CN111234566B - Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating - Google Patents
Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating Download PDFInfo
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Abstract
The invention discloses an acid-base dual-response hollow mesoporous silica composite nano container, which comprises a hollow mesoporous silica sphere core, a corrosion inhibitor and a ZIF-8 nano valve, wherein the corrosion inhibitor is loaded inside the hollow mesoporous silica sphere core, and the ZIF-8 nano valve is coated on the outer surface of the hollow mesoporous silica sphere core.
Description
Technical Field
The invention relates to the field of anticorrosive coatings, in particular to an acid-base dual-response hollow mesoporous silica composite nano container, a self-repairing anticorrosive coating and a preparation method thereof.
Background
The metal material is widely applied to various fields of national economy due to good physical and chemical properties and service performance, but the metal material is difficultly damaged in the service process, such as fracture, abrasion, natural aging, corrosion and the like. Among them, the damage of corrosion to metal materials is the most serious, corrosion is a common technical problem in all countries in the world, and the economic loss caused by metal corrosion in China is up to 4% of GDP every year, which does not cause great harm to safety, personal safety and the like.
The approaches for preventing metal corrosion are more, such as corrosion inhibitor protection, anticorrosive coating protection, electrochemical protection and the like, wherein the organic coating is the most economical, convenient and widely applied mode. The organic coating forms a layer of barrier on the surface of the metal to block corrosive media and a protected substrate, and resists corrosion by means of pigment passivation, cathodic protection and the like. Typical anticorrosive coatings include polyurethane, epoxy, phenolic, fluorocarbon resin, polyester, and the like, according to the resin category. But the coating inevitably forms micropores and cracks in the film forming and using processes, corrosive media can still slowly diffuse to the metal surface through the micropores and the cracks, and the corrosive media directly permeate to the metal substrate and lose the corrosion resistance.
In order to achieve the purpose of long-acting corrosion prevention of common organic polymer coatings, a great deal of research workers improve the corrosion prevention capacity of the coatings by doping various functional nano fillers in the coatings, and the modification modes of the nano filler composite organic coatings are mainly divided into two types of passive nano fillers and active nano fillers. The passive type extends the coating life by enhancing the coating's barrier to corrosive media. For example, graphene, as a two-dimensional layered material, has an ultra-high specific surface area, physicochemical stability and permeation resistance, and many researches are carried out to prolong the diffusion path of corrosive media in a coating and improve the corrosion prevention effect of the coating by doping various modified graphene nanofillers in the coating. However, the graphene-based filler tends to cause galvanic corrosion of the metal in the coating after corrosion occurs, accelerating the destruction of the metal substrate. Inspired by the self-healing ability of natural organisms after being damaged, researchers are making great efforts to develop coating products with the capability of actively repairing coatings to prevent corrosion. The method is mainly characterized in that various microcapsules encapsulating curing agents or repairing agents are added into a coating, when the coating is scratched or impacted, the microcapsules are damaged, the repairing agents or the curing agents loaded in the microcapsules are released to repair cracks, for example, 201711424463.0 King Wen Jing and the like invent an anticorrosion primer containing microcapsules with self-repairing functions, and when the microcapsules are damaged, self-repairing liquid coated in the microcapsules automatically flows out, so that self-repairing is realized. For example, 201510278172, a microcapsule based on urea-formaldehyde resin and melamine-formaldehyde resin is invented by X-Ye chemical research and development (Shanghai) Limited company for anticorrosive coatings, and when a paint film is damaged under the action of external force, the added additive can release a repairing agent and an antirust agent, so that the damage is self-repaired, the corrosion expansion is inhibited, and the service life of the paint film is prolonged. However, the self-repairing coating based on the microcapsule has the following defects that the performance requirements needed by the self-repairing anticorrosive coating are difficult to ensure, and the defects mainly comprise: 1) most of the current self-repairing coatings based on microcapsules are stimulated by mechanical vibration and the like, when the coatings are damaged by pressure, the microcapsule rupture repairing agent escapes and reacts with resin and the like to repair the damaged parts of the film layers, and the stimulation hardly responds to the inside of the coatings, particularly the corrosion of the bottom layer; 2) most microcapsules have poor compatibility with organic polymer coatings, and the repaired coatings tend to agglomerate in the coating. Agglomeration will cause the coating to form more defects, potentially accelerating the diffusion of the corrosive medium.
In order to overcome the defects of the self-repairing coating based on the microcapsules in the aspect of corrosion resistance, a technology of taking a pH-responsive corrosion inhibitor-loaded nano composite container as an intelligent nano corrosion-resistant filler has been developed recently, for example, CN201710794513.8 Libang and the like invent an anti-corrosion self-repairing coating, wherein the anti-corrosion filler is a pH-responsive nano container, the pH-responsive nano microspheres release the corrosion inhibitor when the pH is 6-10, but when most metal substrates are corroded, the pH of a corrosion micro-anode region is acidic, and the nano container lacks responsiveness in the region, so that the local corrosion inhibitor is not supplied enough. The invention relates to an intelligent response self-repairing anticorrosive coating material and a preparation method thereof, such as CN201910365017.X Liweihua and the like. The coating material comprises zinc oxide microcapsules and a coating matrix; the zinc oxide microcapsule comprises a capsule core and a capsule core carrier, wherein the capsule core is a corrosion inhibitor, and the capsule core carrier is porous zinc oxide; the ZIF-8 membrane is arranged on the outer surface of the capsule core carrier. The activity of the corrosion inhibitor is ensured by the porous inorganic material ZnO, meanwhile, a ZIF-8 film generated on the surface of ZnO can not only improve the binding performance, but also can be used as a hole sealing substance to prevent the corrosion inhibitor from being released prematurely, but the pH responsive nano microsphere is an alkaline compound, mainly releases the corrosion inhibitor under the condition that the pH is acidic, and has no acid-base dual responsiveness, so that the requirement of each area of the metal surface on the corrosion inhibitor during corrosion can not be completely met. In addition, most of the existing nano containers still have the problem of poor compatibility of the coating matrix, so that the compactness of the composite coating is poor and the corrosion resistance of the composite coating is not good.
