WO2020076138A1 - Solution de revêtement complexe, structure de substrat métallique fabriquée à l'aide de celle-ci, et son procédé de fabrication - Google Patents

Solution de revêtement complexe, structure de substrat métallique fabriquée à l'aide de celle-ci, et son procédé de fabrication Download PDF

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WO2020076138A1
WO2020076138A1 PCT/KR2019/013425 KR2019013425W WO2020076138A1 WO 2020076138 A1 WO2020076138 A1 WO 2020076138A1 KR 2019013425 W KR2019013425 W KR 2019013425W WO 2020076138 A1 WO2020076138 A1 WO 2020076138A1
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graphite
coating solution
composite coating
polymer
metal substrate
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PCT/KR2019/013425
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English (en)
Korean (ko)
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좌용호
송요셉
김한
임효령
이혜민
장병권
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한양대학교 에리카산학협력단
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Publication of WO2020076138A1 publication Critical patent/WO2020076138A1/fr

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • 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
    • C09D5/08—Anti-corrosive paints
    • 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

Definitions

  • the present application relates to a composite coating solution, a metal substrate structure manufactured using the same, and a method for manufacturing the same, more specifically, a composite coating solution comprising a graphite nanoplate and a silicon-based inorganic polymer, a metal substrate structure produced using the same, And a method of manufacturing the same.
  • Metals have high electrical conductivity and mechanical properties, and are used in various industrial fields. However, the metal can also be oxidized by moisture in the atmosphere, and thus improving the corrosion resistance and oxidation resistance of the metal is an important issue.
  • materials being studied for improving corrosion resistance and oxidation resistance include non-oxidizing metals or metal compounds, and non-metal compounds, and electrochemical deposition, physical vapor deposition, chemical vapor deposition on the metal surface to be protected. It is manufactured by a method such as dip coating.
  • ceramic materials such as metal oxides require high vacuum and high temperature processes, and thus require high process costs.
  • the process cost may be reduced, but at a high temperature, the inherent properties of the material may be lost and carbonized, and cracks may occur in the coating layer.
  • a coating liquid material in which a ceramic material such as an organic polymer and a metal oxide is mixed has been studied.
  • the Republic of Korea Patent Publication No. 10-1081988 (Application No. 10-2008-0132540) is selected from the group consisting of polyester resin, epoxy resin, polyurethane resin, acrylic resin, fluororesin, polycarbonate resin and phenol resin.
  • 100 parts by weight of one or more main resins, 1 to 20 parts by weight of a melamine-based curing agent, 1 to 20 parts by weight of one or more of carbon black and carbon nanotubes, 1 to 40 parts by weight of metal powder, and 0.001 to 20 parts of organic clay Disclosed is a coating composition comprising parts by weight and having excellent conductivity and corrosion resistance.
  • One technical problem to be solved by the present application is to prepare a coating layer containing a metal oxide and a graphite nanoplate by curing a composite coating solution containing a polymer and a graphite nanoplate, and a composite coating solution having improved oxidation resistance and corrosion resistance, and using the same It is to provide a metal substrate structure, and a method for manufacturing the same.
  • Another technical problem to be solved by the present application is to provide a composite coating solution having electrical conductivity, including a graphite nanoplate, a metal substrate structure manufactured using the same, and a method of manufacturing the same.
  • the present application provides a method for producing a composite coating solution.
  • the method for preparing the composite coating solution comprises: preparing a base solution containing a metal salt, providing graphite to the base solution, providing graphite to the base solution, and anion of the metal salt to the graphite Inserting into the interlayer of, preparing a graphite interlayer compound, heat-treating the graphite interlayer compound to form expanded graphite, dispersing the expanded graphite to prepare a graphite nanoplate, and the graphite nanoplate, and By mixing the polymer, it may include the step of preparing a composite coating solution.
  • the step of heat-treating the graphite interlayer compound, the thermal decomposition of the anion of the metal salt contained in the graphite interlayer compound, and the expansion force of the gas formed by the thermal decomposition of the anion, the graphite interlayer compound may include the step of manufacturing the expanded graphite is increased interlayer distance.
  • the amount of defects provided in the graphite nanoplate may be increased.
  • the amount of defects provided in the graphite nanoplate increases It can include.
