CN116855950A - Corrosion inhibition material of smart carrier controlled green corrosion inhibitor, and preparation method and application thereof - Google Patents
Corrosion inhibition material of smart carrier controlled green corrosion inhibitor, and preparation method and application thereof Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to the technical field of steel anticorrosion coating materials, and discloses a corrosion inhibition material of a smart carrier controlled green corrosion inhibitor, a preparation method and application thereof. The corrosion inhibition material comprises cabbage extract CAE and a luminescent metal-organic framework MIL-53 (Al), and the cabbage extract is loaded on the luminescent metal-organic framework. The corrosion inhibition material has high fluorescence response and can produce ion Fe in the steel corrosion induction stage in marine environment 3+ Has high sensitivity and selective recognition performance, fe 3+ MIL-53 (Al) with high fluorescence effect can be converted into MIL-53 (Fe) with low fluorescence effect through metal cation exchange, so that fluorescence is quenched, self-early warning of corrosion induction period is realized, meanwhile, a pore canal is opened in the ion exchange process, and the smart release corrosion inhibitor CAE can quickly conduct targeted repair on a corrosion site, and further corrosion is inhibited for a long time.
Description
Technical Field
The invention relates to the technical field of steel anticorrosion coating materials, in particular to a corrosion inhibition material of a smart carrier controlled green corrosion inhibitor, a preparation method and application thereof.
Background
With the implementation of ocean national strategies, ocean engineering develops for one day and one thousand days, and great opportunities and challenges are met. Ocean tunnels, offshore industries, offshore drilling platforms, etc. are rapidly evolving, but are facing serious corrosion challenges. The steel corrosion in the ocean not only causes economic loss, but also causes serious threat to the ocean environment and even human life health. Development of advanced marine preservative measures is of paramount importance.
The corrosion inhibitor is widely studied because of low dosage, good effect and simple construction. However, once highly effective inorganic corrosion inhibitors are gradually being replaced by organic corrosion inhibitors due to their low environmental protection and high toxicity. The organic corrosion inhibitor may be adsorbed onto the metal surface at the cathode/anode sites by p-electrons of the double bond and/or electron pairs of the heteroatom (N, O, S), thereby forming a protective layer. However, organic synthetic corrosion inhibitors generally require chemical synthesis, which presents environmental pollution and toxicity risks, and safety precautions and operating regulations are required during use. Therefore, their use is greatly limited. Plant extracts have been of great interest due to their more environmentally friendly, renewable, lower safety risk and good corrosion inhibition properties. The plant is used as a rich compound library, the compound extracted from the plant can be used as a green corrosion inhibitor, particularly a compound rich in N, S, O and other polar groups, and the lone pair electrons contained in the compound are easily transferred to an empty track of Fe, so that firm coordination bonds are formed, further corrosion of a corrosion medium is prevented, and low-concentration addition can be realized to reduce the corrosion rate. They are capable of a) altering the rate or mechanism of the anode/cathode reaction, b) affecting the diffusion of aggressive ions to the metal surface, and c) forming a protective layer on the metal surface and increasing the resistance of the overall electrochemical system. The Casaletto et al extract from rape extracts 'green' respectively researches the corrosion inhibition effect of the extract on steel in sodium chloride and acid solution, found that flavonoid compounds, thioglucoside, hydroxycinnamic acid derivatives, hydroxy fatty acids and sucrose exist in the extract, and the extract is rich in various polar groups to provide lone pair electrons, and the research result shows that the optimal corrosion inhibition efficiency of the extract on steel in sodium chloride solution is 79.3%, and the optimal corrosion inhibition efficiency in acid solution is 38% (Casaletto M P, figa V, privitera A, et al Inhibition of Cor-Ten steel corrosion by 'green' extracts of Brassica campestris [ J ]. Corros, sci., 2018, 136:91-105 ]) the extract not only contains a large amount of unsaturated bonds, N, O and other polar groups, can interact with Fe and be adsorbed on the surface of steel, but also can effectively reduce the cost of corrosion inhibitor and pollution to the environment.
