CN115926522B - Polyaniline-carbon nitride composite, resin composite coating and preparation method thereof - Google Patents
Polyaniline-carbon nitride composite, resin composite coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyaniline-carbon nitride compound, a resin composite coating and a preparation method thereof, wherein the polyaniline-carbon nitride compound takes polyaniline as a coating layer, flaky carbon nitride is taken as a carrier, and the mass ratio of polyaniline to carbon nitride is 5-15:100; the resin composite coating is doped with polyaniline-carbon nitride compound, and the doping amount of the polyaniline-carbon nitride compound is 0.1-0.5% of the mass of the composite resin; the polyaniline modified carbon nitride effectively improves the weakness of original carbon nitride, improves the light absorption performance and improves the charge separation efficiency; the polyaniline-carbon nitride compound is introduced into the resin material, the synergistic effect of the polyaniline-carbon nitride compound not only improves the corrosion resistance of the original resin coating, but also endows the numerical composite coating with the anti-biofouling property, and the numerical composite coating has extremely high application value in the aspects of corrosion resistance and anti-biofouling.
Description
Technical Field
The invention relates to a polyaniline-carbon nitride compound, and also relates to a resin composite coating containing the polyaniline-carbon nitride compound and a preparation method thereof.
Background
Carbon steel is an important metal material widely used in various industries such as ship equipment and offshore infrastructure equipment, is easily attached by plankton, accelerates corrosion thereof to affect actual performance thereof, and causes a great deal of economic loss and safety problems. Epoxy resin (EP) coatings are widely used in corrosion resistance studies in marine environments due to their remarkable chemical inertness, electrical isolation and strong adhesion, but the defects caused by micropores and solvent evaporation during curing render the coatings ineffective in providing long-term protection.
The prior art introduces two-dimensional materials into the resin to improve the corrosion resistance of the coating, wherein polymeric Carbon Nitride (CN) is a candidate material for corrosion resistance due to its ease of manufacture, low cost, non-toxicity and outstanding stability. However, its rapid carrier recombination, poor specific surface area and weak visible light absorption range, exposing active sites, is susceptible to a reduction reaction, limiting the activity of carbon nitride and its application in corrosion protection in conjunction with resins.
Disclosure of Invention
The invention aims to: the invention aims at providing a polyaniline-carbon nitride composite capable of improving the corrosion resistance and biofouling resistance of a resin coating, and also aims at providing a resin composite coating containing the polyaniline-carbon nitride composite and a preparation method thereof.
The technical scheme is as follows: the polyaniline-carbon nitride compound is characterized in that polyaniline is used as a coating layer, flaky carbon nitride is used as a carrier, and the mass ratio of polyaniline to carbon nitride is 5-15:100.
Wherein, the polyaniline-carbon nitride composite-containing resin composite coating is doped with polyaniline-carbon nitride composite; the doping amount of the polyaniline-carbon nitride compound is 0.1 to 0.5 percent of the mass of the compound resin.
Preferably, the composite resin is a mixture of epoxy resin and polyamide resin, and the mass ratio of the epoxy resin to the polyamide resin is 1-4:2-5.
The preparation method of the resin composite coating comprises the following steps:
(1) Synthesizing carbon nitride by thermal polymerization reaction: calcining and thermally polycondensing urea to obtain platy carbon nitride;
(2) Preparation of polyaniline-carbon nitride composite: uniformly mixing the flaky carbon nitride prepared in the step (1) with polyaniline, and calcining to form a polyaniline-carbon nitride compound;
(3) Preparing polyaniline-carbon nitride-resin composite coating: dispersing the polyaniline-carbon nitride compound prepared in the step (2) in an organic solvent, carrying out ultrasonic treatment to obtain a uniform dispersion, mixing epoxy resin and polyamide resin, and stirring to obtain the polyaniline-carbon nitride-resin composite coating.
Preferably, in the step (1), the temperature rising rate of the calcination is 3-5 ℃/min, the heat preservation temperature is 500-550 ℃, and the heat preservation time is 1.5-3 h.
Preferably, in the step (2), the mass ratio of the polyaniline to the carbon nitride is 5-15%.