Hollow mesoporous silica has received much attention in the field of molecular loading and release because it has the following characteristics: (1) the large void space and specific surface area make the carrier have large small molecular loading; (2) good mechanical properties; (3) the shape and the size are controllable in the synthesis process; (4) surface modification is easy to perform. In addition, the silica is also a material responding to an alkaline environment, and the structure of the silica is easy to collapse in the alkaline environment, so that the requirement of responding to the stimulation of the alkaline environment and releasing loads can be met, and the application of the hollow mesoporous silica to the acid-base dual-response composite nano container is not researched at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an acid-base dual-response hollow mesoporous silica composite nano container, a self-repairing anticorrosive coating and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
an acid-base double-response hollow mesoporous silica composite nano container is characterized in that: the corrosion inhibitor is loaded inside the hollow mesoporous silica sphere core, the ZIF-8 nanometer valve is coated on the outer surface of the hollow mesoporous silica sphere core, the particle size of the hollow mesoporous silica sphere core is 50-200 nm, and the particle size of the hollow mesoporous silica composite nanometer container is 200-350 nm.
Preferably, the particle size of the hollow mesoporous silica sphere core is 100-150 nm, and the particle size of the hollow mesoporous silica composite nano container is 250-300 nm.
The invention also discloses a preparation method of the acid-base dual-response hollow mesoporous silica composite nano container, which comprises the following steps:
s1, uniformly dispersing ZIF-8 nano powder in a mixed solution of water, absolute ethyl alcohol and a pH value regulator, adding a surfactant and the pH value regulator, stirring at a stirring speed of 600-1200 rpm/min, dropwise adding tetraethoxysilane, and uniformly mixing; centrifugally washing, namely adding the collected solid product into dilute hydrochloric acid for etching; and (4) centrifugally washing, and drying the product in vacuum to obtain the hollow mesoporous silica nanoparticles.
S2, activating hollow mesoporous silica nanoparticles, uniformly dispersing the hollow mesoporous silica nanoparticles in a saturated corrosion inhibitor solution, placing the saturated corrosion inhibitor solution in a closed container, and vacuumizing; stirring and centrifuging to obtain a solid product; adding the solid product into the organic ligand solution, uniformly stirring, adding the zinc salt hydrate solution, and stirring for 5-30 min at the rotating speed of 2000-3000 rpm/min; and (4) centrifugally washing, collecting a product, and drying in vacuum to obtain the hollow mesoporous silica composite nano container.
The preparation method of the ZIF-8 nano powder comprises the following steps:
adding a zinc salt hydrate and an imidazole organic ligand into methanol respectively, fully stirring and dissolving to obtain a solution A and a solution B, mixing the solution A and the solution B, stirring and reacting at room temperature at 2000-3000 rpm/min, centrifuging, washing and drying to obtain a solid product.
Specifically, the zinc salt hydrate is one or more of zinc nitrate hexahydrate, zinc chloride, zinc sulfate and zinc acetate; the concentration of the zinc salt hydrate is 42-50 mM; the imidazole organic ligand is 2-methylimidazole; the dosage concentration of the imidazole organic ligand substance is 0.65-0.75M; the concentration ratio of the zinc salt hydrate to the 2-methylimidazole is 1: 2-1: 4, and the stirring reaction time is 3-4 h.
In S1, the volume of a mixed solution of water, absolute ethyl alcohol and a pH value regulator is 400-600 mL, wherein the volume ratio of water to absolute ethyl alcohol is 5: 4; the surfactant is cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide, and the concentration of the surfactant is 0.17-0.20M; the acid-base regulator is one of ammonia water, sodium hydroxide and 2-methylimidazole, and the concentration is 62 mM-70 mM; the concentration of the ethyl orthosilicate is 30-50 mM; dispersing ZIF-8 nano powder in an ethanol water solution by using ultrasonic for 30-60 min; the stirring time after the surfactant is added is 30-90 min; the concentration of the dilute hydrochloric acid is 0.01-0.1M; the etching time is 30-90 min.
In S2, the solvent used by the saturated solution of the corrosion inhibitor is acetone, absolute ethyl alcohol or butanone; the organic ligand solution is a 2-methylimidazole aqueous solution, and the concentration is 2.3-4.0M; the zinc salt hydrate is one or more of zinc nitrate hexahydrate, zinc acetate, zinc sulfate and zinc gluconate, and the concentration of the zinc salt hydrate is 0.3-0.5M; adding the corrosion inhibitor, stirring for 3-6 h, and vacuum drying at 40-70 ℃.
Preferably, the corrosion inhibitor is one or more of benzotriazole, 2-mercaptobenzothiazole, 8-hydroxyquinoline, methylbenzotriazole and nitrobenzotriazole.
The invention also discloses a self-repairing anticorrosive coating, which comprises a resin matrix and an acid-base dual-response hollow mesoporous silica composite nano container, wherein the addition amount of the hollow mesoporous silica composite nano container is 1-4% of that of the resin matrix.
The invention also discloses a preparation method of the self-repairing anticorrosive coating, which comprises the steps of mixing the hollow mesoporous silica composite nano container with a resin matrix, and dispersing to obtain a nano particle size. The dispersion treatment can be grinding with a nanometer mill or ultrasonic dispersion.