The metal-organic frameworks (MOFs) have different pore topological structures, accessible cage-like structures and tunnel-like structures, have unique characteristics of permanent nano-porosity, high specific surface area, intra-pore functionality and external surface modification, and have bright application prospects in the fields of gas storage catalysis, drug delivery, imaging and the like. So far, a variety of luminescent MOFs have been explored to recognize metal ions. Cu is achieved based on metal-ligand coordination interactions (weak binding of metal ions to heteroatoms (N or O) within the ligand) and intramolecular energy transfer from ligand to metal ion 2+ 、Fe 3+ 、Co 2+ 、Ag + 、Zn 2+ 、Mg 2+ MOFs sensing of (Allendorf MD, bauer CA, bhakta RK, houk RJT. Luminescent metal-organic frameworks. Chemical Society reviews. 2009; 38:1330-52.). In addition, tian et al found that MOFs gradually and continuously released the smart carrier of the Corrosion inhibitor, prolonging the duration of the Corrosion inhibitor action (Tian HW, li WH, liu A, gao X, han P, ding R, et al Controlled delivery of multi-substituted triazole by metal-organic framework for efficient inhibition of mild steel Corrosion in neutral chloride solution, corrosion Sci.2018; 131:1-16.). The invention combines the green of plant extractThe color property and the fluorescence and sensitivity of MOFs material construct a corrosion inhibition material with high efficiency, quick response, high sensitivity and high selection, and can be applied to the marine environment to identify the occurrence of steel corrosion and inhibit the progress of steel corrosion.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, meet the requirements of low carbon and environmental protection, and provide a corrosion inhibition material of a smart carrier controlled green corrosion inhibitor, and a preparation method and application thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows: a corrosion inhibition material of smart carrier controlled green corrosion inhibitor comprises cabbage extract and luminescent metal-organic frame, wherein the cabbage extract is loaded on the luminescent metal-organic frame;
the extraction method of the cabbage extract comprises the following steps: crushing cabbage, adding ultrapure water, steaming to a mass volume ratio of 1g to (0.5-1) mL, filtering, and freeze-drying filtrate to obtain cabbage extract, called CAE;
the preparation method of the luminescent metal-organic framework MIL-53 (Al) comprises the following steps: al (NO) 3 ) 3 ·9H 2 O, 1, 4-phthalic acid (BDC) and dimethylformamide are mixed for 20-60 min, then heated at 130 ℃ for 60-100 h, cooled, washed by dimethylformamide and ultrapure water, and dried to obtain luminescent metal-organic framework powder, namely MIL-53 (Al).
CAE is used as a green corrosion inhibitor, so that the green low-carbon sustainable requirement is met, the acquisition cost is low, and the corrosion inhibition effect is obvious. The main active ingredients of CAE are 1, 2-diazaindolizine, 2 (3H) -furanone, dihydro-5-propyl and vinylfuran, contain a large number of lone pair electrons, are easy to form chemical bonds with steel, and are potential excellent corrosion inhibitor objects in the field of maritime industry.
Luminescent metal-organic frameworks MIL-53 (Al) as detection and identification of early corrosion product ions (induction phase) Fe 3+ The fluorescent probe and the smart release carrier of the green corrosion inhibitor CAE can realize Fe in the steel corrosion induction period 3+ The high sensitivity visual intelligent detection of specific response and high effective load and sensitivity release to CAE. MIL-53 (Al) is made of Al 3+ BDC and OH - The group composition has excellent chemical and solvent stability, does not hydrolyze in aqueous solution, and lays a foundation for the application of the corrosion inhibition material. MIL-53 (Al) vs. Fe 3+ Has high selectivity, and is common in marine environment such as Na + 、Cl - In particular Fe 2+ For Fe 3+ The fluorescence quenching effect of the corrosion inhibition material is hardly interfered, so that the corrosion inhibition material can be used as a corrosion inhibition material for early warning of the occurrence stage of corrosion; in addition MIL-53 (Al) vs. Fe 3+ Has high sensitivity and can identify Fe in aqueous solution 3+ The linear concentration range of (2) is 3-200 mu M, and the lowest concentration detection lower limit is 0.9 mu M. The luminescent metal-organic framework MIL-53 (Al) has the advantages of simple synthesis method and low cost, and CAE does not complex with central metal ions of MIL-53 (Al) in the loading process, so that the original structure is not damaged, and the loading capacity can reach 35.2%. The corrosion inhibition material CAE@MIL-53 (Al) is mixed with Fe 3+ When cation exchange occurs, a plurality of pore channels are opened, the corrosion inhibitor CAE needs to be released, and the protection efficiency can reach 95.0% after 5 minutes of release, which is far faster than that of the existing corrosion inhibition material.