Preferably, in the step (2), the temperature rising rate of the calcination is 3-5 ℃/min, the heat preservation temperature is 270-300 ℃, and the heat preservation time is 1.5-2 h.
Preferably, in the step (3), the mass ratio of the polyaniline-carbon nitride composite to the organic solvent is 1:3-1:10.
Preferably, in the step (3), the ultrasonic time is 0.5-1 h; the stirring speed is 800-1200 r/min, and the stirring time is 0.5-2 h.
Preferably, the polyaniline-carbon nitride-resin composite coating is coated on the surface of a carbon steel matrix by using a spin coater to form a composite coating with the thickness of 50-150 mu m.
Preferably, the coating is specifically performed by first performing low-speed spin coating for 1-2 min at a rotating speed of 300-600 r/min, and then performing high-speed spin coating for 3-5 min at a rotating speed of 1200-1500 r/min.
The principle of the invention: the invention adopts the flaky carbon nitride as a carrier and the polyaniline as a coating layer, the polyaniline-carbon nitride compound obtained by low-temperature polymerization has excellent light absorption capacity as a black material, and the carbon nitride has a good lamellar structure, can be effectively dispersed in the coating, provides a good shielding effect, prolongs the path of corrosive ions reaching a metal matrix, and improves the corrosion resistance of the metal matrix. The photo-generated electrons and free radicals are provided by the polyaniline modified carbon nitride, so that the weaknesses of the original carbon nitride, such as weak light absorption capacity, easiness in recombination of photo-generated carriers and the like, are effectively improved, and the light absorption performance and the charge separation efficiency of the original carbon nitride can be effectively improved by compounding the polyaniline modified carbon nitride; meanwhile, polyaniline is rich in a large amount of positive nitrogen ions, and free radicals generated by carbon nitride can promote the combination of polyaniline and negative ions in the cell walls of algae to destroy the structures of the cell walls, further kill the algae cells and achieve the aim of resisting biofouling.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The resin composite coating containing polyaniline-carbon nitride composite has excellent corrosion resistance, and the EIS resistance radius of the coating formed by coating the resin composite coating on the surface of a carbon steel substrate is 1.62 multiplied by 10 10 Ω·cm 2 Corrosion current of 1.05X10 -10 A·cm -2 Compared with other coatings, the EIS impedance of the coating is improved by 2-3 orders of magnitude; after 60 days of corrosion immersion experiments, corrosion points do not appear on the surface of the coating, and the corrosion resistance is durable and stable;
(2) The resin composite coating provided by the invention has extremely strong anti-biofouling performance, and through 60 days of immersion experiments, only a small amount of algae attachments exist on the surface of the coating, and the attachment area is reduced by 95% compared with the similar coating in the prior art.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) of PANI@CN-10 and CN in examples and comparative examples; wherein FIG. a is a PANI@CN-10 Scanning Electron Microscope (SEM) of example 1 and FIG. b is a Scanning Electron Microscope (SEM) of comparative example CN;
FIG. 2 is an X-ray diffraction (XRD) pattern of examples and comparative examples PANI@CN-10 and PANI@CN-5, PANI@CN-10, CN;
FIG. 3 is a Fourier infrared transform spectrum (FT-IR) plot of examples and comparative examples PANI@CN-10 and PANI@CN-5, PANI@CN-10, CN;
FIG. 4 is an X-ray photoelectron spectroscopy (XPS) spectrum of the PANI@CN-10 and CN in examples and comparative examples;
FIG. 5 is a high resolution X-ray photoelectron spectroscopy (XPS) spectrum of the PANI@CN-10 and CN in examples and comparative examples;
FIG. 6 is a graph showing the photoelectrochemical properties of examples and comparative examples PANI@CN-10 and PANI@CN-5, PANI@CN-10, CN; wherein (a) is a solid ultraviolet (UV-vis) absorption spectrum, (b) is a fluorescence (PL) spectrum, (c) is a transient photocurrent response, (d) an impedance Nyquist (Nyquist) plot;
FIG. 7 is a spin-trapping ESR spectra of PANI@CN-10 and CN in examples and comparative examples; wherein (a) is a hydroxyl radical capture spectrum and (b) is a superoxide radical capture spectrum;