Compared with the prior art, the invention has the following advantages:
(1) the hollow mesoporous silica nano container has the function of acid-base dual response-release. The ZIF-8 nanometer valve coated on the surface of the nanometer container can block the holes on the silicon dioxide spherical shell, and the corrosion inhibitor loaded in the nanometer container is prevented from leaking in advance. After corrosion occurs, the ZIF-8 nano valve can respond to a local acidic microenvironment caused by corrosion and control and release the corrosion inhibitor loaded in the nano container. The hollow mesoporous silica spherical core wrapped inside the ZIF-8 nanometer valve can respond to local alkaline environment caused by corrosion, collapse of a silica framework can occur, and the corrosion inhibitor can be released.
(2) According to the invention, the thickness and the compactness of the ZIF-8 layer are controlled by controlling the reaction time in S2, the ZIF-8 layer not only can prevent the corrosion inhibitor from leaking to a great extent, but also enables local alkaline substances to enter the hollow mesoporous silica sphere core through the ZIF-8 layer and react with the hollow mesoporous silica sphere core to promote the collapse of the silica framework and release the corrosion inhibitor.
(3) Imidazolyl contained on the surface of the ZIF-8 nano valve in the hollow mesoporous silica nano container can be used as an accelerator for curing epoxy resin, and participates in the curing process of an epoxy coating matrix, so that the nano container is not simply physically dispersed in the coating, but is combined with the epoxy matrix in a covalent bond mode. Effectively improves the compatibility and the dispersibility of the nano-containers in the coating and prevents the nano-containers from agglomerating to damage the performance of the coating. In addition, the epoxy coating obtained after the imidazole group participates in curing has higher crosslinking density and hydrophobic property, so that the compactness and the barrier property of the coating are further improved.
(4) Different from a common organic polymer coating, the acid-base dual-response self-repairing anticorrosive coating material can actively respond to the change of the pH value of a microenvironment caused by corrosion, release a corrosion inhibitor to fulfill the aim of repairing the protective function of the coating, and can repair local corrosion and microcracks generated under the coating without external human interference. The loss of manpower and material resources caused by manually brushing and repairing the coating in the past is avoided.
Drawings
FIG. 1 is a scanning electron microscope image of hollow mesoporous silica spherical cores prepared in examples 1 to 6 of the present invention.
FIG. 2 is a transmission electron microscope image of the hollow mesoporous silica spherical core prepared in examples 1 to 6 of the present invention.
FIG. 3 is a transmission electron microscope image of the hollow mesoporous silica nano container prepared in examples 1 to 6 of the present invention.
Fig. 4 is a release kinetic curve of the hollow mesoporous silica composite nanocontainer prepared in example 1 of the present invention in aqueous solutions with different pH.
FIG. 5 is a graph of Bode after various stages of immersion in 3.5 wt% NaCl in water.
FIG. 6 is a graph of Bode phase angle after various stages of immersion in 3.5 wt% NaCl in water.
Detailed description of the preferred embodiments
In order to better understand the technical solution, the technical solution will be described in detail with reference to the drawings and the specific embodiments.
Example 1
1. Preparation of ZIF-8 self-sacrifice template:
dissolving zinc nitrate hexahydrate in 100mL of methanol to form a solution A, wherein the concentration of the zinc nitrate is 42 mM; 2-methylimidazole was weighed and dissolved in 100mL of methanol to form solution B, the concentration of 2-methylimidazole was 0.65M. The solution B was poured into the solution A, and the mixed solution was vigorously stirred for 3 hours at a stirring speed of 3000 rpm/min. And (4) centrifugally washing, washing for 3 times by using methanol, and drying at 60 ℃ overnight to obtain the ZIF-8 nano particles.
2. Preparing a hollow mesoporous silica sphere core:
400mL of a mixed solution of water and absolute ethyl alcohol is prepared, the volume ratio of the water to the absolute ethyl alcohol is 5:4, 2-methylimidazole is added, and the concentration of the 2-methylimidazole is controlled to be 62 mM. The ZIF-8 nanoparticles obtained by the steps are subjected to ultrasonic dispersion for 30min in a mixed solution consisting of water, absolute ethyl alcohol and 2-methylimidazole, a CTAC surfactant is added, and the mixture is fully stirred for 30min (stirring speed is not indicated, mild stirring is adopted, in the embodiment, the stirring speed is 1000rpm/min, the same applies below), and the CTAC concentration is 0.17M. And (3) dropwise adding tetraethoxysilane into the system, wherein the concentration of tetraethoxysilane in the mixed solution is 40mM, and continuously stirring for 2 hours. The solid product was added to 100mL of 0.1M HCl aqueous solution and stirred for 30 min. And (4) centrifuging and washing, and drying the solid product at 70 ℃ for 12h to obtain the hollow mesoporous silica sphere core.
3. Preparing a hollow mesoporous silica nano container:
activating the hollow silica spherical shell at the high temperature of 200 ℃ for 2h, dispersing the hollow silica spherical shell in a benzotriazole acetone saturated solution, transferring the mixed solution into a closed container, vacuumizing the container by using a vacuum pump until no continuous bubbles emerge in the system, gently stirring for 2h, then unloading the vacuum, and repeating the loading step for 3 times. After centrifugation at 7000rpm, the solid product was poured into 20mL of 2-methylimidazole (2.3M) aqueous solution and stirred well, and 2mL of Zn (NO) was added to the system3)2·H2O (0.3M) aqueous solution. The mixture was stirred vigorously for 5min at a speed of 3000 rpm/min. Centrifugally washing, and vacuum drying at 70 deg.C for 12 hr. Obtaining the hollow mesoporous silica nano container.