Further; the load mass content of MIL-53 (Al) to CAE is 35.2%.
Further; the Al (NO) 3 ) 3 ·9H 2 The mass volume ratio of O, BDC to dimethylformamide is 19.7mg to 12.95mg to 1mL.
The other technical scheme of the invention is as follows: the preparation method of the corrosion inhibition material of the smart carrier controlled green corrosion inhibitor comprises the following steps: and adding MIL-53 (Al) into the methanol solution of the CAE, stirring for 10-15 hours, centrifuging for 20-30 minutes at 5000-6000 rpm, collecting precipitate, and vacuum drying at 100 ℃ to remove residual solvent to obtain the light-emitting metal-organic framework corrosion inhibition material CAE@MIL-53 (Al) loaded with the CAE.
Further; the mass volume ratio of CAE, MIL-53 (Al) and methanol is 6 mg:8.5 mg:10 mL.
The invention further provides a technical scheme that: the corrosion inhibition material of the smart carrier controlled green corrosion inhibitor is applied to the preparation of ocean anti-corrosion coating materials.
The invention has the beneficial effects that:
(1) "green" efficiency: the green corrosion inhibitor used by the corrosion inhibition material of the smart carrier controlled green corrosion inhibitor is extracted from cabbage, is nontoxic and degradable, meets the requirement of green chemistry, is simple to prepare and low in cost, has the corrosion inhibition efficiency of CAE on carbon steel in simulated seawater which is far higher than that of the prior organic corrosion inhibitor Benzotriazole (BTA), and has an electrochemical impedance spectrum value of 95.9%.
(2) The synthesis is simple, and the load is high: the luminescent metal-organic framework MIL-53 (Al) is selected as the corrosion inhibition material of the smart carrier controlled green corrosion inhibitor, and the synthesis method is simple and the cost is low; in the process of loading the corrosion inhibitor CAE, no adverse side reaction exists, and the loading capacity reaches 35.2 percent.
(3) High sensitivity and high selectivity: the corrosion inhibition material of the smart carrier controlled green corrosion inhibitor of the invention produces ions Fe in the corrosion induction stage 3+ Has specific fluorescence response, and only needs 0.9 mu M Fe 3+ Quenching the original fluorescence of the corrosion inhibition material, and other anions and cations such as Na common in marine environment + 、Cl - 、Fe 2+ For Fe 3+ The identification of (2) has no obvious influence, and the characteristic provides a quick response visualization means for efficiently monitoring the early stage of steel corrosion in the marine environment, thereby being convenient for workers to maintain the steel engineering.
(4) Quick-acting property: the corrosion inhibition material of the smart carrier controlled green corrosion inhibitor of the invention is used in combination with Fe 3+ And when fluorescence is quenched, a pore canal of MIL-53 (Al) is opened, a corrosion inhibitor CAE is released in a sensitive way, and after the corrosion inhibitor CAE is released into the environment for 5 minutes, effective protection of steel can be realized, and the corrosion inhibition efficiency is as high as 95.0%.
Drawings
FIG. 1 is a synthetic route and application principle of a corrosion inhibition material of a smart carrier controlled green corrosion inhibitor prepared in example 1 of the present invention.
Detailed Description
The following examples are intended to illustrate the present invention in further detail. The following examples are only illustrative of the present invention, but the present invention is not limited to these examples. All equivalent changes and modifications within the scope of the present invention should be made. The various materials referred to in the specification are all available from the market.
