CN110699691A - Metal organic framework corrosion inhibitor hydrogel composite material and preparation method and application thereof - Google Patents
Metal organic framework corrosion inhibitor hydrogel composite material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000463 material Substances 0.000 claims abstract description 38
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910016644 EuCl3 Inorganic materials 0.000 description 1
- 229910018957 MClx Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
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- 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
- C23F11/14—Nitrogen-containing compounds
-
- 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
- C23F11/12—Oxygen-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
The invention discloses a metal organic framework corrosion inhibitor hydrogel composite material and application thereof, wherein the metal organic framework corrosion inhibitor hydrogel composite material is prepared by functionalizing a gallium-based metal organic framework material Eu by europium ions3+The @ MIL-124(Ga) carries the corrosion inhibitor and is packaged by the temperature-sensitive hydrogel to form the recyclable corrosion inhibitor hydrogel compound. The corrosion inhibitor hydrogel compound can release a corrosion inhibitor through a windowing effect to carry out targeted repair on corrosion sites, and after the corrosion inhibitor is subjected to film formation protection, the temperature-sensitive hydrogel can be easily stripped through phase separation and the MOF and the temperature-sensitive hydrogel are recovered, so that the corrosion-resistant flaw-detection band-aid for the marine engineering steel structure plays a role in corrosion detection of the marine engineering steel structure. The corrosion inhibitor hydrogel compound can realize the integration of quantitative detection, smart response and protection and repair functions of marine corrosion, and has remarkable application value and wide market prospect.
Description
Technical Field
The invention relates to the technical field of marine steel anticorrosive coating materials, in particular to a metal organic framework corrosion inhibitor hydrogel composite material and a preparation method and application thereof.
Background
At present, the development of oceans in China enters the golden period, however, oceanic corrosion is a big problem in the process of ocean development, and the development of ocean economy in China is severely restricted. The marine environment is the most corrosive natural environment. Seawater is a very corrosive electrolyte solution, and contains a large amount of salts, including sodium chloride and salts containing elements such as potassium, bromine, and iodine. The ocean corrosion can cause the damage of the steel structure of the ocean engineering and shorten the service life, thereby causing serious economic loss and even safety accidents. An organic Migration Corrosion Inhibitor (MCI) is used as a simple, economic and efficient marine steel Corrosion-resistant material, and is an important method for preventing and treating marine Corrosion.
Although the corrosion inhibitor has excellent corrosion resistance, the corrosion inhibitor is easy to occur in marine environment and has very limited service life. The current common solution is to utilize a nano microcapsule encapsulated corrosion inhibitor to dope the corrosion inhibitor to the coating and then coat the coating on the surface of a substrate, thereby achieving the effect of slow release and even controllable release. However, the response of the microcapsules to the corrosion primary sites is mainly based on stress cracking of the coating under the condition of microcracks, belongs to the response under the condition of physical action, and compared with the response under the condition of chemical action of corrosion product ions, the microcapsules have slow sensitivity, are difficult to identify the induction stage of corrosion, and can only be used for protection and repair in the corrosion development stage. In addition, the barrier of the coating can also influence the flexibility of the microcapsule and the permeability of a corrosion inhibitor, and the corrosion inhibition effect is reduced.
The Metal-Organic Frameworks (MOFs) have the advantages of pore size adjustability, functional designability, excellent thermal stability and chemical stability, convenience and simplicity in synthesis and the like, and have great potential application prospects in the fields of gas storage and separation, catalysis, chemical and physical sensing, drug delivery, proton conduction, photoelectricity, imaging and the like. The luminescent MOFs material has the advantages that metal ions, organic ligands and guest molecules in the components can be used as luminescent centers, the framework structure is adjustable, host-guest interaction exists and the like, and is widely reported in the fields of ion detection and temperature imaging because luminescent sites are rich. In marine engineering, corrosion is inducedThe corrosion product ion of the stage is Fe3+The corrosion product ion at the corrosion development stage is Fe2+. Xu et al (2015) disclose a method for the treatment of Fe3+And Fe2+Fluorescent probe Eu with high selectivity and sensitivity of ions3+@ MIL-124, the first reported to have very good detection of Fe in an aqueous environment3+And Fe2+(III) europium ion-Functionalized doped metal-Organic framework material (Xu X Y, Yan B. Eu (III) -Functionalized MIL-124as Fluorescent Probe for high hly Selective Sensing Ions and Organic Small Molecules for Fe (III) and Fe (II) without any structural disintegration of the metal framework [ J. X, III) -functional doped metal-Organic framework material].ACS Applied Materials&Interfaces,2015,7(1): 721-; however, no reports are available for responding, recognizing the chemical action of marine corrosion product ions and performing targeted repair on corrosion sites; and the existing nano microcapsule encapsulation corrosion inhibitor for marine corrosion prevention is basically disposable and cannot be recycled.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a metal organic framework corrosion inhibitor hydrogel composite material.