  • the polymer is polysilazane
  • the solvent of the composite coating solution may include a non-polar solvent
  • the polymer is polysiloxane
  • the solvent of the composite coating solution may include a polar solvent
  • the metal salt may include at least one of azide salt, carbonate, nitrate, sulfate, or phosphate.
  • the present application provides a composite coating solution.
  • the composite coating solution includes a graphite nanoplate and a polymer, and with respect to 100 parts by weight of the total of the graphite nanoplate and the polymer, the graphite nanoplate is 10 parts by weight or more and 50 parts by weight or less , And the polymer may include 50 parts by weight or more and 90 parts by weight or less.
  • the polymer may include either an organic polymer or an inorganic polymer.
  • the organic polymer may include at least one of an epoxy polymer, a cellulose polymer, a vinyl polymer, an acrylic polymer, a fluorine polymer, an amide polymer, an imide polymer, or an acetate polymer. .
  • the inorganic polymer may include at least one of polysiloxane, polysilazane, or polysilicate.
  • the present application provides a coating method using a composite coating solution.
  • the composite coating solution when the polymer of the composite coating solution is polysilazane, the composite coating solution is coated on a metal substrate by either a spray coating method or a spin coating method. It may include.
  • the coating method using the composite coating solution when the polymer of the composite coating solution is polysiloxane, coats the composite coating solution on a metal substrate by either a bar coating method or a doctor blade coating method It may include.
  • the step of preparing a coating layer by hot pressing the pre-coating layer prepared by the coating method using the composite coating solution, the amount of the graphite nanoplate in the pre-coating layer increases, reducing the process pressure It may include.
  • the present application provides a metal substrate structure.
  • the metal substrate structure, a metal substrate, and disposed on the metal substrate comprises a graphite nanoplate, and a coating layer comprising silicon oxide, the coating layer, the silicon-carbon bond in the IR analysis method It does not include, it may include a higher oxidation resistance and stone resistance than the metal substrate.
  • the metal substrate structure may include that as the amount of the silicon oxide in the coating layer increases, corrosion resistance increases.
  • Method of manufacturing a composite coating solution preparing a base solution containing a metal salt, providing graphite to the base solution, inserting anions of the metal salt into the interlayer of the graphite, graphite interlayer compound
  • the step of preparing, forming the expanded graphite by heat-treating the graphite interlayer compound, dispersing the expanded graphite, preparing a graphite nanoplate, and mixing the graphite nanoplate and the polymer to prepare a composite coating solution It may include the steps.
  • the anion inserted between the graphite interlayers may be thermally decomposed. Accordingly, a gas may be formed, and the expanded graphite may be generated by the expanding force of the gas. At this time, the expansion force of the gas is directly received, the carbon-carbon bond is broken, and the expanded graphite having defects can be produced. Therefore, the more the anions inserted, the more defects can be increased in the expanded graphite.
  • the anion contains oxygen
  • the oxidizing gas may be formed, and accordingly, an oxygen-based functional group may be formed on the expanded graphite.
  • the defects may increase as the process time and process temperature of the heat treatment step increase. That is, according to the above, the amount of the defect in the expanded graphite can be adjusted.
  • the step of preparing the composite coating solution may include mixing the graphite nanoplate with 10 to 50 parts by weight, and the polymer with the remaining parts by weight, compared to 100 parts by weight of the total of the graphite nanoplate and the polymer. Accordingly, a composite coating solution in which the graphite nanoplate and the polymer are uniformly dispersed without aggregation, and the adhesion between the metal substrate and the metal is improved may be prepared.
  • the composite coating solution prepared according to the above may be coated on the metal substrate and then cured to form a coating layer.
  • the composite coating solution may include a silicon-based inorganic polymer, and the coating layer prepared accordingly may include the graphite nanoplate and silicon oxide prepared by curing the silicon-based inorganic polymer.
  • the silicon oxide may exhibit corrosion resistance and oxidation resistance
  • the graphite nanoplate may exhibit electrical conductivity. Accordingly, the metal substrate on which the coating layer is formed can be improved in corrosion resistance and oxidation resistance, and also has electrical conductivity, so that it can be easily used in an industrial field where electrical conductivity of the metal is required.