4. Preparing an acid-base response self-repairing anticorrosive coating:
grinding 100mg of hollow mesoporous silica nanocontainer and 5g E20 epoxy resin by a nano grinder for 30 min. Adding 5mL of xylene-n-butanol mixed solution (V: V ═ 7:3), stirring uniformly, fully dissolving, and then carrying out ultrasonic dispersion for 30 min. 2.5g of 650 polyamide curing agent was added and stirred well. And (3) placing the mixed solution in a vacuum box, exhausting air at room temperature for 5min, standing for 30min, uniformly coating the mixed solution on the surface of a substrate by using a coating rod, and drying at room temperature for 3 days to obtain the acid-base response self-repairing anticorrosive coating with the addition of the nano container being 2% of that of the epoxy matrix.
Example 2
1. Preparation of ZIF-8 self-sacrifice template:
dissolving zinc nitrate hexahydrate in 100mL of methanol to form a solution A, wherein the concentration of the zinc nitrate is 50 mM; 2-methylimidazole was weighed out and dissolved in 100mL of methanol to form solution B, the concentration of 2-methylimidazole being 0.75M. The solution B was poured into the solution A, and the mixed solution was vigorously stirred for 3 hours at a stirring speed of 3000 rpm/min. And (4) centrifugally washing, washing for 3 times by using methanol, and drying at 60 ℃ overnight to obtain the ZIF-8 nano particles.
2. Preparing a hollow mesoporous silica sphere core:
400mL of a mixed solution of water and absolute ethyl alcohol is prepared, the volume ratio of the water to the absolute ethyl alcohol is 5:4, 2-methylimidazole is added, and the concentration of the 2-methylimidazole is controlled to be 70 mM. And (2) ultrasonically dispersing the ZIF-8 nano particles obtained by the steps in a mixed solution consisting of water, absolute ethyl alcohol and 2-methylimidazole for 30min, adding a CTAC surfactant, and fully stirring for 30min, wherein the concentration of CTAC is 0.20M. And (3) dropwise adding tetraethoxysilane into the system, wherein the concentration of tetraethoxysilane in the mixed solution is 60mM, and continuously stirring for 2 hours. The solid product was added to 100mL of 0.1M HCl aqueous solution and stirred for 30 min. The solid product was dried at 70 ℃ for 12 h. Obtaining the hollow mesoporous silica sphere core.
3. Preparing a hollow mesoporous silica nano container:
activating the hollow silica spherical shell at the high temperature of 200 ℃ for 2h, dispersing the hollow silica spherical shell in a benzotriazole acetone saturated solution, transferring the mixed solution into a closed container, vacuumizing the container by using a vacuum pump until no continuous bubbles emerge in the system, gently stirring for 2h, then unloading the vacuum, and repeating the loading step for 3 times. After centrifugation at 7000rpm, the solid product was poured into 20mL of 2-methylimidazole (2.3M) aqueous solution and stirred well, and 2mL of Zn (NO) was added to the system3)2·H2O (0.3M) aqueous solution. The mixture was stirred vigorously for 5min at a speed of 3000 rpm/min. Centrifugally washing, and vacuum drying at 70 deg.C for 12 hr. Obtaining the hollow mesoporous silica nano container.
4. Preparing an acid-base response self-repairing anticorrosive coating:
grinding 100mg of hollow mesoporous silica nanocontainer and 5g E20 epoxy resin by a nano grinder for 30 min. Adding 8mL of xylene-n-butanol mixed solution (V: V ═ 7:3), stirring uniformly, fully dissolving, and then carrying out ultrasonic dispersion for 30 min. 2.5g of 650 polyamide curing agent was added and stirred well. And (3) placing the mixed solution in a vacuum box, exhausting air at room temperature for 5min, standing for 30min, uniformly coating the mixed solution on the surface of a substrate by using a coating rod, and drying at room temperature for 3 days to obtain the acid-base response self-repairing anticorrosive coating with the addition of the nano container being 2% of that of the epoxy matrix.
Example 3
1. Preparation of ZIF-8 self-sacrifice template:
dissolving zinc nitrate hexahydrate in 100mL of methanol to form a solution A, wherein the concentration of the zinc nitrate is 42 mM; 2-methylimidazole was weighed and dissolved in 100mL of methanol to form solution B, the concentration of 2-methylimidazole was 0.65M. The solution B was poured into the solution A, and the mixed solution was vigorously stirred for 3 hours at a stirring speed of 3000 rpm/min. And (4) centrifugally washing, washing for 3 times by using methanol, and drying at 60 ℃ overnight to obtain the ZIF-8 nano particles.
2. Preparing a hollow mesoporous silica sphere core:
preparing 600mL of mixed solution of water and absolute ethyl alcohol, wherein the volume ratio of the water to the absolute ethyl alcohol is 5:4, adding 2-methylimidazole, and controlling the concentration of the 2-methylimidazole to be 62 mM. And (2) ultrasonically dispersing the ZIF-8 nano particles obtained by the steps in a mixed solution consisting of water, absolute ethyl alcohol and 2-methylimidazole for 30min, adding a CTAC surfactant, and fully stirring for 30min, wherein the concentration of CTAC is 0.17M. And (3) dropwise adding tetraethoxysilane into the system, wherein the concentration of tetraethoxysilane in the mixed solution is 40mM, and continuously stirring for 2 hours. The solid product was added to 100mL of 0.1M HCl aqueous solution and stirred for 30 min. The solid product was dried at 70 ℃ for 12 h. Obtaining the hollow mesoporous silica sphere core.