Example 1
A preparation method of a corrosion inhibition material of a smart carrier controlled green corrosion inhibitor comprises the following steps:
(1) Extraction of green corrosion inhibitor CAE: crushing 300g of cabbage, adding into a beaker, adding 1L of ultrapure water into the beaker, steaming until the water level is reduced to 200 mL, filtering, and freeze-drying the filtrate for 24 hours to obtain cabbage extract CAE;
(2) Preparation of luminescent metal-organic frameworks MILs-53 (Al): 1.1820g of Al (NO) 3 ) 3 ·9H 2 Mixing O, 0.7770g BDC and 60mL Dimethylformamide (DMF) for 30min, transferring to a 100mL polytetrafluoroethylene lining stainless steel autoclave, heating at 130 ℃ for 72 h, cooling, cleaning with DMF and ultrapure water respectively, and drying to obtain luminescent metal-organic framework powder MIL-53 (Al);
(3) 60mg of CAE prepared in the step (1) is added into 100mL of methanol solution, 85mg of MIL-53 (Al) prepared in the step (2) is added after dissolution, continuous stirring is carried out for 12 hours, centrifugation is carried out for 20 minutes at 5500 rpm, precipitation is collected, and residual solvent is removed by vacuum drying at 100 ℃ to obtain the CAE-loaded luminescent metal-organic frame corrosion inhibition material CAE@MIL-53 (Al).
Example 2
A preparation method of a corrosion inhibition material of a smart carrier controlled green corrosion inhibitor comprises the following steps:
(1) Extraction of green corrosion inhibitor CAE: crushing 300g of cabbage, adding into a beaker, adding 1L of ultrapure water into the beaker, steaming until the water level is reduced to 150 mL, filtering, and freeze-drying the filtrate for 24 hours to obtain cabbage extract CAE;
(2) Preparation of luminescent metal-organic frameworks MILs-53 (Al): 1.1820g of Al (NO) 3 ) 3 ·9H 2 Mixing O, 0.7770g BDC and 60mL Dimethylformamide (DMF) for 20min, transferring to 100mL polytetrafluoroethylene lining stainless steel autoclave, heating at 130deg.C for 100 hr, cooling, cleaning with DMF and ultrapure water, drying to obtain luminescent metal-organic framework powder MILs-53 (Al);
(3) 60mg of CAE prepared in the step (1) is added into 100mL of methanol solution, 85mg of MIL-53 (Al) prepared in the step (2) is added after dissolution, continuous stirring is carried out for 10 hours, centrifugation is carried out at 5000 rpm for 30 minutes, sediment is collected, and residual solvent is removed by vacuum drying at 100 ℃ to obtain the CAE-loaded luminescent metal-organic frame corrosion inhibition material CAE@MIL-53 (Al).
Example 3
A preparation method of a corrosion inhibition material of a smart carrier controlled green corrosion inhibitor comprises the following steps:
(1) Extraction of green corrosion inhibitor CAE: crushing 300g of cabbage, adding the crushed cabbage into a beaker, adding 1L of ultrapure water into the beaker, steaming until the water level is reduced to 300 mL, filtering, and freeze-drying the filtrate for 24 hours to obtain cabbage extract CAE;
(2) Preparation of luminescent metal-organic frameworks MILs-53 (Al): 1.1820g of Al (NO) 3 ) 3 ·9H 2 O, 0.7770g BDC and 60mL Dimethylformamide (DMF) are mixed for 60min, then transferred into a 100mL polytetrafluoroethylene lining stainless steel autoclave, heated for 60 hours at 130 ℃, cooled, washed with DMF and ultrapure water respectively, and dried to obtain luminescent metal-organic framework powder MIL-53 (Al);
(3) Adding 60mg of CAE prepared in the step (1) into 100mL of methanol solution, dissolving, adding 85mg of MIL-53 (Al) prepared in the step (2), continuously stirring for 15 hours, centrifuging at 6000 rpm for 20 minutes, collecting precipitate, and vacuum drying at 100 ℃ to remove residual solvent to obtain the CAE-loaded luminescent metal-organic frame corrosion inhibition material CAE@MIL-53 (Al).
Comparative example 1:
the preparation method of BTA@MIL-53 (Al) comprises the following steps:
step (2) is the same as in example 1;
and (3) adding 60mg of BTA into 100mL of methanol solution, uniformly mixing, adding 85mg of MIL-53 (Al) prepared in the step (2), continuously stirring for 12 hours, centrifuging at 5500 rpm for 20 minutes, collecting precipitate, and vacuum drying at 100 ℃ to remove residual solvent to obtain the luminescent metal-organic frame corrosion inhibition material BTA@MIL-53 (Al) loaded with BTA.
