CN108485496B - Application of self-detection anticorrosive paint containing nano-carrier on metal surface - Google Patents
Application of self-detection anticorrosive paint containing nano-carrier on metal surface Download PDFInfo
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- CN108485496B CN108485496B CN201810256033.0A CN201810256033A CN108485496B CN 108485496 B CN108485496 B CN 108485496B CN 201810256033 A CN201810256033 A CN 201810256033A CN 108485496 B CN108485496 B CN 108485496B
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- 239000003973 paint Substances 0.000 title claims abstract description 39
- 238000001514 detection method Methods 0.000 title claims abstract description 36
- 239000002539 nanocarrier Substances 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920002635 polyurethane Polymers 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 4
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 4
- PRZSXZWFJHEZBJ-UHFFFAOYSA-N thymol blue Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C PRZSXZWFJHEZBJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 3
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003822 epoxy resin Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000012802 nanoclay Substances 0.000 claims abstract description 3
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000007611 bar coating method Methods 0.000 claims description 4
- XSFVQEHUVOVFOW-UHFFFAOYSA-N 1,10-phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 XSFVQEHUVOVFOW-UHFFFAOYSA-N 0.000 claims description 2
- OHUPAKOLMUQMMX-UHFFFAOYSA-N NC1=C2C(=C(C=3C(=C(C(=NC3C2=NC=C1)N)N)N)N)N.N1=CC=CC2=CC=C3C=CC=NC3=C12 Chemical compound NC1=C2C(=C(C=3C(=C(C(=NC3C2=NC=C1)N)N)N)N)N.N1=CC=CC2=CC=C3C=CC=NC3=C12 OHUPAKOLMUQMMX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002120 nanofilm Substances 0.000 claims 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011259 mixed solution Substances 0.000 description 18
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229920005749 polyurethane resin Polymers 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3437—Six-membered rings condensed with carbocyclic rings
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
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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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- 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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- 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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Abstract
The application of a self-detection anticorrosive paint containing nano-carriers on a metal surface comprises the following steps: the self-detection chromogenic substance comprises thymol blue, fluorescein, hydroxyquinoline, 1,10-Phenanthroline (1, 10-phenonthroline), 1,10-Phenanthroline penta-amino (1, 10-phenonthroline-5-amine) and phenolphthalein or a mixture thereof, the nano-carrier is any one or a mixture of graphene, nano boron nitride, nano clay and a layered double hydroxide sheet layer, the mass percent of the nano-carrier is 0.4-4%, the film-forming substrate is aqueous organic resin, the aqueous organic resin is any one or a mixture of aqueous polyurethane, aqueous acrylic resin and aqueous epoxy resin, and the mass percent of the aqueous organic resin is more than or equal to 94%.
Description
Technical Field
The invention relates to an anticorrosive paint and a preparation method thereof, belonging to the field of chemical industry.
Background
Organic coatings are currently the most common method of corrosion protection of metal surfaces in production. However, after a long period of use, the organic coating on the metal surface is corroded to protect the substrate, so that peeling occurs between the substrate and the coating, and the protection function of the organic coating is further disabled. When macroscopic corrosion products are generated in the corrosion process of the metal surface, the corrosion degree is very serious, so if a coating which can carry out self detection and can warn in the early stage of corrosion is provided, the coating can greatly improve the corrosion prevention effect of the metal when applied to the corrosion prevention of the metal surface.
Disclosure of Invention
The present invention is made to solve the above problems, and an object of the present invention is to provide an application of a self-detecting anticorrosive coating containing a nano-carrier on a metal surface.
