Application of myricetin as environment-friendly microbial corrosion inhibitor
By using Yameilin as an environmentally friendly microbial corrosion inhibitor, combining with the metal surface and forming a protective layer, the problems of environmental pollution and poor biodegradability in microbial corrosion protection in the prior art are solved, and an efficient microbial corrosion inhibition effect is achieved.
Patent Information
- Application Number
- CN202411711911.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-27
- Publication Date
- 2025-02-25
AI Technical Summary
The prior art has problems such as environmental pollution, poor biodegradability and high cost when using organic and inorganic corrosion inhibitors in preventing microbial corrosion, and lacks effective solutions that are environmentally friendly and biodegradable.
Yameilin is used as an environmentally friendly microbial corrosion inhibitor. By adding Yameilin to an environment that can cause microbial corrosion, it ensures its uniform distribution and combines with the metal surface to form a protective layer, reducing the ability of microorganisms to form a biofilm on the metal surface.
Yameilin significantly reduces the rate of microbial corrosion, inhibits the formation and activity of biological membranes, and achieves a corrosion inhibition rate of 67% to 99%, which has obvious antibacterial and corrosion resistance to various bacteria.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of metal corrosion protection and relates to application of myricetin as an environmentally friendly microbial corrosion inhibitor. Background Art
[0002] Microbiologically influenced corrosion (MIC) refers to the process in which the corrosion of metal materials is accelerated directly by the life activities of microorganisms or indirectly by their metabolites. Microorganisms interact with metals and minerals in natural and artificial environments, changing their physical and chemical states, while metals and minerals can also affect the growth, activity and survival of microorganisms. In the process of interaction between microorganisms and metals, microbial corrosion also occurs. Microbial corrosion is affected by the environment, changes in the physical and chemical properties of the material surface, the effects of inorganic corrosion products, the effects of microbial communities, and the effects of microbial metabolites on the material surface. It is a multi-directional synergistic process. At present, a variety of microbial corrosion mechanisms have been proposed, all of which are believed to be related to the presence of biofilms. Biofilms are complex local systems in which microorganisms form a synergistic microenvironment that allows various species to survive.
[0003] At present, many means of metal corrosion protection have been developed, such as metal coating, passive metal materials, cathodic protection, corrosion inhibitors, etc. For example, adding a coating to the metal surface to separate the metal from the microorganisms and corrosive media in the environment, adding bactericides and corrosion inhibitors to the corrosive medium to cut off the contact between the medium and microorganisms and the metal from the source. Due to its advantages such as ease of use, economy and high efficiency, corrosion inhibitors are the best choice in many fields. Traditional organic and inorganic corrosion inhibitors have been criticized for high synthesis costs, environmental pollution, poor biodegradability and other problems. In recent years, green corrosion inhibitors have become a research hotspot. Green corrosion inhibitors generally refer to compounds extracted from a certain part of a plant. They have the characteristics of good biocompatibility, biodegradability, and renewability, and are easy to obtain, low cost and non-toxic.
[0004] Myricetin (3,5,7,3',4',5' hexahydroxyflavonol, Myricetin) was originally isolated from the bark of bayberry. It is a polyhydroxyflavonol compound composed of light yellow crystals. Myricetin is commonly found in daily foods such as berries, fruits, vegetables, honey, red wine, and tea, and is an important active ingredient and additive in many foods. Only a few articles report that myricetin and myricetin ring have the effect of inhibiting metal corrosion, and there are no reports on the application of myricetin in microbial corrosion protection. Summary of the invention
[0005] The invention provides myricetin as an environmentally friendly microbial corrosion inhibitor, so as to better utilize environmentally friendly plant extracts for antibacterial, anti-biofilm and corrosion inhibition, which is of great significance.
[0006] To achieve the above object, the present invention adopts the following technical solutions:
[0007] The invention discloses an application of myricetin as an environmentally friendly microbial corrosion inhibitor, wherein myricetin is used as the environmentally friendly microbial corrosion inhibitor to inhibit microbial corrosion.
[0008] A further feature is that myricetin is added into an environment capable of producing microbial corrosion to ensure that the uniform mass concentration of myricetin in the environment is 0.1 to 1 g / L, more preferably 0.5 g / L.
[0009] The environment capable of producing microbial corrosion is preferably a marine environment, a soil environment, an oral environment or a transport liquid environment.
[0010] A further feature is that the myricetin can combine with the metal surface to form a protective layer, tending to form a bond between the myricetin and the metal surface, thereby being adsorbed on the metal surface, thereby reducing the metal corrosion rate.