  • FIG. 1 is a flow chart for explaining a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • FIGS. 2 to 4 are views for explaining a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • 5 to 6 are views for explaining a method of manufacturing a metal substrate structure according to an embodiment of the present invention.
  • FIG. 7 to 10 are views showing a scanning electron microscope (SEM) image of a graphite interlayer compound and expanded graphite in a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 11 to 12 are views showing an atomic force microscope (AFM) image, particle size distribution, and particle thickness distribution of a graphite nanoplate in a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • AFM atomic force microscope
  • FIG. 13 is a view illustrating a transmission electron microscope (TEM), a high resolution transmission electron microscope (HRTEM), and a fast Fourier transform (FFT) image of a graphite nanoplate in a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • TEM transmission electron microscope
  • HRTEM high resolution transmission electron microscope
  • FFT fast Fourier transform
  • FIG. 14 is a view showing an image photographed while irradiating light to a composite coating solution according to an embodiment of the present invention.
  • SEM 15 is a view showing a scanning electron microscope (SEM) image of a coating layer of a metal substrate structure according to an embodiment of the present invention.
  • FIG. 16 to 17 are views showing an infrared (IR) spectrum of a coating layer of a metal substrate structure according to an embodiment of the present invention.
  • 18 to 19 are views showing resistance before and after heat treatment of the metal substrate structure according to the embodiment of the present invention.
  • 20 to 21 are views showing a scanning electron microscope (SEM) image before and after heat treatment of a metal substrate structure according to an embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 22 is a view showing an X-ray diffraction pattern (XRD) before and after heat treatment of a metal substrate structure according to an embodiment of the present invention.
  • XRD X-ray diffraction pattern
  • FIGS. 23 to 24 are diagrams showing sample images before and after brine treatment of a metal substrate structure according to Comparative Example 3 and Experimental Example 2-1 of the present invention, and scanning electron microscope (SEM) images.
  • 25 to 26 are views showing a sample image and a scanning electron microscope (SEM) image after saline treatment of the metal substrate structure according to Comparative Example 4 and Experimental Example 2-1 of the present invention.
  • SEM scanning electron microscope
  • FIGS. 27 to 28 are views showing a sample image after sulfuric acid treatment and a scanning electron microscope (SEM) image of the metal substrate structure according to Comparative Example 4 and Experimental Example 2-1 of the present invention.
  • 29 to 30 are diagrams showing a polarization curve and an impedance of a metal substrate structure according to an embodiment of the present invention.
  • FIG. 31 is a view showing the electrical conductivity and adhesion test results according to the graphite nanoplate mass ratio of the metal substrate structure according to Experimental Example 2-2 of the present invention.
  • a component when referred to as being on another component, it means that it may be formed directly on another component, or a third component may be interposed between them.
  • a third component may be interposed between them.
  • the thickness of the films and regions are exaggerated for effective description of the technical content.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another component. Therefore, what is referred to as the first component in one embodiment may be referred to as the second component in another embodiment.
  • first component in one embodiment
  • second component in another embodiment
  • Each embodiment described and illustrated herein also includes its complementary embodiment. Also, in this specification, 'and / or' is used to mean including at least one of the components listed before and after.
  • FIGS. 2 to 4 are views for explaining a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • a base solution containing a metal salt may be prepared (S110).
  • the metal salt may include at least one of azide salt, carbonate, nitrate, sulfate, or phosphate, and specifically, the metal salt may be sodium azide (NaN 2 ).
  • the graphite interlayer compound 200 can be prepared Yes (S120).
  • the graphite 100 may be provided in the base solution.
  • the graphite interlayer compound 200 in which the anion 210 of the metal salt is inserted between the layers of the graphite 100 is prepared by stirring the base solution provided with the graphite 100, as shown in FIG. 2. Can be.
  • the base solution may be prepared by mixing the sodium azide and distilled water. After mixing the graphite (100) in the base solution, stirred and layers the azide Chemistry azide anion of sodium (N 3 -) in the graphite 100 is the above-graphite intercalation compound (200) inserted into a prepared Can be.
  • expanded graphite 300 may be formed by heat-treating the graphite interlayer compound 200 (S130).
  • the expanded graphite 300 may be prepared by thermally decomposing the anion 210 in the graphite interlayer compound 200. That is, the anion 210 provided between the layers of the graphite 100 is thermally decomposed, and gas may be formed. Accordingly, as illustrated in FIG. 3, the interlayer distance of the graphite 100 is increased.