Performance test:
thermogravimetric analyses were performed on CAE, MIL-53 (Al), CAE@MIL-53 (Al), BTA@MIL-53 (Al), and BTA prepared in example 1 and comparative example 1. The loading rate of the corrosion inhibitor is measured by a thermogravimetric method, and the analysis method is as follows: tian HW, li WH, liu A, gao X, han P, ding R, et al Controlled delivery of multi-substituted triazole by metal-organic framework for efficient inhibition of mild steel corrosion in neutral chloride solution Corro. Sci. 2018;131:1-16.
The analysis result shows that the load mass content of CAE in CAE@MIL-53 (Al) is 35.2%; the load mass content of BTA in BTA@MIL-53 (Al) is 10.5%; the load of the corrosion inhibitor CAE is higher than that of BTA by more than 3 times.
The CAE@MIL-53 (Al) and BTA@MIL-53 (Al) prepared in example 1 and comparative example 1 were subjected to corrosion inhibition performance tests by electrochemical impedance spectroscopy. The testing method comprises the following steps: taking simulated seawater (namely 3.5 wt percent NaCl solution) as a corrosion medium, and respectively adding CAE@MIL-53 (Al) and BTA@MIL-53 (Al) into the simulated seawater to ensure that the concentration gradients of the CAE and the BTA are 25mg/L, 50mg/L, 70mg/L and 100mg/L; q235 steel is taken as a research object, the Q235 steel is soaked for 24 hours at room temperature, and the corrosion inhibition performance characterization is carried out by adopting electrochemical alternating current impedance spectroscopy. Experimental test methods reference: fernandes CM, alvarez LX, dos Santos NE, barrios ACM, ponzio EA. Green synthesis of-benzyl-4-phenyl-1H-1, 2,3-triazole, its application as corrosion inhibitor for mild steel in acidic medium and new approach of classical electrochemical analytics, corros, sci.2019; 149:185-94. The experimental results are shown in table 1.
TABLE 1 comparison of Corrosion inhibition effects of BTA@MIL-53 (Al) and CAE@MIL-53 (Al)
| Corrosion inhibiting material | Corrosion inhibitor concentration (mg/L) | Electrochemical impedance spectroscopy |
| BTA@MIL-53 (Al) | 25 | 77.0 % |
| BTA@MIL-53 (Al) | 50 | 83.1 % |
| BTA@MIL-53 (Al) | 75 | 86.4 % |
| BTA@MIL-53 (Al) | 100 | 88.7 % |
| CAE@MIL-53 (Al) | 25 | 88.4 % |
| CAE@MIL-53 (Al) | 50 | 92.3 % |
| CAE@MIL-53 (Al) | 75 | 94.1 % |
| CAE@MIL-53 (Al) | 100 | 95.9 % |
As can be seen from Table 1, the corrosion inhibition effect of the simulated seawater after Q235 steel is soaked for 24 hours under the condition of adding the corrosion inhibitor with the same concentration is far higher than that of BTA@MIL-53 (Al) BTA, and the corrosion inhibition effectiveness of the CAE@MIL-53 (Al) on steel in the simulated seawater can be proved to be an excellent corrosion inhibitor applied to the field of marine engineering.
3. MIL-53 (Al) vs. Fe prepared in example 1 3+ Is selected from the group consisting of a test of selectivity of (a) and (b).
Cations (Na) + 、Mg 2+ 、Ca 2+ 、K + ) And anions (Cl) - 、SO 4 2− 、CO 3 2− 、Br - ) Iron and steel corrosion induction phase product ions (Fe 3+ ) And the product ions of the development stage (Fe 2+ ) Respectively dissolving the ion source into ultrapure water solutions to obtain interference ion solutions, wherein the concentrations of the interference ion solutions are 150 mu M. Equal amounts of pure MIL-53 (Al) (50 mg/L) were mixed with ultrapure water and various interfering ion solutions, respectively, and the solutions were uniformly dispersed by ultrasonic treatment for 5 minutes, and fluorescence spectrometry was performed. Luminescence was measured by fluorescence spectroscopy, test method reference: fan DH, liu XB, qi K, chen ZY, qia YB, liao BK, et al, smart-sensing coating based on dual-emission fluorescent Zr-MOF composite for autonomous warning of coating damage and aluminum corrosion, prog Org coat.2022; 172:9.