[0011] A further feature is that the myricetin can reduce and prevent microorganisms from forming biofilms on metal surfaces, disperse and kill the biofilms that have already formed, reduce the thickness and activity of the biofilms on the metal surfaces, and thus inhibit the corrosion of metals by microorganisms.
[0012] The metal includes, but is not limited to, carbon steel, stainless steel, and titanium alloy.
[0013] The chemical structural formula of myricetin is:
[0014]
[0015] Adding 0.5 g / L of myricetin can inhibit microbial corrosion by 67% to 99%.
[0016] The preferred targeted microorganism is Bacillus licheniformis.
[0017] A method for detecting the application of myricetin as an environmentally friendly microbial corrosion inhibitor comprises the following steps:
[0018] Step 1: Preparation of environmentally friendly microbial corrosion inhibitor
[0019] Myricetin and anhydrous ethanol are mixed evenly to obtain a myricetin solution, wherein the mass concentration of the myricetin solution is 10 g / L, and the myricetin solution is diluted to 0.1-1.0 g / L using a water-soluble culture solution;
[0020] Step 2: Corrosion Inhibition
[0021] The microbial corrosion material is immersed in the myricetin solution to inhibit the microorganisms. The concentration of microbial strains in the microbial corrosion material is 10 4 ~10 7 CFU mL -1 The culture time was 7 days and the culture temperature was 30°C.
[0022] In the step 2, the blank control group is a comparison group without adding myricetin, which uses the same material for microbial corrosion as the experimental group, and adds myricetin solution corrosion inhibitor. After culturing the experimental group and the control group at the same time for 7 days, it is tested that the thickness of the biofilm on the surface of the microbial corrosion material in the experimental group is 0.5 times the thickness of the biofilm on the surface of the corrosion material in the blank control group, and the corrosion rate is 0.32 times that of the blank control group.
[0023] The myricetin of the present invention has strong corrosion inhibition ability, and exerts obvious and effective antibacterial, biofilm inhibition and corrosion resistance performance on various bacteria. As an environmentally friendly and pollution-free bactericidal substance, myricetin not only has good antibacterial and biofilm resistance performance, but also has excellent corrosion resistance performance. DETAILED DESCRIPTION
[0024] The following examples will use a variety of methods to detect the antibacterial and anti-biofilm properties of myricetin solutions and their inhibitory effects on metal corrosion:
[0025] The preparation process of the microbial inhibitor myricetin solution used in the following examples is as follows: myricetin extracted from bayberry trees and fruits is mixed with anhydrous ethanol to completely dissolve the myricetin in the anhydrous ethanol to prepare a myricetin solution with a mass concentration of 10 g / L;
[0026] The corrosion material used in this embodiment is X80 carbon steel, and its composition and the mass percentage of each component are: 1.90Mn, 0.29Ni, 0.28Si, 0.22Mo, 0.20Cu, 0.08Cr, 0.03C, 0.03V, 0.03P, 0.01S, Fe is the balance, and the steel sample size is: 10mm×10mm×5mm;
[0027] Example 1
[0028] The microorganism described in this example is Bacillus licheniformis: ATCC14580 (Oregon, USA);
[0029] The culture medium used in this embodiment is a soil simulation solution, and the specific ingredients are as follows: sucrose, 1g / L; yeast extract, 1g / L, K2HPO4, 13.9g / L; KH2PO4, 2.7g / L; NaCl, 1g / L; NaNO3, 1g / L; MgSO4, 0.25g / L; MnCl2·4H2O, 18mg / L; CoCl2·6H2O, 27mg / L; H3BO3, 5mg / L; CuCl2·2H2O, 2.4mg / L; NaMoO4·2H2O, 2.3mg / L; ZnCl2, 1.9mg / L.
[0030] In this example, electrochemical testing, corrosion morphology characterization, and corrosion product analysis were used to characterize the inhibitory effect of myricetin on microbial corrosion;
[0031] The experiments on myricetin inhibiting metal microbial corrosion caused by Bacillus licheniformis were all divided into four groups, namely, sterile group, sterile + myricetin group, Bacillus licheniformis group, and Bacillus licheniformis + myricetin group;
[0032] The specific experimental operations are as follows:
[0033] 1. Electrochemical analysis
[0034] Take steel samples, cold mount the X80 steel samples, and make electrodes. Insert the electrodes into four different systems, use a three-electrode system, and incubate for 7 days. Use an electrochemical workstation to test the corrosion inhibition performance of myricetin, and test the open circuit potential (OCP), linear polarization resistance (LPR) and electrochemical impedance spectroscopy (EIS) data of steel under four conditions. It was found that when other conditions were the same, the presence of Bacillus licheniformis made R p The value of E OCP In addition, after adding 0.5 g / L myricetin, the R p The values were much higher than those of the control group without myricetin. After 7 days of incubation, the X80 samples were subjected to potentiodynamic polarization tests. The corrosion current density (i corr ). In the sterile culture medium, the addition of myricetin reduced the corrosion current density to a certain extent. For the samples immersed in Bacillus licheniformis, the average corrosion current density increased from 3.3 μA cm to 1.5 μA cm after myricetin was added to the system. -2 Down to 9.9 nA cm -2It can be seen that myricetin has an inhibitory effect on bare metal corrosion of X80 steel and microbial corrosion caused by Bacillus licheniformis. Statistical results show that the corrosion inhibition rate of myricetin on Bacillus licheniformis microorganisms in soil environment is 99% (calculated by formula 1).
