CN114958147A - Nano hybrid material coating material and synthetic method and application thereof - Google Patents
Nano hybrid material coating material and synthetic method and application thereof Download PDFInfo
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- CN114958147A CN114958147A CN202111339118.3A CN202111339118A CN114958147A CN 114958147 A CN114958147 A CN 114958147A CN 202111339118 A CN202111339118 A CN 202111339118A CN 114958147 A CN114958147 A CN 114958147A
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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Images
Classifications
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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
- 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
- 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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the technical field of preparation of nano coatings, in particular to silane modified graphene quantum dots/TiO 2 Preparation of nanotube hybrid material doped epoxy resin coating material and application thereof in the field of marine corrosion protection. The coating material takes silane modified nano hybrid material as a reinforcing phase and takes epoxy resin coating as a matrix phase: and (3) uniformly dispersing the silane modified nano hybrid material in the epoxy resin coating to obtain the nano hybrid material coating material. The silane modified nano hybrid material coating provided by the invention has the advantages of simple synthesis method, low cost and higher practical value in the field of long-acting anticorrosion nano coatings.
Description
Technical Field
The invention relates to the technical field of preparation of nano coatings, in particular to silane modified graphene quantum dots/TiO 2 Preparation of nanotube hybrid material doped epoxy resin coating material and application of nanotube hybrid material doped epoxy resin coating material in marine corrosion protection collarApplication of the domain.
Background
Organic coatings are widely used for corrosion protection of steel surfaces in marine environments due to their low cost, expandability, and versatility. Although the organic coating can directly block the diffusion of corrosive media, the organic coating also has the defects of generating holes and defects in the degradation and curing processes, and the service life of the organic coating is shortened. Therefore, the development of organic coatings for corrosion protection of steel structures has received a great deal of attention.
The nano material can be used as a nano filler of a polymer matrix, and the barrier property of the coating is improved by filling pores, microcracks and defects of the organic coating matrix, so that the defects of the organic coating are overcome. Among various inorganic nanomaterials that improve the corrosion resistance of organic coatings, TiO 2 Nanotubes are good candidates for their inherent properties of inertness, chemical resistance, photostability, uv shielding and precursor availability. Studies have shown that when dispersed in a polymer matrix, the mechanical properties of the coating (abrasion, hardness, frictional resistance) are enhanced and the water permeability in the coating is reduced. In addition, after the TNT nano filler is added, the barrier property of the polymer coating is enhanced, the crosslinking density is increased, and the corrosion resistance of the polymer coating is obviously improved.
GQDs are nanoscale fragments of one or more layers of graphene, consisting of an sp with heteroatom functional groups at the edge 2 Carbon atom composition, a new class of zero-dimensional graphene-based materials, with dimensions below 100nm (mainly between 3-20 nm) is currently receiving increasing attention due to its unique physicochemical properties. GQD presents hydroxyl, epoxy, and carbonyl groups, and exhibits similar properties to graphene oxide; the GQD is hydrophilic and has stronger solubility, and the existence of a surface group p-p conjugated network provides bonding capability for the GQD. The surface area is small, the cytotoxicity is low, the biocompatibility is good, the strength is large, and quantum confinement and edge effects are achieved. Therefore, it is an excellent candidate for the construction of nanomaterials.
Therefore, the invention of the long-acting anticorrosion nano hybrid coating for steel structure anticorrosion is urgently needed, and the hybrid material has high dispersibility and is tightly combined with the coating.
Disclosure of Invention
The invention aims to provide silane modified graphene quantum dot/TiO 2 Preparation of a nanotube hybrid material doped epoxy resin coating and application thereof in the field of marine corrosion protection.
In order to achieve the purpose, the invention adopts the technical scheme that:
a nanometer hybrid material coating material takes silane modified nanometer hybrid material as a reinforcing phase and takes epoxy resin paint as a matrix phase: and (3) uniformly dispersing the silane modified nano hybrid material in the epoxy resin coating to obtain the nano hybrid material coating material.