FIG. 8 is an EIS profile analysis of examples and comparative examples PANI@CN-10/EP and EP, CN/EP, PANI@CN-5/EP, PANI@CN-20/EP; wherein (a) is a Nyquist plot of the Nyquist plot after a 1 day immersion experiment, (b) is a Bode plot after a 1 day immersion experiment, (c) is a Bode plot after a 1 day immersion experiment, (d) is a Nyquist plot after a 60 day immersion experiment, (e) is a Bode plot after a 60 day immersion experiment, and (f) is a Bode plot after a 60 day immersion experiment;
FIG. 9 is a Scanning Electron Microscope (SEM) of the surface of the coating after 14 days of anti-algae test for the CN/EP and examples and comparative examples PANI@CN-10/EP; wherein (a, b, g, h) is an EP coating, (c, d, i, j) is a CN/EP coating, and (e, f, k, l) is a PANI@CN-10/EP coating.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
(1) Thermal polymerization to synthesize carbon nitride: 10g of urea was placed in a 50mL crucible, placed in a muffle furnace, and its temperature was heated from room temperature to 500℃at a heating rate of 3℃per minute, and then kept at constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as CN;
(2) Preparation of polyaniline-carbon nitride composite: 1g of CN and 100mg of polyaniline were uniformly mixed, placed in a crucible, and heated to 250℃from room temperature at a heating rate of 3℃per minute in a muffle furnace, and then kept at a constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as PANI@CN-10;
(3) Preparing polyaniline-carbon nitride-resin composite coating: taking 1g of epoxy resin and 0.6g of polyamide resin, and stirring uniformly at 800r/min by using a magnetic stirrer; 50mg of PANI@CN-10 and a drop of defoaming agent are added, and stirring is continued for half an hour to obtain a composite coating;
coating on the surface of carbon steel by a spin coater, drying at room temperature for 24h, and curing at 60 ℃ for 2h. The resulting coating sample was labeled PANI@CN-10/EP and had a thickness of 67. Mu.m.
Example 2
Compared with example 1, the polyaniline content was changed:
(1) Thermal polymerization to synthesize carbon nitride: 10g of urea was placed in a 50mL crucible, placed in a muffle furnace, and its temperature was heated from room temperature to 500℃at a heating rate of 3℃per minute, and then kept at constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as CN;
(2) Preparation of polyaniline-carbon nitride composite: 1g of CN and 50mg of polyaniline were uniformly mixed, placed in a crucible, and heated to 250℃from room temperature at a heating rate of 3℃per minute in a muffle furnace, and then kept at a constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as PANI@CN-5;
(3) Preparing polyaniline-carbon nitride-resin composite coating: taking 1g of epoxy resin and 0.6g of polyamide resin, and stirring uniformly at 800r/min by using a magnetic stirrer; 50mg of PANI@CN-5 and a drop of defoaming agent are added, and stirring is continued for half an hour to obtain a composite coating;
coating on the surface of carbon steel by a spin coater, drying at room temperature for 24h, and curing at 60 ℃ for 2h. The resulting coating sample was labeled PANI@CN-5/EP and had a thickness of 59. Mu.m.
Example 3
Compared with example 1, the polyaniline content was changed:
(1) Thermal polymerization to synthesize carbon nitride: 10g of urea was placed in a 50mL crucible, placed in a muffle furnace, and its temperature was heated from room temperature to 500℃at a heating rate of 3℃per minute, and then kept at constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as CN;
(2) Preparation of polyaniline-carbon nitride composite: 1g of CN and 150mg of polyaniline were uniformly mixed, placed in a crucible, and heated to 250℃from room temperature at a heating rate of 3℃per minute in a muffle furnace, and then kept at a constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as PANI@CN-15;
(3) Preparing polyaniline-carbon nitride-resin composite coating: taking 1g of epoxy resin and 0.6g of polyamide resin, and stirring uniformly at 800r/min by using a magnetic stirrer; 50mg of PANI@CN-15 and a drop of defoaming agent are added, and stirring is continued for half an hour to obtain a composite coating;
coating on the surface of carbon steel by a spin coater, drying at room temperature for 24h, and curing at 60 ℃ for 2h. The resulting coating sample was labeled PANI@CN-15/EP and had a thickness of 75. Mu.m.
