Method for visual detection of dynamic release of antifouling agents in functional coatings for ships

Abstract

The application discloses a kind of functional coating anti-fouling agent dynamic release visual detection method for ship, and the present application aims at solving the problem that existing detection method is difficult to measure anti-fouling agent in anti-fouling coating.The detection method is as follows: 1, anti-fouling agent in functional coating for ship is used as chemical standard;2, Raman spectrometer is used to determine tracking peak;3, functional coating is detected by Raman spectrometer, and Raman single-window test is carried out on calibration point to obtain tracking peak intensity of different calibration points;4, soak in seawater environment, and carry out Raman single-window test on the same position of calibration point after corrosion;5, based on optical principle, the concentration range is adjusted by adjusting RGB value, and the tracking peak intensity measured before and after corrosion is converted into color concentration information.The visual detection method can realize original position point measurement, and the detection result has high visualization degree, and the process before and after anti-fouling agent dynamic release is intuitively displayed.

Description

Technical Field

[0001] This invention belongs to the field of Raman spectroscopy analysis and detection technology, specifically relating to a visualization method for the dynamic release of key components (antifouling agents) in coatings using Raman spectroscopy detection. Background Technology

[0002] Taking antifouling coatings as an example, their application can significantly mitigate the impact of biofouling. By releasing toxic agents slowly, they aim to eliminate marine fouling organisms, making them one of the most economical and efficient measures. Antifouling agents are a crucial component of antifouling coatings and the main part that enables their functionality. The dynamic release of metallic antifouling agents in antifouling coatings is a key fundamental technology for their antifouling performance. However, current research on the release patterns of antifouling agents in antifouling coatings is limited.

[0003] Raman spectroscopy signals originate from molecular vibrations and rotations, providing detailed molecular vibrational information. It is non-destructive, offers fine "fingerprint-like" resolution, is simple to apply, rapid in measurement, and has good repeatability, making it widely used in non-destructive surface testing. Different substances have different molecular structures and therefore different Raman characteristic spectra, enabling qualitative analysis of substances. Currently, there is limited research on the Raman spectral visualization characterization of key components (antifouling agents) in marine functional coatings, which urgently needs further investigation. Summary of the Invention

[0004] The purpose of this invention is to solve the problem that existing detection methods are difficult to locate and measure antifouling agents in antifouling coatings, and to provide a visual detection method for the dynamic release of antifouling agents in marine functional coatings.

[0005] The present invention provides a method for visually detecting the dynamic release of antifouling agents in marine functional coatings, which is implemented according to the following steps:

[0006] I. Using antifouling agents in marine functional coatings as chemical standard substances;

[0007] 2. Raman spectroscopy was used to perform Raman measurements on chemical standards, and the wavenumbers of the unique chemical bond Raman characteristic peaks in the chemical standards were selected as tracking peaks.

[0008] 3. The functional coatings for marine use were tested using a Raman spectrometer. Multiple calibration points were selected on the surface of the functional coatings for marine use, with the same spacing between adjacent calibration points. Raman single-window tests were performed on the calibration points to obtain the tracking peak intensities of different calibration points.

[0009] IV. The functional coating for marine applications with calibration points is immersed in seawater for corrosion treatment. After corrosion, the calibration points at the same location are subjected to Raman single-window testing. Then, the tracking peak intensity is fitted with Gaussian to obtain a more significant peak shape and perform peak value statistics.

[0010] V. Based on optical principles, the concentration range is adjusted by changing the RGB values ​​of the three primary optical colors. The intensity of the tracking peak measured before corrosion in step three and after corrosion in step four is converted into color concentration information, thereby visualizing the concentration changes of the antifouling agent dynamically released in the antifouling coating.

[0011] This invention utilizes Raman spectroscopy to detect the dynamic release of antifouling agents in antifouling coatings, and establishes an antifouling agent concentration-color correlation model to visualize the concentration changes before and after dynamic release.