  • the expanded graphite 300 may be manufactured, and the expanded graphite 300 may include residues or impurities 310 by thermal decomposition of the anion 210 between layers.
  • the expanded graphite 300 manufactured according to the above-described method may have a larger interlayer distance than the graphite interlayer compound 200. That is, as shown in FIG. 3, the expanded graphite 300 may have an interlayer distance indicated by l 2 , and as shown in FIG. 2, the graphite interlayer compound 200 is indicated by l 1 When having an interlayer distance, the interlayer distance l 2 of the expanded graphite 300 may have a larger value than the interlayer distance l 1 of the graphite interlayer compound 200.
  • the anion 210 is thermally decomposed and the gas generated may rapidly expand in volume.
  • the expansion force of the gas is directly applied between the layers of the graphite, the carbon-carbon bond may be broken, and accordingly, the expanded graphite 300 provided with voids or defects may be manufactured.
  • the amount of gas generated increases, and accordingly, the amount of defects provided to the expanded graphite 300 may increase.
  • the expanded graphite 300 may be manufactured by at least one method among acid treatment, plasma treatment, or microwave in addition to the heat treatment process.
  • the expanded graphite 300 is manufactured by plasma treatment of the graphite interlayer compound 200, as described above, as the plasma pressure increases, defects provided to the expanded graphite 300 The amount of can be increased.
  • the amount of defects provided to the expanded graphite 300 may be controlled.
  • the mixing ratio of the metal salt and the graphite is the same, but different metal salts may be mixed.
  • the amount of defects provided to the expanded graphite 300 may be determined.
  • an oxidizing gas may be generated by thermal decomposition of the anion 210. Accordingly, the expanded graphite 300 in which the amount of defects is increased by oxidation is formed by the oxidizing gas.
  • the metal salt may be at least one of sulfate, nitrate, or carbonate.
  • the anion 210 may not include the oxygen.
  • the gas may provide only an expansion force. Accordingly, the amount of defects provided in the expanded graphite 300 may be relatively small compared to the case where the anion 210 contains oxygen.
  • the metal salt may be an azide salt.
  • the type of the metal salt is the same, but the mixing ratio of the metal salt and the graphite 100 may be changed.
  • the mixing ratio of the metal salt to the graphite 100 increases, the amount of gas generated may increase, and accordingly, the amount of defects provided to the expanded graphite 300 may increase.
  • the expanded graphite 300 is dispersed to prepare a graphite nanoplate 400 (S140).
  • the graphite nanoplate 400 may be manufactured by providing and expanding the expanded graphite 300 in a solvent.
  • the solvent may be at least one of a fatty solvent, an aromatic solvent, a polar solvent, or a non-polar solvent.
  • the expanded graphite 300 may be dispersed by at least one of a stirrer, an ultrasonic disperser, a vibration mixer, a share mixer, a ball mill, an attraction mill, or a planetary mill.
  • the graphite nanoplate 400 may be manufactured by dispersing it using an ultrasonic disperser.
  • a composite coating solution may be prepared by mixing the graphite nanoplate 400 and a polymer (S150).
  • the polymer may be an organic polymer or an inorganic polymer.
  • the organic polymer may be at least one of an epoxy polymer, a cellulose polymer, a vinyl polymer, an acrylic polymer, a fluorine polymer, an amide polymer, an imide polymer, or an acetate polymer.
  • the inorganic polymer may be at least one of polysiloxane, polysilazane, or polysilicate.
  • the graphite nanoplate 400 may include defects, and the polymer may be selected according to the amount of defects in the graphite nanoplate 400.
  • the expanded graphite 300 may include the defect. Accordingly, by dispersing the expanded graphite 300, defects may be distributed in the manufactured graphite nanoplate 400.
  • the expanded graphite 300 may be oxidized by the oxidizing gas, and accordingly, the graphite nanoplate may further include an oxygen-based functional group.
  • the oxygen-based functional group may be at least one of a hydroxy group (hydroxyl) or a carboxyl group (carboxyl).
  • the amount of defects in the graphite nanoplate 400 increases, it may be mixed with the polymer 1120 that exhibits relatively polarity.