The reinforcing phase contains a silane coupling agent and a nano hybrid material, wherein the silane coupling agent and the nano hybrid material are mixed according to the mass ratio of 1: mixing at a ratio of 8-10; the mass ratio of the nano hybrid material is 1: 0.5-2 of Graphene Quantum Dots (GQD) and titanium dioxide nanotubes (TNT).
The content of the reinforced phase in the matrix phase is 0.1-1.0 wt%.
A preparation method of a nano hybrid material coating material comprises the step of uniformly dispersing silane modified nano hybrid materials in epoxy resin coating to obtain the nano hybrid material coating material.
The dispersing means may be selected from: stirring, ultrasonication, disruption with a cell disruptor, and the like.
Adding the reinforced phase into the matrix phase to ensure that the content of the reinforced phase in the matrix phase is 0.1-1.0 wt%; wherein the matrix phase is epoxy resin, a curing agent and a diluent according to the mass ratio of 5: 1: 2 and mixing.
The epoxy resin is a solvent type epoxy resin (for example, bisphenol a type epoxy resins such as E44 and E51); the curing agent is an amine matched curing agent (such as amine curing agents including ethylenediamine, diethylenetriamine, N-diethylaminopropylamine and the like, or modified amine curing agents); the diluent is xylene isomer mixture (e.g., toluene, ethylbenzene, 2-methyl-1-propanol, xylene isomer mixture (thinner 91-92), or a mixture thereof).
The preparation of the silane modified nano hybrid material comprises the following steps: adding the nano hybrid material into deionized water, magnetically stirring at normal temperature for 20-40min, and then ultrasonically dispersing for 50-60 min; dispersing a silane coupling agent in toluene, stirring and uniformly mixing at normal temperature; mixing the two solutions, and performing oil bath at 75-85 ℃ for reflux stirring for 23-26 h; wherein the silane coupling agent and the nano hybrid material are mixed according to the mass ratio of 1: mixing at a ratio of 8-10.
The silane coupling agent is 3-aminopropyl triethoxysilane, phenyl silane, octyl silane, methyl trimethoxysilane, etc.
The preparation method of the nano hybrid material comprises the following steps:
1) GQD synthesis: mixing and stirring citric acid, urea and deionized water according to the mass ratio of 1-1.5:1-1.5:35-40, carrying out hydrothermal reaction at the temperature of 150 ℃ and 180 ℃ for 4-6h, drying and grinding into GQD powder;
2)TiO 2 preparing nano particles: mixing isopropyl titanate and isopropanol according to a mass-volume ratio of 3: 1, mixing; adding the mixture into a nitric acid aqueous solution at normal temperature, stirring at normal temperature for 3-5h, transferring to 70-85 ℃ oil bath, stirring, reacting for 18-22h, and calcining to obtain TiO 2 A nanoparticle;
3) TNT preparation: the above obtained TiO 2 Adding the nano particles into NaOH (10M) solution for full dispersion, carrying out hydrothermal reaction at the temperature of 150 ℃ and 160 ℃ for 45-50h, and adjusting the pH value of the system to 7 after the reaction; wherein, TiO 2 The dosage range of the nano particles and the NaOH solution is 1: 35-40 parts of;
4) synthesizing a nano hybrid material: mixing TNT: mixing and hybridizing GQD in proportion, dissolving the hybridized GQD in deionized water, stirring and uniformly mixing the mixture at normal temperature, performing hydrothermal reaction at the temperature of 150 ℃ and 160 ℃ for 4-5h, and drying to obtain a nano hybrid material; the mass ratio of the Graphene Quantum Dots (GQD) to the titanium dioxide nanotubes (TNT) is 1: 0.5-2.
After the reaction in the step 2), the temperature is raised to 400-450 ℃ at the heating rate of 10-15 ℃/min and calcined for 2-3h to obtain TiO 2 And (3) nanoparticles.
The coating material is coated on the surface of a carbon steel metal matrix, dried for 48 hours at room temperature and then dried for 1-1.5 hours at 80 ℃ to obtain the nano hybrid material coating.