[0012] This invention utilizes Raman spectroscopy to perform Raman measurements on antifouling agent standards, selecting the characteristic peak positions of chemical bonds in the Raman spectra of the antifouling agent in the antifouling coating as the tracking peaks. Then, Raman spectroscopy is used to detect antifouling coating samples. Calibration points with equal spacing are selected on the surface, and the samples are immersed in seawater for corrosion. Single-window Raman tests are performed on the same points before and after corrosion. The tracking peak intensities are statistically analyzed using Gaussian fitting, and the intensities before and after corrosion are compared. The obtained Raman peak signals are converted into color concentration information based on optical principles, visually displaying the concentration changes of the antifouling agent in the antifouling coating before and after dynamic release.

[0013] The method for detecting the dynamic release of antifouling agents in antifouling coatings using Raman spectroscopy, as described in this invention, has the following advantages:

[0014] (1) The present invention is simple to operate, easy to prepare the test sample, and has a short Raman signal collection time.

[0015] (2) It enables on-site measurement, and the detection results are highly visualized, allowing for an intuitive display of the dynamic release process of the antifouling agent.

[0016] (3) Combined with a (handheld) Raman instrument, it can be used for on-site testing in industrial production.

[0017] (4) This invention can not only track and analyze key components at local locations, but also conduct quantitative and visual studies on different calibration points in a certain area before and after corrosion. Attached Figure Description

[0018] Figure 1 The images shown are Raman spectra of the zinc pyridine thione standard and the antifouling coating used in the examples.

[0019] Figure 2 The locations and coordinates of Raman spectral markers before and after corrosion of the antifouling coating in this embodiment are shown.

[0020] Figure 3 This is a comparison of the peak intensity of the calibration point before and after corrosion using Raman spectroscopy in the example, where ■ represents before corrosion and ● represents after corrosion;

[0021] Figure 4This example shows the conversion diagram of peak intensity and color concentration for pre-corrosion calibration point tracking based on optical principles.

[0022] Figure 5 The example shows the conversion diagram of peak intensity and color concentration of the calibration point tracking after corrosion, based on optical principles. Detailed Implementation

[0023] Specific Implementation Method 1: This implementation method, which utilizes Raman spectroscopy to detect the dynamic release of antifouling agents in antifouling coatings, is carried out according to the following steps:

[0024] I. Using antifouling agents in marine functional coatings as chemical standard substances;

[0025] 2. Raman spectroscopy was used to perform Raman measurements on chemical standards, and the wavenumbers of the unique chemical bond Raman characteristic peaks in the chemical standards were selected as tracking peaks.

[0026] 3. The functional coatings for marine use were tested using a Raman spectrometer. Multiple calibration points were selected on the surface of the functional coatings for marine use, with the same spacing between adjacent calibration points. Raman single-window tests were performed on the calibration points to obtain the tracking peak intensities of different calibration points.

[0027] IV. The functional coating for marine applications with calibration points is immersed in seawater for corrosion treatment. After corrosion, the calibration points at the same location are subjected to Raman single-window testing. Then, the tracking peak intensity is fitted with Gaussian to obtain a more significant peak shape and perform peak value statistics.

[0028] V. Based on optical principles, the concentration range is adjusted by changing the RGB values ​​of the three primary optical colors. The intensity of the tracking peak measured before corrosion in step three and after corrosion in step four is converted into color concentration information, thereby visualizing the concentration changes of the antifouling agent dynamically released in the antifouling coating.

[0029] The selection criteria for the antifouling agent tracking peak in step one of this embodiment can also be determined using molecular simulation software (Gaussian).

[0030] In step two of this embodiment, the wavenumber of the Raman characteristic peak of the chemical bond unique to the chemical standard is selected as the tracking peak. That is, the selected tracking peak is a Raman peak that is not present in other components of the antifouling coating.

[0031] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the antifouling agent mentioned in step one is cuprous oxide, cuprous thiocyanate, zinc pyridinethione, or copper pyridinethione.