The invention also aims to provide a preparation method of the metal-organic framework corrosion inhibitor hydrogel composite material.
The invention further aims to provide application of the metal-organic framework corrosion inhibitor hydrogel composite material.
The above object of the present invention is achieved by the following technical solutions:
a hydrogel composite material of a metal organic framework corrosion inhibitor is prepared by a metal organic framework material Eu loaded with the corrosion inhibitor3+@ MIL-124(Ga) and temperature-sensitive hydrogel packaged on the surface of the @ MIL-124 (Ga).
In the invention, the europium ion functionalized gallium-based metal organic framework material Eu3+@ MIL-124(Ga) as carrier of fluorescent probe and corrosion inhibitor for detecting and identifying corrosion product ions, and temperature-sensitive waterThe gel is used as a metal organic framework material Eu loaded with corrosion inhibitor3+The support of @ MIL-124 (Ga). The metal organic framework material Eu3+@ MIL-124(Ga) is Eu3+@ MIL-124, the chemical formula of MIL-124 is Ga2(OH)4(C9O6H4)，Eu3+@ MIL-124 has a chemical formula of [ Eu @3+][Ga2(OH)4(C9O6H4)]3. The metal organic framework material Eu3+The fluorescence characteristic of @ MIL-124(Ga) can realize the corrosion product ions (inducing stage Fe) of steel in marine environment at different stages3+Stage of development Fe2+) The specific response of the probe has the characteristics of high sensitivity, high identification degree and high selectivity, and can realize specific response detection of the whole corrosion stage. The metal organic framework material is used for loading the corrosion inhibitor in a high-loading capacity, and the temperature-sensitive hydrogel is used for packaging to obtain a corrosion inhibitor hydrogel compound, so that the obtained compound can be used for further carrying out corrosion detection and repair on the marine steel structure. It is based on the exchange behavior of corrosion product ions with MOF guest metal ions; meanwhile, the windowing effect of the MOF framework structure caused in the ion exchange process can realize the smart response release of the corrosion inhibitor. In particular Eu3+@ MIL-124(Ga) Eu3+Ions pass through corrosion product ions (Fe) with different induction periods and development periods of steel corrosion3+、Fe2+) Different fluorescence phenomena (quenching and color change) and intensities thereof are generated by exchange, so that the corrosion site is accurately positioned and quantitatively detected, and the encapsulated corrosion inhibitor is released through a windowing effect to carry out targeted repair on the corrosion site. The temperature-sensitive hydrogel is adopted as a carrier, so that the compound has the advantages of easy coating, stripping and recycling, the MOF and the hydrogel can be conveniently recycled, and the whole body has the effect of a flaw detection type band-aid of a marine steel structure; the corrosion inhibitor is not required to be doped in a coating and then coated on the surface of a substrate like the traditional nano microcapsule encapsulated corrosion inhibitor, and the effect of the corrosion inhibitor is fully exerted due to less barrier of the coating.