All solutions were found to exhibit fluorescence peaks at 410nm, and the relative fluorescence intensities were calculated by comparing the fluorescence intensity of pure MIL-53 (Al) with the fluorescence intensity in the presence of various interfering ions to evaluate the occurrence of fluorescence quenching, and the results are shown in Table 2.
TABLE 2 fluorescent response of MIL-53 (Al) to different ions
| Type of cation | Na + | Mg 2+ | Ca 2+ | K + | Fe 3+ | Fe 2+ |
| Relative fluorescence intensity | 0.99 | 0.98 | 0.97 | 0.98 | 0.57 | 0.97 |
| Type of cation | Cl - | SO 4 2− | CO 3 2− | Br - | ||
| Relative fluorescence intensity | 0.96 | 0.96 | 0.94 | 0.97 |
At 150 mu M Fe 3+ The following interfering ions were added to MIL-53 (Al) ultrapure water solutions, respectively, at concentrations of 0.8M Na, respectively + ，0.35 M K + ， 6 mM Ca 2+ ，4 mM Mg 2+ ，3 mM Fe 2+ ，0.8 M Cl − ，60 mM NO 2 − And NO 3 − ，10 mM SO 4 2− ，8 mM CO 3 2− And 5 mM Br - . By fluorescence spectroscopy, the Fe containing 150 mu M is not added with other ions 3+ The ratio of the fluorescence intensities of MIL-53 (Al) ultrapure water solution to obtain the relative fluorescence intensity.
The above-mentioned cation/anion interference ion pair MIL-53 (Al) and Fe 3+ The interference results of the fluorescence quenching phenomenon therebetween are shown in Table 3.
TABLE 3 different interfering ion pairs MIL-53 (Al) and Fe 3+ Interference conditions between fluorescence quenching
| Type of cation | Na + | Mg 2+ | Ca 2+ | K + | Fe 2+ |
| Relative fluorescence intensity | 0.56 | 0.52 | 0.52 | 0.50 | 0.54 |
| Type of cation | Cl - | SO 4 2− | CO 3 2− | Br - | |
| Relative fluorescence intensity | 0.53 | 0.51 | 0.54 | 0.55 |
As is clear from tables 2 and 3, only Fe 3+ So that the relative fluorescence intensity of the aqueous solution of MIL-53 (Al) is less than 0.9 and 0.57, indicating Fe 3+ The existence of the fluorescent dye greatly reduces the luminous intensity of MIL-53 (Al), namely fluorescence quenching phenomenon occurs, and meanwhile, the common positive/negative interference ions in the marine environment have no obvious influence on the fluorescence quenching phenomenon. In particular, MIL-53 (Al) is used for treating ion Fe generated in the development stage of steel corrosion 2+ There was no significant quenching. Thus, these interfering ions are specific to Fe 3+ Metal ion Al with MIL-53 (Al) 3+ The cation exchange process between the two has no obvious effect and does not influence the fluorescence quenching phenomenon between the two. This indicates luminescenceMIL-53 (Al) vs. Fe as metal-organic framework material 3+ Has high selectivity and application potential as marine engineering early warning material.
4. MIL-53 (Al) vs. Fe prepared in example 1 3+ Sensitivity test of (2).
Dispersing 25mg MIL-53 (Al) powder in 5 mL of Fe with different concentrations (0, 1,2,3, 4, 5, 10, 20, 30, 40, 50, 100, 150, 200, 250, 300, 400 [ mu ] M) 3+ In solution. The mixture was then used for fluorescence spectroscopy and the number of fluorescence was collected after 7 minutes. Δi represents the intensity of fluorescence quenching. By Fe 3+ The concentration of (2) is on the abscissa, delta I is on the ordinate, and the lowest concentration and the highest concentration of the fitting curve which are straight lines are the minimum value and the maximum value of the linear concentration range. Will contain 150 mu M of Fe 3+ The solution was repeatedly tested 11 times to obtain a Relative Standard Deviation (RSD), and the limit of detection was calculated according to the calculation formula of the limit of detection. Probe MIL-53 (Al) vs. Fe 3+ Detection range and detection limit calculation reference: joshi BP, park J, lee WI, lee KH. Ratiometric and turn-on monitoring for heavy and transition metal ions in aqueous solution with a fluorescent peptide sensor, talanta 2009;78:903-9.