The application of the nano hybrid material coating material is to coat the material on a metal matrix to form the application of the nano hybrid material coating in marine corrosion protection.
The invention has the advantages that:
according to the invention, GQD/TNT hybridization is utilized to obtain a nano hybrid material with chemical reaction active sites rich in unique characteristics, and then a silane coupling agent is further utilized to modify the surface of the hybrid material, so that the GQD/TNT hybridization and the silane coupling agent are organically combined to obtain the nano hybrid material uniformly dispersed in a polymer matrix, and the nano hybrid material is applied to an organic coating matrix to realize high corrosion resistance; the nano hybrid coating has low cost, environmental protection and long service life, and is a novel marine anticorrosive coating with great application value. The concrete embodiment is that:
1. after the epoxy resin coating of 0.3 wt% of the nano hybrid material is added and subjected to a 90-day electrochemical alternating current impedance spectroscopy test, the impedance value of the epoxy resin coating is 3-4 orders of magnitude higher than that of a blank epoxy resin coating, and the anticorrosion effect is obviously enhanced, as shown in figure 4.
2. Through 90-day neutral salt spray experiment tests, when GQD in the nano hybrid material is: the TNT ratio is 1: 1, the best antiseptic effect is obtained, as shown in figure 4.
3. Compared with a blank epoxy resin coating, the epoxy resin coating added with the nano hybrid material has the advantages that uniformly dispersed fillers and tight combination degree can be obviously seen on the fracture surface, and the effect is best when the hybridization ratio is GQD/TNT (1: 1), as shown in figure 3 (d).
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the nano-hybrid material provided by the practice of the present invention, wherein (a) GQD, (b) high resolution TEM image of GQD, (c) TNT, (d) GQD/TNT (1: 0.5), (e) GQD/TNT (1: 1), (f) GQD/TNT (1: 2).
Fig. 2 is a Scanning Electron Microscope (SEM) image of the fracture surface of the coating provided by the practice of the present invention, wherein (a) the blank epoxy coating, (b) the silane-modified GQD epoxy coating, (c) the silane-modified TNT epoxy coating, (d) the silane-modified GQD/TNT (1: 2) epoxy coating, (e) the silane-modified GQD/TNT (1: 1) epoxy coating, and (f) the silane-modified GQD/TNT (1: 0.5) epoxy coating.
FIG. 3 is a diagram of Electrochemical Impedance Spectroscopy (EIS) of a nano-hybrid coating, wherein (a) GQD/TNT (1: 1), (b) GQD/TNT (1: 2), (c) GQD/TNT (1: 0.5), and (d) a blank epoxy coating.
Fig. 4 is a salt spray experimental diagram of a nano hybrid coating provided by the implementation of the present invention, wherein (a) a blank epoxy coating, (b) a silane-modified GQD epoxy coating, (c) a silane-modified TNT epoxy coating, (d) a silane-modified GQD/TNT (1: 0.5) epoxy coating, (e) a silane-modified GQD/TNT (1: 1) epoxy coating, and (d) a silane-modified GQD/TNT (1: 2) epoxy coating.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
According to the invention, the problem of poor action of the nano hybrid material and the coating is solved by modifying and controlling the hybrid ratio of the nano material, so that the nano filler is uniformly dispersed in the organic coating matrix, and the nano composite coating with good dispersibility and excellent coating corrosion resistance is obtained. The silane modified nano hybrid material coating provided by the invention has the advantages of simple synthesis method, low cost and higher practical value in the field of long-acting anticorrosion nano coatings.
Example 1
The synthesis method of the nano hybrid material coating comprises the following concrete implementation steps:
1) preparation of silane modified nano hybrid material
1.1) GQD synthesis: weighing 2g of citric acid, 2g of urea and 70g of deionized water according to the proportion, mixing the materials in a beaker, magnetically stirring the mixture for 30min at normal temperature, carrying out hydrothermal reaction for 4h at 160 ℃, drying a sample at 80 ℃ after the reaction is finished, and finally grinding the sample into GQD powder;
1.2)TiO 2 preparing nano particles: dissolving 5mL of isopropyl titanate in 15mL of isopropanol, and stirring for 30min at normal temperature for later use; after adjusting the pH of the nitric acid to 2.5, 750mL of deionized water are added, after which the former is added dropwise to an aqueous solution of nitric acid having a pH of 2.5, oftenStirring for 3h, transferring to 80 deg.C oil bath, stirring for 20h, transferring to 80 deg.C oven, and drying to obtain yellowish white powder. Finally, heating to 400 ℃ at a heating rate of 10 ℃/min and calcining for 2h to obtain TiO 2 And (3) nanoparticles.