Preferably, the Eu3+@ MIL-124(Ga) is formed by coupling Eu and carbonyl groups in channels of laminar MIL-124(Ga)3+The cation undergoes a coordination reaction to obtain Eu3+@ MIL-124 (Ga). In particular to MIL-124(Ga) and Eu which are prepared by hydrothermal reaction3+Performing a coordination reaction to obtain Eu3+@ MIL-124(Ga), MIL-124(Ga) and Eu3+The dosage ratio in the coordination reaction is 2: 1; more specifically, MIL-124(Ga) and EuCl are taken3·6H2Soaking O in excessive ethanol for 48-72 h, centrifugally separating, repeatedly washing precipitates with ethanol, and then carrying out vacuum drying to obtain Eu3+@MIL-124(Ga)。
Theoretically, the corrosion inhibitor can prevent or slow down the corrosion of the steel material and can be loaded on the metal organic framework material Eu3+@ MIL-124(Ga) without affecting its respective properties; preferably, the corrosion inhibitor is benzotriazole, also known as Benzotriazole (BTA); the obtained metal organic framework material loaded with the corrosion inhibitor is BTA @ Eu3+@MIL-124(Ga)。
Preferably, the temperature-sensitive hydrogel is P (NIPAM-co-AAc). The P (NIPAM-co-AAc) hydrogel is easy to coat on the surface of a detected steel structure, the P (NIPAM-co-AAc) is a solution at the temperature below 46 ℃, and is crosslinked at the temperature above 46 ℃, the stripping, separation and purification of the compound are realized by temperature-sensitive phase separation, the MOF and the P (NIPAM-co-AAc) are recovered from the compound, and the cost is reduced by recycling.
Preferably, the loading content of the corrosion inhibitor in the metal organic framework material is 7.62-10.6%, and the content is mass content; the load efficiency is 63-68%.
Preferably, the metal-organic framework material Eu loaded with corrosion inhibitor3+The content of @ MIL-124(Ga) in the temperature-sensitive hydrogel is 0.07-0.10%, and the content is mass content.
The invention also provides a preparation method of any of the metal organic framework corrosion inhibitor hydrogel composite material, and Eu is used3+Soaking @ MIL-124(Ga) and a corrosion inhibitor in an excessive alcohol solution, stirring for 12-24 h, then centrifugally collecting precipitates, and drying in vacuum to obtain a metal organic framework material Eu loaded with the corrosion inhibitor3+@ MIL-124 (Ga); then the dissolved temperature-sensitive hydrogel is taken and fully mixed with the metal organic framework material to obtainObtaining the metal organic framework corrosion inhibitor hydrogel compound.
Preferably, the molar ratio of the corrosion inhibitor to Eu3+ @ MIL-124(Ga) is 5: 6-8.
Preferably, the metal-organic framework material Eu loaded with corrosion inhibitor3+The mass ratio of @ MIL-124(Ga) to the temperature-sensitive hydrogel is 0.7-1: 1000.
The invention also claims the metal organic framework material Eu3+The application of @ MIL-124(Ga) in preparing marine anticorrosive coating materials; in particular, the method is used for preparing ion (Fe) capable of specifically responding to corrosion products3+And Fe2+) And the application in the coating material for targeted repair of corrosion sites.
The invention also provides application of any metal organic framework corrosion inhibitor hydrogel composite material in marine corrosion prevention, which is to coat any metal organic framework corrosion inhibitor hydrogel composite material on the surface of a steel structure, change the temperature of hydrogel after repair is completed to enable the hydrogel to be separated, strip the hydrogel from the surface of the steel structure, purify and recycle MIL-124(Ga) and the hydrogel, and recycle the hydrogel.
Specifically, the purification and recovery comprises the steps of dissolving the compound in ultrapure water at room temperature, filtering, recovering the filtrate to obtain hydrogel, repeatedly washing the precipitate with nitric acid, and drying in vacuum to obtain MIL-124 (Ga). The recycled MIL-124(Ga) and the temperature-sensitive hydrogel can be further used for preparing the metal organic framework corrosion inhibitor hydrogel composite material.
Preferably, the composite material is anchored and coated on the surface of the steel structure to be repaired, and the thickness of the composite material is 0.5-2 mm.
Compared with the prior art, the invention has the following beneficial effects:
1. can be recycled. The metal organic framework corrosion inhibitor hydrogel composite material can realize the integration of quantitative detection, smart response and protection and repair functions of marine corrosion, takes hydrogel as a carrier, is coated on a marine steel structure for detection and repair, can be easily peeled off and separated from MOF by utilizing the characteristic of temperature-sensitive phase separation, and obtains MIL-124(Ga) and hydrogel again after washing, thereby greatly saving the application cost. The corrosion inhibitor is not required to be doped in a coating and then coated on the surface of a substrate like the traditional nano microcapsule encapsulated corrosion inhibitor, and the effect of the corrosion inhibitor is fully exerted due to less barrier of the coating.