  • the polymer 1120 may be polysilazane represented by ⁇ Formula 1> below, and also, the The composite coating solution can be prepared using a non-polar solvent.
  • the non-polar solvent may be at least one selected from xylene, dibutyl ether, and the like.
  • the polymer 1120 may be polysiloxane represented by ⁇ Formula 2> below, and the composite coating solution may also be It can be prepared using a polar solvent.
  • the polar solvent may be at least one selected from isopropyl alcohol and the like.
  • the composite coating solution may include 10 to 50 parts by weight of the graphite nanoplate 400, compared to 100 parts by weight of the total of the graphite nanoplate 400 and the polymer 1120, and the polymer (1120) may be included as the remaining weight parts.
  • the composite coating solution contains less than 10 parts by weight of the graphite nanoplate 400, the electrical conductivity of the coating layer manufactured using the composite coating solution may be reduced.
  • the composite coating solution contains more than 50 parts by weight of the graphite nanoplate 400, adhesive strength of the composite coating solution may be reduced, and accordingly, it is easy to manufacture the coating layer using the composite coating solution. You may not.
  • the composite coating solution may include 10 to 50 parts by weight of the graphite nanoplate 400, and accordingly, the coating layer on the metal substrate using the composite coating solution This can be easily manufactured.
  • 5 to 6 are views for explaining a method of manufacturing a metal substrate structure according to an embodiment of the present invention.
  • the coating layer 1200 is a step of preparing a pre-coating layer 1100 by coating a composite coating solution on the metal substrate 1000, and curing the pre-coating layer 1100 Can be manufactured.
  • a method of coating the composite coating solution on the metal substrate 1000 may be selected according to the viscosity of the composite coating solution.
  • the viscosity of the composite coating solution may be relatively low.
  • the composite coating solution does not maintain the shape of droplets on the metal substrate 1000, and spreading may occur.
  • the composite coating solution is any one selected from spray coating, spin coating, etc. It can be coated with.
  • the viscosity of the composite coating solution may be relatively high.
  • the spray nozzle is clogged in the process of spraying the composite coating solution on the metal substrate 1000.
  • it may be aggregated on the metal substrate 1000.
  • the composite coating solution may be coated by any one method selected from a bar coating method, a doctor blade coating method, and the like.
  • a method of curing the pre-coating layer 1100 may be selected according to the viscosity of the composite coating solution, as described above.
  • the coating layer 1200 may be manufactured by any one process among heat treatments. Specifically, for example, the coating layer 1200 may be manufactured by photocuring the preliminary coating layer 1100. Alternatively, for example, the coating layer 1200 may be manufactured by heat-treating the pre-coating layer 1100 in a water vapor or ammonia gas atmosphere.
  • the coating layer 1200 may include the pre-coating layer 1100.
  • the coating layer 1200 may be formed in a shorter time than the photocuring method.
  • the coating layer 1200 may be manufactured by applying a pressure of 5 ton to the pre-coating layer 1100 and performing it at a temperature of 200 ° C. for 10 minutes.
  • the coating layer 1200 manufactured as described above may include an inorganic material formed by curing the polymer 1120 in the pre-coating layer 1100, and the graphite nanoplate 1110.
  • the inorganic material 1220 may be silicon oxide.
  • the inorganic material 1220 may not include the silicon-carbon bond indicated in ⁇ Formula 2>, and accordingly, the coating layer 1200 with improved heat resistance may be manufactured.
  • the corrosion resistance may be improved, and as the amount of the graphite nanoplate 1110 is increased, the electrical conductivity of the coating layer 1200 may be improved.
  • the metal substrate structure may have improved oxidation resistance and corrosion resistance than the metal substrate 1000.
  • the metal substrate structure may have electrical conductivity, and thus, corrosion of the metal substrate 1000 may be prevented, and at the same time, electrical conductivity characteristics of the metal substrate 1000 may be maintained. Accordingly, a coating method using a composite coating solution according to an embodiment of the present invention may be easily used in various industrial fields having oxidation resistance and corrosion resistance, but requiring electrical conductivity of the metal substrate 1000.
  • the alumina container After providing 2.5 g of the graphite interlayer compound powder to an alumina container, the alumina container was charged to a heat treatment equipment.