1.3) TNT preparation: 2g of TiO obtained as described above 2 Adding the nano particles into 70mL of NaOH (10M) solution, magnetically stirring for 20min, and then ultrasonically dispersing for 30 min; the reaction was then hydrothermal at 150 ℃ for 48h and finally washed with 0.1M HCl solution to pH 7.
1.4) synthesis of nano hybrid materials: mixing and hybridizing 4g of GQD and 4g of TNT, dissolving in 70mL of deionized water, stirring at normal temperature for 2h, carrying out hydrothermal reaction at 150 ℃ for 4h, and then drying and grinding at 80 ℃ to obtain the nano hybrid material (see fig. 1 (e)).
1.5) silane modified nano hybrid material: adding 0.2g of the nano hybrid material into 400mL of deionized water, magnetically stirring at normal temperature for 30min, and then ultrasonically dispersing for 50min for later use; dispersing 2g of silane coupling agent in 50mL of toluene, and stirring at normal temperature for 30 min; mixing the two solutions, placing the mixture in a reflux device, and stirring in an oil bath at 80 ℃ for 24 hours;
1.6) concentration calculation: alternately centrifuging and washing the mixed solution by using deionized water and absolute ethyl alcohol, wherein the rotating speed of a centrifuge is 8000rmp, and the centrifuging time is 3 min; dissolving the centrifuged product in a small amount of toluene to obtain a high-concentration solution; preparing a small container using tinfoil paper to measure the concentration of the solution (mg/mL);
2) preparing a nano hybrid material coating: weighing 100g of epoxy resin, 20g of curing agent and 50g of diluent according to the mass ratio to obtain a basic coating, and adding the basic coating into the basic coating to be uniformly dispersed according to the concentration calculation of the nano hybrid filler to obtain a nano hybrid material containing 0.3 wt%, namely obtaining the nano hybrid material coating material.
The epoxy resin is solvent type epoxy resin E44; the curing agent is amine matched curing agent T31; the diluent is a commercial xylene isomer mixture (thinner 91-92), and the silane coupling agent is 3-aminopropyltriethoxysilane.
Coating the obtained nano hybrid material coating material on the surface of a carbon steel metal matrix, drying at room temperature for 48h, and then drying at 80 ℃ for 1.5h to obtain a nano hybrid material coating, as shown in figures 2(d) and 3 (d).
As can be seen from the graphs in FIGS. 1(a-c), the synthesized GQD nano material has a size smaller than 20nm and TNT has a size diameter smaller than 10nm, and FIG. 1(e) shows the morphology of the hybrid material when GQD/TNT (1: 1) is used, so that the GQD can well modify TNT and has a good dispersion effect. As can be seen from fig. 2(e), 3(d) and 4(e), the hybrid material in this ratio can be uniformly and densely dispersed in the epoxy resin coating, and the electrochemical impedance spectroscopy test and the salt spray test of the hybrid material both prove that the hybrid material has the best corrosion resistance compared with the blank coating and other hybrid ratio coatings.