2. The applicability is strong. The metal organic framework corrosion inhibitor hydrogel composite material has a wide application range, and has excellent corrosion detection, repair and protection performances in both the corrosion induction period and the corrosion development period of a marine steel structure.
3. High efficiency. The metal organic framework corrosion inhibitor hydrogel composite material disclosed by the invention is low in consumption, can be coated on the surface of an ocean steel structure in a large area, can detect the corrosion condition of the steel structure, and can effectively inhibit the damage of the steel structure in a corrosion medium.
4. Fluorescence detectability. The metal organic framework corrosion inhibitor hydrogel composite material can realize high-sensitivity, high-identification and high-selectivity fluorescence detection on marine engineering corrosion product ions so as to position sites in a corrosion induction period and a development period.
5. Targeted release and self-reparative properties. The metal organic framework corrosion inhibitor hydrogel composite material provided by the invention acts on a corrosive medium, can perform targeted recognition and release on corrosive ionic chloride ions, and simultaneously performs corrosion repair on corroded steel bars to prevent the steel bars from being further corroded.
6. The durability is good. The metal organic framework corrosion inhibitor hydrogel composite material has the function of resisting corrosion product ions (Fe) in the environment2+And Fe3+Ions) to respond to the release capacity, the corrosion inhibitor can be released, and simultaneously, the corrosion product ions can be detected through fluorescence to position corrosion sites, so that the corrosion inhibition efficiency can be kept high in an acid environment for a long time.
Drawings
FIG. 1 shows the synthetic route and application principle of the corrosion inhibitor hydrogel composite provided by the embodiment of the invention.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The invention is based on BTA @ Eu3+Eu between @ MIL-124(Ga) layers3+The exchange behavior of ions and product ions of different corrosion stages of the steel structure in the marine environment realizes high-sensitivity, high-identification and high-selectivity fluorescence detection, specifically Eu3+Ionic and corrosion induced phase of Fe3+Quenching of fluorescence after ion exchange with Fe during corrosion development2+The fluorescence turns from red to blue and the intensity is weakened after ion exchange, meanwhile, the sealed BTA is released through the windowing effect to repair and protect the corrosion sites, P (NIPAM-co-AAc) hydrogel is taken as a carrier, so that the corrosion inhibitor hydrogel composite is easy to coat on the surface of a marine steel structure, after ion exchange fluorescence detection and corrosion inhibitor repair film-forming protection, the temperature is changed to separate the hydrogel carrier, the stripping is easy, the recovery and utilization of the MOF and the P (NIPAM-co-AAc) are convenient, and the integral flaw detection type band-aid of the marine steel structure plays a role.
In ocean engineering, the fluorescence probe of the compound is used for corrosion product ions in different stages (inducing stage Fe)3+Stage of development Fe2+) The detection principle is based on the exchange behavior of corrosion product ions and guest metal ions in the MOF. Meanwhile, the windowing effect of the MOF framework structure caused in the ion exchange process can realize the smart response release of the corrosion inhibitor. P (NIPAM-co-AAc) as packaging BTA @ Eu3+The carrier of @ MIL-124(Ga) is easy to coat on the surface of a steel structure, can release a corrosion inhibitor to carry out targeted repair on corrosion sites through a windowing effect while accurately positioning and detecting the corrosion-induced and development-period sites, and the temperature-sensitive hydrogel can be easily stripped and recover MOF and P (NIPAM-co-AAc) through phase separation after the corrosion inhibitor is subjected to film formation protection, thereby playing a role of a flaw detection type band-aid in corrosion of the steel structure in ocean engineering. The use of the corrosion inhibitor hydrogel composite can realizeThe quantitative detection, smart response and protection and repair functions of marine corrosion are integrated, and the method has obvious application value and wide market prospect.