3. Preparing a hollow mesoporous silica nano container:
activating the hollow silica spherical shell at the high temperature of 200 ℃ for 2h, dispersing the hollow silica spherical shell in a benzotriazole acetone saturated solution, transferring the mixed solution into a closed container, vacuumizing the container by using a vacuum pump until no continuous bubbles emerge in the system, gently stirring for 2h, then unloading the vacuum, and repeating the loading step for 3 times. After centrifugation at 7000rpm, the solid product was poured into 20mL of 2-methylimidazole (2.3M) aqueous solution and stirred well, and 2mL of Zn (NO) was added to the system3)2·H2O (0.3M) aqueous solution. The mixture was stirred vigorously for 5min at a speed of 3000 rpm/min. Centrifugally washing, and vacuum drying at 70 deg.C for 12 hr. Obtaining the hollow mesoporous silica nano container.
4. Preparing an acid-base response self-repairing anticorrosive coating:
grinding 75mg of hollow mesoporous silica nanocontainer and 5g E20 epoxy resin by a nano grinder for 30 min. Adding 5mL of xylene-n-butanol mixed solution (V: V ═ 7:3), stirring uniformly, fully dissolving, and then carrying out ultrasonic dispersion for 30 min. 2.5g of 650 polyamide curing agent was added and stirred well. And (3) placing the mixed solution in a vacuum box, exhausting air at room temperature for 5min, standing for 30min, uniformly coating the mixed solution on the surface of a substrate by using a coating rod, and drying at room temperature for 3 days to obtain the acid-base response self-repairing anticorrosive coating with the addition of the nano container being 1.5% of the epoxy matrix.
Example 4
1. Preparation of ZIF-8 self-sacrifice template:
dissolving zinc nitrate hexahydrate in 100mL of methanol to form a solution A, wherein the concentration of the zinc nitrate is 42 mM; 2-methylimidazole was weighed and dissolved in 100mL of methanol to form solution B, the concentration of 2-methylimidazole was 0.65M. The solution B was poured into the solution A, and the mixed solution was vigorously stirred for 3 hours at a stirring speed of 3000 rpm/min. And (4) centrifugally washing, washing for 3 times by using methanol, and drying at 60 ℃ overnight to obtain the ZIF-8 nano particles.
2. Preparing a hollow mesoporous silica sphere core:
400mL of a mixed solution of water and absolute ethyl alcohol is prepared, the volume ratio of the water to the absolute ethyl alcohol is 5:4, 2-methylimidazole is added, and the concentration of the 2-methylimidazole is controlled to be 62 mM. And (2) ultrasonically dispersing the ZIF-8 nano particles obtained by the steps in a mixed solution consisting of water, absolute ethyl alcohol and 2-methylimidazole for 30min, adding a CTAC surfactant, and fully stirring for 30min, wherein the concentration of CTAC is 0.17M. And (3) dropwise adding tetraethoxysilane into the system, wherein the concentration of tetraethoxysilane in the mixed solution is 40mM, and continuously stirring for 2 hours. The solid product was added to 100mL of 0.1M HCl aqueous solution and stirred for 30 min. The solid product was dried at 70 ℃ for 12 h. Obtaining the hollow mesoporous silica sphere core.
3. Preparing a hollow mesoporous silica nano container:
activating the hollow silica spherical shell at the high temperature of 200 ℃ for 2 hours, dispersing the hollow silica spherical shell in a benzotriazole acetone saturated solution, and mixing the mixed solutionAnd transferring into a closed container, vacuumizing the container by using a vacuum pump until no continuous bubbles emerge in the system, gently stirring for 2 hours, then unloading vacuum, and repeating the loading step for 3 times. Centrifuging at 7000rpm, adding 20mL of 2-methylimidazole (2.3M) water solution into the solid product, stirring, and adding 2mLZn (NO) into the system3)2·H2O (0.3M) (0.3M) aqueous solution. The mixture was stirred vigorously for 5min at a speed of 3000 rpm/min. Centrifugally washing, and vacuum drying at 70 deg.C for 12 hr. Obtaining the hollow mesoporous silica nano container.
4. Preparing an acid-base response self-repairing anticorrosive coating:
grinding 125mg of hollow mesoporous silica nanocontainer and 5g E20 epoxy resin by a nano grinder for 30 min. Adding 5mL of xylene-n-butanol mixed solution (V: V ═ 7:3), stirring uniformly, fully dissolving, and then carrying out ultrasonic dispersion for 30 min. 2.5g of 650 polyamide curing agent was added and stirred well. And (3) placing the mixed solution in a vacuum box, exhausting air at room temperature for 5min, standing for 30min, uniformly coating the mixed solution on the surface of a substrate by using a coating rod, and drying at room temperature for 3 days to obtain the acid-base response self-repairing anticorrosive coating with the addition of the nano container being 2.5% of the epoxy matrix.
Example 5
1. Preparation of ZIF-8 self-sacrifice template:
dissolving zinc nitrate hexahydrate in 100mL of methanol to form a solution A, wherein the concentration of the zinc nitrate is 42 mM; 2-methylimidazole was weighed and dissolved in 100mL of methanol to form solution B, the concentration of 2-methylimidazole was 0.65M. The solution B was poured into the solution A, and the mixed solution was vigorously stirred for 3 hours at a stirring speed of 3000 rpm/min. And (4) centrifugally washing, washing for 3 times by using methanol, and drying at 60 ℃ overnight to obtain the ZIF-8 nano particles.