[0032] Specific Implementation Method 3: This implementation method differs from Specific Implementation Method 1 or 2 in that the distance between adjacent calibration points in step 3 is 1 to 5 μm.

[0033] Specific Implementation Method Four: This implementation method differs from Specific Implementation Method Three in that the distance between adjacent calibration points is 1 to 2 μm.

[0034] Specific Implementation Method 5: This implementation method differs from Specific Implementation Methods 1 to 4 in that the soaking time of the antifouling coating with calibration points in the seawater environment in step 4 is 8 to 24 hours.

[0035] Specific Implementation Method Six: This implementation method differs from Specific Implementation Method Five in that the soaking time for the antifouling coating with calibration points in the seawater environment in step four is 12 hours.

[0036] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the higher the intensity of the tracking peak in step five, the darker the color of the conversion.

[0037] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Method Seven in that the color concentration information in step five is presented by optical grayscale or monochrome color concentration.

[0038] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One through Eight in that a Raman signal intensity-concentration correlation model is established in step five to visualize the concentration change before and after dynamic release. The correlation model is shown in formula (1):

[0039]

[0040] I represents the Raman signal intensity collected by the optical system on the sample surface, K represents the Raman scattering cross-section of the molecule, Φ represents the laser incident power on the sample surface, C represents the concentration of the antifouling agent, k and k' are the absorption coefficients of the incident light and the scattered light, respectively, Z is the distance traveled by the incident light and the scattered light, h(z) is the transfer function of the optical system, and B is the thickness of the sample cell.

[0041] In this embodiment, the sample cell refers to the effective range of Raman spectroscopy within the sample.

[0042] Example: This example demonstrates a method for detecting the dynamic release of antifouling agents in antifouling coatings using Raman spectroscopy, implemented according to the following steps:

[0043] I. Zinc pyrithione, an antifouling agent in marine functional coatings, was used as a chemical standard.

[0044] II. Raman spectroscopy of the antifouling agent zinc pyrithione standard was performed using a Horiba Lab RAM HR Evolution Raman spectrometer. The Raman test parameters were set as follows: 532 nm laser source, 1% laser intensity, 30 s scan time, and one superposition. The selected concentration in the antifouling coating was 1143±15 cm⁻¹. -1 As a tracer of antifouling agents;

[0045] 3. Raman spectroscopy was used to test the antifouling coating. Multiple calibration points were selected on the surface of the antifouling coating, with a spacing of 2 μm between adjacent calibration points. Figure 2 To determine the location and coordinates of the Raman spectral markers before and after corrosion of the antifouling coating, a single-window Raman test was performed on the calibration points, with the scanning center at 1143 cm⁻¹. -1 This yields an antifouling coating with calibration points;

[0046] IV. Immerse the antifouling coating with calibration points in seawater for 12 hours to corrode the antifouling coating. Perform Raman single-window testing on the calibration points at the same location after corrosion. Then, perform Gaussian fitting on the tracking peak intensity to obtain a more significant peak shape and perform peak value statistics.

[0047] 5. The intensity of the tracking peak measured before and after corrosion is converted into optical grayscale information. The higher the intensity of the tracking peak, the darker the converted color, thereby visualizing the concentration change of the antifouling agent dynamically released in the antifouling coating.

[0048] In this embodiment, the Raman test conditions for the antifouling agent chemical standard are the same as those for the antifouling coating.

[0049] In this embodiment, the Raman test results of the zinc pyridinethione standard and the antifouling coating are as follows: Figure 1 As shown, the selected antifouling coating is 1143±15cm. -1 As a tracking peak, to facilitate positioning when selecting calibration points, scratches are made on the left and bottom sides of the calibration points for positioning, such as... Figure 2 As shown.