EXAMPLE 1 europium ion-functionalized gallium-based Metal organic framework Material Eu3+Preparation of @ MIL-124(Ga)
Synthesis of Eu3+@ MIL-124(Ga), the chemical reaction equation of which is as follows:
2Ga(NO3)3+4H2O+C9H6O6＝Ga2(OH)4(C9O6H4)+6HNO3(1)
Eu3++3Ga2(OH)4(C9O6H4)＝[Eu3+][Ga2(OH)4(C9O6H4)]3(2)
1. first, 1.2g of Ga (NO) is added at room temperature3)3·xH2O, 0.74g trimellitic acid (molar ratio 4:3) and 10mL ultrapure water were mixed and stirred for 30min to obtain a mixture A. And transferring the mixture A to a Teflon-lined hydrothermal synthesis reaction kettle, heating at 210 ℃ for 24 hours to obtain a mixture B, wherein the initial pH values before and after heating are 0.4 and 0.6 respectively. Centrifuging the mixture B at 13000rpm for 5min to obtain white solid powder, washing with ultrapure water for 3 times, and drying at 100 deg.C for 24h to obtain MIL-124 (Ga). 0.2g of prepared MIL-124(Ga) was taken with 0.4mol of EuCl3·6H2O, soaking in 15mL ethanol for 48h, centrifugally separating, washing with ethanol, and vacuum drying at 80 ℃ for 6h to obtain the europium ion functionalized gallium-based metal organic framework material [ Eu ]3+][Ga2(OH)4(C9O6H4)]3Is marked as Eu3+@MIL-124(Ga)。
2. For the Eu obtained above3+@ MIL-124(Ga) to verify Eu3+The successful packaging specifically comprises the following steps:
the test method comprises the following steps: respectively taking 2mg of the Eu3+@ MIL-124(Ga) in a concentration of 1X 10 with 2mL-2mol/L MClx(Mn+＝K+，Na+，Hg2+，Cd2+，Ca2+，Ni2+，Co2+，Mn2+，Cu2+，Fe2+，Fe3+，Al3+) Mixing the solutions at room temperature, and collecting 2mg of Eu3+Mixing @ MIL-124(Ga) with 2mL of ultrapure water at room temperature, respectively carrying out fluorescence spectrum measurement on each group of mixture, and then respectively irradiating the mixture containing Fe by 254nm ultraviolet light3+And Fe2+A mixture of (a).
Fe content was determined experimentally in the manner given above3+The mixture of (A) has no emission peak and contains Fe2+The mixture of (A) has a weak emission peak at 615nm, and the remaining mixture has a strong emission peak at 615 nm; under the irradiation of 254nm ultraviolet light, contains Fe3+The mixture of (A) is non-fluorescent and contains Fe2+The mixture of (a) had a weak blue light and the remaining mixture had a strong red fluorescence. This indicates that Eu3+Has been successfully encapsulated into MIL-124(Ga), and Eu3+Fluorescence characteristics of @ MIL-124(Ga) can specifically detect Fe3+Hair and Fe2+Is present.
Example 2
1. Based on Eu3+Preparation of corrosion inhibitor hydrogel compound of functional Ga-MOF packaged BTA
The first step is as follows: preparation of BTA @ Eu3+@MIL-124(Ga)
0.12g of Eu prepared in the above example3+@ MIL-124(Ga) and 0.013g of Benzotriazole (BTA) are stirred in 15mL of methanol solution for 12h, then centrifuged at 5500rpm for 20min, and dried in vacuum at 100 ℃ for 6h to obtain a BTA-supported metal-organic framework material BTA @ Eu @3+@MIL-124(Ga)。
The second step is that: preparation of BTA @ Eu3+@ MIL-124(Ga) corrosion inhibitor hydrogel composite.
2.26g of isopropylacrylamide, 0.154g N, N' -methylenebisacrylamide and 0.289g of acrylic acid were added to 100mL of ultrapure water, heated to 70 ℃ under nitrogen protection and stirred at 600 rpm. After 1h, 1.5mg of potassium persulfate was dissolved in 1mL of ultrapure water and added dropwise to the mixture to produce turbidity. After 4h, the heating was stopped, the mixture was cooled to room temperature, stirred under nitrogen for 24h and then super-agitatedDialyzing with pure water for 7 days, and freeze-drying to obtain P (NIPAM-co-AAc) hydrogel. 100g of hydrogel solution and 0.1g of prepared BTA @ Eu were taken3+@ MIL-124(Ga), thoroughly mixed to obtain BTA @ Eu3+@ MIL-124(Ga) corrosion inhibitor hydrogel composite.