The invention provides an application of a self-detection anticorrosive paint containing a nano carrier on a metal surface, which is characterized in that: wherein, the self-detection anticorrosive paint containing the nano-carrier comprises: the self-detection chromogenic substance comprises thymol blue, fluorescein, hydroxyquinoline, 1,10-Phenanthroline (1, 10-phenonthroline), 1,10-Phenanthroline pentaamino (1, 10-phenonthroline-5-amine) and phenolphthalein or a mixture thereof, the nano-carrier is any one or a mixture of graphene, nano boron nitride, nano clay and a layered double hydroxide sheet layer, the mass percent of the nano-carrier is 0.4-4%, the film-forming substrate is aqueous organic resin, the aqueous organic resin is any one or a mixture of aqueous polyurethane, aqueous acrylic resin and aqueous epoxy resin, and the mass percent of the aqueous organic resin is more than or equal to 94%.
In addition, the application of the self-detection anticorrosive paint containing the nano-carrier on the metal surface provided by the invention can also have the characteristics that the self-detection anticorrosive paint comprises the following steps: s1, adding deionized water into the self-detection anticorrosive paint containing the nano-carrier, and adjusting the mass percent of the total solid matters of the paint to 10-30%; s2, coating the self-detection anticorrosive paint containing the nano-carrier after adding the deionized water into the S1 on the surface of the metal plate to form a film; s3, drying the metal plate coated with the self-detection anticorrosive paint containing the nano-carrier on the surface in the step S2 at the temperature of 100-120 ℃, taking out the metal plate after the drying time is 20-40 minutes, and obtaining a coating formed on the surface of the metal plate.
In addition, in the application of the self-detection anticorrosive paint containing the nano-carrier provided by the invention on the metal surface, the self-detection anticorrosive paint can also have the following characteristics: wherein the mass percentage of the self-detection chromogenic substance is 0.2-2%.
Action and Effect of the invention
According to the application of the self-detection anticorrosive coating containing the nano-carrier on the metal surface, the coating is used for coating on the surface of a steel plate to prevent the corrosion of the steel plate, the coating has the self-detection chromogenic substance, the nano-carrier and a film forming matrix, the nano loading technology is adopted to prepare the intelligent coating which is used as the carrier of the self-detection chromogenic substance and has the functions of loading and timely releasing the developer, so that the macroscopic color change occurs in the early stage of the corrosion reaction of the steel plate to play the roles of automatic detection and early warning, and in addition, the coating also has excellent anticorrosive performance and belongs to an environment-friendly coating.
Drawings
FIG. 1 is a photograph showing the self-color development function of the coating layer upon corrosion of the surface of the iron plate in the first embodiment of the present invention;
FIG. 2 is a photograph of the coating after an extended etching time according to the first embodiment of the present invention;
FIG. 3 shows examples I, II, and III of the present invention without Fe2+A photograph of the color of the coating before ionization; and
FIG. 4 shows examples of the present invention in which Fe is added2+Photograph of the color of the coating after ionization.
Detailed Description
In order to make the technical means, creation features, achievement objects and effects of the present invention easy to understand, the following embodiments will specifically describe the application of the self-detecting anticorrosive coating containing nano-carrier on the metal surface with reference to the accompanying drawings.
< example one >
The preparation method and application of the self-detection anticorrosive paint containing the nano-carrier comprise the following steps:
step one, preparing graphene oxide by using an improved Hummer's method, and preparing a graphene oxide aqueous solution with the concentration of 2 mg/ml.
Step two, mixing the graphene oxide aqueous solution and 1,10 phenanthroline according to a mass ratio of 2: 1 to obtain a first mixed solution.
And step three, performing ultrasonic dispersion on the first mixed solution in an ultrasonic instrument with the ultrasonic power of 300W for 10 minutes to obtain a second mixed solution.
And step four, removing unreacted solution in the second mixed solution by suction filtration to obtain solid substances, and adding water to the solid substances to prepare a third mixed solution of 2 mg/ml.
And step five, mixing the third mixed solution with the waterborne polyurethane resin to obtain the anticorrosive paint, wherein the resin mass percent of the total solid matters of the paint is 99.4%, the graphene oxide mass percent is 0.4%, and the 1,10 phenanthroline mass percent is 0.2%.
Step six, adding deionized water into the anticorrosive paint to adjust the mass percent of the total solid matters of the paint to 20%.