  • the heat treatment equipment was maintained at a temperature of 500 ° C. for 20 minutes to prepare expanded graphite from the graphite interlayer compound powder.
  • a dispersion solution was prepared by providing the expanded graphite to xylene.
  • the dispersion solution was dispersed with an ultrasonic disperser for 1 hour to prepare a graphite nanoplate.
  • FIG. 7 to 10 are views showing a scanning electron microscope (SEM) image of a graphite interlayer compound and expanded graphite in a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • SEM scanning electron microscope
  • FIG. 7 a surface image of a graphite interlayer compound prepared in a method of preparing a composite coating solution according to Experimental Examples 1-1 to 1-3 of the present invention was photographed.
  • the expanded graphite has a structure that changes depending on the type of the metal salt inserted between the layers of the graphite.
  • the expanded graphite prepared in the composite coating solution according to Experimental Example 1-1 shown in FIG. 8 and the expanded graphite prepared in the composite coating solution according to FIGS. 1-2 are made of different metal salts, and accordingly, different It was confirmed to have a structure.
  • the G peak is a peak observed in the graphite-based material
  • the D peak is a peak indicating a defect in the structure
  • the 2D peak is a peak related to thickness. Accordingly, for the measured G peak, D peak, and 2D peak, the values of the D peak compared to the G peak and the 2D peak compared to the G peak were prepared in ⁇ Table 2> below.
  • the expanded graphite prepared in the composite coating solution according to Experimental Examples 1-3 has the largest interlayer spacing.
  • the thickness of the expanded graphite prepared as described above may be thin, and accordingly, the value of the 2D peak / G peak of the expanded graphite prepared in the composite coating solution according to Experimental Examples 1-1 to Experimental Examples 1-3. It can be seen that these are substantially similar to each other.
  • FIG. 11 to 12 are views showing an atomic force microscope (AFM) image, particle size distribution, and particle thickness distribution of a graphite nanoplate in a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • AFM atomic force microscope
  • the graphite nanoplate has a size of 2um x 2um and a thickness of 6nm.
  • the graphite nanoplate has an average size of 2 to 3 um and a thickness of 10 to 20 nm.
  • FIG. 13 is a view showing a transmission electron microscope (TEM), a high resolution transmission electron microscope (HRTEM), and a fast Fourier transform (FFT) image of a graphite nanoplate in a method of manufacturing a composite coating solution according to an embodiment of the present invention.
  • TEM transmission electron microscope
  • HRTEM high resolution transmission electron microscope
  • FFT fast Fourier transform
  • the graphite nanoplate has a stacked structure of about 15 graphite monolayers of about 0.34 nm.
  • the graphite nanoplate has a (100) plane and a (006) plane.
  • FIG. 14 is a view showing an image photographed while irradiating light to a composite coating solution according to an embodiment of the present invention.
  • the composite coating solution is the graphite nanoplate and the polymer are relatively uniformly dispersed, and accordingly, when irradiating light to the composite coating solution, the light It was confirmed that the course was not visible.
  • the dispersion containing the graphite nanoplate alone without the polymer is relatively As a result, dispersibility may decrease, and accordingly, a tindle phenomenon in which the path of light irradiated to the dispersion is confirmed is observed.
  • the composite coating solution according to Experimental Example 1-3 was used, but the composite coating solution was prepared to include the polysilazane in the polysilazane or the polysiloxane.
  • the composite coating solution according to Experimental Example 1-3 was used, but the composite coating solution was prepared to include the polysiloxane in the polysilazane or the polysiloxane.
  • the composite coating solution was coated on the surface of a copper substrate or an aluminum substrate at a rate of 1 cm / s, and then dried at a temperature of 160 ° C. for 5 minutes to prepare a pre-coating layer.
  • a metal substrate structure according to Experimental Example 2-2 was prepared by hot pressing the pre-coated layer at a pressure of 5 tons and a temperature of 200 ° C. for 10 minutes.
  • SEM 15 is a view showing a scanning electron microscope (SEM) image of a coating layer of a metal substrate structure according to an embodiment of the present invention.
  • FIG. 16 to 17 are views showing an infrared (IR) spectrum of a coating layer of a metal substrate structure according to an embodiment of the present invention.
  • the coating layer prepared according to Comparative Example 2-2 prepared using the polysiloxane had the silicon-oxygen-silicon peak and the silicon-carbon peak.