Comparative example 1
Compared to example 1, pure phase EP was prepared:
taking 1g of epoxy resin and 0.6g of polyamide resin, and stirring uniformly at 800r/min by using a magnetic stirrer; adding a drop of defoaming agent, and continuously stirring for half an hour to obtain pure phase EP;
coating on the surface of carbon steel by a spin coater, drying at room temperature for 24h, and curing at 60 ℃ for 2h. The resulting coating sample was marked EP and had a thickness of 59. Mu.m.
Comparative example 2
Compared to example 1, a carbon nitride-resin coating was prepared:
(1) Thermal polymerization to synthesize carbon nitride: 10g of urea was placed in a 50mL crucible, placed in a muffle furnace, and its temperature was heated from room temperature to 500℃at a heating rate of 3℃per minute, and then kept at constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as CN;
(2) Preparation of carbon nitride-resin coating: taking 1g of epoxy resin and 0.6g of polyamide resin, and stirring uniformly at 800r/min by using a magnetic stirrer; adding 50mg of CN and a drop of defoaming agent, and continuously stirring for half an hour to obtain a composite coating;
coating on the surface of carbon steel by a spin coater, drying at room temperature for 24h, and curing at 60 ℃ for 2h. The resulting coating sample was labeled CN/EP and had a thickness of 65. Mu.m.
Comparative example 3
Compared with example 1, the polyaniline content was changed:
(1) Thermal polymerization to synthesize carbon nitride: 10g of urea was placed in a 50mL crucible, placed in a muffle furnace, and its temperature was heated from room temperature to 500℃at a heating rate of 3℃per minute, and then kept at constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as CN;
(2) Preparation of polyaniline-carbon nitride composite: 1g of CN and 200mg of polyaniline were uniformly mixed, placed in a crucible, and heated to 250℃from room temperature at a heating rate of 3℃per minute in a muffle furnace, and then kept at a constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as PANI@CN-20;
(3) Preparing polyaniline-carbon nitride-resin composite coating: taking 1g of epoxy resin and 0.6g of polyamide resin, and stirring uniformly at 800r/min by using a magnetic stirrer; 50mg of PANI@CN-20 and a drop of defoaming agent are added, and stirring is continued for half an hour to obtain a composite coating; coating on the surface of carbon steel by a spin coater, drying at room temperature for 24h, and curing at 60 ℃ for 2h. The resulting coating sample was labeled PANI@CN-20/EP and had a thickness of 59. Mu.m.
Comparative example 4
Compared with example 1, the polyaniline content was changed: (1) thermally polymerizing and synthesizing carbon nitride: 10g of urea was placed in a 50mL crucible, placed in a muffle furnace, and its temperature was heated from room temperature to 500℃at a heating rate of 3℃per minute, and then kept at constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as CN;
(2) Preparation of polyaniline-carbon nitride composite: 1g of CN and 30mg of polyaniline were uniformly mixed, placed in a crucible, and heated to 250℃from room temperature at a heating rate of 3℃per minute in a muffle furnace, and then kept at a constant temperature for 2 hours. Grinding the obtained sample in an agate mortar, and collecting the sample for later use, wherein the sample is marked as PANI@CN-3;
(3) Preparing polyaniline-carbon nitride-resin composite coating: taking 1g of epoxy resin and 0.6g of polyamide resin, and stirring uniformly at 800r/min by using a magnetic stirrer; 50mg of PANI@CN-3 and a drop of defoaming agent are added, and stirring is continued for half an hour to obtain a composite coating;
coating on the surface of carbon steel by a spin coater, drying at room temperature for 24h, and curing at 60 ℃ for 2h. The resulting coating sample was labeled PANI@CN-3/EP and had a thickness of 58. Mu.m.
As shown in fig. 1, scanning Electron Microscope (SEM) characterization was performed for example 1 and comparative example 2. It can be seen from a Scanning Electron Microscope (SEM) that both are sheet-like structures, which will help to provide a shielding effect in the coating, enhancing corrosion resistance. When the mass ratio of polyaniline to carbon nitride is 5-15%, the lamellar structure of CN will not be destroyed.