Example 2
The synthesis method of the nano hybrid material coating comprises the following concrete implementation steps:
1) preparation of silane modified nano hybrid material
1.1) GQD synthesis: weighing 2g of citric acid, 2g of urea and 70g of deionized water in proportion, mixing the materials in a beaker, magnetically stirring the mixture for 30min at normal temperature, carrying out hydrothermal reaction for 4h at 160 ℃, drying a sample at 80 ℃ after the reaction is finished, and finally grinding the sample into GQD powder;
1.2)TiO 2 preparing nano particles: dissolving 5mL of isopropyl titanate in 15mL of isopropanol, and stirring for 30min at normal temperature for later use; adjusting the pH value of nitric acid to 2.5, adding 750mL of deionized water, dropwise adding the nitric acid into a nitric acid aqueous solution with the pH value of 2.5, stirring at normal temperature for 3h, then stirring in an oil bath at 80 ℃ for 20h, and then drying in an oven at 80 ℃ to obtain yellowish white powder. Finally, heating to 400 ℃ at a heating rate of 10 ℃/min and calcining for 2h to obtain TiO 2 And (3) nanoparticles.
1.3) TNT preparation: 2g of TiO obtained as described above 2 Adding the nano particles into 70mL of NaOH (10M) solution, magnetically stirring for 20min, and then ultrasonically dispersing for 30 min; the reaction was then hydrothermal at 150 ℃ for 48h and finally washed with 0.1M HCl solution to pH 7.
1.4) synthesis of nano hybrid materials: mixing and hybridizing 4g of GQD and 2g of TNT, dissolving in 70mL of deionized water, stirring at normal temperature for 2h, carrying out hydrothermal reaction at 150 ℃ for 4h, and then drying and grinding at 80 ℃ to obtain the nano hybrid material (see fig. 1 (d)).
1.5) silane modified nano hybrid material: adding 0.2g of the nano hybrid material into 400mL of deionized water, magnetically stirring at normal temperature for 40min, and then ultrasonically dispersing for 60min for later use; dispersing 2g of silane coupling agent in 50mL of toluene, and stirring at normal temperature for 30 min; mixing the two solutions, placing the mixture in a reflux device, and stirring the mixture for 24 hours at the temperature of 80 ℃ in an oil bath;
1.6) concentration calculation: alternately centrifuging and washing the mixed solution by using deionized water and absolute ethyl alcohol, wherein the rotating speed of a centrifuge is 10000rmp, and the centrifuging time is 5 min; dissolving the centrifuged product in a small amount of toluene to obtain a high-concentration solution; preparing a small container using tinfoil paper to measure the concentration of the solution (mg/mL);
2) preparing a nano hybrid material coating: weighing 100g of epoxy resin, 20g of curing agent and 50g of diluent according to the mass ratio to obtain a basic coating, and adding the basic coating into the basic coating to be uniformly dispersed according to the concentration calculation of the nano hybrid filler to obtain a nano hybrid material containing 0.3 wt%, namely obtaining the nano hybrid material coating material.
And coating the obtained nano hybrid material coating material on the surface of a carbon steel metal matrix, drying at room temperature for 48 hours, and drying at 80 ℃ for 1.5 hours to obtain the nano hybrid material coating.
The epoxy resin is solvent type epoxy resin E44; the curing agent is amine matched curing agent T31; the diluent is a commercial xylene isomer mixture (thinner 91-92), and the silane coupling agent is 3-aminopropyltriethoxysilane.
FIG. 1(d) shows the morphology of the hybrid material when GQD/TNT (1: 0.5) is used, and it can be seen that the GQD modifies TNT but has poor dispersion effect. As can be seen from FIGS. 2(e), 3(f) and 4(d), the compactness of the cross-section fracture area of the hybrid material coating under the condition of the proportion is better than that of a blank coating, and the electrochemical impedance spectrum test and the salt spray test also prove that the hybrid material coating has excellent corrosion resistance.
Example 3
The synthesis method of the nano hybrid material coating comprises the following concrete implementation steps:
1) preparation of silane modified nano hybrid material
1.1) GQD synthesis: weighing 2g of citric acid, 2g of urea and 70g of deionized water in proportion, mixing the materials in a beaker, magnetically stirring the mixture for 30min at normal temperature, carrying out hydrothermal reaction for 4h at 160 ℃, drying a sample at 80 ℃ after the reaction is finished, and finally grinding the sample into GQD powder;
1.2)TiO 2 preparing nano particles: dissolving 5mL of isopropyl titanate in 15mL of isopropanol, and stirring for 30min at normal temperature for later use; adjusting the pH value of nitric acid to 2.5, adding 750mL of deionized water, dropwise adding the nitric acid into a nitric acid aqueous solution with the pH value of 2.5, stirring at normal temperature for 3h, then stirring in an oil bath at 80 ℃ for 20h, and then drying in an oven at 80 ℃ to obtain yellowish white powder. Finally, heating to 400 ℃ at a heating rate of 10 ℃/min and calcining for 2h to obtain TiO 2 And (3) nanoparticles.
