and the silver matrix; and removing impurities by using an organic solvent to obtain the coating.
2. The method of manufacturing according to claim 1, wherein: in the step 1), the dosage ratio of the oleylamine to the indium acetate to the paraffin is 2-4 g: 2-4 g: 45-60 g.
3. The preparation method according to claim 1 or 2, characterized in that: in the step (1) of the process,
the paraffin is single melting point paraffin or mixed paraffin compounded by a plurality of single melting point paraffin, and the melting point is 48-50 ℃;
the heating temperature is 10-15 ℃ higher than the melting point of paraffin;
the stirring reaction is carried out for 2-3 hours under the condition of 200-300 rpm.
4. The method of manufacturing according to claim 1, wherein: in the step 2) of the process, the process is carried out,
heating and stirring to 230-250 ℃, and stirring for 3-4 hours at 300-500 rpm;
and the continuous stirring is carried out for 1-2 hours at 300-500 rpm.
5. The method of manufacturing according to claim 1, wherein: in the step 3), the graphene/copper foil composite layer comprises a copper foil and 1-5 layers of graphene growing on the surface of the copper foil.
6. The method of claim 1 or 5, wherein: in the step 3), the concentration of the ferric chloride solution is 0.8-1.2 mol/L, and the etching time is 40-50 minutes.
7. The method of manufacturing according to claim 1, wherein: in the step 3), the rotating speed of the rotary gumming machine is 800-1200 revolutions per minute, the rotary gumming machine rotates for 1-3 minutes, and the thickness of the nano indium/paraffin film is controlled to be 15-25 microns.
8. The method of manufacturing according to claim 1, wherein: in the step 4), the rotating speed of the rotary gumming machine is 2500-3500 r/min, and the rotary gumming machine rotates for 1-3 min.
9. The method of manufacturing according to claim 1, wherein: in the step 4), the temperature is raised to 157-165 ℃.
10. The method of manufacturing according to claim 1, wherein: in the step 4), the organic solvent is n-hexane.
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| CN103911123A (en) * | 2014-04-10 | 2014-07-09 | 浙江工业大学 | Preparation method of carbon nano-tube/paraffin thermosensitive composite material modified by nano-copper |
| WO2018113699A1 (en) * | 2016-12-23 | 2018-06-28 | 北京赛特石墨烯科技有限公司 | Method for preparing anticorrosion graphene composite coating for metal |
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| CN103911123A (en) * | 2014-04-10 | 2014-07-09 | 浙江工业大学 | Preparation method of carbon nano-tube/paraffin thermosensitive composite material modified by nano-copper |
| WO2018113699A1 (en) * | 2016-12-23 | 2018-06-28 | 北京赛特石墨烯科技有限公司 | Method for preparing anticorrosion graphene composite coating for metal |
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