As a result of the analysis, it was found that the quenched fluorescence intensity of MIL-53 (Al) was equal to that of Fe 3+ The concentration exhibits a good linear relationship (R 2 =0.997). Contains 150 mu M Fe 3+ The Relative Standard Deviation (RSD) of 11 repeated tests of the mixed solution is 4.0%, which shows that MIL-53 (Al) is used for resisting Fe 3+ The detection accuracy of (2) is higher. Likewise, MIL-53 (Al) probe pair Fe 3+ The detection limit of (2) is also very low, 0.9. Mu.M.
5. The corrosion inhibition material CAE@MIL-53 (Al) prepared in example 1 was analyzed for its quick-acting property.
The quick-acting property of the corrosion inhibition material CAE@MIL-53 (Al) is analyzed by taking the corrosion inhibition material BTA@MIL-53 (Al) prepared in comparative example 1 as a comparison. The testing method comprises the following steps: taking simulated seawater (namely 3.5. 3.5 wt percent NaCl solution) as a corrosion medium, and respectively adding CAE@MIL-53 (Al) and BTA@MIL-53 (Al) into the simulated seawater to ensure that the concentration of the CAE and the BTA is 75mg/L; q235 steel is taken as a research object, and soaked in simulated seawater added with corrosion inhibition materials. First, 1mL of the test solution is taken every minute for fluorescence spectrum analysis until the fluorescence intensity is greatly reduced, namely fluorescence quenching occurs. And using the test solution as a starting point, and testing corrosion inhibition performances of different soaking times after quenching by adopting an electrochemical alternating current impedance spectrum. The experimental results are shown in table 4 below.
TABLE 4 Corrosion inhibition efficiency at various times after Steel Corrosion
| Corrosion inhibiting material | Soaking time after fluorescence quenching | Electrochemical impedance spectroscopy |
| BTA@MIL-53 (Al) | 5 min | 46.7 % |
| BTA@MIL-53 (Al) | 20 min | 54.8 % |
| BTA@MIL-53 (Al) | 1 h | 69.4 % |
| BTA@MIL-53 (Al) | 3 h | 76.5 % |
| BTA@MIL-53 (Al) | 5 h | 82.9 % |
| CAE@MIL-53 (Al) | 5 min | 95.0 % |
As can be seen from Table 4, the corrosion inhibition effect of the corrosion inhibition material CAE@MIL-53 (Al) prepared in example 1 can reach 95.0% after 5 minutes of fluorescence quenching, the action speed is very rapid, and the relatively good corrosion inhibition efficiency of the corrosion inhibition material CAE@MIL-53 (Al) prepared in comparative example 1 can be achieved after 5 hours, so that the quick-acting property of the corrosion inhibition material CAE@MIL-53 (Al) in seawater can be confirmed.
6. Application of corrosion inhibition material CAE@MIL-53 (Al) in anti-corrosion coating
The corrosion inhibition material CAE@MIL-53 (Al) prepared in example 1 is doped into epoxy resin E44 (6101) (purchased from Zhenjiang Danbao resin Co., ltd.) with the mass content of 0.1-0.3%, so as to obtain a corrosion inhibition coating CAE@MIL-53 (Al) @EP, the corrosion inhibition coating is coated on the surface of Q235 steel, then the Q235 steel is soaked in 500 mL simulated seawater (namely 3.5 wt% NaCl solution) at room temperature, and the corrosion inhibition performance of the corrosion inhibition coating is tested by adopting electrochemical alternating current impedance spectrum and a potentiodynamic polarization curve. The corrosion inhibition efficiency is measured by an electrochemical impedance spectroscopy experiment, and the test method is as follows: fernandes CM, alvarez LX, dos Santos NE, barrios ACM, ponzio EA. Green synthesis of-benzyl-4-phenyl-1H-1, 2,3-triazole, its application as corrosion inhibitor for mild steel in acidic medium and new approach of classical electrochemical analytics, corros, sci.2019; 149:185-94.
Potentiodynamic polarization curve experiments determine corrosion inhibition efficiency, test method references: H. tian, W, li, B, hou, novel application of a hormone biosynthetic inhibitor for the corrosion resistance enhancement of copper in synthetic seawater [ J ]. Corros, sci, 2011, 53:3435-3445. Finally, the fluorescence spectrum is measured after coating and soaking respectively, and the relative fluorescence intensity is obtained by comparing the two. The experimental results are shown in table 5.