And step seven, coating the coating added with the deionized water in the step six on the surface of the iron plate by using a bar coating method to form a film, putting the film into an oven, drying the film at the temperature of 110 ℃, and taking out the film after 30 minutes to obtain the coating formed on the surface of the iron plate.
< example two >
The preparation method and application of the self-detection anticorrosive paint containing the nano-carrier comprise the following steps:
step one, preparing graphene oxide by using an improved Hummer's method, and preparing a graphene oxide aqueous solution with the concentration of 2 mg/ml.
Step two, mixing the graphene oxide aqueous solution and 1,10 phenanthroline pentaamino according to a mass ratio of 2: 1 to obtain a first mixed solution.
And step three, performing ultrasonic dispersion on the first mixed solution in an ultrasonic instrument with the ultrasonic power of 300W for 10 minutes to obtain a second mixed solution.
And step four, removing unreacted solution in the second mixed solution by suction filtration to obtain solid substances, and adding water to the solid substances to prepare a third mixed solution of 2 mg/ml.
And step five, mixing the third mixed solution with the waterborne polyurethane resin to obtain the anticorrosive paint, wherein the resin mass percent in the total solid matters of the paint is 94%, the graphene oxide mass percent is 4%, and the phenanthroline pentaamino mass percent is 1, 10% is 2%.
Step six, adding deionized water into the anticorrosive paint to adjust the mass percent of the total solid matters of the paint to 20%.
And step seven, coating the paint added with the deionized water in the step six on the surface of an iron plate by using a bar coating method to form a film, then putting the film into an oven, drying the film at the temperature of 110 ℃, and taking the film out after 30 minutes to obtain the coating formed on the surface of the iron plate.
< example three >
The preparation method and application of the self-detection anticorrosive paint containing the nano-carrier comprise the following steps:
step one, preparing graphene oxide by using an improved Hummer's method, preparing a graphene oxide aqueous solution with the concentration of 2mg/ml, and adding hydrazine hydrate which is not more than 0.3 times of the mass of the graphene to obtain the graphene aqueous solution after the graphene oxide is partially reduced.
Step two, mixing the partially reduced graphene aqueous solution and 1,10 phenanthroline according to a mass ratio of 2: 1 to obtain a first mixed solution.
And step three, performing ultrasonic dispersion on the first mixed solution in an ultrasonic instrument with the ultrasonic power of 300W for 10 minutes to obtain a second mixed solution.
And step four, removing unreacted solution in the second mixed solution by suction filtration to obtain solid substances, and adding water to the solid substances to prepare a third mixed solution of 2 mg/ml.
And step five, mixing the third mixed solution with the waterborne polyurethane resin to obtain the anticorrosive paint, wherein the resin mass percent of the total solid matters of the paint is 97%, the graphene oxide mass percent is 2%, and the phenanthroline mass percent is 1, 10%.
Step six, adding deionized water into the anticorrosive paint to adjust the mass percent of the total solid matters of the paint to 20%.
And step seven, coating the paint added with the deionized water in the step six on the surface of an iron plate by using a bar coating method to form a film, then putting the film into an oven, drying the film at the temperature of 110 ℃, and taking the film out after 30 minutes to obtain the coating formed on the surface of the iron plate.
The chemical properties of the composite aqueous solutions formed by the graphene with different reduction degrees and the self-detection coloring substances prepared according to the first to third embodiments are very stable, and no obvious delamination phenomenon is observed after the composite aqueous solutions are placed for 48 hours. Meanwhile, the chemical property of the prepared coating loaded with graphene formed by self-detection color development and mixed with waterborne polyurethane is very stable, and no obvious layering phenomenon is observed after the coating is placed for 48 hours.
FIG. 1 is a photograph showing the self-color-developing function of the coating layer upon corrosion of the surface of the iron plate in the first embodiment of the present invention.
As shown in FIG. 1, it can be seen that the iron plate has good transparency after being bar-coated at room temperature, and the color change visible to the naked eye is generated at the initial stage of corrosion of the iron plate, and the color reaction of the paint is sensitive.