  • the coating layer prepared according to Comparative Example 2-1 and Comparative Example 2-2 contains silicon oxide.
  • the coating layer prepared according to Comparative Example 2-2 further had a silicon-carbon bond compared to the coating layer according to Comparative Example 2-1.
  • the coating layer prepared according to Comparative Example 2-1 has a comparatively higher heat resistance than the coating layer prepared according to Comparative Example 2-2.
  • the coating layer prepared according to Experimental Example 2-1 further includes the graphite nanoplate, which is a graphite-based material that absorbs light, Accordingly, it was confirmed that the intensity of the peak of the infrared spectrum was reduced.
  • 18 to 19 are views showing resistance before and after heat treatment of the metal substrate structure according to the embodiment of the present invention.
  • the copper substrate which is a metal substrate structure according to Comparative Example 3 of the present invention, exhibits the color of copper before the heat treatment and the resistance value is measured to be 0.0 ⁇ .
  • Fig. 19 (a) it was confirmed that the surface of the copper substrate was oxidized after heat treatment to lose the color of copper, and the resistance value was also increased to 34.7 k ⁇ .
  • the metal substrate structure according to Experimental Example 2-1 of the present invention further comprises the coating layer comprising the silicon oxide and the graphite nanoplate on the surface of the copper substrate It was made to. Accordingly, it was confirmed that the electrical conductivity was reduced than the copper substrate shown in FIG. 18 (a), and the resistance value was increased to 92.8 ⁇ .
  • the metal substrate structure according to Experimental Example 2-1 of the present invention unlike the copper substrate shown in Figure 19 (a), does not oxidize, The resistance value was also confirmed to have a relatively low value of 0.8 ⁇ .
  • 20 to 21 are views showing a scanning electron microscope (SEM) image before and after heat treatment of a metal substrate structure according to an embodiment of the present invention.
  • SEM scanning electron microscope
  • the metal substrate structure according to Experimental Example 2-1 further comprising the coating layer on the copper substrate, regardless of before and after heat treatment, substantially It was confirmed to have the same surface.
  • FIG. 22 is a view showing an X-ray diffraction pattern (XRD) before and after heat treatment of a metal substrate structure according to an embodiment of the present invention.
  • XRD X-ray diffraction pattern
  • the metal substrate structure according to Comparative Example 3 was confirmed to exhibit a copper oxide peak unlike heat treatment after heat treatment.
  • the coating layer prevents oxidation of the copper substrate by heat treatment.
  • FIGS. 23 to 24 are diagrams showing sample images before and after brine treatment of a metal substrate structure according to Comparative Example 3 and Experimental Example 2-1 of the present invention, and scanning electron microscope (SEM) images.
  • the metal substrate structure according to Comparative Example 3 (FIG. 24 (a)) was confirmed that copper oxide is formed on the surface over time, after 72 hours of brine treatment It was confirmed that the size of the copper oxide was increased. On the other hand, it was confirmed that the metal substrate structure according to Experimental Example 2-1 (FIG. 24 (b)) had substantially no change in surface structure even after 72 hours of brine treatment. .
  • 25 to 26 are views showing a sample image after the saline treatment of the metal substrate structure according to Comparative Example 4 and Experimental Example 2-1 of the present invention, and a scanning electron microscope (SEM) image.
  • FIGS. 27 to 28 are views showing a sample image after sulfuric acid treatment and a scanning electron microscope (SEM) image of the metal substrate structure according to Comparative Example 4 and Experimental Example 2-1 of the present invention.
  • the coating layer prevents corrosion of the copper substrate and the aluminum substrate by brine treatment and sulfuric acid.
  • 29 to 30 are diagrams showing a polarization curve and an impedance of a metal substrate structure according to an embodiment of the present invention.
  • the metal substrate structure according to Experimental Example 2-1 increases the amount of current of the graphite nanoplate to 1 to 10 quills, increasing the current. It can be seen that the density value is reduced. Accordingly, it was confirmed that the metal substrate structure according to Experimental Example 2-1 had a corrosion rate about 40 times slower than that of the copper substrate.