Corrosion inhibition efficiency and fluorescence detection of the corrosion inhibition coating material CAE@MIL-53 (Al) @EP described in Table 5
| CAE@MIL-53 (Al) content | Soaking time of carbon steel | Electrochemical impedance spectroscopy | Electrokinetic polarization curve | Relative fluorescence intensity |
| 0.1 wt% | 12 h | 89.1 % | 88.3 % | 5.34 % |
| 0.2 wt% | 12 h | 92.7 % | 92.5 % | 4.67 % |
| 0.3 wt% | 12 h | 94.3 % | 94.2 % | 4.44 % |
| 0.3 wt% | 6 h | 92.4 % | 92.7 % | 5.45 % |
| 0.3 wt% | 24 h | 93.6 % | 93.8 % | 4.30 % |
| 0.3 wt% | 48 h | 93.5 % | 92.7 % | 4.21 % |
As can be seen from Table 5, the corrosion inhibition material of the smart carrier controlled green corrosion inhibitor of the invention can be applied to gain coating in the field of coating corrosion prevention, and is loaded into epoxy resin E44 (6101) to induce product ion Fe 3+
The method also has high-sensitivity and high-selectivity fluorescence detection to monitor and position the occurrence site of the corrosion induction period, and the smart release green corrosion inhibitor can quickly repair corroded steel, prevent further development of corrosion in the early corrosion induction period, and maintain high corrosion inhibition efficiency in a long-time seawater environment. The corrosion inhibition material CAE@MIL-53 (Al) of the smart carrier controlled green corrosion inhibitor can realize the functional upgrading of commercial common coatings such as E44 (6101) epoxy coating, realize the multifunctional integration of marine corrosion protection, early warning, repair and the like, and has remarkable application value and wide market prospect.
Claims (6)
1. A corrosion inhibition material of smart carrier controlled green corrosion inhibitor is characterized in that: comprises a cabbage extract and a luminescent metal-organic framework, wherein the cabbage extract is supported on the luminescent metal-organic framework;
the extraction method of the cabbage extract comprises the following steps: crushing cabbage, adding ultrapure water, steaming to a mass volume ratio of 1g to (0.5-1) mL, filtering, and freeze-drying filtrate to obtain cabbage extract, called CAE;
the preparation method of the luminescent metal-organic framework MIL-53 (Al) comprises the following steps: al (NO) 3 ) 3 ·9H 2 Mixing O, 1, 4-phthalic acid and dimethylformamide for 20-60 min, heating at 130 ℃ for 60-100 h, cooling, cleaning with dimethylformamide and ultrapure water, and drying to obtain luminescent metal-organic framework powder, namely MIL-53 (Al).
2. The corrosion inhibition material of the smart carrier controlled-release green corrosion inhibitor according to claim 1, which is characterized in that: the load mass content of MIL-53 (Al) to CAE is 35.2%.
3. The corrosion inhibition material of the smart carrier controlled-release green corrosion inhibitor according to claim 1, which is characterized in that: the Al (NO) 3 ) 3 ·9H 2 The mass volume ratio of O, 1, 4-phthalic acid and dimethylformamide is 19.7 mg:12.95 mg:1 mL.
4. The method for preparing the corrosion inhibition material of the smart carrier controlled-release green corrosion inhibitor according to any one of claims 1-3, which is characterized by comprising the following steps: and adding MIL-53 (Al) into the methanol solution of the CAE, stirring for 10-15 hours, centrifuging for 20-30 minutes at 5000-6000 rpm, collecting precipitate, and vacuum drying at 100 ℃ to remove residual solvent to obtain the light-emitting metal-organic framework corrosion inhibition material CAE@MIL-53 (Al) loaded with the CAE.
5. The method for preparing the corrosion inhibition material of the smart carrier controlled-release green corrosion inhibitor, which is characterized in that: the mass volume ratio of CAE, MIL-53 (Al) and methanol is 6 mg:8.5 mg:10 mL.
6. Use of a corrosion inhibition material of a smart green corrosion inhibitor according to any one of claims 1 to 3 for the preparation of marine anti-corrosion coating materials.
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