[0035] Formula 1:
[0036] where i corr represents the corrosion current density in the Bacillus licheniformis group, i' corr Represents the corrosion current density in the Bacillus licheniformis + myricetin group.
[0037] 2. Corrosion morphology characterization:
[0038] The corrosion morphology characterization was still carried out according to four different systems. The X80 steel sample was immersed in a conical flask containing four culture solutions and incubated for 7 days. After removing the corrosion products on the surface of the metal sample, its corrosion morphology was characterized by scanning electron microscopy. The results showed that the surface corrosion marks of the metal sample without adding myricetin were obvious, and the corrosion pits on the surface were many and deep. When 0.5g / L myricetin was added to the system, the corrosion pits on the surface of the sample became fewer and shallower. At the same time, after the metal sample was treated in the same way as above, the pitting pits on the metal surface were photographed by laser confocal microscopy. The results showed that the diameter of the sample pitting pits was larger and deeper in the medium containing Bacillus licheniformis, while the depth and width of the pitting pits on the surface of the X80 sample were significantly reduced in the sterile and bacterial media with the addition of myricetin. The above results can all show that myricetin has the ability to reduce the rate of metal corrosion regardless of the presence or absence of Bacillus licheniformis.
[0039] 3. Corrosion product analysis:
[0040] The corrosion product analysis was still carried out according to four different systems. The X80 steel sample was immersed in a conical flask containing four culture solutions for 7 days. The corrosion products formed on the surface of the sample were analyzed using X-ray photoelectron spectroscopy. In the system without the addition of myricetin, the surface of the immersed sample was mainly composed of trivalent iron ion oxides and divalent iron ion oxides. In the system with the addition of myricetin, the FeO content on the surface of X80 increased significantly, and Fe was detected. These results further confirm that myricetin can effectively inhibit the corrosion of X80 carbon steel regardless of the presence of Bacillus licheniformis.
[0041] Example 2
[0042] The microorganism described in this example is Bacillus licheniformis: ATCC14580 (Oregon, USA);
[0043] The culture medium used in this embodiment is soil simulation liquid, and the specific composition is shown in Example 1;
[0044] In this example, a tungsten filament scanning electron microscope (SEM, EVO 10, Zeiss, Germany) was used;
[0045] In this example, a confocal laser scanning microscope (CLSM, LSM 900, Zeiss, Germany) was used;
[0046] 1. Myricetin inhibits the formation of biofilm on the surface of X80 carbon steel samples:
[0047] The steel samples were placed in a licheniformis solution containing 0.5 g / L myricetin, and a control group was set up at the same time. The control group was a sample of the same species as the experimental group placed in a licheniformis solution without myricetin. After 3 and 7 days of incubation, the biofilm formed on the surface of the X80 sample was observed by scanning electron microscopy. The results showed that a dense biofilm formed on the surface of the metal sample immersed in the system without myricetin, while in the system containing myricetin, there were basically no bacteria on the metal surface. This result shows that the addition of myricetin effectively inhibited the formation of biofilms. At the same time, after 3 and 7 days of incubation, the biofilm formation was detected by laser confocal microscopy. A dense biofilm was detected on the surface of the sample immersed in the solution without myricetin, however, sparse single cells were occasionally detected on the surface of the sample immersed in the solution with 0.5 g / L myricetin. The experimental results are consistent with the results of scanning electron microscopy.
[0048] 2. Myricetin dispels mature biofilm on the surface of X80
[0049] First, the X80 samples were immersed in culture medium and incubated for 3 days to form mature biofilms on the sample surface. Then, the X80 samples were immersed in culture medium containing 0.5g / L myricetin and incubated for 24 hours and 72 hours respectively. The results showed that after 24 hours of myricetin treatment, the biofilm density was significantly reduced to only half of that without treatment. When the treatment time was extended to 72 hours, the biofilm density, bacterial activity and biofilm thickness continued to decrease, and bacterial fluorescence was basically invisible in the field of vision, indicating that the mature biofilm was successfully removed, indicating that myricetin has the effect of removing mature biofilms.