1.3) TNT preparation: 2g of TiO obtained as described above 2 Adding the nano particles into 70mL of NaOH (10M) solution, magnetically stirring for 20min, and then ultrasonically dispersing for 30 min; the reaction was then hydrothermal at 150 ℃ for 48h and finally washed with 0.1M HCl solution to pH 7.
1.4) synthesis of nano hybrid materials: 2g of GQD and 4g of TNT are mixed, hybridized and dissolved in 70mL of deionized water, stirred at normal temperature for 2 hours, then subjected to hydrothermal reaction at 150 ℃ for 4 hours, and then dried and ground at 80 ℃ to obtain the nano hybrid material (see fig. 1 (f)).
1.5) silane modified nano hybrid material: adding 0.2g of the nano hybrid material into 400mL of deionized water, magnetically stirring at normal temperature for 30min, and then ultrasonically dispersing for 60min for later use; dispersing 2g of silane coupling agent in 50mL of toluene, and stirring at normal temperature for 30 min; mixing the two solutions, placing the mixture in a reflux device, and stirring the mixture for 24 hours at the temperature of 80 ℃ in an oil bath;
1.6) concentration calculation: alternately centrifuging and washing the mixed solution by using deionized water and absolute ethyl alcohol, wherein the rotating speed of a centrifuge is 8000rmp, and the centrifuging time is 3 min; dissolving the centrifuged product in a small amount of toluene to obtain a high-concentration solution; preparing a small container using tinfoil paper to measure the concentration of the solution (mg/mL);
2) preparing a nano hybrid material coating material: weighing 100g of epoxy resin, 20g of curing agent and 50g of diluent according to the mass ratio to obtain a basic coating, and adding the basic coating into the basic coating to be uniformly dispersed according to the concentration calculation of the nano hybrid filler to obtain a nano hybrid material containing 0.3 wt%, namely obtaining the nano hybrid material coating material.
And coating the obtained nano hybrid material coating material on the surface of a carbon steel metal matrix, drying at room temperature for 48 hours, and drying at 80 ℃ for 1.5 hours to obtain the nano hybrid material coating.
The epoxy resin is solvent type epoxy resin E-44; the curing agent is amine matched curing agent T31; the diluent is a commercial xylene isomer mixture (thinner 91-92), and the silane coupling agent is 3-aminopropyltriethoxysilane.
FIG. 1(f) shows the morphology of the hybrid material when GQD/TNT (1: 2) is used, and it can be seen that the GQD modifies TNT and has a good dispersion effect. As can be seen from FIGS. 2(f), 3(d) and 4(f), the compactness of the cross-section fracture area of the hybrid material coating under the condition of the proportion is better than that of a blank coating, and the electrochemical impedance spectrum test and the salt spray test also prove that the hybrid material coating has excellent corrosion resistance.
EIS and salt spray experimental tests were carried out on the nano hybrid material coatings obtained in the above examples at different ratios:
EIS measurements were made by using a potentiostat/potentiostat (PGSTAT302N, Metrohm Autolab, Utrecht, Netherlands) at 10 -2 -10 5 Steady state Open Circuit Potential (OCP) of 10mV amplitude over the HZ frequency range was recorded. Saturated Hg/Hg with coated Steel substrate 2 Cl 2 The electrode and the platinum wire are respectively used as a working electrode, a reference electrode and a counter electrode in the electrochemical cell. The salt spray test was performed according to ASTM B-117, with the experimental conditions in the salt spray booth being 5 wt.% NaCl solution at 100% relative humidity, salt spray for 1 minute every 6 minutes.