2. Preparing a hollow mesoporous silica sphere core:
400mL of a mixed solution of water and absolute ethyl alcohol is prepared, the volume ratio of the water to the absolute ethyl alcohol is 5:4, 2-methylimidazole is added, and the concentration of the 2-methylimidazole is controlled to be 62 mM. And (2) ultrasonically dispersing the ZIF-8 nano particles obtained by the steps in a mixed solution consisting of water, absolute ethyl alcohol and 2-methylimidazole for 30min, adding a CTAC surfactant, and fully stirring for 30min, wherein the concentration of CTAC is 0.17M. And (3) dropwise adding tetraethoxysilane into the system, wherein the concentration of tetraethoxysilane in the mixed solution is 40mM, and continuously stirring for 2 hours. The solid product was added to 100mL of 0.1M HCl aqueous solution and stirred for 30 min. The solid product was dried at 70 ℃ for 12 h. Obtaining the hollow mesoporous silica sphere core.
3. Preparing a hollow mesoporous silica nano container:
activating the hollow silica spherical shell at the high temperature of 200 ℃ for 2h, dispersing the hollow silica spherical shell in a benzotriazole acetone saturated solution, transferring the mixed solution into a closed container, vacuumizing the container by using a vacuum pump until no continuous bubbles emerge in the system, gently stirring for 2h, then unloading the vacuum, and repeating the loading step for 3 times. Centrifuging at 7000rpm, adding 20mL of 2-methylimidazole (2.3M) water solution into the solid product, stirring, and adding 2mLZn (NO) into the system3)2·H2O (0.3M) (0.3M) aqueous solution. The mixture was stirred vigorously for 5min at a speed of 3000 rpm/min. Centrifugally washing, and vacuum drying at 70 deg.C for 12 hr. Obtaining the hollow mesoporous silica nano container.
4. Preparing an acid-base response self-repairing anticorrosive coating:
200mg of hollow mesoporous silica nanocontainer and 5g E20 epoxy resin were ground for 30min by a nano grinder. Adding 5mL of xylene-n-butanol mixed solution (V: V ═ 7:3), stirring uniformly, fully dissolving, and then carrying out ultrasonic dispersion for 30 min. Adding 650 g of polyamide curing agent, and stirring uniformly. And (3) placing the mixed solution in a vacuum box, exhausting air at room temperature for 5min, standing for 30min, uniformly coating the mixed solution on the surface of a substrate by using a coating rod, and drying at room temperature for 3 days to obtain the acid-base response self-repairing anticorrosive coating with the addition of the nano container being 4% of that of the epoxy matrix.
Example 6
1. Preparation of ZIF-8 self-sacrifice template:
dissolving zinc nitrate hexahydrate in 100mL of methanol to form a solution A, wherein the concentration of the zinc nitrate is 42 mM; 2-methylimidazole was weighed and dissolved in 100mL of methanol to form solution B, the concentration of 2-methylimidazole was 0.65M. The solution B was poured into the solution A, and the mixed solution was vigorously stirred for 3 hours at a stirring speed of 3000 rpm/min. And (4) centrifugally washing, washing for 3 times by using methanol, and drying at 60 ℃ overnight to obtain the ZIF-8 nano particles.
2. Preparing a hollow mesoporous silica sphere core:
preparing 600mL of mixed solution of water and absolute ethyl alcohol, wherein the volume ratio of the water to the absolute ethyl alcohol is 5:4, adding 2-methylimidazole, and controlling the concentration of the 2-methylimidazole to be 62 mM. And (2) ultrasonically dispersing the ZIF-8 nano particles obtained by the steps in a mixed solution consisting of water, absolute ethyl alcohol and 2-methylimidazole for 30min, adding a CTAC surfactant, and fully stirring for 30min, wherein the concentration of CTAC is 0.17M. And (3) dropwise adding tetraethoxysilane into the system, wherein the concentration of tetraethoxysilane in the mixed solution is 40mM, and continuously stirring for 2 hours. The solid product was added to 100mL of 0.1M HCl aqueous solution and stirred for 30 min. The solid product was dried at 70 ℃ for 12 h. Obtaining the hollow mesoporous silica sphere core.
3. Preparing a hollow mesoporous silica nano container:
activating the hollow silica spherical shell at the high temperature of 200 ℃ for 2h, dispersing the hollow silica spherical shell in a benzotriazole acetone saturated solution, transferring the mixed solution into a closed container, vacuumizing the container by using a vacuum pump until no continuous bubbles emerge in the system, gently stirring for 2h, then unloading the vacuum, and repeating the loading step for 3 times. After centrifugation at 7000rpm, the solid product was poured into 20mL of 2-methylimidazole (4.0M) aqueous solution and stirred well, and 2mL of Zn (NO) was added to the system3)2·H2O (0.3M) (0.5M) aqueous solution. The mixture was stirred vigorously for 5min at a speed of 3000 rpm/min. Centrifugally washing, and vacuum drying at 70 deg.C for 12 hr. Obtaining the hollow mesoporous silica nano container.
4. Preparing an acid-base response self-repairing anticorrosive coating:
grinding 100mg of hollow mesoporous silica nanocontainer and 5g E20 epoxy resin by a nano grinder for 30 min. Adding 5mL of xylene-n-butanol mixed solution (V: V ═ 7:3), stirring uniformly, fully dissolving, and then carrying out ultrasonic dispersion for 30 min. 2.5g of 650 polyamide curing agent was added and stirred well. And (3) placing the mixed solution in a vacuum box, exhausting air at room temperature for 5min, standing for 30min, uniformly coating the mixed solution on the surface of a substrate by using a coating rod, and drying at room temperature for 3 days to obtain the acid-base response self-repairing anticorrosive coating with the addition of the nano container being 2% of that of the epoxy matrix.