  • the metal substrate structure according to Experimental Example 2-1 is increased in resistance by about 200 times compared to the copper substrate, and accordingly, the metal substrate structure according to Experimental Example 2-1 is the copper substrate. It can be seen that it has a corrosion efficiency of about 99% or more.
  • FIG. 31 is a view showing the electrical conductivity and adhesion test results according to the graphite nanoplate mass ratio of the metal substrate structure according to Experimental Example 2-2 of the present invention.
  • the metal substrate structure according to Experimental Example 2-2 was confirmed that the higher the mass ratio of the graphite nanoplate, the higher the electrical conductivity.
  • the graphite nanoplate is included in 50 parts by weight, it has the highest electrical conductivity, and when the graphite nanoplate exceeds 50 parts by weight, the value of electrical conductivity is reduced again.
  • the metal substrate structure should be able to provide electrical conductivity to the metal substrate in the metal substrate structure, and accordingly, it can be seen that the graphite nanoplate is included in 10 to 50 parts by weight.
  • Composite coating solution according to an embodiment of the present application, a metal substrate structure manufactured using the same, and a method of manufacturing the electrical conductivity, such as an electrically conductive material, a secondary battery material, a building material, a field for detecting destruction and deformation inside a building structure , It can be applied to various industrial fields that require oxidation resistance and corrosion resistance.

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  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
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Abstract

L'invention concerne un procédé de fabrication d'une solution de revêtement complexe pouvant comprendre les étapes consistant à : préparer une solution de base contenant un sel métallique ; préparer un composé d'intercalation de graphite en fournissant du graphite à la solution de base pour intercaler un anion du sel métallique entre des couches du graphite ; former un graphite expansible par traitement thermique du composé d'intercalation de graphite ; préparer une nanoplaque de graphite par dispersion du graphite expansible ; et préparer une solution de revêtement complexe par mélange de la nanoplaque de graphite et d'un polymère.
PCT/KR2019/013425 2018-10-12 2019-10-14 Solution de revêtement complexe, structure de substrat métallique fabriquée à l'aide de celle-ci, et son procédé de fabrication WO2020076138A1 (fr)

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KR102549351B1 (ko) * 2023-01-18 2023-06-30 웰텍 주식회사 탄소볼의 제조방법, 그 방법에 의한 탄소볼, 이를 이용한 탄소볼 융합 분체도료 및 이를 코팅한 강관 말뚝

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KR19990065389A (ko) * 1998-01-13 1999-08-05 최상원 팽창흑연 제조방법
KR20100015534A (ko) * 2007-03-13 2010-02-12 바스프 코포레이션 실란을 함유하는 막―형성 물질, 가교제 및 코팅 조성물, 코팅 조성물 제조 방법 및 코팅된 기판
KR20100072001A (ko) * 2007-08-28 2010-06-29 알코아 인코포레이티드 내식성 알루미늄 합금 기판 및 이의 제조 방법
KR20100117684A (ko) * 2008-02-28 2010-11-03 바스프 에스이 흑연 나노판 및 조성물
US20150239742A1 (en) * 2008-11-25 2015-08-27 The Board Of Trustees Of The University Of Alabama Exfoliation of graphite using ionic liquids

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WO2001005703A1 (fr) * 1999-07-14 2001-01-25 Toyo Tanso Co., Ltd. Feuille de graphite expanse thermoresistante et procede de production associe
JP5291275B2 (ja) * 2000-07-27 2013-09-18 有限会社コンタミネーション・コントロール・サービス コーティング膜が施された部材及びコーティング膜の製造方法

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KR19990065389A (ko) * 1998-01-13 1999-08-05 최상원 팽창흑연 제조방법
KR20100015534A (ko) * 2007-03-13 2010-02-12 바스프 코포레이션 실란을 함유하는 막―형성 물질, 가교제 및 코팅 조성물, 코팅 조성물 제조 방법 및 코팅된 기판
KR20100072001A (ko) * 2007-08-28 2010-06-29 알코아 인코포레이티드 내식성 알루미늄 합금 기판 및 이의 제조 방법
KR20100117684A (ko) * 2008-02-28 2010-11-03 바스프 에스이 흑연 나노판 및 조성물
US20150239742A1 (en) * 2008-11-25 2015-08-27 The Board Of Trustees Of The University Of Alabama Exfoliation of graphite using ionic liquids

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