2. The relative fluorescence intensity of the corrosion inhibitor hydrogel compound is measured
Conditions are as follows: the experimental material is carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), and the corrosion inhibitor is the corrosion inhibitor hydrogel compound prepared in the above embodiment 3-12; the medium is 3.5 percent sodium chloride solution, the dosage is 300mL, and the temperature is 35 ℃; the carbon steel is subjected to environment dry-wet alternate treatment for 8 times in advance before being coated with the corrosion inhibitor hydrogel compound; and (3) respectively measuring fluorescence spectra when the coating is finished and after the coating is carried out for 48 hours, then heating hydrogel to 50 ℃ to enable the hydrogel to be subjected to phase separation and to be stripped from the surface of the carbon steel, placing the compound after stripping into 100mL of ultrapure water to be dissolved at room temperature, filtering, recovering filtrate to obtain P (NIPAM-co-AAc), repeatedly washing precipitate with nitric acid, and carrying out vacuum drying to obtain MIL-124 (Ga). The recovered MIL-124(Ga) and P (NIPAM-co-AAc) were used to prepare a corrosion inhibitor hydrogel composite anew as described in examples 1 and 2 and the experiment was performed anew as described above, and the fluorescence spectrum was measured, which was repeated 8 times.
The relative fluorescence intensity of the corrosion inhibitor hydrogel compound obtained by experimental tests for 8 times of repeated operations according to the determination method given above is respectively as follows: 2.46%, 2.44%, 2.45%, 2.42%, 2.38%, 2.39%, 2.36%, 2.34%, indicating that the complex is a recyclable and stable-effect fluorescent probe for corrosion product ions.
Examples 3 to 12
According to the preparation process of the corrosion inhibitor hydrogel composite described in the embodiment 2, BTA @ Eu is supported by adjusting the dosage of the raw materials according to the recorded use range of the raw materials3+Different amounts of the corrosion inhibitor hydrogel compounds of @ MIL-124(Ga) change the times of the dry-wet alternative treatment of the carbon steel (namely, before coating the corrosion inhibitor hydrogel compounds, the carbon steel is immersed in 3.5 percent sodium chloride solution for 8 hours, then taken out and dried for 16 hours at the humidity of 50 percent and the temperature of 25 ℃ for one treatment weekPeriod 24h), and the temperature of the sodium chloride solution for carbon steel soaking (see table 1).
TABLE 1 Condition design for examples 3-12
Performance testing
The corrosion inhibitor hydrogel compound of the embodiment 3-12 is used for measuring the ion detection performance and the corrosion inhibition efficiency of the corrosion product.
1. Conditions are as follows: the experimental material is carbon steel (Fe: 99.5%, Mn: 0.4-0.5%, C: 0.1-0.2%), and the corrosion inhibitor is the corrosion inhibitor hydrogel compound prepared in the above embodiment 3-12; the medium is 3.5% sodium chloride solution, the dosage is 300mL, and the temperature is set according to the solution temperature in the table 1; before coating the corrosion inhibitor hydrogel compound, carbon steel is subjected to environment dry-wet alternate treatment for several times in advance according to the setting in the table 1, then the corrosion inhibitor hydrogel compound obtained in the embodiment is coated, the temperature is 35 ℃, after 48 hours, the compound is stripped through physical crosslinking, and fluorescence spectra are respectively measured after coating and before stripping.
A weight loss test is carried out according to GB10124-88 'method for testing uniform corrosion in a metal material laboratory', and corrosion inhibition performance characterization is carried out by two electrochemical methods, namely an electrochemical alternating-current impedance spectrum and potentiodynamic polarization. The experimental test methods used are from the literature: 【1】 Li, L.Hu, S.Zhang, B.Hou, Effects of two functides on the corrosion resistance and of the counter in 3.5% NaCl solution under variations conditions [ J ], Corros Sci.2011,53: 735-.