As can be seen from FIGS. 3 and 4, the silane-modified GQD/TNT (1: 1) epoxy resin coating has the highest impedance modulus value at a frequency of 0.01Hz after the coating is subjected to the EIS test for 30 days; through the salt spray experiment test, the corrosion degree of the hybrid material coating under the cover proportion can be seen to be lightest in a clear contrast manner. Therefore, when the nano-hybrid material GQD/TNT (1: 1) is used, the coating has the best anti-corrosion performance.
The invention utilizes silane coupling agent to modify the nano hybrid material, wherein the silane coupling agent has amino (-NH2) and ethoxy (CH3CH2O) functional groups, silanol (Si-OH) groups can be formed after hydrolysis, and the Si-OH groups are chemically combined with hydroxyl (-OH) on the surface of the nano material. Meanwhile, Si-OH groups are subjected to condensation reaction to form Si-O-Si bonds on the surface of the hybrid material, so that modification is realized, and except the silane coupling agent recorded in the embodiment, other silane coupling agents with the same characteristics can achieve the same purpose.
Meanwhile, the silane modified nano hybrid material can be added into other epoxy resins to achieve the corresponding purpose.
From the foregoing, it should be understood that various changes, substitutions, and combinations can be made by those skilled in the art without departing from the scope of the invention as defined by the appended claims.
Claims (9)
1. A nanometer hybrid material coating material is characterized in that: the coating material takes silane modified nano hybrid material as a reinforcing phase and takes epoxy resin coating as a matrix phase: and (3) uniformly dispersing the silane modified nano hybrid material in the epoxy resin coating to obtain the nano hybrid material coating material.
2. The hybrid nanomaterial coating material of claim 1, wherein: the reinforcing phase contains a silane coupling agent and a nano hybrid material, wherein the silane coupling agent and the nano hybrid material are mixed according to the mass ratio of 1: mixing at a ratio of 8-10; the mass ratio of the nano hybrid material is 1: 0.5-2 of Graphene Quantum Dots (GQD) and titanium dioxide nanotubes (TNT).
3. The hybrid nanomaterial coating material of claim 1, wherein: the content of the reinforced phase in the matrix phase is 0.1-1.0 wt%.
4. A method for preparing the nano-hybrid material coating material of claim 1, which is characterized in that: and (3) uniformly dispersing the silane modified nano hybrid material in the epoxy resin coating to obtain the nano hybrid material coating material.
5. The preparation method of the nanometer hybrid material coating material according to claim 3, characterized in that: adding the reinforced phase into the matrix phase to ensure that the content of the reinforced phase in the matrix phase is 0.1-1.0 wt%; wherein the matrix phase is epoxy resin, a curing agent and a diluent according to the mass ratio of 5: 1: 2 and mixing.
6. The preparation method of the nano-hybrid material coating material according to claim 4, characterized in that: the epoxy resin is solvent type epoxy resin E-44; the curing agent is amine matched curing agent T31; the diluent is xylene isomer mixture 91-92.
7. The preparation method of the nano-hybrid material coating material according to claim 4, characterized in that: the preparation of the silane modified nano hybrid material comprises the following steps: adding the nano hybrid material into deionized water, magnetically stirring at normal temperature for 20-40min, and then ultrasonically dispersing for 50-60 min; dispersing a silane coupling agent in toluene, stirring and uniformly mixing at normal temperature; mixing the two solutions, and performing oil bath at 75-85 ℃ for reflux stirring for 23-26 h; wherein the silane coupling agent and the nano hybrid material are mixed according to the mass ratio of 1: mixing at a ratio of 8-10.
8. The preparation method of the nano-hybrid material coating material according to claim 4, characterized in that: the coating material is coated on the surface of a carbon steel metal matrix, dried for 48 hours at room temperature and then dried for 1-1.5 hours at 80 ℃ to obtain the nano hybrid material coating.
9. The use of the nano-hybrid coating material of claim 1, wherein: the material is coated on a metal matrix to form the application of a nano hybrid material coating in marine corrosion protection.
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