As shown in fig. 2-4, material related characterization of polyaniline/carbon nitride composites was performed for examples and comparative examples. Indicating that the polyaniline carbon nitride is successfully compounded through low-temperature thermal polymerization.
As shown in fig. 5, for the N1s spectra of the high-resolution X-ray photoelectron spectroscopy (XPS) in example 1 and comparative example 2, it was shown that PANI's nitrogen cation free radicals exist on the surface of pani@cn-10, which helps to bind to the negative charges of the algae cell wall, and the synergy of carbon nitride and polyaniline helps to improve the anti-algae performance of the coating.
As shown in fig. 6-7, the composite materials of example 1 were characterized by the photoelectric properties, and the composite materials of example 1 were found to have good photoelectrochemical properties and excellent photo-generated carrier separation efficiency, which would help to improve the corrosion resistance and biofouling resistance of the coating.
As shown in fig. 8, the low frequency impedance modulus of example 1 is two orders of magnitude higher than that of comparative example 1, and y is one order of magnitude higher than that of comparative example 2, and has excellent corrosion resistance. Example 1 maintains the highest impedance modulus after 60 days of immersion experiments, demonstrating excellent corrosion resistance stability. FIG. 9 shows the anti-biofouling properties of example 1 and comparative examples 1 and 2, where the surfaces of the examples have only a small amount of bioadhesion, exhibiting relatively excellent anti-biofouling properties. When the polyaniline content is too small, N in the coating layer + The ion content is too low to achieve the ideal anti-biofouling effect; excessive polyaniline content can cause agglomeration of the added filler, damage the lamellar structure of the carbon nitride and weaken the barrier effect of the carbon nitride in the coating.
Claims (5)
1. The resin composite coating is characterized in that the resin composite coating is doped with polyaniline-carbon nitride composite, the doping amount of the polyaniline-carbon nitride composite is 0.1-0.5% of the mass of composite resin, the polyaniline-carbon nitride composite takes polyaniline as a coating layer, flaky carbon nitride as a carrier, the mass ratio of polyaniline to carbon nitride is 5-15:100, and the preparation method of the resin composite coating is as follows:
(1) Calcining and thermally polycondensing urea to obtain platy carbon nitride, wherein the temperature rising rate of the calcining is 3-5 ℃/min, the heat preservation temperature is 500-550 ℃, and the heat preservation time is 1.5-3 h;
(2) Uniformly mixing flaky carbon nitride and polyaniline, and calcining to form a polyaniline-carbon nitride compound, wherein the calcining has the temperature rising rate of 3-5 ℃/min, the heat preservation temperature of 270-300 ℃ and the heat preservation time of 1.5-2 h;
(3) Dispersing polyaniline-carbon nitride composite in organic solvent, ultrasonic treating to obtain homogeneous dispersion, mixing epoxy resin and polyamide resin, and stirring to obtain polyaniline-carbon nitride-resin composite paint.
2. The composite coating according to claim 1, wherein the composite resin is a mixture of epoxy resin and polyamide resin, and the mass ratio of the polyamide resin to the epoxy resin is 1-4:2-5.
3. The composite coating according to claim 1, wherein in the step (3), the mass ratio of the polyaniline-carbon nitride composite to the organic solvent is 1:3 to 1:10.
4. The composite coating according to claim 1, wherein in step (3), the ultrasonic time is 0.5 to 1h.
5. The composite coating according to claim 1, wherein in the step (3), the stirring speed is 800-1200 r/min, and the stirring time is 0.5-2 h.
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| CN110517898A (en) * | 2019-08-14 | 2019-11-29 | 上海应用技术大学 | The preparation method of the graphene@CoAl-LDH combination electrode material of polyaniline-coated |
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| Polyaniline/g-C3N4 composites as novel media for anticorrosion coatings;Zuo SX, et al.;Journal of Coatings Technology and Research;第14卷(第6期);第1307-1314页 * |
| Zuo SX, et al..Polyaniline/g-C3N4 composites as novel media for anticorrosion coatings.Journal of Coatings Technology and Research.2017,第14卷(第6期),第1307-1314页. * |
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