FIG. 2 is a photograph of the coating after an extended etching time according to the first embodiment of the present invention.
As shown in fig. 2, the iron plate in the figure is the iron plate after the rod is coated with the paint in example one and then soaked in the 3.5% NaCl aqueous solution for 1 day, and it can be seen that the iron plate has obvious discoloration phenomenon on the coating layer, which indicates that the base metal has large-area corrosion, and the paint prepared in example one has the self-detection and coloration function.
FIG. 3 shows examples I, II, and III of the present invention without Fe2+Photograph of the color of the coating before ionization.
As shown in FIG. 3, the drawing of FIG. 3The first embodiment, the second embodiment and the third embodiment are sequentially without adding Fe from left to right2+The coating containing the self-detection chromogenic substance before ionization can be seen to be very stable, and the intelligent coating containing the self-detection chromogenic substance loaded by the nano carrier is also shown to not change the stability of the coating.
FIG. 4 shows examples of the present invention in which Fe is added2+Photograph of the color of the coating after ionization.
As shown in FIG. 4, Fe is added to the first embodiment, the second embodiment and the third embodiment sequentially from left to right in the drawing of FIG. 42+The ionized coating containing the self-detecting chromogenic substance produces obvious color change. The intelligent coating containing the self-detection chromogenic substance prepared by the nano loading technology effectively solves the problems of loading, dispersion, release and the like of the chromogenic agent in the coating, simultaneously retains the characteristics of the chromogenic agent, and can be used for preparing the coating with the self-detection chromogenic function and good corrosion resistance and a coating thereof.
Effects and effects of the embodiments
In a preferred embodiment of the present invention, since the nano-support of the coating is selected from graphene, the graphene may be selected from graphene oxide, partially reduced graphene oxide, and chemically surface-modified graphene. In a more preferred embodiment, the graphene is graphene oxide, which may be in the form of a graphene oxide solution prepared by a modified Hummer's method, for example. The functional group on the surface of the graphene is regulated and controlled by partially reducing or chemically modifying the surface of the graphene, so that the load function of the nano carrier on the self-detection chromogenic molecule is controlled. In a preferred embodiment of the present invention, the partially reduced graphene oxide may be prepared by using a reducing agent. The reducing agent may be selected from hydrazine and its derivatives, vitamin C and glucose. In the case where the graphene is in the form of a graphene oxide solution prepared by the modified Hummer's method, the reducing agent is preferably hydrazine hydrate in a trace amount (less than the mass of the graphene oxide). The graphene and the derivatives thereof have good physical barrier property and ultra-large specific surface area. On one hand, the coating can be used as a barrier in the coating to enhance the corrosion resistance of the coating; on the other hand, the carrier can be used as a carrier for self-detection of the color developing molecules, and has the functions of loading and timely releasing the color developing agent.
In addition, in a preferred embodiment of the present invention, since the self-detecting color developing molecule of the coating material may be one selected from 1,10 Phenanthroline (1,10-Phenanthroline), 1,10 Phenanthroline pentaamino (1,10-Phenanthroline-5-amine) phenolphthalein, thymol blue, fluorescein and hydroxyquinoline. In a more preferred embodiment, the self-detecting chromogenic molecule can employ 1,10 phenanthroline, which provides self-detecting color by providing 1,10 phenanthroline.
Further, in the preferred embodiment of the present invention, since the solid content of the coating material is controlled to be about 20%, the optimum film forming property and the flatness of the coating surface are obtained.