Example 7
1. Preparation of ZIF-8 self-sacrifice template:
dissolving zinc nitrate hexahydrate in 100mL of methanol to form a solution A, wherein the concentration of the zinc nitrate is 42 mM; 2-methylimidazole was weighed and dissolved in 100mL of methanol to form solution B, the concentration of 2-methylimidazole was 0.65M. The solution B was poured into the solution A, and the mixed solution was vigorously stirred for 3 hours at a stirring speed of 3000 rpm/min. And (4) centrifugally washing, washing for 3 times by using methanol, and drying at 60 ℃ overnight to obtain the ZIF-8 nano particles.
2. Preparing a hollow mesoporous silica sphere core:
500mL of a mixed solution of water and absolute ethyl alcohol is prepared, the volume ratio of the water to the absolute ethyl alcohol is 5:4, 2-methylimidazole is added, and the concentration of the 2-methylimidazole is controlled to be 62 mM. And (2) ultrasonically dispersing the ZIF-8 nano particles obtained by the steps in a mixed solution consisting of water, absolute ethyl alcohol and 2-methylimidazole for 30min, adding a CTAC surfactant, and fully stirring for 30min, wherein the concentration of CTAC is 0.17M. And (3) dropwise adding tetraethoxysilane into the system, wherein the concentration of tetraethoxysilane in the mixed solution is 40mM, and continuously stirring for 2 hours. The solid product was added to 100mL of 0.1M HCl aqueous solution and stirred for 30 min. The solid product was dried at 70 ℃ for 12 h. Obtaining the hollow mesoporous silica sphere core.
3. Preparing a hollow mesoporous silica nano container:
activating the hollow silica spherical shell at the high temperature of 200 ℃ for 2h, dispersing the hollow silica spherical shell in a benzotriazole acetone saturated solution, transferring the mixed solution into a closed container, vacuumizing the container by using a vacuum pump until no continuous bubbles emerge in the system, gently stirring for 2h, then unloading the vacuum, and repeating the loading step for 3 times. After centrifugation at 7000rpm, the solid product was poured into 20mL of 2-methylimidazole (4.0M) aqueous solution and stirred well, and 2mL of Zn (NO) was added to the system3)2H2O (0.3M) (0.5M) aqueous solution. The mixture was stirred vigorously for 30min at a speed of 3000 rpm/min. Centrifuging, washing at 70 deg.C under vacuumDrying for 12 h. Obtaining the hollow mesoporous silica nano container.
4. Preparing an acid-base response self-repairing anticorrosive coating:
grinding 100mg of hollow mesoporous silica nanocontainer and 5g E20 epoxy resin by a nano grinder for 30 min. Adding 5mL of xylene-n-butanol mixed solution (V: V ═ 7:3), stirring uniformly, fully dissolving, and then carrying out ultrasonic dispersion for 30 min. 2.5g of 650 polyamide curing agent was added and stirred well. And (3) placing the mixed solution in a vacuum box, exhausting air at room temperature for 5min, standing for 30min, uniformly coating the mixed solution on the surface of a substrate by using a coating rod, and drying at room temperature for 3 days to obtain the acid-base response self-repairing anticorrosive coating with the addition of the nano container being 2% of that of the epoxy matrix.
The scanning electron microscope and the transmission electron microscope of the hollow mesoporous silica sphere core prepared in the embodiments 1 to 7 are shown in fig. 1 to 2, the particle size of the hollow mesoporous silica sphere core is 50 to 200nm, the transmission electron microscope of the prepared hollow mesoporous silica nanocapsule is shown in fig. 3, the hollow mesoporous silica nanocapsule prepared in the embodiments 1 to 7 is mainly spherical, the particle size is concentrated in 200 to 350nm, the size is uniform, and the hollow mesoporous silica nanocapsule in the particle size range enables a ZIF-8 layer to prevent the corrosion inhibitor from leaking to a large extent, enables a local alkaline substance to enter the hollow mesoporous silica sphere core through the ZIF-8 layer and react with the hollow mesoporous silica sphere core, so that the silica collapses the skeleton, releases the corrosion inhibitor, and realizes the acid-base dual response.
The hollow mesoporous silica composite nanocontainer prepared in example 1 of the present invention was placed in aqueous solutions of different pH to obtain the release kinetics curve of fig. 4. As can be seen from fig. 4, in a neutral environment (pH 7), only a very small amount of the corrosion inhibitor leaked from the nano-container. In the solution with pH 4 and 10, the release of the corrosion inhibitor is in a rapid and then gentle rule. The hollow mesoporous silica is shown to have good response and release capacity under both acidic and alkaline conditions.