[0050] Example 3
[0051] The metal used in this embodiment is X80 carbon steel;
[0052] The culture medium used in this embodiment is soil simulation liquid, and the specific composition is shown in Example 1;
[0053] In this example, a contact angle tester (TBU 95, DataPhysics, German) was used;
[0054] In this example, an atomic force microscope (AFM, Bruker Dimension ICON, USA) was used;
[0055] 1. Contact angle detection
[0056] The steel samples were immersed in a soil simulation solution containing 0.5g / L myricetin for 4 hours, and a control group was set up at the same time. The control group was the same sample as the experimental group immersed in a soil simulation solution without myricetin for 4 hours and the sample was not immersed. The samples were air-dried and the contact angle was tested. The test results showed that the contact angle of the metal sample that was not immersed in the solution remained basically unchanged and stabilized at 55°. The sample was immersed in the soil simulation solution for 4 hours and the contact angle was measured after air-drying. The surface contact angle of the sample became smaller, about 15°, because corrosion products were formed on the metal surface after immersion, which increased the hydrophilicity of the metal surface. However, when the sample was immersed in a 0.5g / L myricetin solution, after the same immersion time, the contact angle of X80 carbon steel increased significantly and remained greater than 10° of the sample immersed in the soil simulation solution, about 30°. Myricetin is a hydrophobic substance that can increase the hydrophobicity of the sample surface, thereby increasing the contact angle, so the experimental results of the contact angle test show that myricetin can be adsorbed on the metal surface.
[0057] 2. Atomic force microscope photography
[0058] The steel samples were immersed in soil simulation solution containing 0.5g / L myricetin for 0, 1, 5, and 30 minutes respectively, and the adsorption of myricetin on the surface of the X80 metal sample after immersion in the soil simulation solution was directly observed by atomic force microscopy. The results showed that with the increase of immersion time, the irregular adsorbents on the surface of the metal sample continued to increase, the sample preparation scratches decreased, and the surface undulations increased. This shows that the adsorption of myricetin on the metal surface is a spontaneous dynamic process. With the extension of time, the adsorption amount of myricetin on the surface of X80 carbon steel increased, and a corrosion inhibitor protective layer was gradually formed, achieving the effect of inhibiting corrosion.
Claims
1. An application of myricetin as an environmentally friendly microbial corrosion inhibitor, wherein myricetin is used as an environmentally friendly microbial corrosion inhibitor to inhibit microbial corrosion.
2. The use according to claim 1, characterized in that: Myricetin is added into an environment where microbial corrosion can occur, and the uniform mass concentration of myricetin in the environment is ensured to be 0.1-1 g / L.
3. The use according to claim 2, characterized in that: The average mass concentration of myricetin is 0.5g / L.
4. The use according to claim 2 or 3, characterized in that: The environment that can cause microbial corrosion is a marine environment, a soil environment, an oral environment or a liquid transportation environment.
5. The use according to claim 2 or 3, characterized in that: The myricetin can reduce the thickness of the biofilm formed on the metal surface in an environment causing microbial corrosion, and is used to inhibit microbial corrosion of metals.
6. The use of myricetin as an environmentally friendly microbial corrosion inhibitor according to claim 5, characterized in that: The metal includes, but is not limited to, carbon steel, stainless steel, and titanium alloy.
7. The use of myricetin as an environmentally friendly microbial corrosion inhibitor according to claim 2 or 3, characterized in that: The chemical structural formula of myricetin is:
8. The use of myricetin as an environmentally friendly microbial corrosion inhibitor according to claim 2 or 3, characterized in that: Adding myricetin can inhibit microbial corrosion by 67% to 99%.
9. The use of myricetin as an environmentally friendly microbial corrosion inhibitor according to claim 1, characterized in that: The detection method for the application of myricetin as an environmentally friendly microbial corrosion inhibitor comprises the following steps: Step 1: Preparation of environmentally friendly microbial corrosion inhibitor Myricetin and anhydrous ethanol are mixed evenly to obtain a myricetin solution, wherein the mass concentration of the myricetin solution is 10 g / L, and the myricetin solution is diluted to 0.1-1.0 g / L using a water-soluble culture solution; Step 2: Corrosion Inhibition The material corroded by microorganisms was immersed in the myricetin solution to inhibit the microorganisms. The concentration of microorganisms in the microbial corrosion system was 10 4 ~10 7 CFU mL -1 ; The culture time is 7 days and the culture temperature is 30℃.