Furthermore, the coating of the present invention, after being applied on a metal surface, usually needs to be dried to form a corresponding coating, preferably at 100 ℃ to 120 ℃ for 20 to 40 minutes, and such drying conditions can ensure the stability of the obtained coating and optimize the self-repairability thereof.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (1)
1. The application of the self-detection anticorrosive paint containing the nano-carrier on the metal surface is characterized by comprising the following steps:
s1, adding deionized water into the self-detection anticorrosive paint containing the nano-carrier to adjust the mass percent of the total solid matters of the paint to 20%,
s2, coating the paint added with the deionized water in the S1 on the surface of an iron plate by using a bar coating method to form a film, putting the iron plate into an oven, drying the iron plate at the temperature of 110 ℃, taking the iron plate out after 30 minutes to obtain a coating formed on the surface of the iron plate,
wherein, the self-detection anticorrosive paint containing the nano-carrier comprises: self-detecting chromogenic substance, nano-carrier and film-forming substrate,
the self-detection chromogenic substance is any one or a mixture of thymol blue, fluorescein, hydroxyquinoline, 1,10-Phenanthroline (1,10-Phenanthroline), 1,10-Phenanthroline penta-amino (1,10-Phenanthroline-5-amine) and phenolphthalein,
the nano-carrier is any one or a mixture of graphene, nano-boron nitride, nano-clay and layered double hydroxide sheets,
the mass percentage of the nano-carrier is 0.4-4%,
the film-forming substrate is an aqueous organic resin,
the waterborne organic resin is any one or a mixture of waterborne polyurethane, waterborne acrylic resin and waterborne epoxy resin,
the mass percentage of the water-based organic resin is more than or equal to 94 percent.
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| CN201810256033.0A CN108485496B (en) | 2016-07-19 | 2016-07-19 | Application of self-detection anticorrosive paint containing nano-carrier on metal surface |
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| CN201810256033.0A CN108485496B (en) | 2016-07-19 | 2016-07-19 | Application of self-detection anticorrosive paint containing nano-carrier on metal surface |
| CN201610566796.6A CN106189771B (en) | 2016-07-19 | 2016-07-19 | A kind of self-test anticorrosive paint containing nano-carrier and its preparation method and application |
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| CN201810256033.0A Expired - Fee Related CN108485496B (en) | 2016-07-19 | 2016-07-19 | Application of self-detection anticorrosive paint containing nano-carrier on metal surface |
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| CN106189771B (en) * | 2016-07-19 | 2018-06-19 | 上海理工大学 | A kind of self-test anticorrosive paint containing nano-carrier and its preparation method and application |
| CN106634422B (en) * | 2016-12-14 | 2019-01-08 | 中国科学院过程工程研究所 | A kind of polymeric coating material and preparation method thereof for detecting metal erosion |
| CN108300141A (en) * | 2017-07-04 | 2018-07-20 | 河北晨阳工贸集团有限公司 | Sealing wax and its preparation method and application |
| CN107446464B (en) * | 2017-07-20 | 2019-07-19 | 中国科学院过程工程研究所 | Polymeric coating material and preparation method with Corrosion monitoring and self-repair function |
| CN110183569B (en) * | 2019-05-30 | 2020-12-29 | 江南大学 | Metal corrosion early warning polymer coating material and preparation method thereof |
| US11236195B2 (en) * | 2020-02-24 | 2022-02-01 | Saudi Arabian Oil Company | Corrosion-indicating materials and methods of making and using the same |
| CN112403409A (en) * | 2020-10-06 | 2021-02-26 | 青岛羚智涂料科技有限责任公司 | Self-detection capsule for water-based anticorrosive paint and preparation method thereof |
| CN112175498A (en) * | 2020-10-06 | 2021-01-05 | 青岛羚智涂料科技有限责任公司 | Self-detection water-based self-repairing anticorrosive coating and preparation method thereof |
| CN114574977A (en) * | 2022-02-24 | 2022-06-03 | 中国海洋大学 | Self-early-warning coaxial electrostatic spinning fiber and preparation method and application thereof |
| CN116004093B (en) * | 2022-12-26 | 2023-10-03 | 中国科学院福建物质结构研究所 | Anticorrosive coating and preparation method thereof |
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| CN105111836A (en) * | 2015-08-13 | 2015-12-02 | 蚌埠市时代电子有限公司 | Anti-corrosion heat-dissipation paint and preparation method therefor |
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| CN108485495B (en) | 2020-02-18 |
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| CN106189771B (en) | 2018-06-19 |
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