The acid-base response self-repairing anticorrosive coating prepared in the embodiment 5 of the invention is coated on the surface of Q235 carbon steel, and Bode diagrams after soaking in 3.5 wt% NaCl aqueous solution at different stages are measured by an Electrochemical Impedance Spectroscopy (EIS) technology, wherein FIG. 5(a) is a Bode model diagram, and FIG. 6(b) is a Bode phase angle diagram. The result shows that in the process of soaking the coating for the first 21 days, along with the diffusion of the electrolyte solution through micropores in the coating, the measured low-frequency impedance value (| Z0.01Hz |) in the Bode diagram (figure 5) is gradually reduced, and the frequency range of the high-frequency region phase angle at-90 DEG in the Bode phase angle diagram (figure 6) is reduced, which reflects the gradual reduction of the barrier performance of the coating. But after 30 days of soaking, the low-frequency impedance value is greatly increased, the phase angle of the intermediate-frequency region is increased to minus 90 degrees again, and the corrosion inhibitor is released to be adsorbed on the exposed metal surface to form a new protective film to prevent the corrosion reaction from proceeding mainly due to the response of the hollow mesoporous silica nano container to the pH change caused by corrosion. The electrochemical impedance spectrogram fully shows the self-repairing and anti-corrosion effects of the acid-base dual-response self-repairing and anti-corrosion coating.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A preparation method of an acid-base double-response hollow mesoporous silica composite nano container is characterized by comprising the following steps:
s1, uniformly dispersing ZIF-8 nano powder in a mixed solution of water, absolute ethyl alcohol and a pH value regulator, adding a surfactant, stirring at a stirring speed of 600-1200 rpm/min, dropwise adding tetraethoxysilane, and uniformly mixing; centrifugally washing, namely adding the collected solid product into dilute hydrochloric acid for etching; centrifugally washing, and drying the product in vacuum to obtain hollow mesoporous silica nanoparticles;
s2, activating hollow mesoporous silica nanoparticles, uniformly dispersing the hollow mesoporous silica nanoparticles in a saturated corrosion inhibitor solution, placing the saturated corrosion inhibitor solution in a closed container, and vacuumizing; stirring and centrifuging to obtain a solid product; adding the solid product into the organic ligand solution, uniformly stirring, adding the zinc salt hydrate solution, and stirring for 5-30 min at the rotating speed of 2000-3000 rpm/min; centrifugally washing, collecting a product, and drying in vacuum to obtain a hollow mesoporous silica composite nano container;
the concentration of the zinc salt hydrate is 42-50 mM; the imidazole organic ligand is 2-methylimidazole; the dosage concentration of the imidazole organic ligand substance is 0.65-0.75M;
the preparation method of the ZIF-8 nano powder comprises the following steps: adding a zinc salt hydrate and an imidazole organic ligand into methanol respectively, fully stirring and dissolving to obtain a solution A and a solution B, mixing the solution A and the solution B, stirring and reacting at room temperature at 2000-3000 rpm/min, centrifuging, washing and drying to obtain a solid product.
2. The method for preparing the acid-base dual-response hollow mesoporous silica composite nanocontainer according to claim 1, wherein: the zinc salt hydrate is one or more of zinc nitrate hexahydrate, zinc chloride, zinc sulfate, zinc acetate and zinc gluconate; the concentration ratio of the zinc salt hydrate to the 2-methylimidazole is 1: 2-1: 4, and the stirring reaction time is 3-4 h.
3. The method for preparing the acid-base dual-response hollow mesoporous silica composite nanocontainer according to claim 1 or 2, wherein: in S1, the volume of a mixed solution of water, absolute ethyl alcohol and a pH value regulator is 400-600 mL, wherein the volume ratio of water to absolute ethyl alcohol is 5: 4; the surfactant is cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide, and the concentration of the surfactant is 0.17-0.20M; the acid-base regulator is one of ammonia water, sodium hydroxide and 2-methylimidazole, and the concentration is 62 mM-70 mM;
the concentration of the ethyl orthosilicate is 30-50 mM; dispersing ZIF-8 nano powder in an ethanol water solution by using ultrasonic for 30-60 min; the stirring time after the surfactant is added is 30-90 min; the concentration of the dilute hydrochloric acid is 0.01-0.1M; the etching time is 30-90 min.
4. The method for preparing the acid-base dual-response hollow mesoporous silica composite nanocontainer according to claim 1 or 2, wherein: in S2, the solvent used by the saturated solution of the corrosion inhibitor is acetone, absolute ethyl alcohol or butanone; the organic ligand solution is a 2-methylimidazole aqueous solution, and the concentration is 2.3-4.0M; the zinc salt hydrate solution is one or more of zinc nitrate hexahydrate aqueous solution, zinc chloride aqueous solution, zinc acetate aqueous solution and zinc gluconate aqueous solution, and the concentration of the zinc salt hydrate solution is 0.3-0.5M; adding the corrosion inhibitor, stirring for 3-6 h, and vacuum drying at 40-70 ℃.
5. The method for preparing the acid-base dual-response hollow mesoporous silica composite nanocontainer according to claim 1 or 2, wherein: the corrosion inhibitor is one or more of benzotriazole, 2-mercapto benzothiazole, 8-hydroxyquinoline, methylbenzotriazole and nitrobenzotriazole.
6. An acid-base dual-response hollow mesoporous silica composite nanocontainer prepared by the method of any one of claims 1 to 5, wherein: the corrosion inhibitor is loaded inside the hollow mesoporous silica sphere core, the ZIF-8 nanometer valve is coated on the outer surface of the hollow mesoporous silica sphere core, the particle size of the hollow mesoporous silica sphere core is 50-200 nm, and the particle size of the hollow mesoporous silica composite nanometer container is 200-350 nm.
7. The acid-base dual-response hollow mesoporous silica composite nanocontainer of claim 6, wherein: the particle size of the hollow mesoporous silica sphere core is 100-150 nm, and the particle size of the hollow mesoporous silica composite nano container is 250-300 nm.
8. The self-repairing anticorrosive coating is characterized by comprising a resin matrix and the acid-base dual-response hollow mesoporous silica composite nano container produced by the method of claim 1 or 2, wherein the addition amount of the hollow mesoporous silica composite nano container is 1% -4% of that of the resin matrix.
9. The preparation method of the self-repairing anticorrosive coating of claim 8, characterized by comprising the following steps: and mixing the hollow mesoporous silica composite nano container with a resin matrix, and dispersing to obtain a nano particle size.
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| CN114163860A (en) * | 2021-11-30 | 2022-03-11 | 上海应用技术大学 | ZIF-8 structure-based nano container and sol-gel coating and preparation method thereof |
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