2. Results
The corrosion inhibitor hydrogel compound obtained in examples 3 to 12 was tested by experiments according to the determination method given above, and the corrosion inhibition efficiency and the relative fluorescence intensity are shown in table 2:
table 2 Corrosion inhibition efficiency and relative fluorescence intensity of the hydrogel compounds of the corrosion inhibitors described in examples 3-12
| Weight loss | Electrochemical impedance spectroscopy | Potentiodynamic polarization curve | Relative fluorescence intensity | |
| Example 3 | 93.4％ | 93.7％ | 94.6％ | 2.44％ |
| Example 4 | 94.3％ | 94.5％ | 94.8％ | 2.38％ |
| Example 5 | 95.3％ | 96.1％ | 96.6％ | 2.53％ |
| Example 6 | 96.3％ | 96.6％ | 96.8％ | 2.47％ |
| Example 7 | 98.3％ | 97.7％ | 98.5％ | 48.2％ |
| Example 8 | 96.5％ | 97.1％ | 97.6％ | 0.23％ |
| Example 9 | 95.4％ | 95.3％ | 96.1％ | 1.77％ |
| Example 10 | 96.5％ | 96.7％ | 96.9％ | 2.32％ |
| Example 11 | 96.1％ | 96.3％ | 95.9％ | 2.47％ |
| Example 12 | 95.6％ | 95.8％ | 96.2％ | 2.45％ |
The test result shows that the metal organic framework corrosion inhibitor hydrogel composite material has the advantages of being recyclable, low in dosage, high in sensitivity, high in identification degree and high in selectivity, can be used in corrosive media by positioning the sites in the corrosion induction period and the development period, can perform targeted identification and release on corrosive ions and chloride ions, can perform corrosion repair on corroded steel bars, prevents the steel bars from being corroded further, and can keep high corrosion inhibition efficiency in an acidic environment for a long time. The metal organic framework corrosion inhibitor hydrogel composite material can realize the integration of quantitative detection, smart response and protection and repair functions of marine corrosion, and has remarkable application value and wide market prospect.
Claims (10)
1. The hydrogel composite material of the metal organic framework corrosion inhibitor is characterized in that the metal organic framework material Eu loaded with the corrosion inhibitor3+@ MIL-124(Ga) and temperature-sensitive hydrogel packaged on the surface of the @ MIL-124 (Ga).
2. The metal-organic framework corrosion inhibitor hydrogel composite material of claim 1, wherein the corrosion inhibitor is benzotriazole.
3. The metal-organic framework corrosion inhibitor hydrogel composite material according to claim 1, wherein the temperature-sensitive hydrogel is P (NIPAM-co-AAc).
4. The metal-organic framework corrosion inhibitor hydrogel composite material according to claim 1 or 2, wherein the loading content of the corrosion inhibitor in the metal-organic framework material is 7.62-10.6%.
5. The metal-organic framework corrosion inhibitor hydrogel composite material according to claim 1 or 3, wherein the corrosion inhibitor-loaded metal-organic framework material Eu3+The content of @ MIL-124(Ga) in the temperature-sensitive hydrogel is 0.07-0.10%.
6. The method for preparing the metal-organic framework corrosion inhibitor hydrogel composite material of any one of claims 1 to 5, wherein Eu is added3+Soaking @ MIL-124(Ga) and a corrosion inhibitor in an excessive alcohol solution, stirring for 12-24 h, then centrifugally collecting precipitates, and drying in vacuum to obtain a metal organic framework material Eu loaded with the corrosion inhibitor3+@ MIL-124 (Ga); and then the dissolved temperature-sensitive hydrogel is fully mixed with the metal organic framework material loaded with the corrosion inhibitor to obtain the metal organic framework corrosion inhibitor hydrogel compound.
7. The preparation method according to claim 6, wherein the molar ratio of the corrosion inhibitor to Eu3+ @ MIL-124(Ga) is 5: 6-8.
8. The method according to claim 6, wherein the corrosion inhibitor-loaded metal-organic framework material Eu3+The mass ratio of @ MIL-124(Ga) to the temperature-sensitive hydrogel is 0.7-1: 1000.
9. Metal organic framework material Eu3+Application of @ MIL-124(Ga) in preparing marine anticorrosive coating materials.
10. The application of the metal organic framework corrosion inhibitor hydrogel composite material as claimed in any one of claims 1 to 5 in marine corrosion prevention is characterized in that the metal organic framework corrosion inhibitor hydrogel composite material as claimed in any one of claims 1 to 5 is coated on the surface of a steel structure, after the repair is completed, the temperature of hydrogel is changed to enable the hydrogel to be subjected to phase separation, the hydrogel is stripped from the surface of the steel structure, and MIL-124(Ga) and the hydrogel are purified and recovered for recycling.
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