[0050] In this embodiment, the Raman tracking peak intensity at the calibration point without seawater immersion is: Figure 3 The upper curve, after being soaked in seawater for 12 hours, showed the Raman tracking peak intensity at the calibration point as follows: Figure 3 The lower curve. According to quantitative analysis of Raman spectroscopy, the higher the intensity of the characteristic peak, the greater the concentration of zinc pyrithione. The peak intensities before and after corrosion were visualized and allocated using optical principles. Figure 4 and Figure 5 The results before and after corrosion are visualized. After corrosion, the concentration decreases and the concentration at each point becomes more uniform. This indicates that zinc pyrithione slowly diffuses to the outside world and transfers inside the antifouling coating during the process of preventing biofouling.

[0051] This embodiment, combined with a handheld Raman instrument, allows for rapid analysis of the production site, comparing the measured data with... Figure 4 By comparing, the concentration of zinc pyrithione can be quickly determined.

Claims

1. A method for visual detection of dynamic release of antifouling agents in functional coatings for ships, characterised in that The anti-fouling agent dynamic release visual detection method is realized according to the following steps: I. The anti-fouling agent in the functional coating for ships is used as a chemical standard; II. The Raman spectrometer is used to determine the chemical standard, and the Raman characteristic peak wave number of the unique chemical bond in the chemical standard is selected as the tracking peak; III. The Raman spectrometer is used to detect the functional coating for ships, multiple calibration points are selected on the surface of the functional coating for ships, the adjacent calibration points have the same spacing, the Raman single window test is performed on the calibration points, and the tracking peak intensity of different calibration points is obtained; IV. The functional coating for ships with calibration points is immersed in seawater environment for corrosion treatment, the Raman single window test is performed on the calibration points at the same position after corrosion, then the tracking peak intensity is Gaussian fitted, a more significant peak type is obtained, and the peak value is counted; V. Based on the optical principle, the concentration range is adjusted by adjusting the optical three primary colors RGB values, the tracking peak intensity measured in steps III and IV is converted into color concentration information, so that the concentration change of the dynamic release of the anti-fouling agent in the anti-fouling coating can be visualized.

2. The method for visualizing the dynamic release of antifouling agents in functional coatings for ships according to claim 1, characterized in that The anti-fouling agent in step I is cuprous oxide, cuprous thiocyanate, zinc pyrithione or copper pyrithione.

3. The method of claim 1, wherein the functional coating for ships is a coating for a ship that is applied to the surface of the ship to prevent marine biofouling. The spacing between adjacent calibration points in step III is 1-5 μm.

4. The method of visualizing the dynamic release of antifouling agents from functional marine coatings according to claim 3, characterized in that The spacing between adjacent calibration points is 1-2 μm.

5. The method of visualizing the dynamic release of antifouling agents from functional marine coatings according to claim 1, characterized in that The time for immersing the anti-fouling coating with calibration points in seawater environment in step IV is 8-24 h.

6. The method of visualizing the dynamic release of antifouling agents from functional marine coatings according to claim 5, characterized in that The time for immersing the anti-fouling coating with calibration points in seawater environment in step IV is 12 h.

7. The method of visualizing the dynamic release of antifouling agents from functional marine coatings according to claim 1, characterized in that The higher the tracking peak intensity is, the deeper the converted color is.

8. The method of visualizing the dynamic release of antifouling agents from functional marine coatings according to claim 7, characterized in that The color concentration information is presented by optical gray scale or single color concentration in step V.

9. The method of visualizing the dynamic release of antifouling agents from functional marine coatings according to claim 1, characterized in that A Raman signal intensity-concentration correlation model is established to visualize the concentration change before and after the dynamic release in step V, and the correlation model is shown in formula (1): Wherein I is the Raman signal intensity collected by the optical system on the surface of the sample, K is the Raman scattering cross section area of the molecule, Φ is the laser incident power on the surface of the sample, C represents the concentration of the anti-fouling agent, k and k' are the absorption coefficients of the incident light and the scattered light, Z is the distance through which the incident light and the scattered light pass, h(z) is the transmission function of the optical system, and B is the thickness of the sample cell.

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